Influence of Al content on non-equilibrium solidification behavior of Ni-Al-Ta model single crystal alloys

NASA Astrophysics Data System (ADS)

Ai, Cheng; Zhou, Jian; Zhang, Heng; Zhao, Xinbao; Pei, Yanling; Li, Shusuo; Gong, Shengkai

2016-01-01

The non-equilibrium solidification behaviors of five Ni-Al-Ta ternary model single crystal alloys with different Al contents were investigated by experimental analysis and theoretical calculation (by JMatPro) in this study. These model alloys respectively represented the γ' phase with various volume fractions (100%, 75%, 50%, 25% and 0%) at 900 °C. It was found that with decreasing Al content, liquidus temperature of experimental alloys first decreased and then increased. Meanwhile, the solidification range showed a continued downward trend. In addition, with decreasing Al content, the primary phases of non-equilibrium solidified model alloys gradually transformed from γ' phase to γ phase, and the area fraction of which first decreased and then increased. Moreover, the interdendritic/intercellular precipitation of model alloys changed from β phase (for 100% γ') to (γ+γ')Eutectic (for 75% γ'), (γ+γ')Eutectic+γ' (for 50% γ' and 25% γ') and none interdendritic precipitation (for 0% γ'), and the last stage non-equilibrium solidification sequence of model alloys was determined by the nominal Al content and different microsegregation behaviors of Al element.

Molecular finite-size effects in stochastic models of equilibrium chemical systems.

PubMed

Cianci, Claudia; Smith, Stephen; Grima, Ramon

2016-02-28

The reaction-diffusion master equation (RDME) is a standard modelling approach for understanding stochastic and spatial chemical kinetics. An inherent assumption is that molecules are point-like. Here, we introduce the excluded volume reaction-diffusion master equation (vRDME) which takes into account volume exclusion effects on stochastic kinetics due to a finite molecular radius. We obtain an exact closed form solution of the RDME and of the vRDME for a general chemical system in equilibrium conditions. The difference between the two solutions increases with the ratio of molecular diameter to the compartment length scale. We show that an increase in the fraction of excluded space can (i) lead to deviations from the classical inverse square root law for the noise-strength, (ii) flip the skewness of the probability distribution from right to left-skewed, (iii) shift the equilibrium of bimolecular reactions so that more product molecules are formed, and (iv) strongly modulate the Fano factors and coefficients of variation. These volume exclusion effects are found to be particularly pronounced for chemical species not involved in chemical conservation laws. Finally, we show that statistics obtained using the vRDME are in good agreement with those obtained from Brownian dynamics with excluded volume interactions.

Phase behavior, rheological characteristics and microstructure of sodium caseinate-Persian gum system.

PubMed

Sadeghi, Farzad; Kadkhodaee, Rassoul; Emadzadeh, Bahareh; Phillips, Glyn O

2018-01-01

In this study, the phase behavior of sodium caseinate-Persian gum mixtures was investigated. The effect of thermodynamic incompatibility on phase distribution of sodium caseinate fractions as well as the flow behavior and microstructure of the biopolymer mixtures were also studied. The phase diagram clearly demonstrated the dominant effect of Persian gum on the incompatibility of the two biopolymers. SDS-PAGE electrophoresis indicated no selective fractionation of sodium caseinate subunits between equilibrium phases upon de-mixing. The microstructure of mixtures significantly changed depending on their position within the phase diagram. Fitting viscometric data to Cross and Bingham models revealed that the apparent viscosity, relaxation time and shear thinning behavior of the mixtures is greatly influenced by the volume ratio and concentration of the equilibrium phases. There is a strong dependence of the flow behavior of sodium caseinate-Persian gum mixtures on the composition of the equilibrium phases and the corresponding microstructure of the system. Copyright © 2017. Published by Elsevier Ltd.

Mechanisms of decreased left ventricular preload during continuous positive pressure ventilation in ARDS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dhainaut, J.F.; Devaux, J.Y.; Monsallier, J.F.

1986-07-01

Continuous positive pressure ventilation is associated with a reduction in left ventricular preload and cardiac output, but the mechanisms responsible are controversial. The decrease in left ventricular preload may result exclusively from a decreased systemic venous return due to increased pleural pressure, or from an additional effect such as decreased left ventricular compliance. To determine the mechanisms responsible, we studied the changes in cardiac output induced by continuous positive pressure ventilation in eight patients with the adult respiratory distress syndrome. We measured cardiac output by thermodilution, and biventricular ejection fraction by equilibrium gated blood pool scintigraphy. Biventricular end-diastolic volumes weremore » then calculated by dividing stroke volume by ejection fraction. As positive end-expiratory pressure increased from 0 to 20 cm H/sub 2/O, stroke volume and biventricular end-diastolic volumes fell about 25 percent, and biventricular ejection fraction remained unchanged. At 20 cm H/sub 2/O positive end-expiratory pressure, volume expansion for normalizing cardiac output restored biventricular end-diastolic volumes without markedly changing biventricular end-diastolic transmural pressures. The primary cause of the reduction in left ventricular preload with continuous positive pressure ventilation appears to be a fall in venous return and hence in right ventricular stroke volume, without evidence of change in left ventricular diastolic compliance.« less

An experimental and modeling study of grain-scale uranium desorption from field-contaminated sediments and the potential influence of microporosity on mass-transfer

NASA Astrophysics Data System (ADS)

Stoliker, D.; Liu, C.; Kent, D. B.; Zachara, J. M.

2012-12-01

The aquifer below the 300-Area of the Hanford site (Richland, WA, USA) is plagued by a persistent plume of dissolved uranium (U(VI)) in excess of the Environmental Protection Agency drinking water maximum contamination level even after the removal of highly contaminated sediments. The aquifer sediments in the seasonally saturated lower vadose zone act as both a source and sink for uranium during stage changes in the nearby Columbia River. Diffusion limitation of uranium mass-transfer within these sediments has been cited as a potential cause of the plume's persistence. Equilibrium U(VI) sorption is a strong function of variable chemical conditions, especially carbonate, hydrogen, and uranyl ion activities. Field-contaminated sediments from the site require up to 1,000 hours to reach equilibrium in static batch reactors. Increases in U(VI) concentrations over longer time-scales result from changes in chemical conditions, which drive reactions with sediments that favor U(VI) desorption. Grain-scale U(VI) sorption/desorption rates are slow, likely owing to diffusion of U(VI) and other solutes through intra-granular pore domains. In order to improve understanding of the impact of intra-granular diffusion and chemical reactions controlling grain-scale U(VI) release, experiments were conducted on individual particle size fractions of a <8 mm composite of field-contaminated, lower vadose zone sediments. For each size fraction, equilibrium U(VI) sorption/desorption in static batch reactors was well-described by surface complexation models over a range of chemical conditions applicable to the field site. Desorption rates from individual size fractions in flow-through batch reactors, examined under a single set of constant chemical conditions with multiple stop-flow events, were similar for all size fractions <2 mm. Kinetic U(VI) desorption in flow-through batch reactors was modeled using a multi-rate surface complexation approach, where sorption/desorption rates were assumed to be proportional to the displacement from equilibrium and multiple diffusion domains were described with a two-parameter lognormal distribution of mass-transfer rate coefficients. Parameters describing mass transfer were the same for all size fractions <2 mm but differed for the largest (2-8 mm) size fraction. The evolution of pH, along with dissolved cation and carbonate concentrations, was modeled using equilibrium cation exchange, rate-limited calcite dissolution, aerobic respiration, and silica dissolution. Desorption and chemical reaction models calibrated with individual size fractions predicted U(VI) and chemical composition as a function of time for the bulk sediment sample. Volumes of pores less than 2.4 nm, quantified using nitrogen adsorption-desorption isotherms, were the same for all size fractions < 2 mm, nearly double that of the 2-8 mm size fraction. Similarity in the observed pore volumes and multi-rate mass-transfer parameters across all size fractions <2 mm suggest the importance of pores in this size class in controlling slow grain-scale U(VI) desorption rates. Models like these provide a means for testing the influence of grain-scale mass-transfer on the persistence of U(VI) plume at the site.

Table and charts of equilibrium normal-shock properties for hydrogen-helium mixtures with velocities to 70 km/sec. Volume 1: 0.95 H2-0.05 He (by volume)

NASA Technical Reports Server (NTRS)

Miller, C. G., III; Wilder, S. E.

1976-01-01

Equilibrium thermodynamic and flow properties are presented in tabulated and graphical form for moving, standing, and reflected normal shock waves into hydrogen-helium mixtures representative of postulated outer planet atmospheres. These results are presented in four volumes and the volmetric compositions of the mixtures are 0.95H2-0.05He in Volume 1, 0.90H2-0.10He in Volume 2, 0.85H2-0.15He in Volume 3, and 0.75H2-0.25He in Volume 4. Properties include pressure, temperature, density, enthalpy, speed of sound, entropy, molecular-weight ratio, isentropic exponent, velocity, and species mole fractions. Incident (moving) shock velocities are varied from 4 to 70 km/sec for a range of initial pressure of 5 N/sq m to 100 kN/sq m. Results are applicable to shock-tube flows and for determining flow conditions behind the normal portion of the bow shock about a blunt body at high velocities in postulated outer planet atmospheres. The document is a revised version of the original edition of NASA SP-3085 published in 1974.

Water content dependence of trapped air in two soils

USGS Publications Warehouse

Stonestrom, David A.; Rubin, Jacob

1989-01-01

An improved air pycnometer method was used to examine the water content dependence of trapped-air volumes in two repacked, nonswelling soils. Trapped-air volumes were determined at a series of hydrostatic equilibrium stages which were attained during water pressure-controlled wetting and drying cycles over a range of 0 to −10 kPa for a sand and 0 to −20 kPa for a loam. Small pressure perturbations, between 0.2 and 0.6 kPa, were used in the air pycnometer method. Volumes of trapped air obtained at each hydrostatic equilibrium stage were independent of perturbation level and remained relatively constant over the time required to make repeated determinations. In contrast with most of the results obtained in previous studies, which often showed irregular relations, in this study the volume fraction of trapped air was found to be a regular, monotonically increasing (though possibly hysteretic) function of water content. For the soils studied, the function definitely exceeded zero only at water contents greater than 70% of saturation. However, during the initial drying from complete water saturation, the volume fraction of trapped air was virtually zero. Air trapping influenced the water retention curves significantly only at water contents higher than about 60% of saturation. Except at zero water pressure, however, not all of the differences between the initial and the other drying retention curves were accounted for by observed differences in trapped-air volumes. Air trapping was not required for the onset of hysteresis in the water retention relation for the cases studied, i.e., when drying-to-wetting reversals were imposed at about 27% and 40% of saturation for the sand and loam soils, respectively.

Thermocouple psychrometry

USGS Publications Warehouse

Andraski, Brian J.; Scanlon, Bridget R.; Dane, Jacob H.; Topp, G. Clarke

2002-01-01

Thermocouple psychrometry is a technique that infers the water potential of the liquid phase of a sample from measurements within the vapor phase that is in equilibrium with the sample. The theoretical relation between water potential of the liquid phase and relative humidity of the vapor phase is given by the Kelvin equation Ψ = energy/volume = (RT/Vw) ln(p/po) [3.2.3–1]where ψ is water potential (sum of matric and osmotic potential, MPa), R is the universal gas constant (8.314 × 10-6 MJ mol-1 K-1), T is temperature (K), Vw is molar volume of water (1.8 × 10-5 m3 mol-1), and p/po is relative humidity expressed as a fraction where p is actual vapor pressure of air in equilibrium with the liquid phase (MPa) and po is saturation vapor pressure (MPa) at T.

Predicting equilibrium uranium isotope fractionation in crystals and solution

NASA Astrophysics Data System (ADS)

Schauble, E. A.

2015-12-01

Despite the rapidly growing interest in using 238U/235U measurements as a proxy for changes in oxygen abundance in surface and near-surface environments, the present theoretical understanding of uranium isotope fractionation is limited to a few simple gas-phase molecules and analogues of dissolved species (e.g., 1,2,3). Understanding uranium isotope fractionation behavior in more complicated species, such as crystals and adsorption complexes, will help in the design and interpretation of experiments and field studies, and may suggest other uses for 38U/235U measurements. In this study, a recently developed first-principles method for estimating the nuclear volume component of field shift fractionation in crystals and complex molecular species (4) is combined with mass-dependent fractionation theory to predict equilibrium 38U/235U fractionations in aqueous and crystalline uranium compounds, including uraninite (UO2). The nuclear field shift effect, caused by the interaction of electrons with the finite volume of the positive charge distribution in uranium nuclei, is estimated using Density Functional Theory and the Projector Augmented Wave method (DFT-PAW). Tests against relativistic electronic structure calculations and Mössbauer isomer shift data indicate that the DFT-PAW method is reasonably accurate, while being much better suited to models of complex and crystalline species. Initial results confirm previous predictions that the nuclear volume effect overwhelms mass depdendent fractionation in U(VI)-U(IV) exchange reactions, leading to higher 238U/235U in U(IV) species (i.e., for UO2 xtal vs. UO22+aq, ln αNV ≈ +1.8‰ , ln αMD ≈ -0.8‰, ln αTotal ≈ +1.0‰ at 25ºC). UO2 and U(H2O)94+, are within ~0.4‰ of each other, while U(VI) species appear to be more variable. This suggests that speciation is likely to significantly affect natural uranium isotope fractionations, in addition to oxidation state. Tentatively, it appears that uranyl-type (UO22+-bearing) structures will tend to have higher 238U/235U than uranate-type structures that lack strong U=O bonds. References: 1. Bigeleisen (1996) JACS 118:3676; 2. Schauble (2006) Eos 87:V21B-0570; 3. Abe et al. (2008) J Chem Phys 128:144309, 129:164309, & Abe et al. (2010) J Chem Phys 133:044309; 4. Schauble (2013) PNAS 110:17714.

The Effect of Post-heat Treatment on the Microstructures of Single Crystal DD6 Superalloy

NASA Astrophysics Data System (ADS)

Li, Dongfan; Gao, Hangshan; Wen, Zhixun; Li, Zhenwei; Yue, Zhufeng

2016-09-01

Various thermal cycles at the end of solution heat treatment and their influences on microstructure of single crystal superalloy DD6 were studied by experiments. During various thermal cycles, the qualitative and quantitative microstructure of samples quenched of the transformations is microscopically characterized. This completely includes the large changes in volume fraction, size distribution and morphology of gamma prime precipitate experienced in the upper temperature transformation. Noticeable deviation from the equilibrium volume fraction of γ' phase is detected in both the dissolution and precipitation processes above 1,120°C for both moderate cooling and heating rate; differences were mainly attributed to the unsteady nature of the turbulent flow. The growth and alignment of the γ' precipitates are deeply influenced by several factors, e.g. ageing time, cooling rate and quenching temperature. In addition, interesting findings such as "labyrinth" and "cluster" morphologies were observed by scanning electron microscope. During precipitation processes, the complicated microstructure evolution is illustrated by considering the consecutive equilibrium shapes of a coherent precipitate, which grows under the interaction with its neighbors and the coherency of the precipitates improves their potential to resist dissolution.

Micelle Morphology and Mechanical Response of Triblock Gels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seitz, Michelle E.; Burghardt, Wesley R.; Shull, Kenneth R.

2010-01-12

The effect of polymer concentration on mechanical response and micelle morphology of ABA and AB copolymers in B-selective solvents has been systematically studied. Micelle morphology was determined using a combination of small-angle X-ray scattering, shear, and birefringence while mechanical response at low and high strains was determined using indentation techniques. Self-consistent field theory calculations were used to determine micelle volume fraction profiles and to construct an equilibrium phase map. The transition from spherical to cylindrical micelles increases the triblock gel modulus and energy dissipation. Combining knowledge of gel relaxation time, which determines the rate at which the gel can equilibratemore » its micelle structure, with the equilibrium phase map allows estimation of the experimental temperatures and time scales over which kinetic trapping will arrest micelle structure evolution. Kinetic trapping enables cylindrical morphologies to be obtained at significantly lower polymer fractions than is possible in equilibrated systems.« less

About the choice of Gibbs' potential for modelling of FCC ↔ HCP transformation in FeMnSi-based shape memory alloys

NASA Astrophysics Data System (ADS)

Evard, Margarita E.; Volkov, Aleksandr E.; Belyaev, Fedor S.; Ignatova, Anna D.

2018-05-01

The choice of Gibbs' potential for microstructural modeling of FCC ↔ HCP martensitic transformation in FeMn-based shape memory alloys is discussed. Threefold symmetry of the HCP phase is taken into account on specifying internal variables characterizing volume fractions of martensite variants. Constraints imposed on model constants by thermodynamic equilibrium conditions are formulated.

Dynamic-contrast-enhanced-MRI with extravasating contrast reagent: Rat cerebral glioma blood volume determination

NASA Astrophysics Data System (ADS)

Li, Xin; Rooney, William D.; Várallyay, Csanád G.; Gahramanov, Seymur; Muldoon, Leslie L.; Goodman, James A.; Tagge, Ian J.; Selzer, Audrey H.; Pike, Martin M.; Neuwelt, Edward A.; Springer, Charles S.

2010-10-01

The accurate mapping of the tumor blood volume (TBV) fraction ( vb) is a highly desired imaging biometric goal. It is commonly thought that achieving this is difficult, if not impossible, when small molecule contrast reagents (CRs) are used for the T1-weighted (Dynamic-Contrast-Enhanced) DCE-MRI technique. This is because angiogenic malignant tumor vessels allow facile CR extravasation. Here, a three-site equilibrium water exchange model is applied to DCE-MRI data from the cerebrally-implanted rat brain U87 glioma, a tumor exhibiting rapid CR extravasation. Analyses of segments of the (and the entire) DCE data time-course with this "shutter-speed" pharmacokinetic model, which admits finite water exchange kinetics, allow TBV estimation from the first-pass segment. Pairwise parameter determinances were tested with grid searches of 2D parametric error surfaces. Tumor blood volume ( vb), as well as ve (the extracellular, extravascular space volume fraction), and Ktrans (a CR extravasation rate measure) parametric maps are presented. The role of the Patlak Plot in DCE-MRI is also considered.

First-principles investigations of equilibrium Ca, Mg, Si and O isotope fractionations between silicate melts and minerals

NASA Astrophysics Data System (ADS)

Qi, Y.; Liu, X.; Kang, J.; He, L.

2017-12-01

Equilibrium isotope fractionation factors are essential for using stable isotope data to study many geosciences processes such as planetary differentiation and mantle evolution. The mass-dependent equilibrium isotope fractionation is primarily controlled by the difference in bond energies triggered by the isotope substitution. With the recent advances in computational capabilities, first-principles calculation has become a reliable tool to investigate equilibrium isotopic fractionations, greatly improving our understanding of the factors controlling isotope fractionations. It is important to understand the isotope fractionation between melts and minerals because magmatism is critical for creating and shaping the Earth. However, because isotope fractionation between melts and minerals is small at high temperature, it is difficult to experimentally calibrate such small signature. Due to the disordered and dynamic character of melts, calculations of equilibrium isotope fractionation of melts are more challenging than that for gaseous molecules or minerals. Here, we apply first-principles molecular dynamics method to calculate equilibrium Ca, Mg, Si, and O isotope fractionations between silicate melts and minerals. Our results show that equilibrium Mg, Si, and O isotope fractionations between olivine and pure Mg2SiO4 melt are close to zero at high temperature (e.g. δ26Mgmelt-ol = 0.03 ± 0.04‰, δ30Simelt-ol = -0.06 ± 0.07‰, δ18Omelt-ol = 0.07‰ ± 0.08 at 1500 K). Equilibrium Ca, Mg, Si, and O isotope fractionations between diopside and basalt melt (67% CaMgSi2O6 + 33% CaAl2Si2O8) are also negligible at high temperature (e.g. δ44/40Camelt-cpx = -0.01 ± 0.02‰, δ26Mgmelt-cpx = -0.05 ± 0.14‰, δ30Simelt-cpx = 0.04 ± 0.04‰, δ18Omelt-cpx = 0.03 ± 0.07‰ at 1500 K). These results are consistent with the observations in natural samples that there is no significant Ca, Mg, Si, and O isotope fractionation during mantle partial melting, demonstrating the reliability of our methods. Thus, our results can be used to understand stable isotope fractionation during partial melting of mantle peridotite or fractional crystallization during magmatic differentiation. The first-principles molecular dynamics method is a promising tool to obtain equilibrium fractionation of more isotope systems for complicate liquids.

Corresponding-states laws for protein solutions.

PubMed

Katsonis, Panagiotis; Brandon, Simon; Vekilov, Peter G

2006-09-07

The solvent around protein molecules in solutions is structured and this structuring introduces a repulsion in the intermolecular interaction potential at intermediate separations. We use Monte Carlo simulations with isotropic, pair-additive systems interacting with such potentials. We test if the liquid-liquid and liquid-solid phase lines in model protein solutions can be predicted from universal curves and a pair of experimentally determined parameters, as done for atomic and colloid materials using several laws of corresponding states. As predictors, we test three properties at the critical point for liquid-liquid separation: temperature, as in the original van der Waals law, the second virial coefficient, and a modified second virial coefficient, all paired with the critical volume fraction. We find that the van der Waals law is best obeyed and appears more general than its original formulation: A single universal curve describes all tested nonconformal isotropic pair-additive systems. Published experimental data for the liquid-liquid equilibrium for several proteins at various conditions follow a single van der Waals curve. For the solid-liquid equilibrium, we find that no single system property serves as its predictor. We go beyond corresponding-states correlations and put forth semiempirical laws, which allow prediction of the critical temperature and volume fraction solely based on the range of attraction of the intermolecular interaction potential.

Equilibrium points, stability and numerical solutions of fractional-order predator-prey and rabies models

NASA Astrophysics Data System (ADS)

Ahmed, E.; El-Sayed, A. M. A.; El-Saka, H. A. A.

2007-01-01

In this paper we are concerned with the fractional-order predator-prey model and the fractional-order rabies model. Existence and uniqueness of solutions are proved. The stability of equilibrium points are studied. Numerical solutions of these models are given. An example is given where the equilibrium point is a centre for the integer order system but locally asymptotically stable for its fractional-order counterpart.

Hot interstellar tunnels. 1: Simulation of interacting supernova remnants

NASA Technical Reports Server (NTRS)

Smith, B. W.

1976-01-01

The theory required to build a numerical simulation of interacting supernova remnants is developed. The hot cavities within a population of remnants will become connected, with varying ease and speed, for a variety of assumed conditions in the outer shells of old remnants. Apparently neither radiative cooling nor thermal conduction in a large-scale galactic magnetic field can destroy hot cavity regions, if they grow, faster than they are reheated by supernova shock waves, but interstellar mass motions disrupt the contiguity of extensive cavities necessary for the dispersal of these shocks over a wide volume. Monte Carlo simulations show that a quasi-equilibrium is reached in the test space within 10 million yrs of the first supernova and is characterized by an average cavity filling fraction of the interstellar volume. Aspects of this equilibrium are discussed for a range of supernova rates. Two predictions are not confirmed within this range: critical growth of hot regions to encompass the entire medium, and the efficient quenching of a remnant's expansion by interaction with other cavities.

Cardiac T1 mapping in congenital heart disease: bolus vs. infusion protocols for measurements of myocardial extracellular volume fraction.

PubMed

Al-Wakeel-Marquard, Nadya; Rastin, Sanaz; Muench, Frédéric; O H-Ici, Darach; Yilmaz, Sevim; Berger, Felix; Kuehne, Titus; Messroghli, Daniel R

2017-12-01

Myocardial extracellular volume fraction (ECV) reflecting diffuse myocardial fibrosis can be measured with T1 mapping cardiovascular magnetic resonance (CMR) before and after the application of a gadolinium-based extracellular contrast agent. The equilibrium between blood and myocardium contrast concentration required for ECV measurements can be obtained with a primed contrast infusion (equilibrium contrast-CMR). We hypothesized that equilibrium can also be achieved with a single contrast bolus to accurately measure diffuse myocardial fibrosis in patients with congenital heart disease (CHD). Healthy controls (n = 17; median age 24.0 years) and patients with CHD (n = 19; 25.0 years) were prospectively enrolled. Using modified Look-Locker inversion recovery T1 mapping before, 15 min after bolus injection, and during constant infusion of gadolinium-DOTA, T1 values were obtained for blood pool and myocardium of the left ventricle (LV), the interventricular septum (IVS), and the right ventricle (RV) in a single midventricular plane in short axis or in transverse orientation. ECV of LV, IVS and RV by bolus-only and bolus-infusion correlated significantly in CHD patients (r = 0.94, 0.95, and 0.74; p < 0.01, respectively) and healthy controls (r = 0.96, 0.89, and 0.64; p < 0.05, respectively). Bland-Altman plots revealed no significant bias between the techniques for any of the analyzed regions. ECV of LV and RV myocardium measured by bolus-only T1 mapping agrees well with bolus-infusion measurements in patients with CHD. The use of a bolus-only approach facilitates the integration of ECV measurements into existing CMR imaging protocols, allowing for assessment of diffuse myocardial fibrosis in CHD in clinical routine.

A two phase Mach number description of the equilibrium flow of nitrogen in ducts

NASA Technical Reports Server (NTRS)

Bursik, J. W.; Hall, R. M.; Adcock, J. B.

1979-01-01

Some additional thermodynamic properties of the usual two-phase form which is linear in the moisture fraction are derived which are useful in the analysis of many kinds of duct flow. The method used is based on knowledge of the vapor pressure and Gibbs function as functions of temperature. With these, additional two-phase functions linear in moisture fraction are generated, which ultimately reveal that the squared ratio of mixture specific volume to mixture sound speed depends on liquid mass fraction and temperature in the same manner as do many weighted mean two-phase properties. This leads to a simple method of calculating two-phase Mach numbers for various duct flows. The matching of one- and two-phase flows at a saturated vapor point with discontinuous Mach number is also discussed.

[Interaction of surface-active base with fraction of membrane-bound Williams's protons].

PubMed

Iaguzhinskiĭ, L S; Motovilov, K A; Volkov, E M; Eremeev, S A

2013-01-01

In the process of mitochondrial respiratory H(+)-pumps functioning, the fraction membrane-bound protons (R-protons), which have an excess of free energy is formed. According to R.J. Williams this fraction is included as energy source in the reaction of ATP synthesis. Previously, in our laboratory was found the formation of this fraction was found in the mitochondria and on the outer surface of mitoplast. On the mitoslast model we strictly shown that non-equilibrium R-proton fraction is localized on the surface of the inner mitochondrial membrane. In this paper a surface-active compound--anion of 2,4,6-trichloro-3-pentadecylphenol (TCP-C15) is described, which selectively interacts with the R-protons fraction in mitochondria. A detailed description of the specific interaction of the TCP-C15 with R-protons fraction in mitochondria is presented. Moreover, in this work it was found that phosphate transport system reacts with the R-protons fraction in mitochondria and plays the role of the endogenous volume regulation system of this fraction. The results of experiments are discussed in the terms of a local coupling model of the phosphorylation mechanism.

Cryogenic Calcite: A Morphologic and Isotopic Analog to the ALH84001 Carbonates

NASA Technical Reports Server (NTRS)

Niles, P. B.; Leshin, L. A.; Socki, R. A.; Guan, Y.; Ming, D. W.; Gibson, E. K.

2004-01-01

Martian meteorite ALH84001 carbonates preserve large and variable microscale isotopic compositions, which in some way reflect their formation environment. These measurements show large variations (>20%) in the carbon and oxygen isotopic compositions of the carbonates on a 10-20 micron scale that are correlated with chemical composition. However, the utilization of these data sets for interpreting the formation conditions of the carbonates is complex due to lack of suitable terrestrial analogs and the difficulty of modeling under non-equilibrium conditions. Thus, the mechanisms and processes are largely unknown that create and preserve large microscale isotopic variations in carbonate minerals. Experimental tests of the possible environments and mechanisms that lead to large microscale isotopic variations can help address these concerns. One possible mechanism for creating large carbon isotopic variations in carbonates involves the freezing of water. Carbonates precipitate during extensive CO2 degassing that occurs during the freezing process as the fluid s decreasing volume drives CO2 out. This rapid CO2 degassing results in a kinetic isotopic fractionation where the CO2 gas has a much lighter isotopic composition causing an enrichment of 13C in the remaining dissolved bicarbonate. This study seeks to determine the suitability of cryogenically formed carbonates as analogs to ALH84001 carbonates. Specifically, our objective is to determine how accurately models using equilibrium fractionation factors approximate the isotopic compositions of cryogenically precipitated carbonates. This includes determining the accuracy of applying equilibrium fractionation factors during a kinetic process, and determining how isotopic variations in the fluid are preserved in microscale variations in the precipitated carbonates.

Size effects in martensitic microstructures: Finite-strain phase field model versus sharp-interface approach

NASA Astrophysics Data System (ADS)

Tůma, K.; Stupkiewicz, S.; Petryk, H.

2016-10-01

A finite-strain phase field model for martensitic phase transformation and twinning in shape memory alloys is developed and confronted with the corresponding sharp-interface approach extended to interfacial energy effects. The model is set in the energy framework so that the kinetic equations and conditions of mechanical equilibrium are fully defined by specifying the free energy and dissipation potentials. The free energy density involves the bulk and interfacial energy contributions, the latter describing the energy of diffuse interfaces in a manner typical for phase-field approaches. To ensure volume preservation during martensite reorientation at finite deformation within a diffuse interface, it is proposed to apply linear mixing of the logarithmic transformation strains. The physically different nature of phase interfaces and twin boundaries in the martensitic phase is reflected by introducing two order-parameters in a hierarchical manner, one as the reference volume fraction of austenite, and thus of the whole martensite, and the second as the volume fraction of one variant of martensite in the martensitic phase only. The microstructure evolution problem is given a variational formulation in terms of incremental fields of displacement and order parameters, with unilateral constraints on volume fractions explicitly enforced by applying the augmented Lagrangian method. As an application, size-dependent microstructures with diffuse interfaces are calculated for the cubic-to-orthorhombic transformation in a CuAlNi shape memory alloy and compared with the sharp-interface microstructures with interfacial energy effects.

Glass transition of soft colloids

NASA Astrophysics Data System (ADS)

Philippe, Adrian-Marie; Truzzolillo, Domenico; Galvan-Myoshi, Julian; Dieudonné-George, Philippe; Trappe, Véronique; Berthier, Ludovic; Cipelletti, Luca

2018-04-01

We explore the glassy dynamics of soft colloids using microgels and charged particles interacting by steric and screened Coulomb interactions, respectively. In the supercooled regime, the structural relaxation time τα of both systems grows steeply with volume fraction, reminiscent of the behavior of colloidal hard spheres. Computer simulations confirm that the growth of τα on approaching the glass transition is independent of particle softness. By contrast, softness becomes relevant at very large packing fractions when the system falls out of equilibrium. In this nonequilibrium regime, τα depends surprisingly weakly on packing fraction, and time correlation functions exhibit a compressed exponential decay consistent with stress-driven relaxation. The transition to this novel regime coincides with the onset of an anomalous decrease in local order with increasing density typical of ultrasoft systems. We propose that these peculiar dynamics results from the combination of the nonequilibrium aging dynamics expected in the glassy state and the tendency of colloids interacting through soft potentials to refluidize at high packing fractions.

Phase behavior and kinetics of phase separation of a nonionic microemulsion of C12E5/water/1-chlorotetradecane upon a temperature quench.

PubMed

Roshan Deen, G; Oliveira, Cristiano L P; Pedersen, Jan Skov

2009-05-21

The phase behavior and phase separation kinetics of a model ternary nonionic microemulsion system composed of pentaethylene glycol dodecyl ether (C12E5), water, and 1-chlorotetradecane were studied. With increasing temperature, the microemulsion exhibits the following rich phase behavior: oil-in-water phase (L1+O), droplet microemulsion phase (L1), lamellar liquid crystalline phase (Lproportional), and sponge-like (liquid) phase (L3). The microemulsion with a fixed surfactant-to-oil volume fraction ratio (Phis/Phio) of 0.81 and droplet volume fraction of 0.087 was perturbed from equilibrium by a temperature quench from the L1 region (24 degrees C) to an unstable region L1+O (13 degrees C), where the excess oil phase is in equilibrium with the microemulsion droplets. The process of phase separation in the unstable region was followed by time-resolved small-angle X-ray scattering (TR-SAXS) and time-resolved turbidity methods. Due to the large range of scattering vector (q=0.004-0.22 A(-1)) that is possible to access with the TR-SAXS method, the growth of the oil droplets and shrinking of the microemulsion droplets as a result of phase separation could be studied simultaneously. By using an advanced polydisperse ellipsoidal hard-sphere model, the experimental curves have been quantitatively analyzed. The microemulsion droplets were modeled as polydisperse core-shell ellipsoidal particles, using molecular constraints, and the oil droplets are modeled as polydisperse spheres. The radius of gyration (Rg) of the growing oil droplets, volume fraction of oil in the microemulsion droplets, and polydispersity were obtained from the fit parameters. The volume equivalent radius at the neutral plane between the surfactant head and tail of the microemulsion droplet decreased from 76 to 51 A, while the radius of oil drop increased to 217 A within the 160 min of the experiment. After about 48 min from the temperature quench, the system reaches a steady state and continues to coarsen at a constant fraction of the oil of 0.51 in the oil phase by Ostwald ripening with the power law dependence of Roil proportional, variant t1/3. The size of the oil droplets determined by the time-resolved turbidity method is in good agreement with that of the TR-SAXS, highlighting the usefulness of the method in the size determination of oil-in-water microemulsions on an absolute scale.

Sintering of viscous droplets under surface tension

NASA Astrophysics Data System (ADS)

Wadsworth, Fabian B.; Vasseur, Jérémie; Llewellin, Edward W.; Schauroth, Jenny; Dobson, Katherine J.; Scheu, Bettina; Dingwell, Donald B.

2016-04-01

We conduct experiments to investigate the sintering of high-viscosity liquid droplets. Free-standing cylinders of spherical glass beads are heated above their glass transition temperature, causing them to densify under surface tension. We determine the evolving volume of the bead pack at high spatial and temporal resolution. We use these data to test a range of existing models. We extend the models to account for the time-dependent droplet viscosity that results from non-isothermal conditions, and to account for non-zero final porosity. We also present a method to account for the initial distribution of radii of the pores interstitial to the liquid spheres, which allows the models to be used with no fitting parameters. We find a good agreement between the models and the data for times less than the capillary relaxation timescale. For longer times, we find an increasing discrepancy between the data and the model as the Darcy outgassing time-scale approaches the sintering timescale. We conclude that the decreasing permeability of the sintering system inhibits late-stage densification. Finally, we determine the residual, trapped gas volume fraction at equilibrium using X-ray computed tomography and compare this with theoretical values for the critical gas volume fraction in systems of overlapping spheres.

The role of elastic restoring forces in right-ventricular filling

PubMed Central

Pérez Del Villar, Candelas; Bermejo, Javier; Rodríguez-Pérez, Daniel; Martínez-Legazpi, Pablo; Benito, Yolanda; Antoranz, J. Carlos; Desco, M. Mar; Ortuño, Juan E.; Barrio, Alicia; Mombiela, Teresa; Yotti, Raquel; Ledesma-Carbayo, Maria J.; Del Álamo, Juan C.; Fernández-Avilés, Francisco

2015-01-01

Aims The physiological determinants of RV diastolic function remain poorly understood. We aimed to quantify the contribution of elastic recoil to RV filling and determine its sensitivity to interventricular interaction. Methods and results High-fidelity pressure–volume loops and simultaneous 3-dimensional ultrasound sequences were obtained in 13 pigs undergoing inotropic modulation, volume overload, and acute pressure overload induced by endotoxin infusion. Using a validated method, we isolated elastic restoring forces from ongoing relaxation using conventional pressure–volume data. The RV contracted below the equilibrium volume in >75% of the data sets. Consequently, elastic recoil generated strong sub-atmospheric passive pressure at the onset of diastole [−3 (−4 to −2) mmHg at baseline]. Stronger restoring suction pressure was related to a shorter isovolumic relaxation period, a higher rapid filling fraction, and lower atrial pressures (all P < 0.05). Restoring forces were mostly determined by the position of operating volumes around the equilibrium volume. By this mechanism, the negative inotropic effect of beta-blockade reduced and sometimes abolished restoring forces. During acute pressure overload, restoring forces initially decreased, but recovered at advanced stages. This biphasic response was related to alterations of septal curvature induced by changes in the diastolic LV–RV pressure balance. The constant of elastic recoil was closely related to the constant of passive stiffness (R = 0.69). Conclusion The RV works as a suction pump, exploiting contraction energy to facilitate filling by means of strong elastic recoil. Restoring forces are influenced by the inotropic state and RV conformational changes mediated by direct ventricular interdependence. PMID:25691537

Measurement of activity coefficients of mixtures by head-space gas chromatography: general procedure.

PubMed

Luis, Patricia; Wouters, Christine; Van der Bruggen, Bart; Sandler, Stanley I

2013-08-09

Head-space gas chromatography (HS-GC) is an applicable method to perform vapor-liquid equilibrium measurements and determine activity coefficients. However, the reproducibility of the data may be conditioned by the experimental procedure concerning to the automated pressure-balanced system. The study developed in this work shows that a minimum volume of liquid in the vial is necessary to ensure the reliability of the activity coefficients since it may become a parameter that influences the magnitude of the peak areas: the helium introduced during the pressurization step may produce significant variations of the results when too small volume of liquid is selected. The minimum volume required should thus be evaluated prior to obtain experimentally the concentration in the vapor phase and the activity coefficients. In this work, the mixture acetonitrile-toluene is taken as example, requiring a sample volume of more than 5mL (about more than 25% of the vial volume). The vapor-liquid equilibrium and activity coefficients of mixtures at different concentrations (0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 molar fraction) and four temperatures (35, 45, 55 and 70°C) have been determined. Relative standard deviations (RSD) lower than 5% have been obtained, indicating the good reproducibility of the method when a sample volume larger than 5mL is used. Finally, a general procedure to measure activity coefficients by means of pressure-balanced head-space gas chromatography is proposed. Copyright © 2013 Elsevier B.V. All rights reserved.

Condition of Mechanical Equilibrium at the Phase Interface with Arbitrary Geometry

NASA Astrophysics Data System (ADS)

Zubkov, V. V.; Zubkova, A. V.

2017-09-01

The authors produced an expression for the mechanical equilibrium condition at the phase interface within the force definition of surface tension. This equilibrium condition is the most general one from the mathematical standpoint and takes into account the three-dimensional aspect of surface tension. Furthermore, the formula produced allows describing equilibrium on the fractal surface of the interface. The authors used the fractional integral model of fractal distribution and took the fractional order integrals over Euclidean space instead of integrating over the fractal set.

Permeabilization Activated Reduction in Fluorescence (PARF): a novel method to measure kinetics of protein interactions with intracellular structures

PubMed Central

Singh, Pali P.; Hawthorne, Jenci L.; Davis, Christie A.; Quintero, Omar A.

2016-01-01

Understanding kinetic information is fundamental in understanding biological function. Advanced imaging technologies have fostered the development of kinetic analyses in cells. We have developed Permeabilization Activated Reduction in Fluorescence (PARF) analysis for determination of apparent t1/2 and immobile fraction, describing the dissociation of a protein of interest from intracellular structures. To create conditions where dissociation events are observable, cells expressing a fluorescently-tagged protein are permeabilized with digitonin, diluting the unbound protein into the extracellular media. As the media volume is much larger than the cytosolic volume, the concentration of the unbound pool decreases drastically, shifting the system out of equilibrium--favoring dissociation events. Loss of bound protein is observed as loss of fluorescence from intracellular structures and can be fit to an exponential decay. We compared PARF dissociation kinetics with previously published equilibrium kinetics as determined by FRAP. PARF dissociation rates agreed with the equilibrium-based FRAP analysis predictions of the magnitude of those rates. When used to investigate binding kinetics of a panel of cytoskeletal proteins, PARF analysis revealed that filament stabilization resulted in slower fluorescence loss. Additionally, commonly used “general” F-actin labels display differences in kinetic properties, suggesting that not all fluorescently-tagged actin labels interact with the actin network in the same way. We also observed differential dissociation kinetics for GFP-VASP depending on which cellular structure was being labeled. These results demonstrate that PARF analysis of non-equilibrium systems reveals kinetic information without the infrastructure investment required for other quantitative approaches such as FRAP, photoactivation, or in vitro reconstitution assays. PMID:27126922

Scaling of the space-time correlation function of particle currents in a suspension of hard-sphere-like particles: exposing when the motion of particles is Brownian.

PubMed

van Megen, W; Martinez, V A; Bryant, G

2009-12-18

The current correlation function is determined from dynamic light scattering measurements of a suspension of particles with hard spherelike interactions. For suspensions in thermodynamic equilibrium we find scaling of the space and time variables of the current correlation function. This finding supports the notion that the movement of suspended particles can be described in terms of uncorrelated Brownian encounters. However, in the metastable fluid, at volume fractions above freezing, this scaling fails.

Hybrid functional study of α-uranium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaur, Gurpreet, E-mail: gurpreet@igcar.gov.in; Chinnappan, Ravi; Panigrahi, B. K.

2016-05-23

We have used the hybrid density functionals to study the structural and electronic properties of alpha-U. The fraction of exact Hartree Folk exchange used is varied from 0.0 to 0.6. The equilibrium volume is found to be underestimated and bulk modulus overestimated with HSE as compared to both calculated by PBE and the experimental values. Electronic bands below the Fermi level are found to shift to lower energy with respect to PBE electronic bands which itself gives the bands shifted to lower energies as compared to UPS experiments.

First third filling parameters of left ventricle assessed from gated equilibrium studies in patients with various heart diseases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adatepe, M.H.; Nichols, K.; Powell, O.M.

1984-01-01

The authors determined the first third filling fraction (1/3 FF), the maximum filling rate (1/3 FR) and the mean filling rate (1/3 MFR) for the first third diastolic filling period of the left ventricle in patients with coronary artery disease (CAD), valvular heart disease (VHD), pericardial effusion (PE), cardiomyopathies (CM), chronic obstructive lung disease (COPD) and in 5 normals-all from resting gated equilibrium studies. Parameters are calculated from the third order Fourier fit to the LV volume curve and its derivative. 1/3 FF% = 1/3 diastolic count - end systolic count / 1/3 diastolic count x 100. Patients with CADmore » are divided into two groups: Group I with normal ejection fraction (EF) and wall motion (WM); Group II with abnormal EF and WM. Results are shown in the table. Abnormal filling parameters are found not only in CAD but in VHD, PE and CM. The authors conclude that the first third LV filling parameters are sensitive but non-specific indicators of filling abnormalities caused by diverse etiologic factors. Abnormal first third filling parameters may occur in the presence of a normal resting EF and WM in CAD.« less

Experimental characterization and modelization of ion exchange kinetics for a carboxylic resin in infinite solution volume conditions. Application to monovalent-trivalent cations exchange.

PubMed

Picart, Sébastien; Ramière, Isabelle; Mokhtari, Hamid; Jobelin, Isabelle

2010-09-02

This study is devoted to the characterization of ion exchange inside a microsphere of carboxylic resin. It aims at describing the kinetics of this exchange reaction which is known to be controlled by interdiffusion in the particle. The fractional attainment of equilibrium function of time depends on the concentration of the cations in the resin which can be modelized by the Nernst-Planck equation. A powerful approach for the numerical resolution of this equation is introduced in this paper. This modeling is based on the work of Helfferich but involves an implicit numerical scheme which reduces the computational cost. Knowing the diffusion coefficients of the cations in the resin and the radius of the spherical exchanger, the kinetics can be hence completely determined. When those diffusion parameters are missing, they can be deduced by fitting experimental data of fractional attainment of equilibrium. An efficient optimization tool coupled with the implicit resolution has been developed for this purpose. A monovalent/trivalent cation exchange had been experimentally characterized for a carboxylic resin. Diffusion coefficients and concentration profiles in the resin were then deduced through this new model.

Experimental study of combustion characteristics of nanoscale metal and metal oxide additives in biofuel (ethanol)

PubMed Central

2011-01-01

An experimental investigation of the combustion behavior of nano-aluminum (n-Al) and nano-aluminum oxide (n-Al2O3) particles stably suspended in biofuel (ethanol) as a secondary energy carrier was conducted. The heat of combustion (HoC) was studied using a modified static bomb calorimeter system. Combustion element composition and surface morphology were evaluated using a SEM/EDS system. N-Al and n-Al2O3 particles of 50- and 36-nm diameters, respectively, were utilized in this investigation. Combustion experiments were performed with volume fractions of 1, 3, 5, 7, and 10% for n-Al, and 0.5, 1, 3, and 5% for n-Al2O3. The results indicate that the amount of heat released from ethanol combustion increases almost linearly with n-Al concentration. N-Al volume fractions of 1 and 3% did not show enhancement in the average volumetric HoC, but higher volume fractions of 5, 7, and 10% increased the volumetric HoC by 5.82, 8.65, and 15.31%, respectively. N-Al2O3 and heavily passivated n-Al additives did not participate in combustion reactively, and there was no contribution from Al2O3 to the HoC in the tests. A combustion model that utilized Chemical Equilibrium with Applications was conducted as well and was shown to be in good agreement with the experimental results. PMID:21711760

Atomistic simulation of the thermal conductivity in amorphous SiO2 matrix/Ge nanocrystal composites

NASA Astrophysics Data System (ADS)

Kuryliuk, Vasyl V.; Korotchenkov, Oleg A.

2017-04-01

We use nonequilibrium molecular dynamics computer simulations with the Tersoff potential aiming to provide a comprehensive picture of the thermal conductivity of amorphous SiO2 (a-SiO2) matrix with embedded Ge nanocrystals (nc-Ge). The modelling predicts the a-SiO2 matrix thermal conductivity in a temperature range of 50 < T < 500 K yielding a fair agreement with experiment at around room temperature. It is worth noticing that the predicted room-temperature thermal conductivity in a-SiO2 is in very good agreement with the experimental result, which is in marked contrast with the thermal conductivity calculated employing the widely used van Beest-Kramer-van Santen (BKS) potential. We show that the thermal conductivity of composite nc-Ge/a-SiO2 systems decreases steadily with increasing the volume fraction of Ge inclusions, indicative of enhanced interface scattering of phonons imposed by embedded Ge nanocrystals. We also observe that increasing the volume fractions above a certain threshold value results in a progressively increased thermal conductivity of the nanocomposite, which can be explained by increasing volume fraction of a better thermally conducting Ge. Finally, non-equilibrium molecular dynamics simulations with the Tersoff potential are promising for computing the thermal conductivity of nanocomposites based on amorphous SiO2 and can be readily scaled to more complex composite structures with embedded nanoparticles, which thus help design nanocomposites with desired thermal properties.

Comment on “Isotopic fractionation between Fe(III) and Fe(II) in aqueous solutions” by Clark Johnson et al., [Earth Planet. Sci. Lett. 195 (2002) 141–153

USGS Publications Warehouse

Bullen, Thomas D.; White, Arthur F.; Childs, Cyril W.

2003-01-01

In a recent contribution [1], Johnson et al. reported the equilibrium isotope fractionation factor between dissolved Fe(II) and Fe(III) in aqueous solutions at pH=2.5 and 5.5. They suggest that because the iron isotope fractionation observed in their experiments spans virtually the entire range observed in sedimentary rocks, Fe(II)–Fe(III) aqueous speciation may play a major role in determining iron isotope variations in nature where Fe(II) and Fe(III) can become physically separated. They discounted earlier conclusions by us and others [2] ;  [3] that significant equilibrium fractionation between specific coexisting Fe(II)- or Fe(III)-aqueous complexes (e.g., between aqueous Fe(II)(OH)x(aq)and Fe(II)(aq) ion) is capable of producing iron isotope contrasts that can be preserved in nature. This is an important contribution not only because the authors recognize the importance of abiotic equilibrium iron isotope fractionation in nature in contrast to previous assertions [4], but also because it will help to focus discussion on the development and evaluation of experimental approaches that can reveal abiotic fractionation mechanisms. However, in this Comment we propose that the experiments presented in this paper cannot be interpreted as straightforwardly as Johnson et al. contend. In particular, we show that in one of their critical experiments attainment of either isotope mass balance or equilibrium was not demonstrated, and thus the results of that experiment cannot be used to calculate an Fe(II)–Fe(III) equilibrium fractionation factor.

Parameterizing the equilibrium distribution of chemicals between the dissolved, solid particulate matter, and colloidal matter compartments in aqueous systems

USGS Publications Warehouse

Pankow, J.F.; McKenzie, S.W.

1991-01-01

The manner in which a chemical material partitions among the dissolved (D), participate (P), and colloidal (C) phases affects both its chemical and physical behavior in the aquatic environment. The fractions of the chemical that are present in each of these three phases will be determined by the values of two simple parameters, KpSp/??w and KcSc/??w. The variables Kp and Kc are the particle/water and colloid/water partition constants (mL/g), respectively, Sp and Sc are the volume concentrations of particulate and colloidal material (mg/L), respectively, and ??w is the fractional volume of the system that is aqueous. This parameterization allows a rapid overview of how partitioning (1) changes as a function of chemical partitioning properties and water type, (2) affects apparent partition constants (i.e., Kpapp values) computed between the particulate phase and the remainder of the system, and (3) causes Kpapp values to become independent of chemical properties at high values of KcSc/??w. ?? 1991 American Chemical Society.

Effects of Small Addition of Ti on Strength and Microstructure of a Cu-Ni-Si Alloy

NASA Astrophysics Data System (ADS)

Watanabe, Chihiro; Takeshita, Satoshi; Monzen, Ryoichi

2015-06-01

The effect of addition of 0.04 or 0.2 mass pct Ti on the mechanical properties of a Cu-2.0 mass pct Ni-0.5 mass pct Si alloy has been investigated. The addition of 0.04 mass pct Ti enhances the strength of the Cu-Ni-Si alloy without reducing its electrical conductivity. This increase in strength is caused by the decrease in inter-precipitate spacing of δ-Ni2Si precipitates. The addition of trace Ti reduces the equilibrium concentration of Ni and Si atoms in the alloy bearing the δ precipitates, resulting in an increase in the volume fraction of δ precipitates and decrease in the inter-precipitate spacing. However, the addition of 0.2 mass pct Ti to the Cu-Ni-Si alloy decreases the strength of the alloy. The reduction in strength is attributed to the decrease in the volume fraction of δ precipitates caused by the reduction in Ni and Si atoms in the Cu matrix resulting from the formation of Ni16Si7Ti6 particles.

Tables and charts of equilibrium thermodynamic properties of ammonia for temperatures from 500 to 50,000 K.

NASA Technical Reports Server (NTRS)

Simmonds, A. L.; Miller, C. G., III; Nealy, J. E.

1976-01-01

Equilibrium thermodynamic properties for pure ammonia were generated for a range of temperature from 500 to 50,000 K and pressure from 0.01 to 40 MN/sq m and are presented in tabulated and graphical form. Properties include pressure, temperature, density, enthalpy, speed of sound, entropy, molecular-weight ratio, specific heat at constant pressure, specific heat at constant volume, isentropic exponent, and species mole fractions. These properties were calculated by the method which is based on minimization of the Gibbs free energy. The data presented herein are for an 18-species ammonia model. Heats of formation and spectroscopic constants used as input data are presented. Comparison of several thermodynamic properties calculated with the present program and a second computer code is performed for a range of pressure and for temperatures up to 30,000 K.

Observation of dynamic equilibrium cluster phase in nanoparticle-polymer system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, Sugam, E-mail: sugam@barc.gov.in; Mehan, S.; Aswal, V. K.

2016-05-23

Small-angle neutron scattering (SANS) and dynamic light scattering (DLS) have been used to investigate the existence of a cluster phase in a nanoparticle-polymer system. The nanoparticle-polymer system shows an interesting reentrant phase behavior where the charge stabilized silica nanoparticles undergo particle clustering and back to individual nanoparticles as a function of polymer concentration. This kind of phase behavior is believed to be directed by opposing attractive and repulsive interactions present in the system. The phase behavior shows two narrow regions of polymer concentration immediately before and after the two-phase formation indicating the possibility of the existence of some equilibrium clusters.more » DLS results show a much higher size of particles than individuals in these two regions which remains unchanged even after dilution. The SANS data show the evolution of attraction with increased volume fraction of the particles supporting the dynamic nature of these clusters.« less

Determining Quiescent Colloidal Suspension Viscosities Using the Green-Kubo Relation and Image-Based Stress Measurements

NASA Astrophysics Data System (ADS)

Lin, Neil Y. C.; Bierbaum, Matthew; Cohen, Itai

2017-09-01

By combining confocal microscopy and stress assessment from local structural anisotropy, we directly measure stresses in 3D quiescent colloidal liquids. Our noninvasive and nonperturbative method allows us to measure forces ≲50 fN with a small and tunable probing volume, enabling us to resolve the stress fluctuations arising from particle thermal motions. We use the Green-Kubo relation to relate these measured stress fluctuations to the bulk Brownian viscosity at different volume fractions, comparing against simulations and conventional rheometry measurements. We find that the Green-Kubo analysis gives excellent agreement with these prior results, suggesting that similar methods could be applied to investigations of local flow properties in many poorly understood far-from-equilibrium systems, including suspensions that are glassy, strongly sheared, or highly confined.

Near infrared study of water-benzene mixtures at high temperatures and pressures.

PubMed

Jin, Yusuke; Ikawa, Shun-Ichi

2004-08-08

Near-infrared absorption of water-benzene mixtures has been measured at temperatures and pressures in the ranges of 473-673 K and 100-400 bar, respectively. Concentrations of water and benzene in the water-rich phase of the mixtures were obtained from the integrated absorption intensities of the OH stretching overtone transition of water and the CH stretching overtone transition of benzene, respectively. Using these concentrations, the densities of the water-rich phase were estimated and compared with the average densities before mixing, which were calculated from literature densities of neat water and neat benzene. It is found that anomalously large volume expansion on the mixing occurs in the region enclosed by an extended line of the three-phase equilibrium curve and the one-phase critical curve of the mixtures, and the gas-liquid equilibrium curve of water. Furthermore, magnitude of the relative volume change increases with decreasing molar fraction of benzene in the present experimental range. It is suggested that dissolving a small amount of benzene in water induces a change in the fluid density from a liquidlike condition to a gaslike condition in the vicinity of the critical region.

Sintering of viscous droplets under surface tension

PubMed Central

Vasseur, Jérémie; Llewellin, Edward W.; Schauroth, Jenny; Dobson, Katherine J.; Scheu, Bettina; Dingwell, Donald B.

2016-01-01

We conduct experiments to investigate the sintering of high-viscosity liquid droplets. Free-standing cylinders of spherical glass beads are heated above their glass transition temperature, causing them to densify under surface tension. We determine the evolving volume of the bead pack at high spatial and temporal resolution. We use these data to test a range of existing models. We extend the models to account for the time-dependent droplet viscosity that results from non-isothermal conditions, and to account for non-zero final porosity. We also present a method to account for the initial distribution of radii of the pores interstitial to the liquid spheres, which allows the models to be used with no fitting parameters. We find a good agreement between the models and the data for times less than the capillary relaxation timescale. For longer times, we find an increasing discrepancy between the data and the model as the Darcy outgassing time-scale approaches the sintering timescale. We conclude that the decreasing permeability of the sintering system inhibits late-stage densification. Finally, we determine the residual, trapped gas volume fraction at equilibrium using X-ray computed tomography and compare this with theoretical values for the critical gas volume fraction in systems of overlapping spheres. PMID:27274687

Stochastic entangled chain dynamics of dense polymer solutions.

PubMed

Kivotides, Demosthenes; Wilkin, S Louise; Theofanous, Theo G

2010-10-14

We propose an adjustable-parameter-free, entangled chain dynamics model of dense polymer solutions. The model includes the self-consistent dynamics of molecular chains and solvent by describing the former via coarse-grained polymer dynamics that incorporate hydrodynamic interaction effects, and the latter via the forced Stokes equation. Real chain elasticity is modeled via the inclusion of a Pincus regime in the polymer's force-extension curve. Excluded volume effects are taken into account via the combined action of coarse-grained intermolecular potentials and explicit geometric tracking of chain entanglements. We demonstrate that entanglements are responsible for a new (compared to phantom chain dynamics), slow relaxation mode whose characteristic time scale agrees very well with experiment. Similarly good agreement between theory and experiment is also obtained for the equilibrium chain size. We develop methods for the solution of the model in periodic flow domains and apply them to the computation of entangled polymer solutions in equilibrium. We show that the number of entanglements Π agrees well with the number of entanglements expected on the basis of tube theory, satisfactorily reproducing the latter's scaling of Π with the polymer volume fraction φ. Our model predicts diminishing chain size with concentration, thus vindicating Flory's suggestion of excluded volume effects screening in dense solutions. The predicted scaling of chain size with φ is consistent with the heuristic, Flory theory based value.

Carbon and oxygen isotope fractionation in non-marine ostracods: results from a 'natural culture' environment

NASA Astrophysics Data System (ADS)

Keatings, K. W.; Heaton, T. H. E.; Holmes, J. A.

2002-05-01

Carbon and oxygen isotope analysis of ostracods living in the near-constant conditions of spring-fed ponds in southern England allowed accurate determination of the ostracod's calcite-water 13C/12C and 18O/16O fractionations. The 13C/12C fractionations of two species, Candona candida and Pseudocandona rostrata, correspond to values expected for isotopic equilibrium with the pond's dissolved inorganic carbon at the measured temperature (11°C) and pH (6.9), whilst those of a third species, Herpetocypris reptans, would represent equilibrium at a slightly higher pH (7.1). The 18O/16O fractionations confirm two previous studies in being larger, by up to 3‰, than those 'traditionally' regarded as representing equilibrium. When the measured fractionations are considered in the context of more recent work, however, they can be explained in terms of equilibrium if the process of calcite formation at the ostracod lamella occurs at a relatively low pH (≤7) irrespective of the pH of the surrounding water. The pH of calcite formation, and therefore the calcite-water 18O/16O fractionation, may be species and stage (adult versus juvenile) specific, and related to the rate of calcification.

Experimental determination of iron isotope fractionations among Fe aq 2 + -FeSaq-Mackinawite at low temperatures: Implications for the rock record

NASA Astrophysics Data System (ADS)

Wu, Lingling; Druschel, Greg; Findlay, Alyssa; Beard, Brian L.; Johnson, Clark M.

2012-07-01

The Fe isotope fractionation factors among aqueous ferrous iron (Fe aq 2 +), aqueous FeS clusters (FeSaq), and nanoparticulate mackinawite under neutral and mildly acidic and alkaline pH conditions have been determined using the three-isotope method. Combined voltammetric analysis and geochemical modeling were used to determine the Fe speciation in the experimental systems. The equilibrium 56Fe/54Fe fractionation factor at 20 °C and pH 7 has been determined to be -0.32 ± 0.29 (2σ)‰ between Fe aq 2 + (minor FeSaq also present in the experiment) and mackinawite. This fractionation factor was essentially constant when pH was changed to 6 or 8. When equal molarity of HS- and Fe aq 2 + were added to the system, however, the isotopic fractionation at pH 7 changed to -0.64 ± 0.36 (2σ)‰, correlating with a significant increase in the proportion of FeHS+ and FeSaq. These results highlight a more important role of aqueous Fe-S speciation in the equilibrium Fe isotope fractionation factor than recognized in previous studies. The isotopic fractionation remained constant when temperature was increased from 20 °C to 35 °C for fractionation factors between Fe aq 2 + , and mackinawite and between dominantly FeHS+ and mackinawite. Synthesis experiments similar to those of Butler et al. (2005) and Guilbaud et al. (2010) at pH 4 show consistent results: over time, the aqueous Fe-mackinawite fractionation decreases but even after 38 days of aging the fractionation factor is far from the equilibrium value inferred using the three-isotope method. In contrast, at near-neutral pH the fractionation factor for the synthesis experiment reached the equilibrium value in 38 days. These differences are best explained by noting that at low pH the FeS mackinawite particles coarsen more rapidly via particle aggregation, which limits isotopic exchange, whereas at higher pH mackinawite aggregation is limited, and Fe isotope exchange occurs more rapidly, converging on the equilibrium value. These results suggest that mackinawite formed in natural environments at near-neutral or alkaline pH are unlikely to retain kinetic isotope fractionations, but are more likely to reflect equilibrium isotope compositions. This in turn has important implications for interpreting iron isotope compositions of Fe sulfides in natural systems.

Capillary equilibrium and sintering kinetics in dispersed media and catalysts

NASA Astrophysics Data System (ADS)

Delannay, Francis

2016-06-01

The evolution of an aggregate of particles embedded in a fluid phase, no matter whether a liquid, a vapor, or a mixture of both, is determined by the dependence of the equilibrium interface area on porosity volume fraction. In system with open porosity, this equilibrium can be analyzed using a model representing the particles as a collection of cones of revolution, the number of which is the average particle coordination number. The accuracy of the model has been assessed using in situ X-ray microtomography. The model makes possible the computation of the driving force for sintering, commonly called sintering stress. It allows the mapping of the domains of relative density, coordination number, and dihedral angle that bring about aggregate densification or expansion. The contribution of liquid/vapor interfaces is enlightened, as well as the dependence of the equilibrium fluid phase distribution on particle size. Applied to foams and emulsions, the model provides insight into the relationship between osmotic pressure and coordination. Interface-governed transport mechanisms are considered dominant in the macroscopic viscosity. Both sintering stress and viscosity parameters strongly depend on particle size. The capacity of modeling the simultaneous particle growth is thus essential. The analysis highlights the microstructural parameters and material properties needed for kinetics simulation.

Theoretical isotopic fractionation between structural boron in carbonates and aqueous boric acid and borate ion

NASA Astrophysics Data System (ADS)

Balan, Etienne; Noireaux, Johanna; Mavromatis, Vasileios; Saldi, Giuseppe D.; Montouillout, Valérie; Blanchard, Marc; Pietrucci, Fabio; Gervais, Christel; Rustad, James R.; Schott, Jacques; Gaillardet, Jérôme

2018-02-01

The 11B/10B ratio in calcite and aragonite is an important proxy of oceanic water pH. However, the physico-chemical mechanisms underpinning this approach are still poorly known. In the present study, we theoretically determine the equilibrium isotopic fractionation properties of structural boron species in calcium carbonates, BO33-, BO2(OH)2- and B(OH)4- anions substituted for carbonate groups, as well as those of B(OH)4- and B(OH)3 species in vacuum. Significant variability of equilibrium isotopic fractionation properties is observed among these structural species which is related to their contrasted coordination state, Bsbnd O bond lengths and atomic-scale environment. The isotopic composition of structural boron does not only depend on its coordination number but also on its medium range environment, i.e. farther than its first coordination shell. The isotopic fractionation between aqueous species and their counterparts in vacuum are assessed using previous investigations based on similar quantum-mechanical modeling approaches. At 300 K, the equilibrium isotope composition of structural trigonal species is 7-15‰ lighter than that of aqueous boric acid molecules, whereas substituted tetrahedral borate ions are heavier than their aqueous counterparts by 10-13‰. Although significant uncertainties are known to affect the theoretical prediction of fractionation factors between solids and solutions, the usually assumed lack of isotopic fractionation during borate incorporation in carbonates is challenged by these theoretical results. The present theoretical equilibrium fractionation factors between structural boron and aqueous species differ from those inferred from experiments which may indicate that isotopic equilibrium, unlike chemical equilibrium, was not reached in most experiments. Further research into the isotopic fractionation processes at the interface between calcium carbonates and aqueous solution as well as long duration experiments aimed at investigating the kinetics of equilibration of boron environment and isotopic composition are therefore required to refine our understanding of boron coprecipitation in carbonates and thus the theory behind the use of boron isotopes as an ocean pH proxy.

Equilibrium 2H/1H fractionation in organic molecules: III. Cyclic ketones and hydrocarbons

NASA Astrophysics Data System (ADS)

Wang, Ying; Sessions, Alex L.; Nielsen, Robert J.; Goddard, William A.

2013-04-01

Quantitative interpretation of stable hydrogen isotope ratios (2H/1H) in organic compounds is greatly aided by knowledge of the relevant equilibrium fractionation factors (ɛeq). Previous efforts have combined experimental measurements and hybrid Density Functional Theory (DFT) calculations to accurately predict equilibrium fractionations in linear (acyclic) organic molecules (Wang et al., 2009a,b), but the calibration produced by that study is not applicable to cyclic compounds. Here we report experimental measurements of equilibrium 2H/1H fractionation in six cyclic ketones, and use those data to evaluate DFT calculations of fractionation in diverse monocyclic and polycyclic compounds commonly found in sedimentary organic matter and petroleum. At 25, 50, and 75 °C, the experimentally measured ɛeq values for secondary and tertiary Hα in isotopic equilibrium with water are in the ranges of -130‰ to -150‰ and +10‰ to -40‰ respectively. Measured data are similar to DFT calculations of ɛeq for axial Hα but not equatorial Hα. In tertiary Cα positions with methyl substituents, this can be understood as a result of the methyl group forcing Hα atoms into a dominantly axial position. For secondary Cα positions containing both axial and equatorial Hα atoms, we propose that axial Hα exchanges with water significantly faster than the equatorial Hα does, due to the hyperconjugation-stabilized transition state. Interconversion of axial and equatorial positions via ring flipping is much faster than isotopic exchange at either position, and as a result the steady-state isotopic composition of both H's is strongly weighted toward that of axial Hα. Based on comparison with measured ɛeq values, a total uncertainty of 10-30‰ remains for theoretical ɛeq values. Using DFT, we systematically estimated the ɛeq values for individual H positions in various cyclic structures. By summing over all individual H positions, the molecular equilibrium fractionation was estimated to be -75‰ to -95‰ for steroids, -90‰ to -105‰ for hopanoids, and -65‰ to -100‰ for typical cycloparaffins between 0 and 100 °C relative to water. These are distinct from the typical biosynthetic fractionations of -150‰ to -300‰, but are similar to equilibrium fractionations for linear hydrocarbons (Wang et al., 2009b). Thus post-burial H exchange will generally remove the ˜50-100‰ biosynthetic fractionations between cyclic isoprenoid and n-alkyl lipid molecules, which can be used to evaluate the extent of H exchange in sedimentary organic matter and oils.

Rheology and microstructure of filled polymer melts

NASA Astrophysics Data System (ADS)

Anderson, Benjamin John

The states of particle dispersion in polymer nanocomposite melts are studied through rheological characterization of nanocomposite melt mechanical properties and small angle X-ray scattering measurement of the particle microstructure. The particle microstructure probed with scattering is related to bulk flow mechanics to determine the origin of slow dynamics in these complex dispersions: whether a gel or glass transition or a slowing down of dispersing phase dynamics. These studies were conducted to understand polymer mediated particle-particle interactions and potential particle-polymer phase separation. The phase behavior of the dispersion will be governed by enthalpic and entropic contributions. A variety of phases are expected: homogeneous fluid, phase separated, or non-equilibrium gel. The effects of dispersion control parameters, namely particle volume fraction, polymer molecular weight, and polymer-particle surface affinity, on the phase behavior of 44 nm silica dispersions are studied in low molecular weight polyethylene oxide (PEO), polyethylene oxide dimethylether (PEODME), and polytetrahydrofuran (PTHF). Scattering measurements of the particle second virial coefficient in PEO melts indicates repulsive particles by a value slightly greater than unity. In PEO nanocomposites, dispersion dynamics slow down witnessed by a plateau in the elastic modulus as the particle separation approaches the length scale of the polymer radius of gyration. As the polymer molecular weight is increased, the transition shifts to lower particle volume fractions. Below polymer entanglement, the slow dynamics mimics that of a colloidal glass by the appearance of two relaxation times in the viscous modulus that display power law scaling with volume fraction. Above entanglement, the slow dynamics is qualitatively different resembling the behavior of a gelled suspension yet lacking any sign of scattering from particle agglomerates. As polymer molecular weight is increased at a fixed volume fraction, two strain yielding events emerge. Further particle loading leads to the formation of a particle-polymer network and the onset of brittle mechanical behavior. The performance of PEO nanocomposites is contrasted by PEODME and PTHF nanocomposites where a change in the polymer segment-surface activity changes the slow dynamics of the nanocomposite and the microstructure of particles in the melt. Slow dynamics and the particle microstructure indicate a gelled suspension as volume fraction is raised with particles in or near contact and support the turning on of particle attractions in the melt.

Differential Selectivity of the Escherichia coli Cell Membrane Shifts the Equilibrium for the Enzyme-Catalyzed Isomerization of Galactose to Tagatose▿

PubMed Central

Kim, Jin-Ha; Lim, Byung-Chul; Yeom, Soo-Jin; Kim, Yeong-Su; Kim, Hye-Jung; Lee, Jung-Kul; Lee, Sook-Hee; Kim, Seon-Won; Oh, Deok-Kun

2008-01-01

An Escherichia coli galactose kinase gene knockout (ΔgalK) strain, which contains the l-arabinose isomerase gene (araA) to isomerize d-galactose to d-tagatose, showed a high conversion yield of tagatose compared with the original galK strain because galactose was not metabolized by endogenous galactose kinase. In whole cells of the ΔgalK strain, the isomerase-catalyzed reaction exhibited an equilibrium shift toward tagatose, producing a tagatose fraction of 68% at 37°C, whereas the purified l-arabinose isomerase gave a tagatose equilibrium fraction of 36%. These equilibrium fractions are close to those predicted from the measured equilibrium constants of the isomerization reaction catalyzed in whole cells and by the purified enzyme. The equilibrium shift in these cells resulted from the higher uptake and lower release rates for galactose, which is a common sugar substrate, than for tagatose, which is a rare sugar product. A ΔmglB mutant had decreased uptake rates for galactose and tagatose, indicating that a methylgalactoside transport system, MglABC, is the primary contributing transporter for the sugars. In the present study, whole-cell conversion using differential selectivity of the cell membrane was proposed as a method for shifting the equilibrium in sugar isomerization reactions. PMID:18263746

Differential selectivity of the Escherichia coli cell membrane shifts the equilibrium for the enzyme-catalyzed isomerization of galactose to tagatose.

PubMed

Kim, Jin-Ha; Lim, Byung-Chul; Yeom, Soo-Jin; Kim, Yeong-Su; Kim, Hye-Jung; Lee, Jung-Kul; Lee, Sook-Hee; Kim, Seon-Won; Oh, Deok-Kun

2008-04-01

An Escherichia coli galactose kinase gene knockout (DeltagalK) strain, which contains the l-arabinose isomerase gene (araA) to isomerize d-galactose to d-tagatose, showed a high conversion yield of tagatose compared with the original galK strain because galactose was not metabolized by endogenous galactose kinase. In whole cells of the DeltagalK strain, the isomerase-catalyzed reaction exhibited an equilibrium shift toward tagatose, producing a tagatose fraction of 68% at 37 degrees C, whereas the purified l-arabinose isomerase gave a tagatose equilibrium fraction of 36%. These equilibrium fractions are close to those predicted from the measured equilibrium constants of the isomerization reaction catalyzed in whole cells and by the purified enzyme. The equilibrium shift in these cells resulted from the higher uptake and lower release rates for galactose, which is a common sugar substrate, than for tagatose, which is a rare sugar product. A DeltamglB mutant had decreased uptake rates for galactose and tagatose, indicating that a methylgalactoside transport system, MglABC, is the primary contributing transporter for the sugars. In the present study, whole-cell conversion using differential selectivity of the cell membrane was proposed as a method for shifting the equilibrium in sugar isomerization reactions.

Seasonal variability of equilibrium factor and unattached fractions of radon and thoron in different regions of Punjab, India.

PubMed

Saini, Komal; Singh, Parminder; Singh, Prabhjot; Bajwa, B S; Sahoo, B K

2017-02-01

A survey was conducted to estimate equilibrium factor and unattached fractions of radon and thoron in different regions of Punjab state, India. Pin hole based twin cup dosimeters and direct progeny sensor techniques have been utilized for estimation of concentration level of radon, thoron and their progenies. Equilibrium factor calculated from radon, thoron and their progenies concentration has been found to vary from 0.15 to 0.80 and 0.008 to 0.101 with an average value of 0.44 and 0.036 for radon and thoron respectively. Equilibrium factor for radon has found to be highest in winter season and lowest in summer season whereas for thoron highest value is observed in winter and rainy season and lowest in summer. Unattached fractions of radon and thoron have been found to vary from 0.022 to 0.205 and 0.013 to 0.212 with an average value of 0.099 and 0.071 respectively. Unattached fractions have found to be highest in winter season and lowest in rainy and summer season. Copyright © 2016 Elsevier Ltd. All rights reserved.

Equilibrium radionuclide gated angiography in patients with tricuspid regurgitation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Handler, B.; Pavel, D.G.; Pietras, R.

Equilibrium gated radionuclide angiography was performed in 2 control groups (15 patients with no organic heart disease and 24 patients with organic heart disease but without right- or left-sided valvular regurgitation) and in 9 patients with clinical tricuspid regurgitation. The regurgitant index, or ratio of left to right ventricular stroke counts, was significantly lower in patients with tricuspid regurgitation than in either control group. Time-activity variation over the liver was used to compute a hepatic expansion fraction which was significantly higher in patients with tricuspid regurgitation than in either control group. Fourier analysis of time-activity variation in each pixel wasmore » used to generate amplitude and phase images. Only pixels with values for amplitude at least 7% of the maximum in the image were retained in the final display. All patients with tricuspid regurgitation had greater than 100 pixels over the liver automatically retained by the computer. These pixels were of phase comparable to that of the right atrium and approximately 180 degrees out of phase with the right ventricle. In contrast, no patient with no organic heart disease and only 1 of 24 patients with organic heart disease had any pixels retained by the computer. In conclusion, patients with tricuspid regurgitation were characterized on equilibrium gated angiography by an abnormally low regurgitant index (7 of 9 patients) reflecting increased right ventricular stroke volume, increased hepatic expansion fraction (7 of 9 patients), and increased amplitude of count variation over the liver in phase with the right atrium (9 of 9 patients).« less

User's guide for vectorized code EQUIL for calculating equilibrium chemistry on Control Data STAR-100 computer

NASA Technical Reports Server (NTRS)

Kumar, A.; Graves, R. A., Jr.; Weilmuenster, K. J.

1980-01-01

A vectorized code, EQUIL, was developed for calculating the equilibrium chemistry of a reacting gas mixture on the Control Data STAR-100 computer. The code provides species mole fractions, mass fractions, and thermodynamic and transport properties of the mixture for given temperature, pressure, and elemental mass fractions. The code is set up for the electrons H, He, C, O, N system of elements. In all, 24 chemical species are included.

Chemical structure influence on NAPL mixture nonideality evolution, rate-limited dissolution, and contaminant mass flux.

PubMed

Padgett, Mark C; Tick, Geoffrey R; Carroll, Kenneth C; Burke, William R

2017-03-01

The influence of chemical structure on NAPL mixture nonideality evolution, rate-limited dissolution, and contaminant mass flux was examined. The variability of measured and UNIFAC modeled NAPL activity coefficients as a function of mole fraction was compared for two NAPL mixtures containing structurally-different contaminants of concern including toluene (TOL) or trichloroethene (TCE) within a hexadecane (HEXDEC) matrix. The results showed that dissolution from the NAPL mixtures transitioned from ideality for mole fractions >0.05 to nonideality as mole fractions decreased. In particular, the TCE generally exhibited more ideal dissolution behavior except at lower mole fractions, and may indicate greater structural/polarity similarity between the two compounds. Raoult's Law and UNIFAC generally under-predicted the batch experiment results for TOL:HEXDEC mixtures especially for mole fractions ≤0.05. The dissolution rate coefficients were similar for both TOL and TCE over all mole fractions tested. Mass flux reduction (MFR) analysis showed that more efficient removal behavior occurred for TOL and TCE with larger mole fractions compared to the lower initial mole fraction mixtures (i.e. <0.2). However, compared to TOL, TCE generally exhibited more efficient removal behavior over all mole fractions tested and may have been the result of structural and molecular property differences between the compounds. Activity coefficient variability as a function of mole fraction was quantified through regression analysis and incorporated into dissolution modeling analyses for the dynamic flushing experiments. TOL elution concentrations were modeled (predicted) reasonable well using ideal and equilibrium assumptions, but the TCE elution concentrations could not be predicted using the ideal model. Rather, the dissolution modeling demonstrated that TCE elution was better described by the nonideal model whereby NAPL-phase activity coefficient varied as a function of COC mole fraction. For dynamic column flushing experiments, dissolution rate kinetics can vary significantly with changes in NAPL volume and surface area. However, under conditions whereby NAPL volume and area are not significantly altered during dissolution, mixture nonideality effects may have a greater relative control on dissolution (elution) and MFR behavior compared to kinetic rate limitations. Copyright © 2017 Elsevier B.V. All rights reserved.

Chemical structure influence on NAPL mixture nonideality evolution, rate-limited dissolution, and contaminant mass flux

NASA Astrophysics Data System (ADS)

Padgett, Mark C.; Tick, Geoffrey R.; Carroll, Kenneth C.; Burke, William R.

2017-03-01

The influence of chemical structure on NAPL mixture nonideality evolution, rate-limited dissolution, and contaminant mass flux was examined. The variability of measured and UNIFAC modeled NAPL activity coefficients as a function of mole fraction was compared for two NAPL mixtures containing structurally-different contaminants of concern including toluene (TOL) or trichloroethene (TCE) within a hexadecane (HEXDEC) matrix. The results showed that dissolution from the NAPL mixtures transitioned from ideality for mole fractions > 0.05 to nonideality as mole fractions decreased. In particular, the TCE generally exhibited more ideal dissolution behavior except at lower mole fractions, and may indicate greater structural/polarity similarity between the two compounds. Raoult's Law and UNIFAC generally under-predicted the batch experiment results for TOL:HEXDEC mixtures especially for mole fractions ≤ 0.05. The dissolution rate coefficients were similar for both TOL and TCE over all mole fractions tested. Mass flux reduction (MFR) analysis showed that more efficient removal behavior occurred for TOL and TCE with larger mole fractions compared to the lower initial mole fraction mixtures (i.e. < 0.2). However, compared to TOL, TCE generally exhibited more efficient removal behavior over all mole fractions tested and may have been the result of structural and molecular property differences between the compounds. Activity coefficient variability as a function of mole fraction was quantified through regression analysis and incorporated into dissolution modeling analyses for the dynamic flushing experiments. TOL elution concentrations were modeled (predicted) reasonable well using ideal and equilibrium assumptions, but the TCE elution concentrations could not be predicted using the ideal model. Rather, the dissolution modeling demonstrated that TCE elution was better described by the nonideal model whereby NAPL-phase activity coefficient varied as a function of COC mole fraction. For dynamic column flushing experiments, dissolution rate kinetics can vary significantly with changes in NAPL volume and surface area. However, under conditions whereby NAPL volume and area are not significantly altered during dissolution, mixture nonideality effects may have a greater relative control on dissolution (elution) and MFR behavior compared to kinetic rate limitations.

Concentration effect on inter-mineral equilibrium isotope fractionation: insights from Mg and Ca isotopic systems

NASA Astrophysics Data System (ADS)

Huang, F.; Wang, W.; Zhou, C.; Kang, J.; Wu, Z.

2017-12-01

Many naturally occurring minerals, such as carbonate, garnet, pyroxene, and feldspar, are solid solutions with large variations in chemical compositions. Such variations may affect mineral structures and modify the chemical bonding environment around atoms, which further impacts the equilibrium isotope fractionation factors among minerals. Here we investigated the effects of Mg content on equilibrium Mg and Ca isotope fractionation among carbonates and Ca content on equilibrium Ca isotope fractionation between orthopyroxene (opx) and clinopyroxene (cpx) using first-principles calculations. Our results show that the average Mg-O bond length increases with decreasing Mg/(Mg+Ca) in calcite when it is greater than 1/48[1] and the average Ca-O bond length significantly decreases with decreasing Ca/(Ca+Mg+Fe) in opx when it ranges from 2/16 to 1/48[2]. Equilibrium isotope fractionation is mainly controlled by bond strengths, which could be measured by bond lengths. Thus, 103lnα26Mg/24Mg between dolomite and calcite dramatically increases with decreasing Mg/(Mg+Ca) in calcite [1] and it reaches a constant value when it is lower than 1/48. 103lnα44Ca/40Ca between opx and cpx significantly increases with decreasing Ca content in opx when Ca/(Ca+Mg+Fe) ranges from 2/16 to 1/48 [2]. If Ca/(Ca+Mg+Fe) is below 1/48, 103lnα44Ca/40Ca is not sensitive to Ca content. Based on our results, we conclude that the concentration effect on equilibrium isotope fractionation could be significant within a certain range of chemical composition of minerals, which should be a ubiquitous phenomenon in solid solution systems. [1] Wang, W., Qin, T., Zhou, C., Huang, S., Wu, Z., Huang, F., 2017. GCA 208, 185-197. [2] Feng, C., Qin, T., Huang, S., Wu, Z., Huang, F., 2014. GCA 143, 132-142.

Analytical Phase Equilibrium Function for Mixtures Obeying Raoult's and Henry's Laws

NASA Astrophysics Data System (ADS)

Hayes, Robert

When a mixture of two substances exists in both the liquid and gas phase at equilibrium, Raoults and Henry's laws (ideal solution and ideal dilute solution approximations) can be used to estimate the gas and liquid mole fractions at the extremes of either very little solute or solvent. By assuming that a cubic polynomial can reasonably approximate the intermediate values to these extremes as a function of mole fraction, the cubic polynomial is solved and presented. A closed form equation approximating the pressure dependence on mole fraction of the constituents is thereby obtained. As a first approximation, this is a very simple and potentially useful means to estimate gas and liquid mole fractions of equilibrium mixtures. Mixtures with an azeotrope require additional attention if this type of approach is to be utilized. This work supported in part by federal Grant NRC-HQ-84-14-G-0059.

Coulomb energy of uniformly charged spheroidal shell systems.

PubMed

Jadhao, Vikram; Yao, Zhenwei; Thomas, Creighton K; de la Cruz, Monica Olvera

2015-03-01

We provide exact expressions for the electrostatic energy of uniformly charged prolate and oblate spheroidal shells. We find that uniformly charged prolate spheroids of eccentricity greater than 0.9 have lower Coulomb energy than a sphere of the same area. For the volume-constrained case, we find that a sphere has the highest Coulomb energy among all spheroidal shells. Further, we derive the change in the Coulomb energy of a uniformly charged shell due to small, area-conserving perturbations on the spherical shape. Our perturbation calculations show that buckling-type deformations on a sphere can lower the Coulomb energy. Finally, we consider the possibility of counterion condensation on the spheroidal shell surface. We employ a Manning-Oosawa two-state model approximation to evaluate the renormalized charge and analyze the behavior of the equilibrium free energy as a function of the shell's aspect ratio for both area-constrained and volume-constrained cases. Counterion condensation is seen to favor the formation of spheroidal structures over a sphere of equal area for high values of shell volume fractions.

Recovery of phosphonate surface contaminants from glass using a simple vacuum extractor with a solid-phase microextraction fiber.

PubMed

Groenewold, Gary S; Scott, Jill R; Rae, Catherine

2011-07-04

Recovery of chemical contaminants from fixed surfaces for analysis can be challenging, particularly if it is not possible to acquire a solid sample to be taken to the laboratory. A simple device is described that collects semi-volatile organic compounds from fixed surfaces by creating an enclosed volume over the surface, then generating a modest vacuum. A solid-phase microextraction (SPME) fiber is then inserted into the evacuated volume where it functions to sorb volatilized organic contaminants. The device is based on a syringe modified with a seal that is used to create the vacuum, with a perforable plunger through which the SPME fiber is inserted. The reduced pressure speeds partitioning of the semi-volatile compounds into the gas phase and reduces the boundary layer around the SPME fiber, which enables a fraction of the volatilized organics to partition into the SPME fiber. After sample collection, the SPME fiber is analyzed using conventional gas chromatography/mass spectrometry. The methodology has been used to collect organophosphorus compounds from glass surfaces, to provide a simple test for the functionality of the devices. Thirty minute sampling times (ΔT(vac)) resulted in fractional recovery efficiencies that ranged from 10(-3) to >10(-2), and in absolute terms, collection of low nanograms was demonstrated. Fractional recovery values were positively correlated to the vapor pressure of the compounds being sampled. Fractional recovery also increased with increasing ΔT(vac) and displayed a roughly logarithmic profile, indicating that an operational equilibrium is being approached. Fractional recovery decreased with increasing time between exposure and sampling; however, recordable quantities of the phosphonates could be collected three weeks after exposure. Copyright © 2011 Elsevier B.V. All rights reserved.

Polydispersity effects in colloid-polymer mixtures.

PubMed

Liddle, S M; Narayanan, T; Poon, W C K

2011-05-18

We study phase separation and transient gelation experimentally in a mixture consisting of polydisperse colloids (polydispersity: ≈ 6%) and non-adsorbing polymers, where the ratio of the average size of the polymer to that of the colloid is ≈ 0.062. Unlike what has been reported previously for mixtures with somewhat lower colloid polydispersity (≈ 5%), the addition of polymers does not expand the fluid-solid coexistence region. Instead, we find a region of fluid-solid coexistence which has an approximately constant width but an unexpected re-entrant shape. We detect the presence of a metastable gas-liquid binodal, which gives rise to two-stepped crystallization kinetics that can be rationalized as the effect of fractionation. Finally, we find that the separation into multiple coexisting solid phases at high colloid volume fractions predicted by equilibrium statistical mechanics is kinetically suppressed before the system reaches dynamical arrest.

Achieving Radiation Tolerance through Non-Equilibrium Grain Boundary Structures.

PubMed

Vetterick, Gregory A; Gruber, Jacob; Suri, Pranav K; Baldwin, Jon K; Kirk, Marquis A; Baldo, Pete; Wang, Yong Q; Misra, Amit; Tucker, Garritt J; Taheri, Mitra L

2017-09-25

Many methods used to produce nanocrystalline (NC) materials leave behind non-equilibrium grain boundaries (GBs) containing excess free volume and higher energy than their equilibrium counterparts with identical 5 degrees of freedom. Since non-equilibrium GBs have increased amounts of both strain and free volume, these boundaries may act as more efficient sinks for the excess interstitials and vacancies produced in a material under irradiation as compared to equilibrium GBs. The relative sink strengths of equilibrium and non-equilibrium GBs were explored by comparing the behavior of annealed (equilibrium) and as-deposited (non-equilibrium) NC iron films on irradiation. These results were coupled with atomistic simulations to better reveal the underlying processes occurring on timescales too short to capture using in situ TEM. After irradiation, NC iron with non-equilibrium GBs contains both a smaller number density of defect clusters and a smaller average defect cluster size. Simulations showed that excess free volume contribute to a decreased survival rate of point defects in cascades occurring adjacent to the GB and that these boundaries undergo less dramatic changes in structure upon irradiation. These results suggest that non-equilibrium GBs act as more efficient sinks for defects and could be utilized to create more radiation tolerant materials in future.

Nucleation of an oil phase in a nonionic microemulsion-containing chlorinated oil upon systematic temperature quench.

PubMed

Deen, G Roshan; Pedersen, Jan Skov

2010-06-17

A clear and stable nonionic model microemulsion consisting of pentaoxyethylene glycol dodecyl ether (C(12)E(5)), water, and 1-chlorotetradecane (CLTD) was prepared. This system was subjected to a systematic temperature quench (perturbation out of equilibrium) in steps of 1.0 degrees C from 20.4 to 15.3 degrees C in the unstable region of its phase diagram. The change in turbidity (for droplet volume fractions of 0.02 and 0.08) and hydrodynamic radius (R(h)) (for a droplet volume fraction of 0.02) of the system on its way to its new equilibrium was measured at each quench temperature. For small systematic temperature quenches just below the emulsification failure boundary (EFB) the turbidity decreases and remains constant indicating quick changes in the microstructures. Further lowering of temperature brings the system to the unstable region where the turbidity and light scattering increase sharply as function of time because of expulsion of excess oil from the microemulsion droplets. The newly formed oil-rich droplets grow in size as a function of time. These observations indicate the existence of a narrow but observable metastable region en route to the new equilibrium where both microemulsion droplets and larger oil-rich droplets coexist. The region in which microemulsion droplets are metastable is very narrow and is concentration-dependent. The presence of a metastable region is as for other similar systems attributed to the presence of a free energy barrier for the formation of the larger oil-rich droplets associated with curvature free energy of the surfactant film. The turbidity-time curves were converted to the radius-time curves using a model assuming monodisperse spherical droplets. The obtained results are in good agreement with the results for the hydrodynamic radius. The observed average radius from both type of measurements decreases in the metastable region. By performing calculation of the influence of eccentricity and size polydispersity on the observed radius, we have shown that the distribution of the microemulsion droplets becomes more homogeneous in the metastable region.

Mapping Isobaric Aging onto the Equilibrium Phase Diagram.

PubMed

Niss, Kristine

2017-09-15

The linear volume relaxation and the nonlinear volume aging of a glass-forming liquid are measured, directly compared, and used to extract the out-of-equilibrium relaxation time. This opens a window to investigate how the relaxation time depends on temperature, structure, and volume in parts of phase space that are not accessed by the equilibrium liquid. It is found that the temperature dependence of relaxation time is non-Arrhenius even in the isostructural case-challenging the Adam-Gibbs entropy model. Based on the presented data and the idea that aging happens through quasiequilibrium states, we suggest a mapping of the out-of-equilibrium states during isobaric aging to the equilibrium phase diagram. This mapping implies the existence of isostructural lines in the equilibrium phase diagram. The relaxation time is found to depend on the bath temperature, density, and a just single structural parameter, referred to as an effective temperature.

Comparison of ash behavior of different fuels in fluidised bed combustion using advanced fuel analysis and global equilibrium calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zevenhoven-Onderwater, M.; Blomquist, J.P.; Skrifvars, B.J.

1999-07-01

The behavior of different ashes is predicted by means of a combination of an advanced fuel analysis and global equilibrium calculations. In order to cover a broad spectrum of fuels a coal, a peat, a forest residue and Salix (i.e. willow) are studied. The latter was taken with and without soil contamination, i.e. with a high and low content of silica , respectively. It is shown that mineral matter in fossil and biomass fuels can be present in the matrix of the fuel itself or as included minerals. Using an advanced fuel analysis, i.e. a fractionation method, this mineral contentmore » can be divided into four fractions. The first fraction mainly contains those metal ions, that can be leached out of the fuel by water and mainly contains alkali sulfates, carbonates and chlorides. The second fraction mainly consists of those ions leached out by ammonium acetate and covers those ions, that are connected to the organic matrix. The third fraction contains the metals leached out by hydrochloric acid and contains earth alkali carbonates and sulfates as well as pyrites. The rest fraction contains those minerals, that are not leached out by any of the above mentioned solvents, such as silicates. A global equilibrium analysis is used to predict the thermal and chemical behavior of the combined first and second fractions and of the combined third and rest fractions under pressurized and/or atmospheric combustion conditions. Results of both the fuel analysis and the global equilibrium analysis are discussed and practical implications for combustion processes are pointed out.« less

The Voronoi volume and molecular representation of molar volume: equilibrium simple fluids.

PubMed

Hunjan, Jagtar Singh; Eu, Byung Chan

2010-04-07

The Voronoi volume of simple fluids was previously made use of in connection with volume transport phenomena in nonequilibrium simple fluids. To investigate volume transport phenomena, it is important to develop a method to compute the Voronoi volume of fluids in nonequilibrium. In this work, as a first step to this goal, we investigate the equilibrium limit of the nonequilibrium Voronoi volume together with its attendant related molar (molal) and specific volumes. It is proved that the equilibrium Voronoi volume is equivalent to the molar (molal) volume. The latter, in turn, is proved equivalent to the specific volume. This chain of equivalences provides an alternative procedure of computing the equilibrium Voronoi volume from the molar volume/specific volume. We also show approximate methods of computing the Voronoi and molar volumes from the information on the pair correlation function. These methods may be employed for their quick estimation, but also provide some aspects of the fluid structure and its relation to the Voronoi volume. The Voronoi volume obtained from computer simulations is fitted to a function of temperature and pressure in the region above the triple point but below the critical point. Since the fitting function is given in terms of reduced variables for the Lennard-Jones (LJ) model and the kindred volumes (i.e., specific and molar volumes) are in essence equivalent to the equation of state, the formula obtained is a reduced equation state for simple fluids obeying the LJ model potential in the range of temperature and pressure examined and hence can be used for other simple fluids.

Equilibrium stable-isotope fractionation of thallium and mercury

NASA Astrophysics Data System (ADS)

Schauble, E. A.

2005-12-01

In this study first-principles quantum mechanical and empirical force-field models are used to estimate equilibrium mass-dependent isotopic fractionations among a variety of thallium and mercury compounds. High-precision MC-ICP-MS measurements have recently uncovered evidence of stable isotope fractionation for many elements, including 2-4‰ variability in the isotopic compositions of thallium[1] (atomic no. 81) and mercury[2] (atomic no. 80). The observed thallium- and mercury-isotope fractionations are remarkable, given that the magnitude of isotopic fractionation typically decreases as atomic number increases[3]. Stable isotope measurements could improve our understanding of geochemical and biogeochemical cycling of both elements, but little is known about the mechanisms driving these fractionations. A better understanding of the chemical processes controlling stable isotope compositions could help maximize the utility of these new geochemical tracers. Standard equilibrium stable isotope fractionation theory holds that the energy driving fractionation comes from isotopic effects on vibrational frequencies, which have generally not been measured. In the present study both quantum-mechanical and empirical force fields are used to estimate unknown frequencies. Results suggest that thallium and mercury fractionations of ≥ 0.5‰ are likely during the relevant redox reactions Tl+ ↔ Tl3+ and HgO ↔ Hg2+. Methyl-mercury and mercury-halide compounds like CH3HgCl will have ~ 1‰ higher 202Hg/198Hg than atomic vapor at room temperature. Fractionations between coexisting Hg2+ species appear to be much smaller, however. 205Tl/203Tl in Tl(H2O)_63+ is predicted to be ~0.5‰ higher than in coexisting Tl+-bearing substances. This result is in qualitative agreement with data from ferromanganese crusts [1], suggesting that Tl3+ in manganese-oxides will have higher 205Tl/203Tl than aqueous Tl+. Equilibrium fractionations for both elements are much smaller than the observed range of isotopic fractionations, however, which could point to a major role for kinetic-fractionation or Rayleigh-like distillation processes. Refs.: [1] Rehämper et al. (2002) EPSL 197:65. [2] Xie et al. (2005) J. Anal. Atomic Spectrom. 20:515. [3] Bigeleisen and Mayer (1947) J. Chem. Phys. 15:261.

Universal patterns of equilibrium cluster growth in aqueous sugars observed by dynamic light scattering.

PubMed

Sidebottom, D L; Tran, Tri D

2010-11-01

Dynamic light scattering performed on aqueous solutions of three sugars (glucose, maltose and sucrose) reveal a common pattern of sugar cluster formation with a narrow cluster size distribution. In each case, equilibrium clusters form whose size increases with increasing sugar content in an identical power law manner in advance of a common, critical-like, percolation threshold near 83 wt % sugar. The critical exponent of the power law divergence of the cluster size varies with temperature, increasing with decreasing temperature, due to changes in the strength of the intermolecular hydrogen bond and appears to vanish for temperatures in excess of 90 °C. Detailed analysis of the cluster growth process suggests a two-stage process: an initial cluster phase formed at low volume fractions, ϕ, consisting of noninteracting, monodisperse sugar clusters whose size increases ϕ(1/3) followed by an aggregation stage, active at concentrations above about ϕ=40%, where cluster-cluster contact first occurs.

Persistence of airline accidents.

PubMed

Barros, Carlos Pestana; Faria, Joao Ricardo; Gil-Alana, Luis Alberiko

2010-10-01

This paper expands on air travel accident research by examining the relationship between air travel accidents and airline traffic or volume in the period from 1927-2006. The theoretical model is based on a representative airline company that aims to maximise its profits, and it utilises a fractional integration approach in order to determine whether there is a persistent pattern over time with respect to air accidents and air traffic. Furthermore, the paper analyses how airline accidents are related to traffic using a fractional cointegration approach. It finds that airline accidents are persistent and that a (non-stationary) fractional cointegration relationship exists between total airline accidents and airline passengers, airline miles and airline revenues, with shocks that affect the long-run equilibrium disappearing in the very long term. Moreover, this relation is negative, which might be due to the fact that air travel is becoming safer and there is greater competition in the airline industry. Policy implications are derived for countering accident events, based on competition and regulation. © 2010 The Author(s). Journal compilation © Overseas Development Institute, 2010.

Calculation of individual isotope equilibrium constants for implementation in geochemical models

USGS Publications Warehouse

Thorstenson, Donald C.; Parkhurst, David L.

2002-01-01

Theory is derived from the work of Urey to calculate equilibrium constants commonly used in geochemical equilibrium and reaction-transport models for reactions of individual isotopic species. Urey showed that equilibrium constants of isotope exchange reactions for molecules that contain two or more atoms of the same element in equivalent positions are related to isotope fractionation factors by , where is n the number of atoms exchanged. This relation is extended to include species containing multiple isotopes, for example and , and to include the effects of nonideality. The equilibrium constants of the isotope exchange reactions provide a basis for calculating the individual isotope equilibrium constants for the geochemical modeling reactions. The temperature dependence of the individual isotope equilibrium constants can be calculated from the temperature dependence of the fractionation factors. Equilibrium constants are calculated for all species that can be formed from and selected species containing , in the molecules and the ion pairs with where the subscripts g, aq, l, and s refer to gas, aqueous, liquid, and solid, respectively. These equilibrium constants are used in the geochemical model PHREEQC to produce an equilibrium and reaction-transport model that includes these isotopic species. Methods are presented for calculation of the individual isotope equilibrium constants for the asymmetric bicarbonate ion. An example calculates the equilibrium of multiple isotopes among multiple species and phases.

Equilibrium fractionation of H and O isotopes in water from path integral molecular dynamics

NASA Astrophysics Data System (ADS)

Pinilla, Carlos; Blanchard, Marc; Balan, Etienne; Ferlat, Guillaume; Vuilleumier, Rodolphe; Mauri, Francesco

2014-06-01

The equilibrium fractionation factor between two phases is of importance for the understanding of many planetary and environmental processes. Although thermodynamic equilibrium can be achieved between minerals at high temperature, many natural processes involve reactions between liquids or aqueous solutions and solids. For crystals, the fractionation factor α can be theoretically determined using a statistical thermodynamic approach based on the vibrational properties of the phases. These calculations are mostly performed in the harmonic approximation, using empirical or ab-initio force fields. In the case of aperiodic and dynamic systems such as liquids or solutions, similar calculations can be done using finite-size molecular clusters or snapshots obtained from molecular dynamics (MD) runs. It is however difficult to assess the effect of these approximate models on the isotopic fractionation properties. In this work we present a systematic study of the calculation of the D/H and 18O/16O equilibrium fractionation factors in water for the liquid/vapour and ice/vapour phases using several levels of theory within the simulations. Namely, we use a thermodynamic integration approach based on Path Integral MD calculations (PIMD) and an empirical potential model of water. Compared with standard MD, PIMD takes into account quantum effects in the thermodynamic modeling of systems and the exact fractionation factor for a given potential can be obtained. We compare these exact results with those of modeling strategies usually used, which involve the mapping of the quantum system on its harmonic counterpart. The results show the importance of including configurational disorder for the estimation of isotope fractionation in liquid phases. In addition, the convergence of the fractionation factor as a function of parameters such as the size of the simulated system and multiple isotope substitution is analyzed, showing that isotope fractionation is essentially a local effect in the investigated system.

Using Triple Oxygen Isotope Analyses of Biogenic Carbonate to Reconstruct Early Triassic Ocean Oxygen Isotopic Values and Temperatures

NASA Astrophysics Data System (ADS)

Gibbons, J. A.; Sharp, Z. D.; Atudorei, V.

2017-12-01

The calcite-water triple oxygen isotope fractionation is used to determine isotopic equilibrium and ancient ocean oxygen isotopic values and temperatures. Unlike conventional δ18O analysis where the formation water's isotopic value is assumed, paired δ17O-δ18O measurements allow for the water's isotopic composition to be calculated because there is only one unique solution for equilibrium fractionation using Δ17O-δ18O values (where Δ17O=δ17O-0.528δ18O). To a first approximation, the calcite-water equilibrium fractionation factor, θ (where θ=ln17α/ln18α), varies with temperature by 0.00001/°. The calcite-water equilibrium fractionation line was determined at two temperatures, 30° and 0°, by using modern carbonate samples that formed in ocean water with a δ18O value of 0‰. The θ values for the 30° and 0° samples are 0.52515 and 0.52486, respectively. Oxygen values were measured using complete fluorination in nickel tubes with BrF5 as the reaction reagent. We calibrated all oxygen values to the SMOW-SLAP scale by measuring SMOW, SLAP, San Carlos olivine, NBS-18, NBS-19, and PDB. The triple oxygen isotope calcite-water equilibrium fractionation line was applied to well preserved Early Triassic ammonite shells from the Western United States. Based on paired δ17O-δ18O measurements, the samples did not form in equilibrium with an ice-free ocean with an oxygen isotopic value of -1‰ or the modern ocean value of 0‰. Assuming the calcite is still primary and formed in equilibrium with the ocean water, our data indicate that the δ18O value of the ocean in the early Triassic was 3-5‰ lower than modern. Samples from the Smithian thermal maximum formed in water 10° warmer than samples from after the thermal maximum. Paired δ17O-δ18O measurements of pristine ancient carbonates may provide a better understanding of past ocean conditions during climate change events.

Dynamical analysis of a fractional SIR model with birth and death on heterogeneous complex networks

NASA Astrophysics Data System (ADS)

Huo, Jingjing; Zhao, Hongyong

2016-04-01

In this paper, a fractional SIR model with birth and death rates on heterogeneous complex networks is proposed. Firstly, we obtain a threshold value R0 based on the existence of endemic equilibrium point E∗, which completely determines the dynamics of the model. Secondly, by using Lyapunov function and Kirchhoff's matrix tree theorem, the globally asymptotical stability of the disease-free equilibrium point E0 and the endemic equilibrium point E∗ of the model are investigated. That is, when R0 < 1, the disease-free equilibrium point E0 is globally asymptotically stable and the disease always dies out; when R0 > 1, the disease-free equilibrium point E0 becomes unstable and in the meantime there exists a unique endemic equilibrium point E∗, which is globally asymptotically stable and the disease is uniformly persistent. Finally, the effects of various immunization schemes are studied and compared. Numerical simulations are given to demonstrate the main results.

Experimental investigation on V isotope equilibrium fractionation factor between metal and silicate melt

NASA Astrophysics Data System (ADS)

Zhang, S.; Zhang, H.; Huang, F.

2017-12-01

Equilibrium fractionation factors of stable isotopes between metal and silicate melt are of vital importance for understanding the isotope variations within meteorites and planetary bodies. The V isotope composition (reported as δ51V = 1000 × [(51V/50Vsample/51V/50VAA)-1] ) of the bulk silicate Earth (BSE) has been estimated as δ51V = -0.7 ± 0.2‰ (2sd) [1], which is significantly heavier than most meteorites by 1‰ [2]. Such isotopic offset may provide insights for the core formation and core-mantle segregation. Therefore, it is important to understand V isotope equilibrium fractionation factor between silicate melt and metal. Nielsen et al. (2014) [2] had performed 3 experiments using starting materials of pure Fe metal and An50Di28Fo22 composition, revealing no resolvable V isotope fractionation. However, it is not clear whether chemical compositions in the melts can affect V isotope fractionations. Therefore, we experimentally calibrated equilibrium V isotope fractionation between Fe metallic and basaltic melt, with particular focus on the effect of Ni and other light elements. Experiments were performed at 1 GPa and 1600 oC using a 3/4″ end-loaded piston cylinder. The starting materials consisted of 1:1 mixture of pure Fe metal and basaltic composition [3]. The isotope equilibrium was assessed using time series experiments combined with the reverse reaction method. Carbon saturation and C-free experiments were achieved by using graphite and silica capsules, respectively. The Ni series experiments were doped with 6 wt% Ni into the starting Fe metal. The metal and silicate phases of samples were mechanically separated, V was purified using a chromatographic technique, and V isotope ratios were measured using MC-ICP-MS [4]. Carbon saturation, C-free experiments and Ni series experiment all show non-resolvable V isotope fractionation between metal and basaltic melt, which indicates that the presence of C and Ni could not affect V isotope fractionation during core formation. More experiments will be performed to explore the effect of Si and S in the metal on V isotope fractionation between metal and silicate melt.References: [1] Prytulak et al. (2013) EPSL 365, 177-189 [2] Nielsen et al. (2014) EPSL 389, 167-175 [3] Cottrell et al. (2009) CG 268, 167-179 [4] Wu et al. (2016) CG 421, 17-25

Soil tension mediates isotope fractionation during soil water evaporation

NASA Astrophysics Data System (ADS)

Gaj, Marcel; McDonnell, Jeffrey

2017-04-01

Isotope tracing of the water cycle is increasing in its use and usefulness. Many new studies are extracting soil waters and relating these to streamflow, groundwater recharge and plant transpiration. Nevertheless, unlike isotope fractionation factors from open water bodies, soil water fractionation factors are poorly understood and until now, only empirically derived. In contrast to open water evaporation where temperature, humidity and vapor pressure gradient define fractionation (as codified in the well-known Craig and Gordon model), soil water evaporation includes additionally, fractionation by matrix effects. There is yet no physical explanation of kinetic and equilibrium fraction from soil water within the soil profile. Here we present a simple laboratory experiment with four admixtures of soil grain size (from sand to silt to clay). Oven-dried samples were spiked with water of known isotopic composition at different soil water contents. Soils were then stored in sealed bags and the headspace filled with dry air and allowed to equilibrate for 24hours. Isotopic analysis of the headspace vapor was done with a Los Gatos Inc. water vapor isotope analyzer. Soil water potential of subsamples were measured with a water potential meter. We show for the first time that soil tension controls isotope fractionation in the resident soil water. Below a Pf 3.5 the δ-values of 18O and 2H of the headspace vapor is more positive and increases with increasing soil water potential. Surprisingly, we find that the relationship between soil tension and equilibrium fractionation is independent of soil type. However, δ-values of each soil type plot along a distinct evaporation line. These results indicate that equilibrium fractionation is affected by soil tension in addition to temperature. Therefore, at high soil water tension (under dry conditions) equilibrium fractionation is not consistent with current empirical formulations that ignore these effects. These findings may have implications for plant water uptake studies since plant root water uptake imparts tension to extract water from the soil matrix. Since this is the same physical force as soil water potential, root water uptake at high soil water potential might cause fractionation of soil water. Our work is ongoing to examine these knock-on effects.

Equilibrium and kinetic models for colloid release under transient solution chemistry conditions

USDA-ARS?s Scientific Manuscript database

We present continuum models to describe colloid release in the subsurface during transient physicochemical conditions. Our modeling approach relates the amount of colloid release to changes in the fraction of the solid surface area that contributes to retention. Equilibrium, kinetic, equilibrium and...

Barium isotope fractionation during witherite (BaCO3) dissolution, precipitation and at equilibrium

NASA Astrophysics Data System (ADS)

Mavromatis, Vasileios; van Zuilen, Kirsten; Purgstaller, Bettina; Baldermann, Andre; Nägler, Thomas F.; Dietzel, Martin

2016-10-01

This study examines the behavior of Ba isotope fractionation between witherite and fluid during mineral dissolution, precipitation and at chemical equilibrium. Experiments were performed in batch reactors at 25 °C in 10-2 M NaCl solution where the pH was adjusted by continuous bubbling of a water saturated gas phase of CO2 or atmospheric air. During witherite dissolution no Ba isotope fractionation was observed between solid and fluid. In contrast, during witherite precipitation, caused by a pH increase, a preferential uptake of the lighter 134Ba isotopomer in the solid phase was observed. In this case, the isotope fractionation factor αwitherite-fluid is calculated to be 0.99993 ± 0.00004 (or Δ137/134Bawitherite-fluid ≈ -0.07 ± 0.04‰, 2 sd). The most interesting feature of this study, however, is that after the attainment of chemical equilibrium, the Ba isotope composition of the aqueous phase is progressively becoming lighter, indicating a continuous exchange of Ba2+ ions between witherite and fluid. Mass balance calculations indicate that the detachment of Ba from the solid is not only restricted to the outer surface layer of the solid, but affects several (∼7 unit cells) subsurface layers of the crystal. This observation comes in excellent agreement with the concept of a dynamic system at chemical equilibrium in a mineral-fluid system, denoting that the time required for the achievement of isotopic equilibrium in the witherite-fluid system is longer compared to that observed for chemical equilibrium. Overall, these results indicate that the isotopic composition of Ba bearing carbonates in natural environments may be altered due to changes in fluid composition without a net dissolution/precipitation to be observed.

Thermodynamic analysis of energy density in pressure retarded osmosis: The impact of solution volumes and costs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reimund, Kevin K.; McCutcheon, Jeffrey R.; Wilson, Aaron D.

A general method was developed for estimating the volumetric energy efficiency of pressure retarded osmosis via pressure-volume analysis of a membrane process. The resulting model requires only the osmotic pressure, π, and mass fraction, w, of water in the concentrated and dilute feed solutions to estimate the maximum achievable specific energy density, uu, as a function of operating pressure. The model is independent of any membrane or module properties. This method utilizes equilibrium analysis to specify the volumetric mixing fraction of concentrated and dilute solution as a function of operating pressure, and provides results for the total volumetric energy densitymore » of similar order to more complex models for the mixing of seawater and riverwater. Within the framework of this analysis, the total volumetric energy density is maximized, for an idealized case, when the operating pressure is π/(1+√w⁻¹), which is lower than the maximum power density operating pressure, Δπ/2, derived elsewhere, and is a function of the solute osmotic pressure at a given mass fraction. It was also found that a minimum 1.45 kmol of ideal solute is required to produce 1 kWh of energy while a system operating at “maximum power density operating pressure” requires at least 2.9 kmol. Utilizing this methodology, it is possible to examine the effects of volumetric solution cost, operation of a module at various pressure, and operation of a constant pressure module with various feed.« less

Predicting the ash behavior during biomass combustion in FBC conditions by combining advanced fuel analyses with thermodynamic multicomponent equilibrium calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Skrifvars, B.J.; Blomquist, J.P.; Hupa, M.

1998-12-31

Previous work at Aabo Akademi University has focused on identification and quantification of various sintering mechanisms which are relevant for problematic ash behavior during biomass combustion in fluidized bed combustion conditions, and on multi-component multi-phase thermodynamic phase equilibrium calculations of ash chemistry in these conditions. In both areas new information has been developed and useful modeling capabilities have been created. Based on the previous work, the authors now present a novel approach of using a combination of an advanced fuel analysis method and thermodynamic phase equilibrium calculations to predict the chemical and thermal behavior of the ash when firing biomass.more » Four different fuels [coal, forest residues, wood chips, and a mixture of forest residue and wood chips] were analyzed using the chemical fractionation analysis technique. Based on the results from these analyses, the authors formed two different ash fractions, (1) one fine sized fraction consisting of those elements found in the water and weak acid leach, and (2) a coarse ash particle fraction consisting of those elements found in the strong acid leach and non-leachable rest. The small sized ash fraction was then assumed to be carried up with the flue gases and consequently formed the base for any ash related problems in the flue gas channel. This fraction was therefore analyzed on its chemical and thermal behavior using multi-component multi-phase equilibrium calculations, by which the composition and the melting behavior was estimated as a function of the temperature. The amount of melt, which has earlier been found to be strongly related to problematic ash behavior, was finally expressed as a function of the temperature for the fraction. The coarse fraction was treated separately. Here the authors estimate the composition only. The paper discusses the results and their relevance to full scale combustion.« less

Isochoric structural recovery in molecular glasses and its analog in colloidal glasses

NASA Astrophysics Data System (ADS)

Banik, Sourya; McKenna, Gregory B.

2018-06-01

Concentrated colloidal dispersions have been regarded as models for molecular glasses. One of the many ways to compare the behavior in these two different systems is by comparing the structural recovery or the physical aging behavior. However, recent investigations from our group to examine structural recovery in thermosensitive colloidal dispersions have shown contrasting results between the colloidal and the molecular glasses. The differences in the behaviors of the two systems have led us to pose this question: Is structural recovery behavior in colloidal glasses truly distinct from that of molecular glasses or is the conventional experimental condition (isobaric temperature-jumps) in determining the structural recovery in molecular glasses different from the experimental condition in the colloidal experiments (concentration- or volume fraction-jumps); i.e., are colloidal glasses inherently different from molecular glasses or not? To address the question, we resort to model calculations of structural recovery in a molecular glass under constant volume (isochoric) conditions following temperature only- and simultaneous volume- and temperature-jumps, which are closer to the volume fraction-jump conditions used in the thermosensitive-colloidal experiments. The current model predictions are then compared with the signatures of structural recovery under the conventional isobaric state in a molecular glass and with structural recovery behavior in colloidal glasses following volume fraction-jumps. We show that the results obtained from the experiments conducted by our group were contrasting to classical molecular glass behavior because the basis of our comparisons were incorrect (the histories were not analogous). The present calculations (with analogous histories) are qualitatively closer to the colloidal behavior. The signatures of "intrinsic isotherms" and "asymmetry of approach" in the current isochoric model predictions are quite different from those in the classical isobaric conditions while the "memory" signatures remain essentially the same. While there are qualitative similarities between the current isochoric model predictions and results from colloidal glasses, it appears from the calculations that the origins of these are different. The isochoric histories in the molecular glasses have compensating effects of pressure and departure from equilibrium which determines the structure dependence on mobility of the molecules. On the other hand, in the colloids it simply appears that the volume fraction-jump conditions simply do not exhibit such structure mobility dependence. The determining interplay of thermodynamic phase variables in colloidal and molecular systems might be very different or at least their correlations are yet to be ascertained. This topic requires further investigation to bring the similarities and differences between molecular and colloidal glass formers into fuller clarity.

Diffusion in jammed particle packs

NASA Astrophysics Data System (ADS)

Bolintineanu, Dan S.; Silbert, Leonardo E.; Grest, Gary S.; Lechman, Jeremy B.

2015-03-01

Diffusive transport in jammed particle packs is of interest for a number of applications, as well as being a potential indicator of structural properties near the jamming point. To this end, we report stochastic simulations of equilibrium diffusion through monodisperse sphere packs near the jamming point in the limit of a perfectly insulating surrounding medium. The time dependence of various diffusion properties is resolved over several orders of magnitude. Two time regimes of expected Fickian diffusion are observed, separated by an intermediate regime of anomalous diffusion. This intermediate regime grows as the particle volume fraction approaches the critical jamming transition. The diffusion behavior is fully controlled by the extent of the contacts between neighboring particles, which in turn depend on proximity to the jamming point. In particular, the mean first passage time associated with the escape of random walkers between neighboring particles is shown to control both the time to recover Fickian diffusion and the long time diffusivity. Scaling laws are established that relate these quantities to the difference between the actual and critical jamming volume fractions. Sandia National Laboratories is a multiprogram laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's NNSA under Contract DE- AC04-94AL85000.

Behaviours and influence factors of radon progeny in three typical dwellings.

PubMed

Li, Hongzhao; Zhang, Lei; Guo, Qiuju

2011-03-01

To investigate the behaviours and influence factors of radon progeny in rural dwellings in China, site measurements of radon equilibrium factor, unattached fraction and some important indoor environmental factors, such as aerosol concentration, aerosol size distribution and ventilation rate, were carried out in three typical types of dwellings, and a theoretical study was also performed synchronously. Good consistency between the results of site measurements and the theoretical calculation on equilibrium factor F and unattached fraction f(p) was achieved. Lower equilibrium factor and higher unattached fraction in mud or cave houses were found compared to those in brick houses, and it was suggested by the theoretical study that the smaller aerosol size distribution in mud or cave houses might be the main reason for what was observed. The dose conversion factor in the mud houses and the cave houses may be higher than that in brick houses.

Using chromium stable isotope ratios to quantify Cr(VI) reduction: Lack of sorption effects

USGS Publications Warehouse

Ellis, A.S.; Johnson, T.M.; Bullen, T.D.

2004-01-01

Chromium stable isotope values can be effectively used to monitor reduction of Cr(VI) in natural waters. We investigate effects of sorption during transport of Cr(VI) which may also shift Cr isotopes values, complicating efforts to quantify reduction. This study shows that Cr stable isotope fractionation caused by sorption is negligible. Equilibrium fractionation of Cr stable isotopes between dissolved Cr-(VI) and Cr(VI) adsorbed onto ??-Al2O3 and goethite is less than 0.04???. (53Cr/52Cr) under environmentally relevant pH conditions. Batch experiments at pH 4.0 and pH 6.0 were conducted in series to sequentially magnify small isotope fractionations. A simple transport model suggests that adsorption may cause amplification of a small isotope fractionation along extreme fringes of a plume, leading to shifts in 53Cr/52Cr values. We therefore suggest that isotope values at extreme fringes of Cr plumes be critically evaluated for sorption effects. A kinetic effect was observed in experiments with goethite at pH 4 where apparently lighter isotopes diffuse into goethite clumps at a faster rate before eventually reaching equilibrium. This observed kinetic effect may be important in a natural system that has not attained equilibrium and is in need of further study. Cr isotope fractionation caused by speciation of Cr(VI) between HCrO4- and CrO42- was also examined, and we conclude that it is not measurable. In the absence of isotope fractionation caused by equilibrium speciation and sorption, most of the variation in ??53 Cr values may be attributed to reduction, and reliable estimates of Cr reduction can be made.

Phase equilibria constraints on the chemical and physical evolution of the campanian ignimbrite

USGS Publications Warehouse

Fowler, S.J.; Spera, F.J.; Bohrson, W.A.; Belkin, H.E.; de Vivo, B.

2007-01-01

The Campanian Ignimbrite is a > 200 km3 trachyte-phonolite pyroclastic deposit that erupted at 39.3 ?? 0.1 ka within the Campi Flegrei west of Naples, Italy. Here we test the hypothesis that Campanian Ignimbrite magma was derived by isobaric crystal fractionation of a parental basaltic trachyandesitic melt that reacted and came into local equilibrium with small amounts (5-10 wt%) of crustal rock (skarns and foid-syenites) during crystallization. Comparison of observed crystal and magma compositions with results of phase equilibria assimilation-fractionation simulations (MELTS) is generally very good. Oxygen fugacity was approximately buffered along QFM+1 (where QFM is the quartz-fayalite-magnetite buffer) during isobaric fractionation at 0.15 GPa (???6 km depth). The parental melt, reconstructed from melt inclusion and host clinopyroxene compositions, is found to be basaltic trachyandesite liquid (51.1 wt% SiO2, 9.3 wt% MgO, 3 wt% H2O). A significant feature of phase equilibria simulations is the existence of a pseudo-invariant temperature, ???883??C, at which the fraction of melt remaining in the system decreases abruptly from ???0.5 to < 0.1. Crystallization at the pseudo-invariant point leads to abrupt changes in the composition, properties (density, dissolved water content), and physical state (viscosity, volume fraction fluid) of melt and magma. A dramatic decrease in melt viscosity (from 1700 Pa s to ???200 Pa s), coupled with a change in the volume fraction of water in magma (from ??? 0.1 to 0.8) and a dramatic decrease in melt and magma density acted as a destabilizing eruption trigger. Thermal models suggest a timescale of ??? 200 kyr from the beginning of fractionation until eruption, leading to an apparent rate of evolved magma generation of about 10-3 km3/year. In situ crystallization and crystal settling in density-stratified regions, as well as in convectively mixed, less evolved subjacent magma, operate rapidly enough to match this apparent volumetric rate of evolved magma production. ?? Copyright 2007 Oxford University Press.

Para hydrogen equilibration in the atmospheres of the outer planets

NASA Technical Reports Server (NTRS)

Conrath, Barney J.

1986-01-01

The thermodynamic behavior of the atmospheres of the Jovian planets is strongly dependent on the extent to which local thermal equilibration of the ortho and para states of molecular hydrogen is achieved. Voyager IRIS data from Jupiter imply substantial departures of the para hydrogen fraction from equilibrium in the upper troposphere at low latitudes, but with values approaching equilibrium at higher latitudes. Data from Saturn are less sensitive to the orth-para ratio, but suggest para hydrogen fractions near the equilibrium value. Above approximately the 200 K temperature level, para hydrogen conversion can enhance the efficiency of convection, resulting in a substantial increase in overturning times on all of the outer planets. Currently available data cannot definitively establish the ortho-para ratios in the atmospheres of Uranus and Neptune, but suggest values closer to local equilibrium than to the 3.1 normal ratio. Modeling of sub-millimeter wavelength measurements of these planets suggest thermal structures with frozen equilibrium lapse rates in their convective regions.

Quantitative determination of free/bound atazanavir via high-throughput equilibrium dialysis and LC-MS/MS, and the application in ex vivo samples.

PubMed

Xu, Xiaohui Sophia; Rose, Anne; Demers, Roger; Eley, Timothy; Ryan, John; Stouffer, Bruce; Cojocaru, Laura; Arnold, Mark

2014-01-01

The determination of drug-protein binding is important in the pharmaceutical development process because of the impact of protein binding on both the pharmacokinetics and pharmacodynamics of drugs. Equilibrium dialysis is the preferred method to measure the free drug fraction because it is considered to be more accurate. The throughput of equilibrium dialysis has recently been improved by implementing a 96-well format plate. Results/methodology: This manuscript illustrates the successful application of a 96-well rapid equilibrium dialysis (RED) device in the determination of atazanavir plasma-protein binding. This RED method of measuring free fraction was successfully validated and then applied to the analysis of clinical plasma samples taken from HIV-infected pregnant women administered atazanavir. Combined with LC-MS/MS detection, the 96-well format equilibrium dialysis device was suitable for measuring the free and bound concentration of pharmaceutical molecules in a high-throughput mode.

NON-EQUILIBRIUM HELIUM IONIZATION IN AN MHD SIMULATION OF THE SOLAR ATMOSPHERE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Golding, Thomas Peter; Carlsson, Mats; Leenaarts, Jorrit, E-mail: thomas.golding@astro.uio.no, E-mail: mats.carlsson@astro.uio.no, E-mail: jorrit.leenaarts@astro.su.se

The ionization state of the gas in the dynamic solar chromosphere can depart strongly from the instantaneous statistical equilibrium commonly assumed in numerical modeling. We improve on earlier simulations of the solar atmosphere that only included non-equilibrium hydrogen ionization by performing a 2D radiation-magnetohydrodynamics simulation featuring non-equilibrium ionization of both hydrogen and helium. The simulation includes the effect of hydrogen Lyα and the EUV radiation from the corona on the ionization and heating of the atmosphere. Details on code implementation are given. We obtain helium ion fractions that are far from their equilibrium values. Comparison with models with local thermodynamicmore » equilibrium (LTE) ionization shows that non-equilibrium helium ionization leads to higher temperatures in wavefronts and lower temperatures in the gas between shocks. Assuming LTE ionization results in a thermostat-like behavior with matter accumulating around the temperatures where the LTE ionization fractions change rapidly. Comparison of DEM curves computed from our models shows that non-equilibrium ionization leads to more radiating material in the temperature range 11–18 kK, compared to models with LTE helium ionization. We conclude that non-equilibrium helium ionization is important for the dynamics and thermal structure of the upper chromosphere and transition region. It might also help resolve the problem that intensities of chromospheric lines computed from current models are smaller than those observed.« less

Calculation of individual isotope equilibrium constants for geochemical reactions

USGS Publications Warehouse

Thorstenson, D.C.; Parkhurst, D.L.

2004-01-01

Theory is derived from the work of Urey (Urey H. C. [1947] The thermodynamic properties of isotopic substances. J. Chem. Soc. 562-581) to calculate equilibrium constants commonly used in geochemical equilibrium and reaction-transport models for reactions of individual isotopic species. Urey showed that equilibrium constants of isotope exchange reactions for molecules that contain two or more atoms of the same element in equivalent positions are related to isotope fractionation factors by ?? = (Kex)1/n, where n is the number of atoms exchanged. This relation is extended to include species containing multiple isotopes, for example 13C16O18O and 1H2H18O. The equilibrium constants of the isotope exchange reactions can be expressed as ratios of individual isotope equilibrium constants for geochemical reactions. Knowledge of the equilibrium constant for the dominant isotopic species can then be used to calculate the individual isotope equilibrium constants. Individual isotope equilibrium constants are calculated for the reaction CO2g = CO2aq for all species that can be formed from 12C, 13C, 16O, and 18O; for the reaction between 12C18 O2aq and 1H218Ol; and among the various 1H, 2H, 16O, and 18O species of H2O. This is a subset of a larger number of equilibrium constants calculated elsewhere (Thorstenson D. C. and Parkhurst D. L. [2002] Calculation of individual isotope equilibrium constants for implementation in geochemical models. Water-Resources Investigation Report 02-4172. U.S. Geological Survey). Activity coefficients, activity-concentration conventions for the isotopic variants of H2O in the solvent 1H216Ol, and salt effects on isotope fractionation have been included in the derivations. The effects of nonideality are small because of the chemical similarity of different isotopic species of the same molecule or ion. The temperature dependence of the individual isotope equilibrium constants can be calculated from the temperature dependence of the fractionation factors. The derivations can be extended to calculation of individual isotope equilibrium constants for ion pairs and equilibrium constants for isotopic species of other chemical elements. The individual isotope approach calculates the same phase isotopic compositions as existing methods, but also provides concentrations of individual species, which are needed in calculations of mass-dependent effects in transport processes. The equilibrium constants derived in this paper are used to calculate the example of gas-water equilibrium for CO2 in an acidic aqueous solution. ?? 2004 Elsevier Ltd.

One Adaptive Synchronization Approach for Fractional-Order Chaotic System with Fractional-Order 1 < q < 2

PubMed Central

Zhou, Ping; Bai, Rongji

2014-01-01

Based on a new stability result of equilibrium point in nonlinear fractional-order systems for fractional-order lying in 1 < q < 2, one adaptive synchronization approach is established. The adaptive synchronization for the fractional-order Lorenz chaotic system with fractional-order 1 < q < 2 is considered. Numerical simulations show the validity and feasibility of the proposed scheme. PMID:25247207

Phase equilibrium of methane and nitrogen at low temperatures - Application to Titan

NASA Technical Reports Server (NTRS)

Kouvaris, Louis C.; Flasar, F. M.

1991-01-01

Since the vapor phase composition of Titan's methane-nitrogen lower atmosphere is uniquely determined as a function of the Gibbs phase rule, these data are presently computed via integration of the Gibbs-Duhem equation. The thermodynamic consistency of published measurements and calculations of the vapor phase composition is then examined, and the saturated mole fraction of gaseous methane is computed as a function of altitude up to the 700-mbar level. The mole fraction is found to lie approximately halfway between that computed from Raoult's law, for a gas in equilibrium with an ideal solution of liquid nitrogen and methane, and that for a gas in equilibrium with pure liquid methane.

Equilibration and aging of dense soft-sphere glass-forming liquids

NASA Astrophysics Data System (ADS)

Sánchez-Díaz, Luis Enrique; Ramírez-González, Pedro; Medina-Noyola, Magdaleno

2013-05-01

The recently developed nonequilibrium extension of the self-consistent generalized Langevin equation theory of irreversible relaxation [Ramírez-González and Medina-Noyola, Phys. Rev. E10.1103/PhysRevE.82.061503 82, 061503 (2010); Ramírez-González and Medina-Noyola, Phys. Rev. E10.1103/PhysRevE.82.061504 82, 061504 (2010)] is applied to the description of the irreversible process of equilibration and aging of a glass-forming soft-sphere liquid that follows a sudden temperature quench, within the constraint that the local mean particle density remains uniform and constant. For these particular conditions, this theory describes the nonequilibrium evolution of the static structure factor S(k;t) and of the dynamic properties, such as the self-intermediate scattering function FS(k,τ;t), where τ is the correlation delay time and t is the evolution or waiting time after the quench. Specific predictions are presented for the deepest quench (to zero temperature). The predicted evolution of the α-relaxation time τα(t) as a function of t allows us to define the equilibration time teq(ϕ), as the time after which τα(t) has attained its equilibrium value ταeq(ϕ). It is predicted that both, teq(ϕ) and ταeq(ϕ), diverge as ϕ→ϕ(a), where ϕ(a) is the hard-sphere dynamic-arrest volume fraction ϕ(a)(≈0.582), thus suggesting that the measurement of equilibrium properties at and above ϕ(a) is experimentally impossible. The theory also predicts that for fixed finite waiting times t, the plot of τα(t;ϕ) as a function of ϕ exhibits two regimes, corresponding to samples that have fully equilibrated within this waiting time (ϕ≤ϕ(c)(t)), and to samples for which equilibration is not yet complete (ϕ≥ϕ(c)(t)). The crossover volume fraction ϕ(c)(t) increases with t but saturates to the value ϕ(a).

Separation of nitrogen heterocyclic compounds from model coal tar fraction by solvent extraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, S.J.; Chun, Y.J.

2005-07-01

The separation of four kinds of nitrogen heterocyclic compounds (NHCs) from a model mixture comprising NHCs (indole (In), quinoline (Q), iso-quinoline (iQ), quinaldine (Qu)), three kinds of bicyclic aromatic compounds (BACs; 1-methyl-naphthalene (IMN), 2-methyl naphthalene (2MN), dimethylnaphthalene (DMN)), biphenyl (Bp) and phenyl ether (Pe) was examined by a solvent extraction. The model mixture used as a raw material of this work was prepared according to the components and compositions contained in coal tar fraction (the temperature ranges of fraction: 240-265{sup o}C). An aqueous solution of methanol, ethanol, iso-propyl alcohol, N,N-dimethyl acetamide, DMF, formamide, N-methylformamide/methanol, and formamide/methanol were used as solvents.more » An aqueous solution of formamide was found suitable for separating NHCs contained in coal tar fraction based on distribution coefficient and selectivity. The effect of operation factors on separating NHCs was investigated by the distribution equilibrium using an aqueous solution of formamide. Increasing the operation temperature and the volume ratio of solvent to feed at initial (S/F)(o) resulted in improving the distribution coefficients of each NHC, but increasing the volume fraction of water in the solvent at initial (y(w,O)) resulted in deteriorating the distribution coefficients of each NHC. With increasing y(w,O) and (S/F)(o), the selectivities of each NHC in reference to DMN increased. Increase in operation temperature resulted in decrease in selectivities of each NHC in reference to DMN. At an experimental condition fixed, the sequence of the distribution coefficient and selectivity in reference to DMN for each NHC was In {gt} iQ {gt} Q {gt} Qu, and also the sequence of the distribution coefficient for each BAC was IMN {gt} 2MN {gt} DMN. The sequence of the distribution coefficient for entire compounds analyzed by this work was In {gt} iQ {gt} Q {gt} Qu {gt} BP {gt} 1MN {gt} 2MN {gt} Pe {gt} DMN.« less

Accuracy of cancellous bone volume fraction measured by micro-CT scanning.

PubMed

Ding, M; Odgaard, A; Hvid, I

1999-03-01

Volume fraction, the single most important parameter in describing trabecular microstructure, can easily be calculated from three-dimensional reconstructions of micro-CT images. This study sought to quantify the accuracy of this measurement. One hundred and sixty human cancellous bone specimens which covered a large range of volume fraction (9.8-39.8%) were produced. The specimens were micro-CT scanned, and the volume fraction based on Archimedes' principle was determined as a reference. After scanning, all micro-CT data were segmented using individual thresholds determined by the scanner supplied algorithm (method I). A significant deviation of volume fraction from method I was found: both the y-intercept and the slope of the regression line were significantly different from those of the Archimedes-based volume fraction (p < 0.001). New individual thresholds were determined based on a calibration of volume fraction to the Archimedes-based volume fractions (method II). The mean thresholds of the two methods were applied to segment 20 randomly selected specimens. The results showed that volume fraction using the mean threshold of method I was underestimated by 4% (p = 0.001), whereas the mean threshold of method II yielded accurate values. The precision of the measurement was excellent. Our data show that care must be taken when applying thresholds in generating 3-D data, and that a fixed threshold may be used to obtain reliable volume fraction data. This fixed threshold may be determined from the Archimedes-based volume fraction of a subgroup of specimens. The threshold may vary between different materials, and so it should be determined whenever a study series is performed.

Post-Detonation Energy Release from TNT-Aluminum Explosives

NASA Astrophysics Data System (ADS)

Zhang, Fan; Anderson, John; Yoshinaka, Akio

2007-06-01

Detonation and post-detonation energy release from TNT and TNT-aluminum composite have been experimentally studied in an air-filled chamber, 26 m^3 in volume and 3 m in diameter. While TNT has a high oxygen deficiency, experiments with 1.1 kg to 4 kg charges yield energy releases reaching only 86% of theoretical equilibrium values, possibly due to the non-uniform mixing between the detonation products and air. In order to improve mixing and further increase afterburning energy, large mass fractions of large aluminum particles are combined with TNT. The effect of particle distribution is also investigated in two composite configurations, whereby the aluminum particles are uniformly mixed in cast TNT or arranged in a shell surrounding a TNT cylinder. It is shown that the TNT-aluminum composite outperforms pure TNT, while improved performance is achieved for the shell configuration due to enhanced spatial mixing of hot fuels with oxidizing gases. Comparisons with the equilibrium theory and a liquid-based aluminized composite explosive (with an oxygen deficiency less than that of TNT) are conducted to further explore the mixing and afterburning mechanism.

Pasta Nucleosynthesis: Molecular dynamics simulations of nuclear statistical equilibrium

NASA Astrophysics Data System (ADS)

Caplan, Matthew; Horowitz, Charles; da Silva Schneider, Andre; Berry, Donald

2014-09-01

We simulate the decompression of cold dense nuclear matter, near the nuclear saturation density, in order to study the role of nuclear pasta in r-process nucleosynthesis in neutron star mergers. Our simulations are performed using a classical molecular dynamics model with 51 200 and 409 600 nucleons, and are run on GPUs. We expand our simulation region to decompress systems from initial densities of 0.080 fm-3 down to 0.00125 fm-3. We study proton fractions of YP = 0.05, 0.10, 0.20, 0.30, and 0.40 at T = 0.5, 0.75, and 1 MeV. We calculate the composition of the resulting systems using a cluster algorithm. This composition is in good agreement with nuclear statistical equilibrium models for temperatures of 0.75 and 1 MeV. However, for proton fractions greater than YP = 0.2 at a temperature of T = 0.5 MeV, the MD simulations produce non-equilibrium results with large rod-like nuclei. Our MD model is valid at higher densities than simple nuclear statistical equilibrium models and may help determine the initial temperatures and proton fractions of matter ejected in mergers.

Directed self-assembly of diblock copolymers in cylindrical confinement: effect of underfilling and air-polymer interactions on configurations

NASA Astrophysics Data System (ADS)

Carpenter, Corinne L.; Delaney, Kris T.; Laachi, Nabil; Fredrickson, Glenn H.

2015-03-01

Directed self-assembly (DSA) of block copolymers has attracted attention for its use as a simple, cost- effective patterning tool for creating vertical interconnect access (VIA) channels in nanoelectronic devices.1, 2 This technique supplements existing lithographic technologies to allow for the creation of high-resolution cylindrical holes whose diameter and placement can be precisely controlled. In this study, we use self-consistent field theory (SCFT) simulations to investigate the equilibrium configurations of under-filled DSA systems with air-polymer interactions. We report on a series of SCFT simulations of our three species (PMMA-b-PS diblock and air) model in cylindrical confinement to explore the role of template diameter, under-fill fraction (i.e. volume fraction of air), air-polymer surface interaction and polymer-side wall/substrate interactions on equilibrium morphologies in an under-filled template with a free top surface. We identify parameters and system configurations where a meniscus appears and explore cases with PMMA-attractive, PS-attractive, and all-neutral walls to understand the effects of wall properties on meniscus geometry and DSA morphology. An important outcome is an understanding of the parameters that control the contact angle of the meniscus with the wall, as it is one of the simplest quantitative measures of the meniscus shape. Ultimately, we seek to identify DSA formulations, templates, and surface treatments with predictable central cylinder diameter and a shallow contact angle, as these factors would facilitate broad process windows and ease of manufacturing.

Phase and vacancy behaviour of hard "slanted" cubes

NASA Astrophysics Data System (ADS)

van Damme, R.; van der Meer, B.; van den Broeke, J. J.; Smallenburg, F.; Filion, L.

2017-09-01

We use computer simulations to study the phase behaviour for hard, right rhombic prisms as a function of the angle of their rhombic face (the "slant" angle). More specifically, using a combination of event-driven molecular dynamics simulations, Monte Carlo simulations, and free-energy calculations, we determine and characterize the equilibrium phases formed by these particles for various slant angles and densities. Surprisingly, we find that the equilibrium crystal structure for a large range of slant angles and densities is the simple cubic crystal—despite the fact that the particles do not have cubic symmetry. Moreover, we find that the equilibrium vacancy concentration in this simple cubic phase is extremely high and depends only on the packing fraction and not the particle shape. At higher densities, a rhombic crystal appears as the equilibrium phase. We summarize the phase behaviour of this system by drawing a phase diagram in the slant angle-packing fraction plane.

Exchangeable Phosphorus Pools and Equilibrium Characteristics for River Sediment as a Function of Particle Size

DTIC Science & Technology

2010-10-01

Zea mays L .). Can J Soil Sci 75:361-367. Zhang, T. Q., A. F. MacKenzie, B. C. Liang, and C. F. Drury. 2004. Soil test phosphorus and phosphorus...particulate exchangeable P fractions (as a fractional percentage), respectively, Cs is the suspended sediment concentration (M L -3), and Kd is the...groundwater) amended with P to a concentration of 0.120 mg L -1 to maintain in situ P equilibrium conditions (reported in James and Larson 2008

Effect of cold drawing ratio on γ′ precipitation in Inconel X-750

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ha, Jeong Won; Research and Development Center, KOS Limited, Yangsan 626-230; Seong, Baek Seok

2014-10-15

Inconel X-750 is a Ni-based precipitation-hardened superalloy having large tensile and fracture strengths. In the study, X-750 wires were cold drawn to different extents. Small angle neutron scattering was employed to quantitatively measure the size and volume fraction of the γ′ phase as a function of the cold drawing ratio (DR) and aging temperature. The presence and size of γ′ precipitates were confirmed by transmission electron microscopy. The drawing ratio had an important effect on the volume fraction of the γ′ precipitates. However, the size of the precipitates was independent on the drawing ratio. The specimen with the minimum drawingmore » ratio (DR0) produced the largest volume fraction of γ′ as compared with large drawing ratio (DR) specimens such as DR17 and DR42. The small volume fraction of the γ′ phase for a sizeable drawing ratio was associated with the large amount of nucleation sites for secondary carbides, M{sub 23}C{sub 6}, and the fast diffusion path, i.e., dislocation, needed to form M{sub 23}C{sub 6}. A Cr depletion zone around the secondary carbides raised the solubility of γ′. Therefore, the significant drawing ratio contributing to the large volume fraction of the secondary carbides decreased the volume fraction of the γ′ precipitates in Inconel X-750. - Highlights: • The volume fraction of secondary carbides increased with the drawing ratio. • The volume fraction of γ′ decreased as the drawing ratio increased. • The drawing ratio affected the γ′ volume fraction with no variation of the γ' size. • The volume fraction of γ′ was affected by the secondary carbide volume fraction.« less

Calcium Isotope Geochemistry: Research Horizons and Nanoscale Fractionation Processes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, W; Simon, J I; DePaolo, D J

Interest in studies of calcium isotope variations in nature continues to increase. Investigations span human biology, plants and soils, oceanography and paleoclimate, early solar system processes, aqueous geochemistry, and silicate liquid structure. Variations in the 44Ca/40Ca ratio are generally small, about 5 {per_thousand}, but gradual small improvements in analytical capability now yield 0.05 to 0.1 {per_thousand} resolution. The field is still plagued by a lack of universal standards for isotope ratios and data representation, but these are secondary issues. Traditional isotopic systems have been based in equilibrium thermodynamics, which can explain the magnitude and sign of observed mass-dependent fractionation behavior.more » For Ca isotopes this is not the case. There is still no reliable way to estimate the equilibrium free energy associated with isotopic exchange between most phases of interest. Experiments are difficult to interpret because it is almost impossible to precipitate minerals from aqueous solution at equilibrium at low temperature. Some studies suggest that, for example, there is no equilibrium isotopic fractionation between calcite and dissolved aqueous Ca. There is good evidence that most Ca isotopic fractionation is caused by kinetic effects. The details of the controlling processes are still missing, and without this mechanistic understanding it is difficult to fully understand the implications of natural isotopic variations. Recent work on dissolved Ca, calcite, and sulfates in both laboratory and natural settings is shedding light on where the fractionation may arise. There is emerging evidence for mass dependent fractionation associated with aqueous diffusion, but probably the primary source of the effects is in the details of precipitation of minerals from solution. This makes the fractionation potentially dependent on a number of factors, including solution composition and mineral growth rate. The next challenge is to develop appropriate experimental tests and combine them with micro- and nano-scale characterization, and to capture the critical processes in mathematical models. Some of the largest fractionation effects have been observed for silicate liquids, where both chemical and thermal diffusion generate large isotopic variations. Intake and transport of Ca in plants is also associated with substantial fractionation. Continuing work is beginning to place the fractionation into the context of global Ca cycles.« less

Equilibrium isotopic fractionation of copper during oxidation/reduction, aqueous complexation and ore-forming processes: Predictions from hybrid density functional theory

NASA Astrophysics Data System (ADS)

Sherman, David M.

2013-10-01

Copper exists as two isotopes: 65Cu (∼30.85%) and 63Cu (∼69.15%). The isotopic composition of copper in secondary minerals, surface waters and oxic groundwaters is 1-12‰ heavier than that of copper in primary sulfides. Changes in oxidation state and complexation should yield substantial isotopic fractionation between copper species but it is unclear to what extent the observed Cu isotopic variations reflect equilibrium fractionation. Here, I calculate the reduced partition function ratios for chalcopyrite (CuFeS2), cuprite (Cu2O), tenorite (CuO) and aqueous Cu+, Cu+2 complexes using periodic and molecular hybrid density functional theory to predict the equilibrium isotopic fractionation of Cu resulting from oxidation of Cu+ to Cu+2 and by complexation of dissolved Cu. Among the various copper(II) complexes in aqueous environments, there is a significant (1.3‰) range in the reduced partition function ratios. Oxidation and congruent dissolution of chalcopyrite (CuFeS2) to dissolved Cu+2 (as Cu(H2O)5+2) yields 65-63δ(Cu+2-CuFeS2) = 3.1‰ at 25 °C; however, chalcopyrite oxidation/dissolution is incongruent so that the observed isotopic fractionation will be less. Secondary precipitation of cuprite (Cu2O) would yield further enrichment of dissolved 65Cu since 65-63δ(Cu+2-Cu2O) is 1.2‰ at 25 °C. However, precipitation of tenorite (CuO) will favor the heavy isotope by +1.0‰ making dissolved Cu isotopically lighter. These are upper-limit estimates for equilibrium fractionation. Therefore, the extremely large (9‰) fractionations between dissolved Cu+2 (or Cu+2 minerals) and primary Cu+ sulfides observed in supergene environments must reflect Rayleigh (open-system) or kinetic fractionation. Finally the previously proposed (Asael et al., 2009) use of δ65Cu in chalcopyrite to estimate the oxidation state of fluids that transported Cu in stratiform sediment-hosted copper deposits is refined.

Gamma Prime Precipitate Evolution During Aging of a Model Nickel-Based Superalloy

NASA Astrophysics Data System (ADS)

Goodfellow, A. J.; Galindo-Nava, E. I.; Christofidou, K. A.; Jones, N. G.; Martin, T.; Bagot, P. A. J.; Boyer, C. D.; Hardy, M. C.; Stone, H. J.

2018-03-01

The microstructural stability of nickel-based superalloys is critical for maintaining alloy performance during service in gas turbine engines. In this study, the precipitate evolution in a model polycrystalline Ni-based superalloy during aging to 1000 hours has been studied via transmission electron microscopy, atom probe tomography, and neutron diffraction. Variations in phase composition and precipitate morphology, size, and volume fraction were observed during aging, while the constrained lattice misfit remained constant at approximately zero. The experimental composition of the γ matrix phase was consistent with thermodynamic equilibrium predictions, while significant differences were identified between the experimental and predicted results from the γ' phase. These results have implications for the evolution of mechanical properties in service and their prediction using modeling methods.

Liquid rocket combustor computer code development

NASA Technical Reports Server (NTRS)

Liang, P. Y.

1985-01-01

The Advanced Rocket Injector/Combustor Code (ARICC) that has been developed to model the complete chemical/fluid/thermal processes occurring inside rocket combustion chambers are highlighted. The code, derived from the CONCHAS-SPRAY code originally developed at Los Alamos National Laboratory incorporates powerful features such as the ability to model complex injector combustion chamber geometries, Lagrangian tracking of droplets, full chemical equilibrium and kinetic reactions for multiple species, a fractional volume of fluid (VOF) description of liquid jet injection in addition to the gaseous phase fluid dynamics, and turbulent mass, energy, and momentum transport. Atomization and droplet dynamic models from earlier generation codes are transplated into the present code. Currently, ARICC is specialized for liquid oxygen/hydrogen propellants, although other fuel/oxidizer pairs can be easily substituted.

Probing the 5 f electrons in Am-I by hybrid density functional theory

NASA Astrophysics Data System (ADS)

Atta-Fynn, Raymond; Ray, Asok K.

2009-11-01

The ground states of the actinides and their compounds continue to be matters of considerable controversies. Experimentally, Americium-I (Am-I) is a non-magnetic dhcp metal whereas theoretically an anti-ferromagnetic ground state is predicted. We show that hybrid density functional theory, which admixes a fraction, λ, of exact Hartree-Fock (HF) exchange with approximate DFT exchange, can correctly reproduce the ground state properties of Am. In particular, for λ=0.40, we obtain a non-magnetic ground state with equilibrium atomic volume, bulk modulus, 5 f electron population, and the density of electronic states all in good agreement with experimental data. We argue that the exact HF exchange corrects the overestimation of the approximate DFT exchange interaction.

Iron Isotope Fractionation in the Bushveld Igneous Complex Provide Insight into Fractional Crystallization

NASA Astrophysics Data System (ADS)

Rios, K. L.; Feineman, M. D.; Bybee, G. M.

2016-12-01

Dated at 2.056 Ga and encompassing an estimated 65,000 km2 in surface area and 650,000 km3 in volume the Bushveld Igneous Complex in South Africa contains the largest and most unique layered mafic intrusion in the world. It contains 80-90% of the world's minable platinum group elements. Scientists are interested in understanding the origin of this intrusion due to its massive size, unique assemblage of minerals, and strongly zoned stratigraphy. Iron isotopes may help us to understand the roles of partial mantle melting and fractional crystallization in magma genesis and differentiation. For example, it may be possible to determine what role fractional crystallization of oxides and sulfides played in the formation of the Rustenburg Layered Suite (RLS) by comparing δ56Fe in samples from the Lower, Critical, Main and Upper Zones. The use of MC-ICPMS has made it more routine to study the fractionation of stable iron isotopes in natural systems; however, this technique has only been applied in a few studies of the RLS, mostly restricted to the Upper Main and Upper Zones. In this study δ56Fe was determined in Upper Zone magnetite, Critical Zone chromitite and Critical Zone sulfides using MC-ICP-MS. Previous research has shown that early crystallizing mafic phases incorporate the lighter 54Fe isotope leaving a residual magma with a higher δ56Fe value. Therefore, if the Upper Zone magma represents a high-degree differentiate of the parental Bushveld magma, then magmas from the Upper Zone would be expected to have a higher δ56Fe than magmas contributing to the Lower, Critical and Main Zones. The results of this experiment were indeed consistent with this hypothesis. The δ56Fe values recorded for the three sample types were: magnetite 0.19 ±0.03‰; sulfides -0.45 ±0.03‰ to -0.81 ±0.03‰; and chromitite 0.03 ±0.05‰. The sulfides of the Critical Zone are isotopically lighter than would be predicted based on equilibrium sulfide-melt fractionation, if the parental melt of the Critical Zone were in equilibrium with previously published whole rock data for Upper Zone. This is consistent with interpretations of the Upper Zone as a high degree differentiate of the Bushveld Parental Magma.

Thermal and ultrasonic evaluation of porosity in composite laminates

NASA Technical Reports Server (NTRS)

Johnston, Patrick H.; Winfree, William P.; Long, Edward R., Jr.; Kullerd, Susan M.; Nathan, N.; Partos, Richard D.

1992-01-01

The effects of porosity on damage incurred by low-velocity impact are investigated. Specimens of graphite/epoxy composite were fabricated with various volume fractions of voids. The void fraction was independently determined using optical examination and acid resin digestion methods. Thermal diffusivity and ultrasonic attenuation were measured, and these results were related to the void volume fraction. The relationship between diffusivity and fiber volume fraction was also considered. The slope of the ultrasonic attenuation coefficient was found to increase linearly with void content, and the diffusivity decreased linearly with void volume fraction, after compensation for an approximately linear dependence on the fiber volume fraction.

An Interactive Computer Program for Simulating the Effects of Olivine Fractionation from Basaltic and Ultrabasic Liquids.

ERIC Educational Resources Information Center

Pearce, Thomas H.

1983-01-01

Describes interactive computer program (listing available from author) which simulates olivine fractionation from basaltic/ultrabasic liquid. The menu-driven nature of the program (for Apple II microcomputer) allows students to select ideal Rayleigh fractionation or equilibrium crystallization. (JN)

Gasdynamic Model of Turbulent Combustion in TNT Explosions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuhl, A L; Bell, J B; Beckner, V E

2010-01-08

A model is proposed to simulate turbulent combustion in confined TNT explosions. It is based on: (i) the multi-component gasdynamic conservation laws, (ii) a fast-chemistry model for TNT-air combustion, (iii) a thermodynamic model for frozen reactants and equilibrium products, (iv) a high-order Godunov scheme providing a non-diffusive solution of the governing equations, and (v) an ILES approach whereby adaptive mesh refinement is used to capture the energy bearing scales of the turbulence on the grid. Three-dimensional numerical simulations of explosion fields from 1.5-g PETN/TNT charges were performed. Explosions in six different chambers were studied: three calorimeters (volumes of 6.6-l, 21.2-lmore » and 40.5-l with L/D = 1), and three tunnels (L/D = 3.8, 4.65 and 12.5 with volumes of 6.3-l) - to investigate the influence of chamber volume and geometry on the combustion process. Predicted pressures histories were quite similar to measured pressure histories for all cases studied. Experimentally, mass fraction of products, Y{sub p}{sup exp}, reached a peak value of 88% at an excess air ratio of twice stoichiometric, and then decayed with increasing air dilution; mass fractions Y{sub p}{sup calc} computed from the numerical simulations followed similar trends. Based on this agreement, we conclude that the dominant effect that controls the rate of TNT combustion with air is the turbulent mixing rate; the ILES approach along with the fast-chemistry model used here adequately captures this effect.« less

On adiabatic pair potentials of highly charged colloid particles

NASA Astrophysics Data System (ADS)

Sogami, Ikuo S.

2018-03-01

Generalizing the Debye-Hückel formalism, we develop a new mean field theory for adiabatic pair potentials of highly charged particles in colloid dispersions. The unoccupied volume and the osmotic pressure are the key concepts to describe the chemical and thermodynamical equilibrium of the gas of small ions in the outside region of all of the colloid particles. To define the proper thermodynamic quantities, it is postulated to take an ensemble averaging with respect to the particle configurations in the integrals for their densities consisting of the electric potential satisfying a set of equations that are derived by linearizing the Poisson-Boltzmann equation. With the Fourier integral representation of the electric potential, we calculate first the internal electric energy of the system from which the Helmholtz free energy is obtained through the Legendre transformation. Then, the Gibbs free energy is calculated using both ways of the Legendre transformation with respect to the unoccupied volume and the summation of chemical potentials. The thermodynamic functions provide three types of pair potentials, all of which are inversely proportional to the fraction of the unoccupied volume. At the limit when the fraction factor reduces to unity, the Helmholtz pair potential turns exactly into the well known Derjaguin-Landau-Verwey-Overbeek repulsive potential. The Gibbs pair potential possessing a medium-range strong repulsive part and a long-range weak attractive tail can explain the Schulze-Hardy rule for coagulation in combination with the van der Waals-London potential and describes a rich variety of phenomena of phase transitions observed in the dilute dispersions of highly charged particles.

Edwards statistical mechanics for jammed granular matter

NASA Astrophysics Data System (ADS)

Baule, Adrian; Morone, Flaviano; Herrmann, Hans J.; Makse, Hernán A.

2018-01-01

In 1989, Sir Sam Edwards made the visionary proposition to treat jammed granular materials using a volume ensemble of equiprobable jammed states in analogy to thermal equilibrium statistical mechanics, despite their inherent athermal features. Since then, the statistical mechanics approach for jammed matter—one of the very few generalizations of Gibbs-Boltzmann statistical mechanics to out-of-equilibrium matter—has garnered an extraordinary amount of attention by both theorists and experimentalists. Its importance stems from the fact that jammed states of matter are ubiquitous in nature appearing in a broad range of granular and soft materials such as colloids, emulsions, glasses, and biomatter. Indeed, despite being one of the simplest states of matter—primarily governed by the steric interactions between the constitutive particles—a theoretical understanding based on first principles has proved exceedingly challenging. Here a systematic approach to jammed matter based on the Edwards statistical mechanical ensemble is reviewed. The construction of microcanonical and canonical ensembles based on the volume function, which replaces the Hamiltonian in jammed systems, is discussed. The importance of approximation schemes at various levels is emphasized leading to quantitative predictions for ensemble averaged quantities such as packing fractions and contact force distributions. An overview of the phenomenology of jammed states and experiments, simulations, and theoretical models scrutinizing the strong assumptions underlying Edwards approach is given including recent results suggesting the validity of Edwards ergodic hypothesis for jammed states. A theoretical framework for packings whose constitutive particles range from spherical to nonspherical shapes such as dimers, polymers, ellipsoids, spherocylinders or tetrahedra, hard and soft, frictional, frictionless and adhesive, monodisperse, and polydisperse particles in any dimensions is discussed providing insight into a unifying phase diagram for all jammed matter. Furthermore, the connection between the Edwards ensemble of metastable jammed states and metastability in spin glasses is established. This highlights the fact that the packing problem can be understood as a constraint satisfaction problem for excluded volume and force and torque balance leading to a unifying framework between the Edwards ensemble of equiprobable jammed states and out-of-equilibrium spin glasses.

A numerical study of the phase behaviors of drug particle/star triblock copolymer mixtures in dilute solutions for drug carrier application

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Shanhui; Tong, Chaohui; Zhu, Yuejin, E-mail: zhuyuejin@nbu.edu.cn

The complex microstructures of drug particle/ABA star triblock copolymer in dilute solutions have been investigated by a theoretical approach which combines the self-consistent field theory and the hybrid particle-field theory. Simulation results reveal that, when the volume fraction of drug particles is smaller than the saturation concentration, the drug particle encapsulation efficiency is 100%, and micelle loading capacity increases with increasing particle volume fraction. When the volume fraction of drug particles is equal to the saturation concentration, the micelles attain the biggest size, and micelle loading capacity reaches a maximum value which is independent of the copolymer volume fraction. Whenmore » the volume fraction of drug particles is more than the saturation concentration, drug particle encapsulation efficiency decreases with increasing volume fraction of drug particles. Furthermore, it is found that the saturation concentration scales linearly with the copolymer volume fraction. The above simulation results are in good agreement with experimental results.« less

Mechanism for pH-dependent gene regulation by amino-terminus-mediated homooligomerization of Bacillus subtilis anti-trp RNA-binding attenuation protein

PubMed Central

Sachleben, Joseph R.; McElroy, Craig A.; Gollnick, Paul; Foster, Mark P.

2010-01-01

Anti-TRAP (AT) is a small zinc-binding protein that regulates tryptophan biosynthesis in Bacillus subtilis by binding to tryptophan-bound trp RNA-binding attenuation protein (TRAP), thereby preventing it from binding RNA, and allowing transcription and translation of the trpEDCFBA operon. Crystallographic and sedimentation studies have shown that AT can homooligomerize to form a dodecamer, AT12, composed of a tetramer of trimers, AT3. Structural and biochemical studies suggest that only trimeric AT is active for binding to TRAP. Our chromatographic and spectroscopic data revealed that a large fraction of recombinantly overexpressed AT retains the N-formyl group (fAT), presumably due to incomplete N-formyl-methionine processing by peptide deformylase. Hydrodynamic parameters from NMR relaxation and diffusion measurements showed that fAT is exclusively trimeric (AT3), while (deformylated) AT exhibits slow exchange between both trimeric and dodecameric forms. We examined this equilibrium using NMR spectroscopy and found that oligomerization of active AT3 to form inactive AT12 is linked to protonation of the amino terminus. Global analysis of the pH dependence of the trimer-dodecamer equilibrium revealed a near physiological pKa for the N-terminal amine of AT and yielded a pH-dependent oligomerization equilibrium constant. Estimates of excluded volume effects due to molecular crowding suggest the oligomerization equilibrium may be physiologically important. Because deprotonation favors “active” trimeric AT and protonation favors “inactive” dodecameric AT, our findings illuminate a possible mechanism for sensing and responding to changes in cellular pH. PMID:20713740

Theoretical modeling of rhenium isotope fractionation, natural variations across a black shale weathering profile, and potential as a paleoredox proxy

NASA Astrophysics Data System (ADS)

Miller, Christian A.; Peucker-Ehrenbrink, Bernhard; Schauble, Edwin A.

2015-11-01

We present the first data documenting environmental variations in the isotope composition of Re, and the first theoretical models of equilibrium Re isotope fractionation factors. Variations of δ187Re at modern surface temperatures are predicted to be ‰ level for redox (ReVII ⇌ ReIV) and perrhenate thiolation reactions (ReVIIO4- ⇌ReVIIOXS4-X- ⇌ReVII S4-). Nuclear volume fractionations are calculated to be smaller than mass dependent effects. Values of δ187Re from New Albany Shale samples presented in this work and in a previous study show a range of 0.8‰ over a stratigraphic interval of ∼20 m. The magnitude of variation is consistent with theoretical predictions and may provide evidence for changing δ187Re of seawater in the geologic past. A -0.3‰ change in δ187Re across a 14 m horizontal black shale weathering profile is accompanied by a hundred-fold decrease in Re concentration and a 75% decrease in organic carbon associated with the transition from reducing to oxic weathering environment. We attribute decreasing δ187Re to the loss of organically bound Re component (δ187Re = -0.28‰). The Re isotope composition of the complementary detrital silicate fraction varies from -0.59 to -1.5‰, depending on the choice of silicate Re concentration.

Asset Prices and Trading Volume under Fixed Transactions Costs.

ERIC Educational Resources Information Center

Lo, Andrew W.; Mamaysky, Harry; Wang, Jiang

2004-01-01

We propose a dynamic equilibrium model of asset prices and trading volume when agents face fixed transactions costs. We show that even small fixed costs can give rise to large "no-trade" regions for each agent's optimal trading policy. The inability to trade more frequently reduces the agents' asset demand and in equilibrium gives rise to a…

Control of Sediment Availability on the Path of Channel Recovery in Bedload-Dominated Rivers

NASA Astrophysics Data System (ADS)

Doyle, H.; Renshaw, C. E.; Magilligan, F. J.

2015-12-01

Following a disturbance, a channel can recover to an equilibrium form by adjusting its slope, width, depth, grain size, or some combination of these dimensions that define the recovery path. In this study we relate the channel recovery path to the quantity and caliber of sediment introduced due to dam construction/removal or erosion caused by flooding. We suggest that the recovery path of a channel depends on the availability of sediment of a size that is transported as bedload during bankfull flows (the "mobile fraction"). We define a ratio, S*, of the sediment volume added to the channel because of the disturbance to the average annual sediment flux. We compare S* values to the recovery path of New England gravel-bedded streams following two dam emplacements and removals and flooding related to Tropical Storm Irene. Pelham Dam in Pelham, MA (removed 2012) and Kendrick Dam in Pittsford, VT (removed 2014) were on similar streams: drainage areas ~25 km2, slopes 1-2%, and bankfull widths ~10 m. Sediment was excavated from both impoundments prior to removal, resulting in lower S* values. Irene-affected study sites are on ~10 gravel-bedded streams in VT, NH, and MA. Sediment input at these sites is due to bank failures and landslides, many of which continue to supply sediment to the channel four years after flooding. To track recovery we collected annual topographic and sediment size data and calculated Shields numbers to determine if channels had reached an equilibrium form. We define equilibrium for bedload rivers as Shields numbers at bankfull discharge equal to that required to initiate bedload transport. Following dam emplacements the channels failed to recover because mobile sediment was unavailable. Fining dominated the recovery at Irene-affected sites (~10% reduction in sediment size) and dam removal sites (up to 30-60% reduction) with little post-disturbance change in channel geometry, possibly due to the limited mobile fraction.

Dissolution of multi-component LNAPL gasolines: The effects of weathering and composition

NASA Astrophysics Data System (ADS)

Lekmine, Greg; Bastow, Trevor P.; Johnston, Colin D.; Davis, Greg B.

2014-05-01

The composition of light non-aqueous phase liquid (LNAPL) gasoline and other petroleum products changes profoundly over their life once released into aquifers. However limited attention has been given to how such changes affect key parameters such as the activity coefficients which control partitioning of components of petroleum fuel into groundwater and are used to predict long-term risk from fuel releases. Laboratory experiments were conducted on a range of fresh, weathered and synthetic gasoline mixtures designed to mimic the expected changes in composition in an aquifer. Weathered gasoline created under controlled evaporation and water washing, and naturally weathered gasoline, were investigated. Equilibrium concentrations in water and molar fractions in the gasoline mixtures were compared with equilibrium concentrations predicted by Raoult's law assuming ideal behaviour of the solutions. The experiments carried out allowed the relative sensitivity of the activity coefficients of key risk drivers such as benzene, toluene, ethylbenzene and xylene (BTEX) compounds to be quantified with respect to the presence of other types of compounds and where the source LNAPL had undergone different types of weathering. Results differed for the mixtures examined but in some cases higher than predicted dissolved equilibrium concentrations showed non-ideal behaviour for toluene, benzene and xylenes. Comparison of the activity coefficients showed that the naturally weathered gasoline and a 50% evaporated unleaded gasoline present a similar range of values varying between 1.0 and 1.2, suggesting close to ideal partitioning between the LNAPL and water. The fresh and water-washed gasoline had higher values for the activity coefficient, from 1.2 to 1.4, indicating non-ideal partitioning. Results from synthetic mixtures demonstrated that these differences could be due to the different molar fractions of the nC5 and nC6 aliphatic hydrocarbons acting on the molecular interactions, while differences in molar volumes seemed to have less of an influence on ideality.

Strontium isotope fractionation during strontianite (SrCO3) dissolution, precipitation and at equilibrium

NASA Astrophysics Data System (ADS)

Mavromatis, Vasileios; Harrison, Anna L.; Eisenhauer, Anton; Dietzel, Martin

2017-12-01

In this study we examine the behavior of stable Sr isotopes between strontianite [SrCO3] and reactive fluid during mineral dissolution, precipitation, and at chemical equilibrium. Experiments were performed in batch reactors at 25 °C in 0.01 M NaCl solutions wherein the pH was adjusted by bubbling of a water saturated gas phase of pure CO2 or atmospheric air. The equilibrium Sr isotope fractionation between strontianite and fluid after dissolution of the solid under 1 atm CO2 atmosphere was estimated as Δ88/86SrSrCO3-fluid = δ88/86Sr SrCO3 - δ88/86Srfluid = -0.05 ± 0.01‰. On the other hand, during strontianite precipitation, an enrichment of the fluid phase in 88Sr, the heavy isotopomer, was observed. The evolution of the δ88/86Srfluid during strontianite precipitation can be modeled using a Rayleigh distillation approach and the estimated, kinetically driven, fractionation factor αSrCO3-fluid between solid and fluid is calculated to be 0.99985 ± 0.00003 corresponding to Δ88/86SrSrCO3-fluid = -0.15‰. The obtained results further support that under chemical equilibrium conditions between solid and fluid a continuous exchange of isotopes occurs until the system approaches isotopic equilibrium. This isotopic exchange is not limited to the outer surface layer of the strontianite crystal, but extends to ∼7-8 unit cells below the crystal surface. The behavior of Sr isotopes in this study is in excellent agreement with the concept of dynamic equilibrium and it suggests that the time needed for achievement of chemical equilibrium is generally shorter compared to that for isotopic equilibrium. Thus it is suggested that in natural Sr-bearing carbonates an isotopic change may still occur close to thermodynamic equilibrium, despite no observable change in aqueous elemental concentrations. As such, a secondary and ongoing change of Sr isotope signals in carbonate minerals caused by isotopic re-equilibration with fluids has to be considered in order to use Sr isotopes as environmental proxies in aquatic environments.

Chemical equilibrium of ablation materials including condensed species

NASA Technical Reports Server (NTRS)

Stroud, C. W.; Brinkley, K. L.

1975-01-01

Equilibrium is determined by finding chemical composition with minimum free energy. Method of steepest descent is applied to quadratic representation of free-energy surface. Solution is initiated by selecting arbitrary set of mole fractions, from which point on free-energy surface is computed.

The capability of radial basis function to forecast the volume fractions of the annular three-phase flow of gas-oil-water.

PubMed

Roshani, G H; Karami, A; Salehizadeh, A; Nazemi, E

2017-11-01

The problem of how to precisely measure the volume fractions of oil-gas-water mixtures in a pipeline remains as one of the main challenges in the petroleum industry. This paper reports the capability of Radial Basis Function (RBF) in forecasting the volume fractions in a gas-oil-water multiphase system. Indeed, in the present research, the volume fractions in the annular three-phase flow are measured based on a dual energy metering system including the 152 Eu and 137 Cs and one NaI detector, and then modeled by a RBF model. Since the summation of volume fractions are constant (equal to 100%), therefore it is enough for the RBF model to forecast only two volume fractions. In this investigation, three RBF models are employed. The first model is used to forecast the oil and water volume fractions. The next one is utilized to forecast the water and gas volume fractions, and the last one to forecast the gas and oil volume fractions. In the next stage, the numerical data obtained from MCNP-X code must be introduced to the RBF models. Then, the average errors of these three models are calculated and compared. The model which has the least error is picked up as the best predictive model. Based on the results, the best RBF model, forecasts the oil and water volume fractions with the mean relative error of less than 0.5%, which indicates that the RBF model introduced in this study ensures an effective enough mechanism to forecast the results. Copyright © 2017 Elsevier Ltd. All rights reserved.

Abiologic silicon isotope fractionation between aqueous Si and Fe(III)-Si gel in simulated Archean seawater: Implications for Si isotope records in Precambrian sedimentary rocks

NASA Astrophysics Data System (ADS)

Zheng, Xin-Yuan; Beard, Brian L.; Reddy, Thiruchelvi R.; Roden, Eric E.; Johnson, Clark M.

2016-08-01

Precambrian Si-rich sedimentary rocks, including cherts and banded iron formations (BIFs), record a >7‰ spread in 30Si/28Si ratios (δ30Si values), yet interpretation of this large variability has been hindered by the paucity of data on Si isotope exchange kinetics and equilibrium fractionation factors in systems that are pertinent to Precambrian marine conditions. Using the three-isotope method and an enriched 29Si tracer, a series of experiments were conducted to constrain Si isotope exchange kinetics and fractionation factors between amorphous Fe(III)-Si gel, a likely precursor to Precambrian jaspers and BIFs, and aqueous Si in artificial Archean seawater under anoxic conditions. Experiments were conducted at room temperature, and in the presence and absence of aqueous Fe(II) (Fe(II)aq). Results of this study demonstrate that Si solubility is significantly lower for Fe-Si gel than that of amorphous Si, indicating that seawater Si concentrations in the Precambrian may have been lower than previous estimates. The experiments reached ∼70-90% Si isotope exchange after a period of 53-126 days, and the highest extents of exchange were obtained where Fe(II)aq was present, suggesting that Fe(II)-Fe(III) electron-transfer and atom-exchange reactions catalyze Si isotope exchange through breakage of Fe-Si bonds. All experiments except one showed little change in the instantaneous solid-aqueous Si isotope fractionation factor with time, allowing extraction of equilibrium Si isotope fractionation factors through extrapolation to 100% isotope exchange. The equilibrium 30Si/28Si fractionation between Fe(III)-Si gel and aqueous Si (Δ30Sigel-aqueous) is -2.30 ± 0.25‰ (2σ) in the absence of Fe(II)aq. In the case where Fe(II)aq was present, which resulted in addition of ∼10% Fe(II) in the final solid, creating a mixed Fe(II)-Fe(III) Si gel, the equilibrium fractionation between Fe(II)-Fe(III)-Si gel and aqueous Si (Δ30Sigel-aqueous) is -3.23 ± 0.37‰ (2σ). Equilibrium Si isotope fractionation for Fe-Si gel systems is significantly larger in magnitude than estimates of a near-zero solid-aqueous fractionation factor between pure Si gel and aqueous Si, indicating a major influence of Fe atoms on Si-O bonds, and hence the isotopic properties, of Fe-Si gel. Larger Si isotope fractionation in the Fe(II)-bearing systems may be caused by incorporation of Fe(II) into the solid structure, which may further weaken Fe-Si bonds and thus change the Si isotope fractionation factor. The relatively large Si isotope fractionation for Fe-Si gel, relative to pure Si gel, provides a new explanation for the observed contrast in δ30Si values in the Precambrian BIFs and cherts, as well as an explanation for the relatively negative δ30Si values in BIFs, in contrast to previous proposals that the more negative δ30Si values in BIFs reflect hydrothermal sources of Si or sorption to Fe oxides/hydroxides.

D/H fractionation in the H2-H2O system at supercritical water conditions: Compositional and hydrogen bonding effects

NASA Astrophysics Data System (ADS)

Foustoukos, Dionysis I.; Mysen, Bjorn O.

2012-06-01

A series of experiments has been conducted in the H2-D2-D2O-H2O-Ti-TiO2 system at temperatures ranging from 300 to 800 °C and pressures between ∼0.3 and 1.3 GPa in a hydrothermal diamond anvil cell, utilizing Raman spectroscopy as a quantitative tool to explore the relative distribution of hydrogen and deuterium isotopologues of the H2 and H2O in supercritical fluids. In detail, H2O-D2O solutions (1:1) were reacted with Ti metal (3-9 h) in the diamond cell, leading to formation of H2, D2, HD, and HDO species through Ti oxidation and H-D isotope exchange reactions. Experimental results obtained in situ and at ambient conditions on quenched samples indicate significant differences from the theoretical estimates of the equilibrium thermodynamic properties of the H-D exchange reactions. In fact, the estimated enthalpy for the H2(aq)-D2(aq) disproportionation reaction (ΔHrxn) is about -3.4 kcal/mol, which differs greatly from the +0.16 kcal/mol predicted for the exchange reaction in the gas phase by statistical mechanics models. The exothermic behavior of the exchange reaction implies enhanced stability of H2 and D2 relative to HD. Accordingly, the significant energy difference of the internal H2(aq)-D2(aq)-HD(aq) equilibrium translates to strong differences of the fractionation effects between the H2O-H2 and D2O-D2 isotope exchange relationships. The D/H fractionation factors between H2O-H2(aq) and D2O-D2(aq) differ by 365‰ in the 600-800 °C temperature range, and are indicative of the greater effect of D2O contribution to the δD isotopic composition of supercritical fluids. The negative ΔHrxn values for the H2(aq)-D2(aq)-HD(aq) equilibrium and the apparent decrease of the equilibrium constant with increasing temperature might be because of differences of the Henry’s law constant between the H- and D-bearing species dissolved in supercritical aqueous solutions. Such effects may be attributed to the stronger hydrogen bonding in the O-H⋯O relative to the O-D⋯O environment. This difference allows enhanced gas solubility in the denser and more polar H2O clusters, and thus, affects the D/H exchange between the H2-D2 volatiles and the coexisting H2O-D2O mixtures. The proposed role of temperature in promoting differences in the density and polarity of hydrogen-bonded OHO and ODO molecules may be explained with isotope-specific molar volume effects similar to those suggested to account for the hydrogen isotope fractionation between H2O and hydroxide mineral phases (e.g. brucite) across large pressure intervals.

Fractionation in the solar nebula - Condensation of yttrium and the rare earth elements

NASA Technical Reports Server (NTRS)

Boynton, W. V.

1975-01-01

The condensation of Y and the rare earth elements (REE) from the solar nebula may be controlled by thermodynamic equilibrium between gas and condensed solids. Highly fractionated REE patterns may result if condensates are removed from the gas before condensation is complete. It is found that the fractionation is not a smooth function of REE ionic radius but varies in an extremely irregular pattern. Both Yb and Eu are predicted to be extremely depleted in the early condensate without the requirement of condensation in the divalent state. The model is discussed with respect to a highly fractionated pattern observed by Tanaka and Masuda (1973), in a pink Ca-Al-rich inclusion from the Allende meteorite and can account for the abundances of each REE determined. According to the model this inclusion represents a condensate from a previously fractionated gas rather than from a gas of solar composition. Before the condensation of this inclusion, an earlier condensate was formed and was removed from equilibrium with the gas.

Quantitative tomographic measurements of opaque multiphase flows

DOE Office of Scientific and Technical Information (OSTI.GOV)

GEORGE,DARIN L.; TORCZYNSKI,JOHN R.; SHOLLENBERGER,KIM ANN

2000-03-01

An electrical-impedance tomography (EIT) system has been developed for quantitative measurements of radial phase distribution profiles in two-phase and three-phase vertical column flows. The EIT system is described along with the computer algorithm used for reconstructing phase volume fraction profiles. EIT measurements were validated by comparison with a gamma-densitometry tomography (GDT) system. The EIT system was used to accurately measure average solid volume fractions up to 0.05 in solid-liquid flows, and radial gas volume fraction profiles in gas-liquid flows with gas volume fractions up to 0.15. In both flows, average phase volume fractions and radial volume fraction profiles from GDTmore » and EIT were in good agreement. A minor modification to the formula used to relate conductivity data to phase volume fractions was found to improve agreement between the methods. GDT and EIT were then applied together to simultaneously measure the solid, liquid, and gas radial distributions within several vertical three-phase flows. For average solid volume fractions up to 0.30, the gas distribution for each gas flow rate was approximately independent of the amount of solids in the column. Measurements made with this EIT system demonstrate that EIT may be used successfully for noninvasive, quantitative measurements of dispersed multiphase flows.« less

Volume Fraction Determination in Cast Superalloys and DS Eutectic Alloys by a New Practice for Manual Point Counting

NASA Technical Reports Server (NTRS)

Andrews, C. W.

1976-01-01

Volume fraction of a constituent or phase was estimated in six specimens of conventional and DS-eutectic superalloys, using ASTM E562-76, a new standard recommended practice for determining volume fraction by systematic manual point count. Volume fractions determined ranged from 0.086 to 0.36, and with one exception, the 95 percent relative confidence limits were approximately 10 percent of the determined volume fractions. Since the confidence-limit goal of 10 percent, which had been arbitrarily chosen previously, was achieved in all but one case, this application of the new practice was considered successful.

Tutorial for Collecting and Processing Images of Composite Structures to Determine the Fiber Volume Fraction

NASA Technical Reports Server (NTRS)

Conklin, Lindsey

2017-01-01

Fiber-reinforced composite structures have become more common in aerospace components due to their light weight and structural efficiency. In general, the strength and stiffness of a composite structure are directly related to the fiber volume fraction, which is defined as the fraction of fiber volume to total volume of the composite. The most common method to measure the fiber volume fraction is acid digestion, which is a useful method when the total weight of the composite, the fiber weight, and the total weight can easily be obtained. However, acid digestion is a destructive test, so the material will no longer be available for additional characterization. Acid digestion can also be difficult to machine out specific components of a composite structure with complex geometries. These disadvantages of acid digestion led the author to develop a method to calculate the fiber volume fraction. The developed method uses optical microscopy to calculate the fiber area fraction based on images of the cross section of the composite. The fiber area fraction and fiber volume fraction are understood to be the same, based on the assumption that the shape and size of the fibers are consistent in the depth of the composite. This tutorial explains the developed method for optically determining fiber area fraction performed at NASA Langley Research Center.

Identifying apparent local stable isotope equilibrium in a complex non-equilibrium system.

PubMed

He, Yuyang; Cao, Xiaobin; Wang, Jianwei; Bao, Huiming

2018-02-28

Although being out of equilibrium, biomolecules in organisms have the potential to approach isotope equilibrium locally because enzymatic reactions are intrinsically reversible. A rigorous approach that can describe isotope distribution among biomolecules and their apparent deviation from equilibrium state is lacking, however. Applying the concept of distance matrix in graph theory, we propose that apparent local isotope equilibrium among a subset of biomolecules can be assessed using an apparent fractionation difference (|Δα|) matrix, in which the differences between the observed isotope composition (δ') and the calculated equilibrium fractionation factor (1000lnβ) can be more rigorously evaluated than by using a previous approach for multiple biomolecules. We tested our |Δα| matrix approach by re-analyzing published data of different amino acids (AAs) in potato and in green alga. Our re-analysis shows that biosynthesis pathways could be the reason for an apparently close-to-equilibrium relationship inside AA families in potato leaves. Different biosynthesis/degradation pathways in tubers may have led to the observed isotope distribution difference between potato leaves and tubers. The analysis of data from green algae does not support the conclusion that AAs are further from equilibrium in glucose-cultured green algae than in the autotrophic ones. Application of the |Δα| matrix can help us to locate potential reversible reactions or reaction networks in a complex system such as a metabolic system. The same approach can be broadly applied to all complex systems that have multiple components, e.g. geochemical or atmospheric systems of early Earth or other planets. Copyright © 2017 John Wiley & Sons, Ltd.

Evaluating Volatility-controlled Isotope Fractionation During Planet Formation: Kinetics versus Equilibrium

NASA Astrophysics Data System (ADS)

Young, E. D.

2017-12-01

Recent advances in our ability to measure stable isotope ratios of light, rock-forming elements, including those for Zn, K, Fe, Si, and Mg, among others, has resulted in an emerging hypothesis that collisions among rocky planetesimals, planetary embryos, and/or proto-planets caused losses of moderately volatile elements (e.g., K) and "common" or moderately refractory elements (e.g., Mg and Si). The primary evidence is in the form of heavy isotope enrichments in rock-forming elements relative to the chondrite groups that are thought to be representative of planetary precursors. Equilibrium volatility-controlled isotope fractionation for planetesimal magma oceans might have occurred for bodies larger than 0.1% of an Earth mass (½ the mass of Pluto) as these bodies had sufficient gravity to overpower the escape velocities of hot gas at 2000K. Both Jean's escape and viscous drag hydrodynamic escape can obviate the escape velocity limit but will fractionate by mass, not by volatility. Equilibrium vapor/melt fractionation is qualitatively consistent with the greater disparity in 29Si/28Si between Earth and chondrites than in 25Mg/24Mg. However, losses of large masses of vapor are required to record the fractionation in the melts. We consider that if Earth was derived from E chondrite-like materials, the bulk composition of the Earth, assuming refractory Ca was retained, requires > 60% loss of Mg. This is a lot of vapor loss for a process relying on at least intermittent equilibrium, although it comports with the isotopic lever-rule requirements. Paradoxically, the alternative of evaporative loss of rock-forming elements requires less total mass loss. For example, the calculated Mg and Si isotopic compositions of residues resulting from evaporation of chondritic melts can fit the Mg and Si isotopic compositions of Earth, Mars, and angrites with varying background pressures and with total mass losses of near 5% or less. These mass losses are closer to, and even lower than, those suggested by Ca concentrations relative to CI chondrite. Equilibrium models achieve greater Si than Mg isotope fractionation by large mass losses while evaporation models produce this effect for small mass losses. Additional constraints involving other isotope systems as well as models for vapor loss can distinguish between the two scenarios.

Does the Addition of Inert Gases at Constant Volume and Temperature Affect Chemical Equilibrium?

ERIC Educational Resources Information Center

Paiva, Joao C. M.; Goncalves, Jorge; Fonseca, Susana

2008-01-01

In this article we examine three approaches, leading to different conclusions, for answering the question "Does the addition of inert gases at constant volume and temperature modify the state of equilibrium?" In the first approach, the answer is yes as a result of a common students' alternative conception; the second approach, valid only for ideal…

First-principles investigation of vanadium isotope fractionation in solution and during adsorption

NASA Astrophysics Data System (ADS)

Wu, Fei; Qin, Tian; Li, Xuefang; Liu, Yun; Huang, Jen-How; Wu, Zhongqing; Huang, Fang

2015-09-01

Equilibrium fractionation factors of vanadium (V) isotopes among tri- (V(III)), tetra- (V(IV)) and penta-valent (V(V)) inorganic V species in aqueous system and during adsorption of V(V) to goethite are estimated using first-principles calculation. Our results highlight the dependence of V isotope fractionation on valence states and the chemical binding environment. The heavy V isotope (51V) is enriched in the main V species following a sequence of V(III) < V(IV) < V(V). According to our calculations, at 25 °C, the equilibrium isotope fractionation factor between [V5+O2(OH)2]- and [V4+O(H2O)5]2+ (ln ⁡α V (V)- V (IV)) is 3.9‰, and the equilibrium isotope fractionation factor between [V5+O2(OH)2]- and [V3+(OH)3(H2O)3] (ln ⁡α V (V)- V (III)) is 6.4‰. In addition, isotope fractionation between +5 valence species [V5+O2(OH)2]- and [V5+O2(H2O)4]+ is 1.5‰ at 25 °C, which is caused by their different bond lengths and coordination numbers (CN). Theoretical calculations also show that light V isotope (50V) is preferentially adsorbed on the surface of goethite. Our work reveals that V isotopes can be significantly fractionated in the Earth's surface environments due to redox reaction and mineral adsorption, indicating that V isotope data can be used to monitor toxic V(V) attenuation processes through reduction or adsorption in natural water systems. In addition, a simple mass balance model suggests that V isotope composition of seawater might vary with change of ambient oxygen levels. Thus our theoretical investigations imply a promising future for V isotopes as a potential new paleo-redox tracer.

ASHEE: a compressible, Equilibrium-Eulerian model for volcanic ash plumes

NASA Astrophysics Data System (ADS)

Cerminara, M.; Esposti Ongaro, T.; Berselli, L. C.

2015-10-01

A new fluid-dynamic model is developed to numerically simulate the non-equilibrium dynamics of polydisperse gas-particle mixtures forming volcanic plumes. Starting from the three-dimensional N-phase Eulerian transport equations (Neri et al., 2003) for a mixture of gases and solid dispersed particles, we adopt an asymptotic expansion strategy to derive a compressible version of the first-order non-equilibrium model (Ferry and Balachandar, 2001), valid for low concentration regimes (particle volume fraction less than 10-3) and particles Stokes number (St, i.e., the ratio between their relaxation time and flow characteristic time) not exceeding about 0.2. The new model, which is called ASHEE (ASH Equilibrium Eulerian), is significantly faster than the N-phase Eulerian model while retaining the capability to describe gas-particle non-equilibrium effects. Direct numerical simulation accurately reproduce the dynamics of isotropic, compressible turbulence in subsonic regime. For gas-particle mixtures, it describes the main features of density fluctuations and the preferential concentration and clustering of particles by turbulence, thus verifying the model reliability and suitability for the numerical simulation of high-Reynolds number and high-temperature regimes in presence of a dispersed phase. On the other hand, Large-Eddy Numerical Simulations of forced plumes are able to reproduce their observed averaged and instantaneous flow properties. In particular, the self-similar Gaussian radial profile and the development of large-scale coherent structures are reproduced, including the rate of turbulent mixing and entrainment of atmospheric air. Application to the Large-Eddy Simulation of the injection of the eruptive mixture in a stratified atmosphere describes some of important features of turbulent volcanic plumes, including air entrainment, buoyancy reversal, and maximum plume height. For very fine particles (St → 0, when non-equilibrium effects are negligible) the model reduces to the so-called dusty-gas model. However, coarse particles partially decouple from the gas phase within eddies (thus modifying the turbulent structure) and preferentially concentrate at the eddy periphery, eventually being lost from the plume margins due to the concurrent effect of gravity. By these mechanisms, gas-particle non-equilibrium processes are able to influence the large-scale behavior of volcanic plumes.

Experimental evidence for Mo isotope fractionation between metal and silicate liquids

NASA Astrophysics Data System (ADS)

Hin, Remco C.; Burkhardt, Christoph; Schmidt, Max W.; Bourdon, Bernard; Kleine, Thorsten

2013-10-01

Stable isotope fractionation of siderophile elements may inform on the conditions and chemical consequences of core-mantle differentiation in planetary objects. The extent to which Mo isotopes fractionate during such metal-silicate segregation, however, is so far unexplored. We have therefore investigated equilibrium fractionation of Mo isotopes between liquid metal and liquid silicate to evaluate the potential of Mo isotopes as a new tool to study core formation. We have performed experiments at 1400 and 1600 °C in a centrifuging piston cylinder. Tin was used to lower the melting temperature of the Fe-based metal alloys to <1400 °C, while variable Fe-oxide contents were used to vary oxygen fugacity in graphite and MgO capsules. Isotopic analyses were performed using a double spike technique. In experiments performed at 1400 °C, the 98Mo/95Mo ratio of silicate is 0.19±0.03‰ (95% confidence interval) heavier than that of metal. This fractionation is not significantly affected by the presence or absence of carbon. Molybdenum isotope fractionation is furthermore independent of oxygen fugacity in the range IW -1.79 to IW +0.47, which are plausible values for core formation. Experiments at 1600 °C show that, at equilibrium, the 98Mo/95Mo ratio of silicate is 0.12±0.02‰ heavier than that of metal and that the presence or absence of Sn does not affect this fractionation. Equilibrium Mo isotope fractionation between liquid metal and liquid silicate as a function of temperature can therefore be described as ΔMoMetal-Silicate98/95=-4.70(±0.59)×105/T2. Our experiments show that Mo isotope fractionation may be resolvable up to metal-silicate equilibration temperatures of about 2500 °C, rendering Mo isotopes a novel tool to investigate the conditions of core formation in objects ranging from planetesimals to Earth sized bodies.

Effects of resident water and non-equilibrium adsorption on the primary and enhanced coalbed methane gas recovery

NASA Astrophysics Data System (ADS)

Jahediesfanjani, Hossein

The major part of the gas in coalbed methane and shale gas reservoirs is stored as the adsorbed gas in the coal and organic materials of the black shale internal surfaces. The sorption sites in both reservoirs are composed of several macropores that contain very small pore sizes. Therefore, the adsorption/desorption is very slow process and follows a non-equilibrium trend. The time-dependency of the sorption process is further affected by the reservoir resident water. Water can diffuse into the matrix and adsorption sites, plug the pores and affect the reservoir gas production. This study presents an experimental and theoretical procedure to investigate the effects of the resident water and time-dependency of the sorption process on coalbed and shale gas primary and enhanced recovery by simultaneous CO 2/N2 injection. Series of the experiments are conducted to construct both equilibrium and non-equilibrium single and multi-component isotherms with the presence of water. A novel and rapid data interpretation technique is developed based on the nonequilibrium adsorption/desorption thermodynamics, mass conservation law, and volume filling adsorption theory. The developed technique is implemented to construct both equilibrium and non-equilibrium multi-component multi-phase isotherms from the early time experimental measurements. The non-equilibrium isotherms are incorporated in the coalbed methane/shale gas reservoir simulations to account for the time-dependency of the sorption process. The experimental results indicate that the presence of water in the sorption system reduces both carbon dioxide and nitrogen adsorption rates. Reduction in the adsorption rate for carbon dioxide is more than nitrogen. The results also indicate that the resident water reduces the adsorption ability of low rank coals more than high rank ones. The results of the multi-component sorption tests indicate that increasing the initial mole fraction of the nitrogen gas in the injected CO2/N2 mixture will increase the net carbon dioxide sequestration rate on coals in the presence of water. The optimum CO2/N2 ratio that can result in the maximum carbon dioxide sequestration rate can be obtained by conducting the experiments for various CO2/N2 ratios. The results of applying the developed non-equilibrium interpretation technique for several literature and in-house data indicate that both the equilibrium and non-equilibrium isotherms can be constructed in shorter time period (around 70 times less than the time required with the equilibrium techniques) and with higher accuracy using this method. (Abstract shortened by UMI.)

In vitro toxicity testing with microplate cell cultures: Impact of cell binding.

PubMed

Gülden, Michael; Schreiner, Jeannine; Seibert, Hasso

2015-06-05

In vitro generated data on toxic potencies are generally based on nominal concentrations. However, cellular and extracellular binding and elimination processes may reduce the available free fraction of a compound. Then, nominal effective concentrations do not represent appropriate measures of toxic exposure in vitro and underestimate toxic potencies. In this study it was investigated whether cell binding can affect the availability of chemicals in microplate based toxicity assays. To this end the cytotoxicity of compounds like mercury chloride, digitonin and alcohol ethoxylates, accumulated by cells via different modes, was investigated in 96-well microplate cultures with varying concentrations of Balb/c 3T3 cells. The median effective nominal concentrations of all but one of the tested compounds depended linearly from the cell concentration. Applying a previously developed equilibrium distribution model cell concentration-independent median effective extracellular concentrations and cell burdens, respectively, could be calculated. The compounds were accumulated by the cells with bioconcentration factors, BCF, between 480 and ≥ 25,000. Cell binding of the alcohol ethoxylates was correlated with their lipophilicity. The results show that significant cell binding can occur even at the small cell volume fractions (∼ 1 × 10(-5) to 3 × 10(-3) L/L) encountered in microplate assays. To what extent cell binding affects the bioavailability depends on the BCF and the cell volume fraction. EC50 measurements in the presence of at least two different cell concentrations allow for excluding or detecting significant cell binding and for determining more appropriate measures of toxic exposure in vitro like median effective extracellular (free) concentrations or cell burdens. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

Influence of phase composition on microstructure and properties of Mg-5Al-0.4Mn-xRE (x = 0, 3 and 5 wt.%) alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Braszczyńska-Malik, K.N., E-mail: kacha@wip.pcz.pl; Grzybowska, A.

2016-05-15

The microstructure and mechanical properties investigations of two AME503 and AME505 experimental alloys in as-cast conditions were presented. The investigated materials were fabricated on the basis of the AM50 commercial magnesium alloy with 3 and 5 wt.% cerium rich mischmetal. In the as-cast condition, both experimental alloys were mainly composed of α-Mg, Al{sub 11}RE{sub 3} and Al{sub 10}RE{sub 2}Mn{sub 7} intermetallic phases. Additionally, due to non-equilibrium solidification conditions, a small amount of α + γ divorced eutectic and Al{sub 2}RE intermetallic phase were revealed. The obtained results also show a significant influence of rare earth elements on Brinell hardness, tensilemore » and compression properties at ambient temperature and especially on creep properties at 473 K. Improved alloy properties with a rise in rare earth elements mass fraction results from an increase in Al{sub 11}RE{sub 3} phase volume fraction and suppression of α + γ eutectic volume fraction in the alloy microstructure. Additionally, the influence of rare earth elements on the dendrite arm space value was discussed. The presented results also proved the thermal stability of the intermetallic phases during creep testing. - Highlights: • Two different Mg-5Al-0.4Mn alloys containing 3 and 5 wt.% of rare earth elements were fabricated. • Addition of rare earth elements leads to a reduction of dendrite arm spaces. • Mechanical properties depend on the phase composition of the alloys. • The increase of the rare earth elements content causes rise of the creep resistance.« less

A New Chaotic Flow with Hidden Attractor: The First Hyperjerk System with No Equilibrium

NASA Astrophysics Data System (ADS)

Ren, Shuili; Panahi, Shirin; Rajagopal, Karthikeyan; Akgul, Akif; Pham, Viet-Thanh; Jafari, Sajad

2018-02-01

Discovering unknown aspects of non-equilibrium systems with hidden strange attractors is an attractive research topic. A novel quadratic hyperjerk system is introduced in this paper. It is noteworthy that this non-equilibrium system can generate hidden chaotic attractors. The essential properties of such systems are investigated by means of equilibrium points, phase portrait, bifurcation diagram, and Lyapunov exponents. In addition, a fractional-order differential equation of this new system is presented. Moreover, an electronic circuit is also designed and implemented to verify the feasibility of the theoretical model.

Simulating the reactions of CO2 in aqueous monoethanolamine solution by reaction ensemble Monte Carlo using the continuous fractional component method.

PubMed

Balaji, Sayee Prasaad; Gangarapu, Satesh; Ramdin, Mahinder; Torres-Knoop, Ariana; Zuilhof, Han; Goetheer, Earl L V; Dubbeldam, David; Vlugt, Thijs J H

2015-06-09

Molecular simulations were used to compute the equilibrium concentrations of the different species in CO2/monoethanolamine solutions for different CO2 loadings. Simulations were performed in the Reaction Ensemble using the continuous fractional component Monte Carlo method at temperatures of 293, 333, and 353 K. The resulting computed equilibrium concentrations are in excellent agreement with experimental data. The effect of different reaction pathways was investigated. For a complete understanding of the equilibrium speciation, it is essential to take all elementary reactions into account because considering only the overall reaction of CO2 with MEA is insufficient. The effects of electrostatics and intermolecular van der Waals interactions were also studied, clearly showing that solvation of reactants and products is essential for the reaction. The Reaction Ensemble Monte Carlo using the continuous fractional component method opens the possibility of investigating the effects of the solvent on CO2 chemisorption by eliminating the need to study different reaction pathways and concentrate only on the thermodynamics of the system.

Aqueous solubility calculation for petroleum mixtures in soil using comprehensive two-dimensional gas chromatography analysis data.

PubMed

Mao, Debin; Lookman, Richard; Van De Weghe, Hendrik; Vanermen, Guido; De Brucker, Nicole; Diels, Ludo

2009-04-03

An assessment of aqueous solubility (leaching potential) of soil contaminations with petroleum hydrocarbons (TPH) is important in the context of the evaluation of (migration) risks and soil/groundwater remediation. Field measurements using monitoring wells often overestimate real TPH concentrations in case of presence of pure oil in the screened interval of the well. This paper presents a method to calculate TPH equilibrium concentrations in groundwater using soil analysis by high-performance liquid chromatography followed by comprehensive two-dimensional gas chromatography (HPLC-GCXGC). The oil in the soil sample is divided into 79 defined hydrocarbon fractions on two GCXGC color plots. To each of these fractions a representative water solubility is assigned. Overall equilibrium water solubility of the non-aqueous phase liquid (NAPL) present in the sample and the water phase's chemical composition (in terms of the 79 fractions defined) are then calculated using Raoult's law. The calculation method was validated using soil spiked with 13 different TPH mixtures and 1 field-contaminated soil. Measured water solubilities using a column recirculation equilibration experiment agreed well to calculated equilibrium concentrations and water phase TPH composition.

Insight into interfacial effect on effective physical properties of fibrous materials. I. The volume fraction of soft interfaces around anisotropic fibers.

PubMed

Xu, Wenxiang; Wang, Han; Niu, Yanze; Bai, Jingtao

2016-01-07

With advances in interfacial properties characterization technologies, the interfacial volume fraction is a feasible parameter for evaluating effective physical properties of materials. However, there is a need to determine the interfacial volume fraction around anisotropic fibers and a need to assess the influence of such the interfacial property on effective properties of fibrous materials. Either ways, the accurate prediction of interfacial volume fraction is required. Towards this end, we put forward both theoretical and numerical schemes to determine the interfacial volume fraction in fibrous materials, which are considered as a three-phase composite structure consisting of matrix, anisotropic hard spherocylinder fibers, and soft interfacial layers with a constant dimension coated on the surface of each fiber. The interfacial volume fraction actually represents the fraction of space not occupied by all hard fibers and matrix. The theoretical scheme that adopts statistical geometry and stereological theories is essentially an analytic continuation from spherical inclusions. By simulating such three-phase chopped fibrous materials, we numerically derive the interfacial volume fraction. The theoretical and numerical schemes provide a quantitative insight that the interfacial volume fraction depends strongly on the fiber geometries like fiber shape, geometric size factor, and fiber size distribution. As a critical interfacial property, the present contribution can be further drawn into assessing effective physical properties of fibrous materials, which will be demonstrated in another paper (Part II) of this series.

Equilibrium concentration profiles and sedimentation kinetics of colloidal gels under gravitational stress

NASA Astrophysics Data System (ADS)

Buzzaccaro, S.; Secchi, E.; Brambilla, G.; Piazza, R.; Cipelletti, L.

2012-07-01

We study the sedimentation of colloidal gels by using a combination of light scattering, polarimetry and video imaging. The asymptotic concentration profiles φ(z,t → ∞) exhibit remarkable scaling properties: profiles for gels prepared at different initial volume fractions and particle interactions can be superimposed onto a single master curve by using suitable reduced variables. We show theoretically that this behavior stems from a power law dependence of the compressive elastic modulus versus φ, which we directly test experimentally. The sedimentation kinetics comprises an initial latency stage, followed by a rapid collapse where the gel height h decreases at constant velocity and a final compaction stage characterized by a stretched exponential relaxation of h toward a plateau. Analogies and differences with previous works are briefly discussed.

Thermal Equilibrium in Plastic and Glass Microscale Containers

ERIC Educational Resources Information Center

Curbelo, Estela; Cerda, Maria F.; Mendez, Eduardo

2007-01-01

The study describes the various thermal equilibrium conditions, which should be taken care for while designing or selecting the plastic and glass microscale containers for physical chemistry experiments. The results show that the thermal equilibrium completely depends on the material of the container for the same volume and thickness.

Effect of accelerated aging on the cross-link density of medical grade silicones.

PubMed

Mahomed, Aziza; Pormehr, Negin Bagheri

2016-11-25

Four specimens of Nagor silicone of different hardness (soft, medium and hard) were swollen, until they reached equilibrium (i.e. constant mass) in five liquids at 25°C, before and after accelerated aging. For the specimens swollen before accelerated aging, the greatest swelling was obtained in methyl cyclohexane, while for the specimens swollen after accelerated aging, the greatest swelling was obtained in cyclohexane. The cross-link density, υ, was also calculated from the swelling measurements for all the specimens, before and after accelerated aging, using the Flory-Rehner equation. The softer silicones, which swelled the most, had lower υ values than harder silicones. The amount of swelling (measured in terms of ϕ) and υ varied significantly (p<0.05) in some cases, between the different silicone hardness and between different liquids. Furthermore, the cross-link density, υ, significantly (p<0.05) increased after accelerated aging in most liquids.Note: ϕ is defined as the volume fraction of polymer in its equilibrium swollen state. A probability value of statistical significance of 0.05 or 5% was selected, hence if a p value of less than 0.05 was obtained, the null hypothesis was rejected (i.e. significant if p<0.05).

The optimal fiber volume fraction and fiber-matrix property compatibility in fiber reinforced composites

NASA Technical Reports Server (NTRS)

Pan, Ning

1992-01-01

Although the question of minimum or critical fiber volume fraction beyond which a composite can then be strengthened due to addition of fibers has been dealt with by several investigators for both continuous and short fiber composites, a study of maximum or optimal fiber volume fraction at which the composite reaches its highest strength has not been reported yet. The present analysis has investigated this issue for short fiber case based on the well-known shear lag (the elastic stress transfer) theory as the first step. Using the relationships obtained, the minimum spacing between fibers is determined upon which the maximum fiber volume fraction can be calculated, depending on the fiber packing forms within the composites. The effects on the value of this maximum fiber volume fraction due to such factors as fiber and matrix properties, fiber aspect ratio and fiber packing forms are discussed. Furthermore, combined with the previous analysis on the minimum fiber volume fraction, this maximum fiber volume fraction can be used to examine the property compatibility of fiber and matrix in forming a composite. This is deemed to be useful for composite design. Finally some examples are provided to illustrate the results.

SU-E-T-427: Cell Surviving Fractions Derived From Tumor-Volume Variation During Radiotherapy for Non-Small Cell Lung Cancer: Comparison with Predictive Assays

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chvetsov, A; Schwartz, J; Mayr, N

2014-06-01

Purpose: To show that a distribution of cell surviving fractions S{sub 2} in a heterogeneous group of patients can be derived from tumor-volume variation curves during radiotherapy for non-small cell lung cancer. Methods: Our analysis was based on two data sets of tumor-volume variation curves for heterogeneous groups of 17 patients treated for nonsmall cell lung cancer with conventional dose fractionation. The data sets were obtained previously at two independent institutions by using megavoltage (MV) computed tomography (CT). Statistical distributions of cell surviving fractions S{sup 2} and cell clearance half-lives of lethally damaged cells T1/2 have been reconstructed in eachmore » patient group by using a version of the two-level cell population tumor response model and a simulated annealing algorithm. The reconstructed statistical distributions of the cell surviving fractions have been compared to the distributions measured using predictive assays in vitro. Results: Non-small cell lung cancer presents certain difficulties for modeling surviving fractions using tumor-volume variation curves because of relatively large fractional hypoxic volume, low gradient of tumor-volume response, and possible uncertainties due to breathing motion. Despite these difficulties, cell surviving fractions S{sub 2} for non-small cell lung cancer derived from tumor-volume variation measured at different institutions have similar probability density functions (PDFs) with mean values of 0.30 and 0.43 and standard deviations of 0.13 and 0.18, respectively. The PDFs for cell surviving fractions S{sup 2} reconstructed from tumor volume variation agree with the PDF measured in vitro. Comparison of the reconstructed cell surviving fractions with patient survival data shows that the patient survival time decreases as the cell surviving fraction increases. Conclusion: The data obtained in this work suggests that the cell surviving fractions S{sub 2} can be reconstructed from the tumor volume variation curves measured during radiotherapy with conventional fractionation. The proposed method can be used for treatment evaluation and adaptation.« less

The effect of particle volume fraction and temperature on the enhancement of thermal conductivity of maghemite (γ-Fe2O3) water-based nanofluids

NASA Astrophysics Data System (ADS)

Nurdin, Irwan; Satriananda

2017-03-01

Thermal conductivity of maghemite nanofluids were experimentally investigated at different maghemite nanoparticles volume fraction and temperatures. Maghemite nanofluids were prepared by suspending maghemite nanoparticles in water as base fluids. The thermal conductivity ratio of maghemite nanofluids was linearly increase with increasing particle volume fraction and temperature. The highest enhancement of thermal conductivity is 42.5% which is obtained at particle volume fraction 2.5% and temperature 60 °C.

Phase-field simulations of coherent precipitate morphologies and coarsening kinetics

NASA Astrophysics Data System (ADS)

Vaithyanathan, Venugopalan

2002-09-01

The primary aim of this research is to enhance the fundamental understanding of coherent precipitation reactions in advanced metallic alloys. The emphasis is on a particular class of precipitation reactions which result in ordered intermetallic precipitates embedded in a disordered matrix. These precipitation reactions underlie the development of high-temperature Ni-base superalloys and ultra-light aluminum alloys. Phase-field approach, which has emerged as the method of choice for modeling microstructure evolution, is employed for this research with the focus on factors that control the precipitate morphologies and coarsening kinetics, such as precipitate volume fractions and lattice mismatch between precipitates and matrix. Two types of alloy systems are considered. The first involves L1 2 ordered precipitates in a disordered cubic matrix, in an attempt to model the gamma' precipitates in Ni-base superalloys and delta' precipitates in Al-Li alloys. The effect of volume fraction on coarsening kinetics of gamma' precipitates was investigated using two-dimensional (2D) computer simulations. With increase in volume fraction, larger fractions of precipitates were found to have smaller aspect ratios in the late stages of coarsening, and the precipitate size distributions became wider and more positively skewed. The most interesting result was associated with the effect of volume fraction on the coarsening rate constant. Coarsening rate constant as a function of volume fraction extracted from the cubic growth law of average half-edge length was found to exhibit three distinct regimes: anomalous behavior or decreasing rate constant with volume fraction at small volume fractions ( ≲ 20%), volume fraction independent or constant behavior for intermediate volume fractions (˜20--50%), and the normal behavior or increasing rate constant with volume fraction for large volume fractions ( ≳ 50%). The second alloy system considered was Al-Cu with the focus on understanding precipitation of metastable tetragonal theta'-Al 2Cu in a cubic Al solid solution matrix. In collaboration with Chris Wolverton at Ford Motor Company, a multiscale model, which involves a novel combination of first-principles atomistic calculations with a mesoscale phase-field microstructure model, was developed. Reliable energetics in the form of bulk free energy, interfacial energy and parameters for calculating the elastic energy were obtained using accurate first-principles calculations. (Abstract shortened by UMI.)

Analysis of White Matter Damage in Patients with Multiple Sclerosis via a Novel In Vivo MR Method for Measuring Myelin, Axons, and G-Ratio.

PubMed

Hagiwara, A; Hori, M; Yokoyama, K; Nakazawa, M; Ueda, R; Horita, M; Andica, C; Abe, O; Aoki, S

2017-10-01

Myelin and axon volume fractions can now be estimated via MR imaging in vivo, as can the g-ratio, which equals the ratio of the inner to the outer diameter of a nerve fiber. The purpose of this study was to evaluate WM damage in patients with MS via this novel MR imaging technique. Twenty patients with relapsing-remitting MS with a combined total of 149 chronic plaques were analyzed. Myelin volume fraction was calculated based on simultaneous tissue relaxometry. Intracellular and CSF compartment volume fractions were quantified via neurite orientation dispersion and density imaging. Axon volume fraction and g-ratio were calculated by combining these measurements. Myelin and axon volume fractions and g-ratio were measured in plaques, periplaque WM, and normal-appearing WM. All metrics differed significantly across the 3 groups ( P < .001, except P = .027 for g-ratio between periplaque WM and normal-appearing WM). Those in plaques differed most from those in normal-appearing WM. The percentage changes in plaque and periplaque WM metrics relative to normal-appearing WM were significantly larger in absolute value for myelin volume fraction than for axon volume fraction and g-ratio ( P < .001, except P = .033 in periplaque WM relative to normal-appearing WM for comparison between myelin and axon volume fraction). In this in vivo MR imaging study, the myelin of WM was more damaged than axons in plaques and periplaque WM of patients with MS. Myelin and axon volume fractions and g-ratio may potentially be useful for evaluating WM damage in patients with MS. © 2017 by American Journal of Neuroradiology.

Dynamics of the microaggregate composition of chernozem in relation to changes in the content of organic matter

NASA Astrophysics Data System (ADS)

Kryshchenko, V. S.; Zamulina, I. V.; Rybyanets, T. V.; Kravtsova, N. E.; Biryukova, O. A.; Golozubov, O. M.

2016-06-01

Monitoring of soil dispersivity and humus state has been performed in the stationary profile of ordinary chernozem in the Botanic Garden of the Southern Federal University in 2009-2014. The contents of physical clay and sand are almost stable in time, which indicates a quasi-static (climax) equilibrium in the soil. Another (reversible dynamic) process occurs simultaneously: seasonal and annual variation in the mass fractions of clay and silt in physical clay. Variations of humus content in the whole soil and in its physical clay are also observed on the background of seasonal changes in precipitation and temperature. A procedure has been developed for the analysis of the polydisperse soil system with consideration for the quasi-static and dynamic equilibriums. A two-vector coordinate system has been introduced, which consists of scales for changes in the contents of physical clay and physical sand in 100 g of soil and changes in the fractions of clay and silt in 100 g of physical clay. Co-measurements of two dispersivity series of soil samples—actual dynamic and calculated under quasi-static equilibrium (ideal)—have been performed. Dynamic equilibrium coefficients, which cumulatively reflect the varying proportions of physical clay and physical sand in the soil and the mass fractions of clay and silt in physical clay, have been calculated.

Assessment of Stable Isotope Distribution in Complex Systems

NASA Astrophysics Data System (ADS)

He, Y.; Cao, X.; Wang, J.; Bao, H.

2017-12-01

Biomolecules in living organisms have the potential to approach chemical steady state and even apparent isotope equilibrium because enzymatic reactions are intrinsically reversible. If an apparent local equilibrium can be identified, enzymatic reversibility and its controlling factors may be quantified, which helps to understand complex biochemical processes. Earlier research on isotope fractionation tends to focus on specific process and compare mostly two different chemical species. Using linear regression, "Thermodynamic order", which refers to correlated δ13C and 13β values, has been proposed to be present among many biomolecules by Galimov et al. However, the concept "thermodynamic order" they proposed and the approach they used has been questioned. Here, we propose that the deviation of a complex system from its equilibrium state can be rigorously described as a graph problem as is applied in discrete mathematics. The deviation of isotope distribution from equilibrium state and apparent local isotope equilibrium among a subset of biomolecules can be assessed using an apparent fractionation difference matrix (|Δα|). Applying the |Δα| matrix analysis to earlier published data of amino acids, we show the existence of apparent local equilibrium among different amino acids in potato and a kind of green alga. The existence of apparent local equilibrium is in turn consistent with the notion that enzymatic reactions can be reversible even in living systems. The result also implies that previous emphasis on external carbon source intake may be misplaced when studying isotope distribution in physiology. In addition to the identification of local equilibrium among biomolecules, the difference matrix approach has the potential to explore chemical or isotope equilibrium state in extraterrestrial bodies, to distinguish living from non-living systems, and to classify living species. This approach will benefit from large numbers of systematic data and advanced pattern recognition techniques.

Equilibrium sampling of environmental pollutants in fish: comparison with lipid-normalized concentrations and homogenization effects on chemical activity.

PubMed

Jahnke, Annika; Mayer, Philipp; Adolfsson-Erici, Margaretha; McLachlan, Michael S

2011-07-01

Equilibrium sampling of organic pollutants into the silicone polydimethylsiloxane (PDMS) has recently been applied in biological tissues including fish. Pollutant concentrations in PDMS can then be multiplied with lipid/PDMS distribution coefficients (D(Lipid,PDMS) ) to obtain concentrations in fish lipids. In the present study, PDMS thin films were used for equilibrium sampling of polychlorinated biphenyls (PCBs) in intact tissue of two eels and one salmon. A classical exhaustive extraction technique to determine lipid-normalized PCB concentrations, which assigns the body burden of the chemical to the lipid fraction of the fish, was additionally applied. Lipid-based PCB concentrations obtained by equilibrium sampling were 85 to 106% (Norwegian Atlantic salmon), 108 to 128% (Baltic Sea eel), and 51 to 83% (Finnish lake eel) of those determined using total extraction. This supports the validity of the equilibrium sampling technique, while at the same time confirming that the fugacity capacity of these lipid-rich tissues for PCBs was dominated by the lipid fraction. Equilibrium sampling was also applied to homogenates of the same fish tissues. The PCB concentrations in the PDMS were 1.2 to 2.0 times higher in the homogenates (statistically significant in 18 of 21 cases, p < 0.05), indicating that homogenization increased the chemical activity of the PCBs and decreased the fugacity capacity of the tissue. This observation has implications for equilibrium sampling and partition coefficients determined using tissue homogenates. Copyright © 2011 SETAC.

Stable carbon and hydrogen isotope fractionation of dissolved organic groundwater pollutants by equilibrium sorption.

PubMed

Höhener, Patrick; Yu, Xianjing

2012-03-15

Linear free energy relationships (LFERs) were established which relate equilibrium vapor-liquid isotope effects to stable carbon and hydrogen isotope enrichment factors for equilibrium sorption to geosorbents. The LFERs were established for normal, cyclic or branched alkanes, monoaromatic hydrocarbons, and chloroethenes. These LFERs predict that isotopic light compounds sorb more strongly than their heavy counterparts. Defining fractionation as in classical literature by "heavy divided by light", carbon enrichment factors for equilibrium sorption were derived which ranged from -0.13±0.04‰ (benzene) to -0.52±0.19‰ (trichloroethene at 5-15 °C). Hydrogen enrichment factors for sorption of 14 different compounds were between -2.4 and -9.2‰. For perdeuterated hydrocarbons the predicted enrichment factors ranged from -19±5.4‰ (benzene) to -64±30‰ (cyclohexane). Equilibrium sorption experiments with a soil and activated carbon as sorbents were performed in the laboratory for perdeuterocyclohexane and perdeuterotoluene. The measured D/H enrichments agreed with the LFER prediction for both compounds and both sorbents within the uncertainty estimate of the prediction. The results of this work suggest that equilibrium sorption does create only very small isotope shifts for (13)C in groundwater pollutants in aquifers. It is also suggested that deuterium shifts are expected to be higher, especially for strongly sorbing pollutants. Copyright © 2011 Elsevier B.V. All rights reserved.

The density of apical cells of dark-grown protonemata of the moss Ceratodon purpureus

NASA Technical Reports Server (NTRS)

Schwuchow, J. M.; Kern, V. D.; Wagner, T.; Sack, F. D.

2000-01-01

Determinations of plant or algal cell density (cell mass divided by volume) have rarely accounted for the extracellular matrix or shrinkage during isolation. Three techniques were used to indirectly estimate the density of intact apical cells from protonemata of the moss Ceratodon purpureus. First, the volume fraction of each cell component was determined by stereology, and published values for component density were used to extrapolate to the entire cell. Second, protonemal tips were immersed in bovine serum albumin solutions of different densities, and then the equilibrium density was corrected for the mass of the cell wall. Third, apical cell protoplasts were centrifuged in low-osmolarity gradients, and values were corrected for shrinkage during protoplast isolation. Values from centrifugation (1.004 to 1.015 g/cm3) were considerably lower than from other methods (1.046 to 1.085 g/cm3). This work appears to provide the first corrected estimates of the density of any plant cell. It also documents a method for the isolation of protoplasts specifically from apical cells of protonemal filaments.

Geometrical Description of Chemical Equilibrium and Le Cha^telier's Principle: Two-Component Systems

ERIC Educational Resources Information Center

Novak, Igor

2018-01-01

Chemical equilibrium is one of the most important concepts in chemistry. The changes in properties of the chemical system at equilibrium induced by variations in pressure, volume, temperature, and concentration are always included in classroom teaching and discussions. This work introduces a novel, geometrical approach to understanding the…

Mathematical analysis of a power-law form time dependent vector-borne disease transmission model.

PubMed

Sardar, Tridip; Saha, Bapi

2017-06-01

In the last few years, fractional order derivatives have been used in epidemiology to capture the memory phenomena. However, these models do not have proper biological justification in most of the cases and lack a derivation from a stochastic process. In this present manuscript, using theory of a stochastic process, we derived a general time dependent single strain vector borne disease model. It is shown that under certain choice of time dependent transmission kernel this model can be converted into the classical integer order system. When the time-dependent transmission follows a power law form, we showed that the model converted into a vector borne disease model with fractional order transmission. We explicitly derived the disease-free and endemic equilibrium of this new fractional order vector borne disease model. Using mathematical properties of nonlinear Volterra type integral equation it is shown that the unique disease-free state is globally asymptotically stable under certain condition. We define a threshold quantity which is epidemiologically known as the basic reproduction number (R 0 ). It is shown that if R 0 > 1, then the derived fractional order model has a unique endemic equilibrium. We analytically derived the condition for the local stability of the endemic equilibrium. To test the model capability to capture real epidemic, we calibrated our newly proposed model to weekly dengue incidence data of San Juan, Puerto Rico for the time period 30th April 1994 to 23rd April 1995. We estimated several parameters, including the order of the fractional derivative of the proposed model using aforesaid data. It is shown that our proposed fractional order model can nicely capture real epidemic. Copyright © 2017 Elsevier Inc. All rights reserved.

Measuring the fraction of pool volume filled with fine sediment

Treesearch

Sue Hilton; Thomas E. Lisle

1993-01-01

The fraction of pool volume filled with fine sediment (usually fine sand to medium gravel) can be a useful index of the sediment supply and substrate habitat of gravel-bed channels. It can be used to evaluate and monitor channel condition and to detect and evaluate sediment sources. This fraction (V*) is the ratio of fine-sediment volume to pool water volume plus fine-...

A Functional Monomer Is Not Enough: Principal Component Analysis of the Influence of Template Complexation in Pre-Polymerization Mixtures on Imprinted Polymer Recognition and Morphology

PubMed Central

Golker, Kerstin; Karlsson, Björn C. G.; Rosengren, Annika M.; Nicholls, Ian A.

2014-01-01

In this report, principal component analysis (PCA) has been used to explore the influence of template complexation in the pre-polymerization phase on template molecularly imprinted polymer (MIP) recognition and polymer morphology. A series of 16 bupivacaine MIPs were studied. The ethylene glycol dimethacrylate (EGDMA)-crosslinked polymers had either methacrylic acid (MAA) or methyl methacrylate (MMA) as the functional monomer, and the stoichiometry between template, functional monomer and crosslinker was varied. The polymers were characterized using radioligand equilibrium binding experiments, gas sorption measurements, swelling studies and data extracted from molecular dynamics (MD) simulations of all-component pre-polymerization mixtures. The molar fraction of the functional monomer in the MAA-polymers contributed to describing both the binding, surface area and pore volume. Interestingly, weak positive correlations between the swelling behavior and the rebinding characteristics of the MAA-MIPs were exposed. Polymers prepared with MMA as a functional monomer and a polymer prepared with only EGDMA were found to share the same characteristics, such as poor rebinding capacities, as well as similar surface area and pore volume, independent of the molar fraction MMA used in synthesis. The use of PCA for interpreting relationships between MD-derived descriptions of events in the pre-polymerization mixture, recognition properties and morphologies of the corresponding polymers illustrates the potential of PCA as a tool for better understanding these complex materials and for their rational design. PMID:25391043

A functional monomer is not enough: principal component analysis of the influence of template complexation in pre-polymerization mixtures on imprinted polymer recognition and morphology.

PubMed

Golker, Kerstin; Karlsson, Björn C G; Rosengren, Annika M; Nicholls, Ian A

2014-11-10

In this report, principal component analysis (PCA) has been used to explore the influence of template complexation in the pre-polymerization phase on template molecularly imprinted polymer (MIP) recognition and polymer morphology. A series of 16 bupivacaine MIPs were studied. The ethylene glycol dimethacrylate (EGDMA)-crosslinked polymers had either methacrylic acid (MAA) or methyl methacrylate (MMA) as the functional monomer, and the stoichiometry between template, functional monomer and crosslinker was varied. The polymers were characterized using radioligand equilibrium binding experiments, gas sorption measurements, swelling studies and data extracted from molecular dynamics (MD) simulations of all-component pre-polymerization mixtures. The molar fraction of the functional monomer in the MAA-polymers contributed to describing both the binding, surface area and pore volume. Interestingly, weak positive correlations between the swelling behavior and the rebinding characteristics of the MAA-MIPs were exposed. Polymers prepared with MMA as a functional monomer and a polymer prepared with only EGDMA were found to share the same characteristics, such as poor rebinding capacities, as well as similar surface area and pore volume, independent of the molar fraction MMA used in synthesis. The use of PCA for interpreting relationships between MD-derived descriptions of events in the pre-polymerization mixture, recognition properties and morphologies of the corresponding polymers illustrates the potential of PCA as a tool for better understanding these complex materials and for their rational design.

Characterization and Demonstrations of Laser-Induced Incandescence in both Normal and Low-Gravity

NASA Technical Reports Server (NTRS)

VanderWal, Randall L.

1997-01-01

Knowledge of soot volume fraction is important to a wide range of combustion studies in microgravity. Laser-induced incandescence (LII) offers high sensitivity, high temporal and spatial resolution in addition to geometric versatility for real-time determination of soot volume fraction. Implementation of LII into the 2.2 see drop tower at The NASA-Lewis Research Center along with system characterization is described. Absolute soot volume fraction measurements are presented for laminar and turbulent gas-jet flames in microgravity to illustrate the capabilities of LII in microgravity. Comparison between LII radial intensity profiles with soot volume fraction profiles determined through a full-field light extinction technique are also reported validating the accuracy of LII for soot volume fraction measurements in a microgravity environment.

Ortho-para-hydrogen equilibration on Jupiter

NASA Technical Reports Server (NTRS)

Carlson, Barbara E.; Lacis, Andrew A.; Rossow, William B.

1992-01-01

Voyager IRIS observations reveal that the Jovian para-hydrogen fraction is not in thermodynamic equilibrium near the NH3 cloud top, implying that a vertical gradient exists between the high-temperature equilibrium value of 0.25 at depth and the cloud top values. The height-dependent para-hydrogen profile is obtained using an anisotropic multiple-scattering radiative transfer model. A vertical correlation is found to exist between the location of the para-hydrogen gradient and the NH3 cloud, strongly suggesting that paramagnetic conversion on NH3 cloud particle surfaces is the dominant equilibration mechanism. Below the NH3 cloud layer, the para fraction is constant with depth and equal to the high-temperature equilibrium value of 0.25. The degree of cloud-top equilibration appears to depend on the optical depth of the NH3 cloud layer. Belt-zone variations in the para-hydrogen profile seem to be due to differences in the strength of the vertical mixing.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sengupta, M.; Ganesh, R.

The dynamics of cylindrically trapped electron plasma has been investigated using a newly developed 2D Electrostatic PIC code that uses unapproximated, mass-included equations of motion for simulation. Exhaustive simulations, covering the entire range of Brillouin ratio, were performed for uniformly filled circular profiles in rigid rotor equilibrium. The same profiles were then loaded away from equilibrium with an initial value of rigid rotation frequency different from that required for radial force balance. Both these sets of simulations were performed for an initial zero-temperature or cold load of the plasma with no spread in either angular velocity or radial velocity. Themore » evolution of the off-equilibrium initial conditions to a steady state involve radial breathing of the profile that scales in amplitude and algebraic growth with Brillouin fraction. For higher Brillouin fractions, the growth of the breathing mode is followed by complex dynamics of spontaneous hollow density structures, excitation of poloidal modes, leading to a monotonically falling density profile.« less

Warm and cold pasta phase in relativistic mean field theory

NASA Astrophysics Data System (ADS)

Avancini, S. S.; Menezes, D. P.; Alloy, M. D.; Marinelli, J. R.; Moraes, M. M. W.; Providência, C.

2008-07-01

In the present article we investigate the onset of the pasta phase with different parametrizations of the nonlinear Walecka model. At zero temperature two different methods are used, one based on coexistent phases and the other on the Thomas-Fermi approximation. At finite temperature only the coexistence phases method is used. npe matter with fixed proton fractions and in β equilibrium is studied. The pasta phase decreases with the increase of temperature. The internal pasta structure and the beginning of the homogeneous phase vary depending on the proton fraction (or the imposition of β equilibrium), on the method used, and on the chosen parametrization. It is shown that a good parametrization of the surface tension with dependence on the temperature, proton fraction, and geometry is essential to describe correctly large isospin asymmetries and the transition from pasta to homogeneous matter.

Assessment of interpatient heterogeneity in tumor radiosensitivity for nonsmall cell lung cancer using tumor-volume variation data

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chvetsov, Alexei V., E-mail: chvetsov2@gmail.com; Schwartz, Jeffrey L.; Mayr, Nina

2014-06-15

Purpose: In our previous work, the authors showed that a distribution of cell surviving fractionsS{sub 2} in a heterogeneous group of patients could be derived from tumor-volume variation curves during radiotherapy for head and neck cancer. In this research study, the authors show that this algorithm can be applied to other tumors, specifically in nonsmall cell lung cancer. This new application includes larger patient volumes and includes comparison of data sets obtained at independent institutions. Methods: Our analysis was based on two data sets of tumor-volume variation curves for heterogeneous groups of 17 patients treated for nonsmall cell lung cancermore » with conventional dose fractionation. The data sets were obtained previously at two independent institutions by using megavoltage computed tomography. Statistical distributions of cell surviving fractionsS{sub 2} and clearance half-lives of lethally damaged cells T{sub 1/2} have been reconstructed in each patient group by using a version of the two-level cell population model of tumor response and a simulated annealing algorithm. The reconstructed statistical distributions of the cell surviving fractions have been compared to the distributions measured using predictive assays in vitro. Results: Nonsmall cell lung cancer presents certain difficulties for modeling surviving fractions using tumor-volume variation curves because of relatively large fractional hypoxic volume, low gradient of tumor-volume response, and possible uncertainties due to breathing motion. Despite these difficulties, cell surviving fractionsS{sub 2} for nonsmall cell lung cancer derived from tumor-volume variation measured at different institutions have similar probability density functions (PDFs) with mean values of 0.30 and 0.43 and standard deviations of 0.13 and 0.18, respectively. The PDFs for cell surviving fractions S{sub 2} reconstructed from tumor volume variation agree with the PDF measured in vitro. Conclusions: The data obtained in this work, when taken together with the data obtained previously for head and neck cancer, suggests that the cell surviving fractionsS{sub 2} can be reconstructed from the tumor volume variation curves measured during radiotherapy with conventional fractionation. The proposed method can be used for treatment evaluation and adaptation.« less

Assessment of interpatient heterogeneity in tumor radiosensitivity for nonsmall cell lung cancer using tumor-volume variation data.

PubMed

Chvetsov, Alexei V; Yartsev, Slav; Schwartz, Jeffrey L; Mayr, Nina

2014-06-01

In our previous work, the authors showed that a distribution of cell surviving fractions S2 in a heterogeneous group of patients could be derived from tumor-volume variation curves during radiotherapy for head and neck cancer. In this research study, the authors show that this algorithm can be applied to other tumors, specifically in nonsmall cell lung cancer. This new application includes larger patient volumes and includes comparison of data sets obtained at independent institutions. Our analysis was based on two data sets of tumor-volume variation curves for heterogeneous groups of 17 patients treated for nonsmall cell lung cancer with conventional dose fractionation. The data sets were obtained previously at two independent institutions by using megavoltage computed tomography. Statistical distributions of cell surviving fractions S2 and clearance half-lives of lethally damaged cells T(1/2) have been reconstructed in each patient group by using a version of the two-level cell population model of tumor response and a simulated annealing algorithm. The reconstructed statistical distributions of the cell surviving fractions have been compared to the distributions measured using predictive assays in vitro. Nonsmall cell lung cancer presents certain difficulties for modeling surviving fractions using tumor-volume variation curves because of relatively large fractional hypoxic volume, low gradient of tumor-volume response, and possible uncertainties due to breathing motion. Despite these difficulties, cell surviving fractions S2 for nonsmall cell lung cancer derived from tumor-volume variation measured at different institutions have similar probability density functions (PDFs) with mean values of 0.30 and 0.43 and standard deviations of 0.13 and 0.18, respectively. The PDFs for cell surviving fractions S2 reconstructed from tumor volume variation agree with the PDF measured in vitro. The data obtained in this work, when taken together with the data obtained previously for head and neck cancer, suggests that the cell surviving fractions S2 can be reconstructed from the tumor volume variation curves measured during radiotherapy with conventional fractionation. The proposed method can be used for treatment evaluation and adaptation.

Equilibrium sorption and diffusion rate studies with halogenated organic chemical and sandy aquifer material

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ball, W.P.

1990-01-01

Concepts for rate limitation of sorptive uptake of hydrophobic organic solutes by aquifer solids are reviewed, emphasizing physical diffusion models and in the context of effects on contaminant transport. Data for the sorption of tetrachloroethene (PCE) and 1,2,4,5-tetrachlorobenzene (TeCB) on Borden sand are presented, showing that equilibrium is attained very slowly, requiring equilibration times on the order of tens of days for PCE and hundreds of days for TeCB. The rate of approach to equilibrium decreased with increasing particle size and sorption distribution coefficient, in accordance with retarded intragranular diffusion models. Pulverization of the samples significantly decreased the required timemore » to equilibrium without changing the sorption capacity of the solids. Batch sorption methodology was refined to allow accurate measurement of long-term distribution coefficients, using purified {sup 14}C-labelled solute spikes and sealed glass ampules. Sorption isotherms for PCE and TeCB were conducted with size fractions of Borden sand over four to five orders of magnitude in aqueous concentration, and were found to be slightly nonlinear (Freundlich exponent = 0.8). A concentrated set of data in the low concentration range (<50 ug/L) revealed that sorption in this range could be equally well described by a linear isotherm. Distribution coefficients of the two solutes with seven size fractions of Borden sand, measured at low concentration and at full equilibrium, were between seven and sixty times the value predicted on the basis of recent correlations with organic carbon content. Rate results for coarse size fractions support a simple pore diffusion model, with pore diffusion coefficients estimated to be approximately 3 {times} 10{sup {minus}8} cm{sup 2}/sec, more than 200{times} lower than the aqueous diffusivities.« less

Ammonium stability and nitrogen isotope fractionations for NH4+-NH3(aq)-NH3(gas) systems at 20-70 °C and pH of 2-13: Applications to habitability and nitrogen cycling in low-temperature hydrothermal systems

NASA Astrophysics Data System (ADS)

Li, Long; Lollar, Barbara Sherwood; Li, Hong; Wortmann, Ulrich G.; Lacrampe-Couloume, Georges

2012-05-01

Ammonium/ammonia is an essential nutrient and energy source to support life in oceanic and terrestrial hydrothermal systems. Thus the stability of ammonium is crucial to determine the habitability or ecological structure in hydrothermal environments, but still not well understood. To date, the lack of constraints on nitrogen isotope fractionations between ammonium and ammonia has limited the application of nitrogen isotopes to trace (bio)geochemical processes in such environments. In this study, we carried out laboratory experiments to (1) examine the stability of ammonium in an ammonium sulfate solution under temperature conditions from 20 to 70 °C and pH from 2.1 to 12.6 and (2) determine nitrogen isotope fractionation between ammonium and ammonia. Our experimental results show that ammonium is stable under the experimental temperatures when pH is less than 6. In experiments with starting pH greater than 8, significant ammonium was lost as a result of dissociation of ammonium and degassing of ammonia product. Nitrogen concentrations in the fluids decreased by more than 50% in the first two hours, indicating extremely fast effusion rates of ammonia. This implies that ammonium at high pH fluids (e.g., Lost City Hydrothermal Vents, Oman ophiolite hyperalkaline springs) may not be stable. Habitable environments may be more favorable at the leading edge of a pH gradient toward more acidic conditions, where the fluid can efficiently trap any ammonia transferred from a high pH vent. Although modeling shows that high temperature, low pH hydrothermal vents (e.g., Rainbow hydrothermal vent) may have the capability to retain ammonium, their high temperatures may limit habitability. The habitable zone associated with such a hydrothermal vent is likely at the lower front of a temperature gradient. In contrast, modeling of ammonium in deep terrestrial systems, suggests that saline fracture waters in crystalline rocks such as described in the Canadian Shield and in the Witwatersrand Basin, South Africa may also provide habitable environments for life. The nitrogen isotope results of remaining ammonium from the partial dissociation experiments fit well with a batch equilibrium model, indicating equilibrium nitrogen isotope fractionations have been reached between ammonium and its dissociation product aqueous ammonia. Modeling yielded nitrogen isotope fractionations between ammonium and aqueous ammonia were 45.4‰ at 23 °C, 37.7‰ at 50 °C, and 33.5‰ at 70 °C, respectively. A relationship between nitrogen equilibrium isotope fractionation and temperature is determined for the experimental temperature range as: 103·lnα(aq)=25.94×{103}/{T}-42.25 Integrated with three previous theoretical estimates on nitrogen isotope equilibrium fractionations between ammonium and gaseous ammonia, we achieved three possible temperature-dependent nitrogen isotope equilibrium fractionation between aqueous ammonia and gaseous ammonia:

A chemical model for generating the sources of mare basalts - Combined equilibrium and fractional crystallization of the lunar magmasphere

NASA Technical Reports Server (NTRS)

Snyder, Gregory A.; Taylor, Lawrence A.; Neal, Clive R.

1992-01-01

A chemical model for simulating the sources of the lunar mare basalts was developed by considering a modified mafic cumulate source formed during the combined equilibrium and fractional crystallization of a lunar magma ocean (LMO). The parameters which influence the initial LMO and its subsequent crystallization are examined, and both trace and major elements are modeled. It is shown that major elements tightly constrain the composition of mare basalt sources and the pathways to their creation. The ability of this LMO model to generate viable mare basalt source regions was tested through a case study involving the high-Ti basalts.

Stability analysis and nonstandard Grünwald-Letnikov scheme for a fractional order predator-prey model with ratio-dependent functional response

NASA Astrophysics Data System (ADS)

Suryanto, Agus; Darti, Isnani

2017-12-01

In this paper we discuss a fractional order predator-prey model with ratio-dependent functional response. The dynamical properties of this model is analyzed. Here we determine all equilibrium points of this model including their existence conditions and their stability properties. It is found that the model has two type of equilibria, namely the predator-free point and the co-existence point. If there is no co-existence equilibrium, i.e. when the coefficient of conversion from the functional response into the growth rate of predator is less than the death rate of predator, then the predator-free point is asymptotically stable. On the other hand, if the co-existence point exists then this equilibrium is conditionally stable. We also construct a nonstandard Grnwald-Letnikov (NSGL) numerical scheme for the propose model. This scheme is a combination of the Grnwald-Letnikov approximation and the nonstandard finite difference scheme. This scheme is implemented in MATLAB and used to perform some simulations. It is shown that our numerical solutions are consistent with the dynamical properties of our fractional predator-prey model.

Direct numerical simulation of turbulent H2-O2 combustion using reduced chemistry

NASA Technical Reports Server (NTRS)

Montgomery, Christopher J.; Kosaly, George; Riley, James J.

1993-01-01

Results of direct numerical simulations of hydrogen-oxygen combustion using a partial-equilibrium chemistry scheme in constant density, decaying, isotropic turbulence are reported. The simulations qualitatively reproduce many features of experimental results, such as superequilibrium radical species mole fractions, with temperature and major species mole fractions closer to chemical equilibrium. It was also observed that the peak reaction rates occur in narrow zones where the stoichiometric surface intersects regions of high scalar dissipation, as might be expected for combustion conditions close to chemical equilibrium. Another finding was that high OH mole fraction correspond more closely to the stoichiometric surface than to areas of high reaction rate for conditions of the simulations. Simulation results were compared to predictions of the Conditional Moment Closure model. This model was found to give good results for all quantities of interest when the conditionally averaged scalar dissipation was used in the prediction. When the nonconditioned average dissipation was used, the predictions compared well to the simulations for most of the species and temperature, but not for the reaction rate. The comparison would be expected to improve for higher Reynolds number flows, however.

Preferential adsorption of fluorescing fulvic and humic acid components on activated carbon using flow field-flow fractionation analysis.

PubMed

Schmit, Kathryn H; Wells, Martha J M

2002-02-01

Activated carbon treatment of drinking water is used to remove natural organic matter (NOM) precursors that lead to the formation of disinfection byproducts. The innate hydrophobic nature and macromolecular size of NOM render it amenable to sorption by activated carbon. Batch equilibrium and minicolumn breakthrough adsorption studies were performed using granular activated carbon to treat NOM-contaminated water. Ultraviolet (UV) absorption spectroscopy and flow field-flow fractionation analysis using tandem diode-array and fluorescence detectors were used to monitor the activated carbon sorption of NOM. Using these techniques, it was possible to study activated carbon adsorption properties of UV absorbing, fluorescing and nonfluorescing, polyelectrolytic macromolecules fractionated from the total macromolecular and nonmacromolecular composition of NOM. Adsorption isotherms were constructed at pH 6 and pH 9. Data were described by the traditional and modified Freundlich models. Activated carbon capacity and adsorbability were compared among fractionated molecular subsets of fulvic and humic acids. Preferential adsorption (or adsorptive fractionation) of polyelectrolytic, fluorescing fulvic and humic macromolecules on activated carbon was observed. The significance of observing preferential adsorption on activated carbon of fluorescing macromolecular components relative to nonfluorescing components is that this phenomenon changes the composition of dissolved organic matter remaining in equilibrium in the aqueous phase relative to the composition that existed in the aqueous phase prior to adsorption. Likewise, it changes the composition of dissolved organic matter remaining in equilibrium in the aqueous phase relative to the adsorbed phase. This research increases our understanding of NOM interactions with activated carbon which may lead to improved methods of potable water production.

Effect of volume fraction of alpha and transformed beta on the high cycle fatigue properties of bimodal Ti6Al4V alloy

NASA Astrophysics Data System (ADS)

Jadhav, Shital; Powar, Amit; Patil, Sandip; Supare, Ashish; Farane, Bhagwan; Singh, Rajkumar, Dr.

2017-05-01

The present study was performed to investigate the effect of volume fraction of alpha and transformed beta phase on the high-cycle fatigue (HCF) properties of the bimodal titanium Ti6Al4V alloy. The effect of such morphology on mechanical properties was studied using tensile and rotating bending fatigue test as per ASTM standards. Microstructures and fractography of the specimens were studied using optical and scanning electron microscopy (SEM) respectively.Ti6Al4V alloy samples were heat treated to have three distinctive volume fractions of alpha and transformed beta phase. With an increase in quench delay from 30,50 and 70 sec during quenching after solutionizing temperature of 967°C, the volume fraction of alpha was found to be increased from 20% to 67%. Tests on tensile and rotating bending fatigue showed that the specimen with 20% volume fraction of alpha phase exhibited the highest tensile and fatigue strength, however the properties gets deteriorate with increase in volume fraction of alpha.

An experimental study on rheological behavior of a nanofluid containing oxide nanoparticle and proposing a new correlation

NASA Astrophysics Data System (ADS)

Saeedi, Amir Hussein; Akbari, Mohammad; Toghraie, Davood

2018-05-01

In this paper, the nanofluid dynamic viscosity composed of CeO2- Ethylene Glycol is examined within 25-50 °C with 5 °C intervals and at six volume fractions (0.05, 0.1, 0.2, 0.4, 0.8 and 1.2%) experimentally. The nanofluid was exposed to ultrasound waves for various durations to study the effect of this parameter on dynamic viscosity of the fluid. We found that at a constant temperature, nanofluid viscosity increases with increases in the volume fraction of the nanoparticles. Also, at a given volume fraction, nanofluid viscosity decreases when temperature is increased. Maximum increase in nanofluid viscosity compared to the base fluid viscosity occurs at 25 °C and volume fraction of 1.2%. It can be inferred that the obtained mathematical relationship is a suitable predicting model for estimating dynamic viscosity of CeO2- Ethylene Glycol (EG) at different volume fractions and temperatures and its results are consistent to laboratory results in the set volume fraction and temperature ranges.

Supersonic Dislocation Bursts in Silicon

DOE PAGES

Hahn, E. N.; Zhao, S.; Bringa, E. M.; ...

2016-06-06

Dislocations are the primary agents of permanent deformation in crystalline solids. Since the theoretical prediction of supersonic dislocations over half a century ago, there is a dearth of experimental evidence supporting their existence. Here we use non-equilibrium molecular dynamics simulations of shocked silicon to reveal transient supersonic partial dislocation motion at approximately 15 km/s, faster than any previous in-silico observation. Homogeneous dislocation nucleation occurs near the shock front and supersonic dislocation motion lasts just fractions of picoseconds before the dislocations catch the shock front and decelerate back to the elastic wave speed. Applying a modified analytical equation for dislocation evolutionmore » we successfully predict a dislocation density of 1.5 x 10(12) cm(-2) within the shocked volume, in agreement with the present simulations and realistic in regards to prior and on-going recovery experiments in silicon.« less

Supersonic Dislocation Bursts in Silicon

PubMed Central

Hahn, E. N.; Zhao, S.; Bringa, E. M.; Meyers, M. A.

2016-01-01

Dislocations are the primary agents of permanent deformation in crystalline solids. Since the theoretical prediction of supersonic dislocations over half a century ago, there is a dearth of experimental evidence supporting their existence. Here we use non-equilibrium molecular dynamics simulations of shocked silicon to reveal transient supersonic partial dislocation motion at approximately 15 km/s, faster than any previous in-silico observation. Homogeneous dislocation nucleation occurs near the shock front and supersonic dislocation motion lasts just fractions of picoseconds before the dislocations catch the shock front and decelerate back to the elastic wave speed. Applying a modified analytical equation for dislocation evolution we successfully predict a dislocation density of 1.5 × 1012 cm−2 within the shocked volume, in agreement with the present simulations and realistic in regards to prior and on-going recovery experiments in silicon. PMID:27264746

Supersonic Dislocation Bursts in Silicon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hahn, E. N.; Zhao, S.; Bringa, E. M.

Dislocations are the primary agents of permanent deformation in crystalline solids. Since the theoretical prediction of supersonic dislocations over half a century ago, there is a dearth of experimental evidence supporting their existence. Here we use non-equilibrium molecular dynamics simulations of shocked silicon to reveal transient supersonic partial dislocation motion at approximately 15 km/s, faster than any previous in-silico observation. Homogeneous dislocation nucleation occurs near the shock front and supersonic dislocation motion lasts just fractions of picoseconds before the dislocations catch the shock front and decelerate back to the elastic wave speed. Applying a modified analytical equation for dislocation evolutionmore » we successfully predict a dislocation density of 1.5 x 10(12) cm(-2) within the shocked volume, in agreement with the present simulations and realistic in regards to prior and on-going recovery experiments in silicon.« less

Expanding Evolutionary Theory beyond Darwinism with Elaborating, Self-Organizing, and Fractionating Complex Evolutionary Systems

ERIC Educational Resources Information Center

Fichter, Lynn S.; Pyle, E. J.; Whitmeyer, S. J.

2010-01-01

Earth systems increase in complexity, diversity, and interconnectedness with time, driven by tectonic/solar energy that keeps the systems far from equilibrium. The evolution of Earth systems is facilitated by three evolutionary mechanisms: "elaboration," "fractionation," and "self-organization," that share…

A discrete model of Ostwald ripening based on multiple pairwise interactions

NASA Astrophysics Data System (ADS)

Di Nunzio, Paolo Emilio

2018-06-01

A discrete multi-particle model of Ostwald ripening based on direct pairwise interactions is developed for particles with incoherent interfaces as an alternative to the classical LSW mean field theory. The rate of matter exchange depends on the average surface-to-surface interparticle distance, a characteristic feature of the system which naturally incorporates the effect of volume fraction of second phase. The multi-particle diffusion is described through the definition of an interaction volume containing all the particles involved in the exchange of solute. At small volume fractions this is proportional to the size of the central particle, at higher volume fractions it gradually reduces as a consequence of diffusion screening described on a geometrical basis. The topological noise present in real systems is also included. For volume fractions below about 0.1 the model predicts broad and right-skewed stationary size distributions resembling a lognormal function. Above this value, a transition to sharper, more symmetrical but still right-skewed shapes occurs. An excellent agreement with experiments is obtained for 3D particle size distributions of solid-solid and solid-liquid systems with volume fraction 0.07, 0.30, 0.52 and 0.74. The kinetic constant of the model depends on the cube root of volume fraction up to about 0.1, then increases rapidly with an upward concavity. It is in good agreement with the available literature data on solid-liquid mixtures in the volume fraction range from 0.20 to about 0.75.

Experimental investigation on thermal conductivity and viscosity of maghemite (γ –Fe2O3) water-based nanofluids

NASA Astrophysics Data System (ADS)

Nurdin, I.; Johan, M. R.; Ang, B. C.

2018-03-01

Thermal conductivity and kinematic viscosity of maghemite nanofluids were experimentally investigated at a small volume fraction of maghemite nanoparticles and temperatures. Maghemite nanofluids were prepared by suspending maghemite nanoparticles in water as base fluids. Results show that the thermal conductivity of maghemite nanofluids linearly increase with increasing particle volume fraction and temperature, while kinematic viscosity increase with increasing particle volume fraction and decrease with increasing temperature. The highest enhancement of thermal conductivity and kinematic viscosity are 18.84% and 13.66% respectively, at particle volume fraction 0.6% and temperature 35.

Predicting Morphology of Polymers Using Mesotek+

DTIC Science & Technology

2010-02-01

file is then produced for Mesotek+ to reproduce the phase behavior for an experimental system of poly (styrene-b- isoprene ) in the solvent tetradecane...theoretical code 3a and (b) experimental code 3b. .....6  Figure 3. Results from 40/60 volume styrene-b- isoprene + tetradecane using gnuplot: A...styrene volume fraction, B) isoprene volume fraction, and C) tetradecane volume fraction. The color bar to the right of each plot indicates how the

Direct computation of thermodynamic properties of chemically reacting air with consideration to CFD

NASA Astrophysics Data System (ADS)

Iannelli, Joe

2003-10-01

This paper details a two-equation procedure to calculate exactly mass and mole fractions, pressure, temperature, specific heats, speed of sound and the thermodynamic and jacobian partial derivatives of pressure and temperature for a five-species chemically reacting equilibrium air. The procedure generates these thermodynamic properties using as independent variables either pressure and temperature or density and internal energy, for CFD applications. An original element in this procedure consists in the exact physically meaningful solution of the mass-fraction and mass-action equations. Air-equivalent molecular masses for oxygen and nitrogen are then developed to account, within a mixture of only oxygen and nitrogen, for the presence of carbon dioxide, argon and the other noble gases within atmospheric air. The mathematical formulation also introduces a versatile system non-dimensionalization that makes the procedure uniformly applicable to flows ranging from shock-tube flows with zero initial velocity to aerothermodynamic flows with supersonic/hypersonic free-stream Mach numbers. Over a temperature range of more than 10000 K and pressure and density ranges corresponding to an increase in altitude in standard atmosphere of 30000 m above sea level, the predicted distributions of mole fractions, constant-volume specific heat, and speed of sound for the model five species agree with independently published results, and all the calculated thermodynamic properties, including their partial derivatives, remain continuous, smooth, and physically meaningful.

Interfaces at equilibrium: A guide to fundamentals.

PubMed

Marmur, Abraham

2017-06-01

The fundamentals of the thermodynamics of interfaces are reviewed and concisely presented. The discussion starts with a short review of the elements of bulk thermodynamics that are also relevant to interfaces. It continues with the interfacial thermodynamics of two-phase systems, including the definition of interfacial tension and adsorption. Finally, the interfacial thermodynamics of three-phase (wetting) systems is discussed, including the topic of non-wettable surfaces. A clear distinction is made between equilibrium conditions, in terms of minimizing energies (internal, Gibbs or Helmholtz), and equilibrium indicators, in terms of measurable, intrinsic properties (temperature, chemical potential, pressure). It is emphasized that the equilibrium indicators are the same whatever energy is minimized, if the boundary conditions are properly chosen. Also, to avoid a common confusion, a distinction is made between systems of constant volume and systems with drops of constant volume. Copyright © 2016 Elsevier B.V. All rights reserved.

How the dispersion of magnesium oxide nanoparticles effects on the viscosity of water-ethylene glycol mixture: Experimental evaluation and correlation development

NASA Astrophysics Data System (ADS)

Afrand, Masoud; Abedini, Ehsan; Teimouri, Hamid

2017-03-01

In this paper, the effect of dispersion of magnesium oxide nanoparticles on viscosity of a mixture of water and ethylene glycol (50-50% vol.) was examined experimentally. Experiments were performed for various nanofluid samples at different temperatures and shear rates. Measurements revealed that the nanofluid samples with volume fractions of less than 1.5% had Newtonian behavior, while the sample with volume fraction of 3% showed non-Newtonian behavior. Results showed that the viscosity of nanofluids enhanced with increasing nanoparticles volume fraction and decreasing temperature. Results of sensitivity analysis revealed that the viscosity sensitivity of nanofluid samples to temperature at higher volume fractions is more than that of at lower volume fractions. Finally, because of the inability of the existing model to predict the viscosity of MgO/EG-water nanofluid, an experimental correlation has been proposed for predicting the viscosity of the nanofluid.

Diffusion method of seperating gaseous mixtures

DOEpatents

Pontius, Rex B.

1976-01-01

A method of effecting a relatively large change in the relative concentrations of the components of a gaseous mixture by diffusion which comprises separating the mixture into heavier and lighter portions according to major fraction mass recycle procedure, further separating the heavier portions into still heavier subportions according to a major fraction mass recycle procedure, and further separating the lighter portions into still lighter subportions according to a major fraction equilibrium recycle procedure.

A 3D model for rain-induced landslides based on molecular dynamics with fractal and fractional water diffusion

NASA Astrophysics Data System (ADS)

Martelloni, Gianluca; Bagnoli, Franco; Guarino, Alessio

2017-09-01

We present a three-dimensional model of rain-induced landslides, based on cohesive spherical particles. The rainwater infiltration into the soil follows either the fractional or the fractal diffusion equations. We analytically solve the fractal partial differential equation (PDE) for diffusion with particular boundary conditions to simulate a rainfall event. We developed a numerical integration scheme for the PDE, compared with the analytical solution. We adapt the fractal diffusion equation obtaining the gravimetric water content that we use as input of a triggering scheme based on Mohr-Coulomb limit-equilibrium criterion. This triggering is then complemented by a standard molecular dynamics algorithm, with an interaction force inspired by the Lennard-Jones potential, to update the positions and velocities of particles. We present our results for homogeneous and heterogeneous systems, i.e., systems composed by particles with same or different radius, respectively. Interestingly, in the heterogeneous case, we observe segregation effects due to the different volume of the particles. Finally, we analyze the parameter sensibility both for the triggering and the propagation phases. Our simulations confirm the results of a previous two-dimensional model and therefore the feasible applicability to real cases.

Dielectric and piezoelectric properties of percolative three-phase piezoelectric polymer composites

NASA Astrophysics Data System (ADS)

Sundar, Udhay

Three-phase piezoelectric bulk composites were fabricated using a mix and cast method. The composites were comprised of lead zirconate titanate (PZT), aluminum (Al) and an epoxy matrix. The volume fraction of the PZT and Al were varied from 0.1 to 0.3 and 0.0 to 0.17, respectively. The influences of three entities on piezoelectric and dielectric properties: inclusion of an electrically conductive filler (Al), poling process (contact and Corona) and Al surface treatment, were observed. The piezoelectric strain coefficient, d33, effective dielectric constant, epsilon r, capacitance, C, and resistivity were measured and compared according to poling process, volume fraction of constituent phases and Al surface treatment. The maximum values of d33 were 3.475 and 1.0 pC/N for Corona and contact poled samples respectively, for samples with volume fractions of 0.40 and 0.13 of PZT and Al (surface treated) respectively. Also, the maximum dielectric constant for the surface treated Al samples was 411 for volume fractions of 0.40 and 0.13 for PZT and Al respectively. The percolation threshold was observed to occur at an Al volume fraction of 0.13. The composites achieved a percolated state for Al volume fractions >0.13 for both contact and corona poled samples. In addition, a comparative time study was conducted to examine the influence of surface treatment processing time of Al particles. The effectiveness of the surface treatment, sample morphology and composition was observed with the aid of SEM and EDS images. These images were correlated with piezoelectric and dielectric properties. PZT-epoxy-aluminum thick films (200 mum) were also fabricated using a two-step spin coat deposition and annealing method. The PZT volume fraction were varied from 0.2, 0.3 and 0.4, wherein the Aluminum volume fraction was varied from 0.1 to 0.17 for each PZT volume fraction, respectively. The two-step process included spin coating the first layer at 500 RPM for 30 seconds, and the second layer at 1000 RPM for 1 minute. The piezoelectric strain coefficients d33 and d31, capacitance and the dielectric constant were measured, and were studied as a function of Aluminum volume fraction.

Statistical effects related to low numbers of reacting molecules analyzed for a reversible association reaction A + B = C in ideally dispersed systems: An apparent violation of the law of mass action

DOE Office of Scientific and Technical Information (OSTI.GOV)

Szymanski, R., E-mail: rszymans@cbmm.lodz.pl; Sosnowski, S.; Maślanka, Ł.

2016-03-28

Theoretical analysis and computer simulations (Monte Carlo and numerical integration of differential equations) show that the statistical effect of a small number of reacting molecules depends on a way the molecules are distributed among the small volume nano-reactors (droplets in this study). A simple reversible association A + B = C was chosen as a model reaction, enabling to observe both thermodynamic (apparent equilibrium constant) and kinetic effects of a small number of reactant molecules. When substrates are distributed uniformly among droplets, all containing the same equal number of substrate molecules, the apparent equilibrium constant of the association is highermore » than the chemical one (observed in a macroscopic—large volume system). The average rate of the association, being initially independent of the numbers of molecules, becomes (at higher conversions) higher than that in a macroscopic system: the lower the number of substrate molecules in a droplet, the higher is the rate. This results in the correspondingly higher apparent equilibrium constant. A quite opposite behavior is observed when reactant molecules are distributed randomly among droplets: the apparent association rate and equilibrium constants are lower than those observed in large volume systems, being the lower, the lower is the average number of reacting molecules in a droplet. The random distribution of reactant molecules corresponds to ideal (equal sizes of droplets) dispersing of a reaction mixture. Our simulations have shown that when the equilibrated large volume system is dispersed, the resulting droplet system is already at equilibrium and no changes of proportions of droplets differing in reactant compositions can be observed upon prolongation of the reaction time.« less

40 CFR 63.4730 - What records must I keep?

Code of Federal Regulations, 2010 CFR

2010-07-01

... to determine the mass fraction of organic HAP and density for each coating, thinner, and cleaning material and the volume fraction of coating solids for each coating. If you conducted testing to determine mass fraction of organic HAP, density, or volume fraction of coating solids, you must keep a copy of...

Bubble formation in water with addition of a hydrophobic solute.

PubMed

Okamoto, Ryuichi; Onuki, Akira

2015-07-01

We show that phase separation can occur in a one-component liquid outside its coexistence curve (CX) with addition of a small amount of a solute. The solute concentration at the transition decreases with increasing the difference of the solvation chemical potential between liquid and gas. As a typical bubble-forming solute, we consider O2 in ambient liquid water, which exhibits mild hydrophobicity and its critical temperature is lower than that of water. Such a solute can be expelled from the liquid to form gaseous domains while the surrounding liquid pressure is higher than the saturated vapor pressure p cx. This solute-induced bubble formation is a first-order transition in bulk and on a partially dried wall, while a gas film grows continuously on a completely dried wall. We set up a bubble free energy ΔG for bulk and surface bubbles with a small volume fraction ϕ. It becomes a function of the bubble radius R under the Laplace pressure balance. Then, for sufficiently large solute densities above a threshold, ΔG exhibits a local maximum at a critical radius and a minimum at an equilibrium radius. We also examine solute-induced nucleation taking place outside CX, where bubbles larger than the critical radius grow until attainment of equilibrium.

Continuum models of cohesive stochastic swarms: The effect of motility on aggregation patterns

NASA Astrophysics Data System (ADS)

Hughes, Barry D.; Fellner, Klemens

2013-10-01

Mathematical models of swarms of moving agents with non-local interactions have many applications and have been the subject of considerable recent interest. For modest numbers of agents, cellular automata or related algorithms can be used to study such systems, but in the present work, instead of considering discrete agents, we discuss a class of one-dimensional continuum models, in which the agents possess a density ρ(x,t) at location x at time t. The agents are subject to a stochastic motility mechanism and to a global cohesive inter-agent force. The motility mechanisms covered include classical diffusion, nonlinear diffusion (which may be used to model, in a phenomenological way, volume exclusion or other short-range local interactions), and a family of linear redistribution operators related to fractional diffusion equations. A variety of exact analytic results are discussed, including equilibrium solutions and criteria for unimodality of equilibrium distributions, full time-dependent solutions, and transitions between asymptotic collapse and asymptotic escape. We address the behaviour of the system for diffusive motility in the low-diffusivity limit for both smooth and singular interaction potentials and show how this elucidates puzzling behaviour in fully deterministic non-local particle interaction models. We conclude with speculative remarks about extensions and applications of the models.

Equilibrium Tin Isotope Fractionation during Metal-Sulfide-Silicate Differentiation: A Nuclear Resonant Inelastic X-ray Scattering Approach

NASA Astrophysics Data System (ADS)

Roskosz, M.; Amet, Q.; Fitoussi, C.; Laporte, D.; Hu, M. Y.; Alp, E. E.

2016-12-01

Metal-silicate differentiation was recently addressed through the insight of the isotopic composition of siderophile elements (mainly Fe, Si and Cr isotopes) of planetary and extraterrestrial bodies. A key limitation of this approach is however the knowledge of equilibrium fractionation factors between coexisting phases (metal alloys, silicates and sulfides) used to interpret data on natural samples. These properties are difficult to determine experimentally. In this context, tin is generally classified as a chalcophile element but it is also siderophile and volatile. We applied a synchrotron-based method to circumvent difficulties related to determination of equilibrium isotope fractionation. The nuclear resonant inelastic x-ray scattering (NRIXS) was used to measure the phonon excitation spectrum and then to derive the force constant and finally the fractionation factors of Sn-bearing geomaterials. Spectroscopic measurements were carried out at room pressure at Sector 30-ID (APS, USA). A range of Fe-Ni alloys, rhyolitic and basaltic glasses and iron sulfides containing isotopically enriched 119Sn were synthesized. The tin content and the redox conditions prevailing during the synthesis were varied. The data evaluation was carried out using PHOENIX and SciPhon programs. A strong effect of both the redox state and the tin content was measured. In addition, the composition of the silicate glasses was found to be another important factor determining the tin isotope metal-silicate-sulfide fractionation factors. Our results are consistent with trends previously observed in the case of iron isotopes [1,2]. We will discuss the implications of our experimental results in terms of tin isotope planetary signatures. References: [1] Dauphas et al. (2014), EPSL, 398, 127-140; [2] Roskosz et al. (2015), GCA, 169, 184-199.

Shape-retainment control using an antagonistic shape memory alloy system

NASA Astrophysics Data System (ADS)

Ikeda, T.; Sawamura, K.; Senba, A.; Tamayama, M.

2015-04-01

Since shape memory alloy (SMA) actuators can generate large force per unit weight, they are expected as one of the next generation actuators for aircraft. To keep a position of conventional control surfaces or morphing wings with SMA actuators, the SMA actuators must keep being heated, and the heating energy is not small. To save the energy, a new control method proposed for piezoelectric actuators utilizing hysteresis in deformation [Ikeda and Takahashi, Proc. SPIE 8689 (2013), 86890C] is applied to an antagonistic SMA system. By using the control method any position can be an equilibrium point within hysteresis of stress-strain diagrams. To confirm a feasibility of the control method, a fundamental experiment is performed. The SMA wires are heated by applying electric current to the wires. When a pulsed current is applied to the two SMA wires alternately, the equilibrium position changes between two positions alternately, and when a series of pulse whose amplitude increases gradually is applied to one SMA wire, the equilibrium position changes like a staircase. However, just after the pulse the position returns slightly, that is, overshoot takes place. To investigate such a behavior of the system, numerical simulation is also performed. The one-dimensional phase transformation model [Ikeda, Proc. SPIE 5757 (2005), 344-352] is used for a constitutive model of the SMA wires. The simulated result agrees with the experiment qualitatively, including the overshoot. By examining volume fraction of each phase, it is found that the overshoot is caused by that austenite phase transforms into stress-induced martensite phase during the cooling process after the pulse.

Structural mass irregularities and fiber volume influence on morphology and mechanical properties of unsaturated polyester resin in matrix composites

PubMed Central

Ahmed, Khalil; Nasir, Muhammad; Fatima, Nasreen; Khan, Khalid M.; Zahra, Durey N.

2014-01-01

This paper presents the comparative results of a current study on unsaturated polyester resin (UPR) matrix composites processed by filament winding method, with cotton spun yarn of different mass irregularities and two different volume fractions. Physical and mechanical properties were measured, namely ultimate stress, stiffness, elongation%. The mechanical properties of the composites increased significantly with the increase in the fiber volume fraction in agreement with the Counto model. Mass irregularities in the yarn structure were quantitatively measured and visualized by scanning electron microscopy (SEM). Mass irregularities cause marked decrease in relative strength about 25% and 33% which increases with fiber volume fraction. Ultimate stress and stiffness increases with fiber volume fraction and is always higher for yarn with less mass irregularities. PMID:26644920

Thermodynamic and transport properties of gaseous tetrafluoromethane in chemical equilibrium

NASA Technical Reports Server (NTRS)

Hunt, J. L.; Boney, L. R.

1973-01-01

Equations and in computer code are presented for the thermodynamic and transport properties of gaseous, undissociated tetrafluoromethane (CF4) in chemical equilibrium. The computer code calculates the thermodynamic and transport properties of CF4 when given any two of five thermodynamic variables (entropy, temperature, volume, pressure, and enthalpy). Equilibrium thermodynamic and transport property data are tabulated and pressure-enthalpy diagrams are presented.

Geometric confinement influences cellular mechanical properties I -- adhesion area dependence.

PubMed

Su, Judith; Jiang, Xingyu; Welsch, Roy; Whitesides, George M; So, Peter T C

2007-06-01

Interactions between the cell and the extracellular matrix regulate a variety of cellular properties and functions, including cellular rheology. In the present study of cellular adhesion, area was controlled by confining NIH 3T3 fibroblast cells to circular micropatterned islands of defined size. The shear moduli of cells adhering to islands of well defined geometry, as measured by magnetic microrheometry, was found to have a significantly lower variance than those of cells allowed to spread on unpatterned surfaces. We observe that the area of cellular adhesion influences shear modulus. Rheological measurements further indicate that cellular shear modulus is a biphasic function of cellular adhesion area with stiffness decreasing to a minimum value for intermediate areas of adhesion, and then increasing for cells on larger patterns. We propose a simple hypothesis: that the area of adhesion affects cellular rheological properties by regulating the structure of the actin cytoskeleton. To test this hypothesis, we quantified the volume fraction of polymerized actin in the cytosol by staining with fluorescent phalloidin and imaging using quantitative 3D microscopy. The polymerized actin volume fraction exhibited a similar biphasic dependence on adhesion area. Within the limits of our simplifying hypothesis, our experimental results permit an evaluation of the ability of established, micromechanical models to predict the cellular shear modulus based on polymerized actin volume fraction. We investigated the "tensegrity", "cellular-solids", and "biopolymer physics" models that have, respectively, a linear, quadratic, and 5/2 dependence on polymerized actin volume fraction. All three models predict that a biphasic trend in polymerized actin volume fraction as a function of adhesion area will result in a biphasic behavior in shear modulus. Our data favors a higher-order dependence on polymerized actin volume fraction. Increasingly better experimental agreement is observed for the tensegrity, the cellular solids, and the biopolymer models respectively. Alternatively if we postulate the existence of a critical actin volume fraction below which the shear modulus vanishes, the experimental data can be equivalently described by a model with an almost linear dependence on polymerized actin volume fraction; this observation supports a tensegrity model with a critical actin volume fraction.

Robust and novel two degree of freedom fractional controller based on two-loop topology for inverted pendulum.

PubMed

Dwivedi, Prakash; Pandey, Sandeep; Junghare, A S

2018-04-01

A rotary single inverted pendulum (RSIP) typically represents a space booster rocket, Segway and similar systems with unstable equilibrium. This paper proposes a novel two degree of freedom (2-DOF) fractional control strategy based on 2-loop topology for RSIP system which can be extended to control the systems with unstable equilibrium. It comprises feedback and feed-forward paths. Primary controller relates the perturbation attenuation while the secondary controller is accountable for set point tracking. To tune the parameters of proposed fractional controller a simple graphical tuning method based on frequency response is used. The study will serve the outstanding experimental results for both, stabilization and trajectory tracking tasks. The study will also serve to present a comparison of the performance of the proposed controller with the 1-DOF FOPID controller and sliding mode controller (SMC) for the RSIP system. Further to confirm the usability of the proposed controller and to avoid the random perturbations sensitivity, robustness, and stability analysis through fractional root-locus and Bode-plot is investigated. Copyright © 2018 ISA. Published by Elsevier Ltd. All rights reserved.

Kinetics of swelling of polyelectrolyte gels: Fixed degree of ionization

NASA Astrophysics Data System (ADS)

Sen, Swati; Kundagrami, Arindam

2015-12-01

The swelling kinetics of uncharged and charged polymer (polyelectrolyte) gels in salt-free conditions is studied in one dimension by solving the constitutive equation of motion (Newton's law for the elementary gel volume) of the displacement variable by two theoretical methods: one in which the classical definition of stress is used with the bulk modulus taken as a parameter, and the other in which a phenomenological expression of the osmotic stress as a function of polymer density and degree of ionization is taken as an input to the dynamics. The time-evolution profiles for spatially varying polymer density and stress, along with the location of the gel-solvent interface, are obtained from the two methods. We show that both the polymer density (volume fraction) and stress inside the gel follow expected behaviours of being maximum for the uniformly shrunken gel, and relaxing slowly to the lowest values as the gel approaches equilibrium. We further show that, by comparing the temporal profiles of the gel-solvent interface and other variables between the two methods, one may attempt to assign an effective bulk modulus to the polyelectrolyte gel as a function of the degree of ionization and other parameters of the gel such as hydrophobicity, cross-link density, and the temperature. The major result we get is that the effective bulk modulus of a polyelectrolyte gel increases monotonically with its degree of ionization. In the process of identifying the parameters for a monotonic swelling, we calculated using a well-known expression of the free energy the equilibrium results of two-phase co-existence and the critical point of a polyelectrolyte gel with a fixed degree of ionization.

Kinetics of swelling of polyelectrolyte gels: Fixed degree of ionization.

PubMed

Sen, Swati; Kundagrami, Arindam

2015-12-14

The swelling kinetics of uncharged and charged polymer (polyelectrolyte) gels in salt-free conditions is studied in one dimension by solving the constitutive equation of motion (Newton's law for the elementary gel volume) of the displacement variable by two theoretical methods: one in which the classical definition of stress is used with the bulk modulus taken as a parameter, and the other in which a phenomenological expression of the osmotic stress as a function of polymer density and degree of ionization is taken as an input to the dynamics. The time-evolution profiles for spatially varying polymer density and stress, along with the location of the gel-solvent interface, are obtained from the two methods. We show that both the polymer density (volume fraction) and stress inside the gel follow expected behaviours of being maximum for the uniformly shrunken gel, and relaxing slowly to the lowest values as the gel approaches equilibrium. We further show that, by comparing the temporal profiles of the gel-solvent interface and other variables between the two methods, one may attempt to assign an effective bulk modulus to the polyelectrolyte gel as a function of the degree of ionization and other parameters of the gel such as hydrophobicity, cross-link density, and the temperature. The major result we get is that the effective bulk modulus of a polyelectrolyte gel increases monotonically with its degree of ionization. In the process of identifying the parameters for a monotonic swelling, we calculated using a well-known expression of the free energy the equilibrium results of two-phase co-existence and the critical point of a polyelectrolyte gel with a fixed degree of ionization.

Laser-Induced Incandescence Measurements in Low Gravity

NASA Technical Reports Server (NTRS)

VanderWal, R. L.

1997-01-01

A low-gravity environment offers advantages to investigations concerned with soot growth or flame radiation by eliminating of buoyancy-induced convection. Basic to each type of study is knowledge of spatially resolved soot volume fraction, (f(sub v). Laser-induced incandescence (LII) has emerged as a diagnostic for soot volume fraction determination because it possesses high temporal and spatial resolution, geometric versatility and high sensitivity. Implementation and system characterization of LII in a drop tower that provides 2.2 sec of low-gravity (micro)g) at the NASA Lewis Research Center are described here. Validation of LII for soot volume fraction determination in (micro)g is performed by comparison between soot volume fraction measurements obtained by light extinction [20] and LII in low-gravity for a 50/50 mixture (by volume) of 0 acetylene/nitrogen issuing into quiescent air. Quantitative soot volume fraction measurements within other laminar flames of ethane and propane and a turbulent diffusion flame in (micro)g via LII are also demonstrated. An analysis of LII images of a turbulent acetylene diffusion flame in 1-g and (micro)g is presented.

Spinel-olivine-pryoxene equilibrium iron isotopic fractionation and applications to natural peridotites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roskosz, Mathieu; Sio, Corliss K. I.; Dauphas, Nicolas

2015-11-15

Eight spinel-group minerals were synthesized by a flux-growth method producing spinels with varying composition and Fe3+/Fe-tot ratios. The mean force constants of iron bonds in these minerals were determined by synchrotron nuclear resonant inelastic X-ray scattering (NRIXS) in order to determine the reduced isotopic partition function ratios (beta-factors) of these spinels. The mean force constants are strongly dependent on the Fe3+/Fe-tot of the spinel but are independent, or weakly dependent on other structural and compositional parameters. From our spectroscopic data, it is found that a single redox-dependent calibration line accounts for the effects of Fe3+/Fe-tot on the beta-factors of spinels.more » This calibration successfully describes the equilibrium Fe isotopes fractionation factors between spinels and silicates (olivine and pyroxenes). Our predictions are in excellent agreement with independent determinations for the equilibrium Fe isotopic fractionations for the magnetite- fayalite and the magnetite-hedenbergite couples. Our calibration applies to the entire range of Fe3+/Fe-tot ratios found in natural spinels and provides a basis for interpreting iron isotopic variations documented in mantle peridotites. Except for a few exceptions, most of the samples measured so far are in isotopic disequilibrium, reflecting metasomatism and partial melting processes.« less

Diurnal variations of radon and thoron activity concentrations and effective doses in dwellings in Niška Banja, Serbia.

PubMed

Vaupotič, J; Streil, T; Tokonami, S; Žunic, Z S

2013-12-01

In Niška Banja, a spa town in a radon-prone area in southern Serbia, radon ((222)Rn) and thoron ((220)Rn) activity concentrations were measured continuously for one day in indoor air of 10 dwellings with a SARAD RTM 2010-2 Radon/Thoron Monitor, and equilibrium factor between radon and its decay products and the fraction of unattached radon decay products with a SARAD EQF 3020-2 Equilibrium Factor Monitor. Radon concentration in winter time ranged from 26 to 73 100 Bq m(-3) and that of thoron, from 10 to 8650 Bq m(-3). In the same period, equilibrium factor and the unattached fraction varied in the range of 0.08 to 0.90 and 0.01 to 0.27, respectively. One-day effective doses were calculated and were in winter conditions from 4 to 2599 μSv d(-1) for radon and from 0.2 to 73 μSv d(-1) for thoron.

Effects of various assumptions on the calculated liquid fraction in isentropic saturated equilibrium expansions

NASA Technical Reports Server (NTRS)

Bursik, J. W.; Hall, R. M.

1980-01-01

The saturated equilibrium expansion approximation for two phase flow often involves ideal-gas and latent-heat assumptions to simplify the solution procedure. This approach is well documented by Wegener and Mack and works best at low pressures where deviations from ideal-gas behavior are small. A thermodynamic expression for liquid mass fraction that is decoupled from the equations of fluid mechanics is used to compare the effects of the various assumptions on nitrogen-gas saturated equilibrium expansion flow starting at 8.81 atm, 2.99 atm, and 0.45 atm, which are conditions representative of transonic cryogenic wind tunnels. For the highest pressure case, the entire set of ideal-gas and latent-heat assumptions are shown to be in error by 62 percent for the values of heat capacity and latent heat. An approximation of the exact, real-gas expression is also developed using a constant, two phase isentropic expansion coefficient which results in an error of only 2 percent for the high pressure case.

Modelling Equilibrium and Fractional Crystallization in the System MgO-FeO-CaO-Al2O3-SiO2

NASA Technical Reports Server (NTRS)

Herbert, F.

1985-01-01

A mathematical modelling technique for use in petrogenesis calculations in the system MgO-FeO-CaO-Al2O3-SiO2 is reported. Semiempirical phase boundary and elemental distribution information was combined with mass balance to compute approximate equilibrium crystallization paths for arbitrary system compositions. The calculation is applicable to a range of system compositions and fractionation calculations are possible. The goal of the calculation is the computation of the composition and quantity of each phase present as a function of the degree of solidification. The degree of solidification is parameterized by the heat released by the solidifying phases. The mathematical requirement for the solution of this problem is: (1) An equation constraining the composition of the magma for each solid phase in equilibrium with the liquidus phase, and (2) an equation for each solid phase and each component giving the distribution of that element between that phase and the magma.

Quantification of skeletal fraction volume of a soil pit by means of photogrammetry

NASA Astrophysics Data System (ADS)

Baruck, Jasmin; Zieher, Thomas; Bremer, Magnus; Rutzinger, Martin; Geitner, Clemens

2015-04-01

The grain size distribution of a soil is a key parameter determining soil water behaviour, soil fertility and land use potential. It plays an important role in soil classification and allows drawing conclusions on landscape development as well as soil formation processes. However, fine soil material (i.e. particle diameter ≤2 mm) is usually documented more thoroughly than the skeletal fraction (i.e. particle diameter >2 mm). While fine soil material is commonly analysed in the laboratory in order to determine the soil type, the skeletal fraction is typically estimated in the field at the profile. For a more precise determination of the skeletal fraction other methods can be applied and combined. These methods can be volume-related (sampling rings, percussion coring tubes) or non-volume-related (sieve of spade excavation). In this study we present a framework for the quantification of skeletal fraction volumes of a soil pit by means of photogrammetry. As a first step 3D point clouds of both soil pit and skeletal grains were generated. Therefore all skeletal grains of the pit were spread out onto a plane, clean plastic sheet in the field and numerous digital photos were taken using a reflex camera. With the help of the open source tool VisualSFM (structure from motion) two scaled 3D point clouds were derived. As a second step the skeletal fraction point cloud was segmented by radiometric attributes in order to determine volumes of single skeletal grains. The comparison of the total skeletal fraction volume with the volume of the pit (closed by spline interpolation) yields an estimate of the volumetric proportion of skeletal grains. The presented framework therefore provides an objective reference value of skeletal fraction for the support of qualitative field records.

40 CFR 63.3930 - What records must I keep?

Code of Federal Regulations, 2011 CFR

2011-07-01

... formulation data, or test data used to determine the mass fraction of organic HAP and density for each coating... coating. If you conducted testing to determine mass fraction of organic HAP, density, or volume fraction... rather than a record of the volume used. (e) A record of the mass fraction of organic HAP for each...

Empirical calibration of the clinopyroxene-garnet magnesium isotope geothermometer and implications

NASA Astrophysics Data System (ADS)

Li, Wang-Ye; Teng, Fang-Zhen; Xiao, Yilin; Gu, Hai-Ou; Zha, Xiang-Ping; Huang, Jian

2016-07-01

The large equilibrium Mg isotope fractionation between clinopyroxene and garnet observed in eclogites makes it a potential high-precision geothermometer, but calibration of this thermometer by natural samples is still limited. Here, we report Mg isotopic compositions of eclogite whole rocks as well as Mg and O isotopic compositions of clinopyroxene and garnet separates from 16 eclogites that formed at different temperatures from the Dabie orogen, China. The whole-rock δ26Mg values vary from -1.20 to +0.10 ‰. Among them, 11 samples display limited δ26Mg variations from -0.36 to -0.17 ‰, similar to those of their protoliths. The mineral separates exhibit very different δ26Mg values, from -0.39 to +0.39 ‰ for clinopyroxenes and from -1.94 to -0.81 ‰ for garnets. The clinopyroxene-garnet Mg isotope fractionation (Δ26Mgclinopyroxene-garnet = δ26Mgclinopyroxene-δ26Mggarnet) varies from 1.05 to 2.15 ‰. The clinopyroxene-garnet O isotope fractionation (Δ18Oclinopyroxene-garnet = δ18Oclinopyroxene-δ18Ogarnet) varies from -1.01 to +0.98 ‰. Equilibrium Mg isotope fractionation between clinopyroxene and garnet in the investigated samples is selected based on both the δ26Mgclinopyroxene versus δ26Mggarnet plot and the state of O isotope equilibrium between clinopyroxene and garnet. The equilibrium Δ26Mgclinopyroxene-garnet and corresponding temperature data obtained in this study, together with those available so far in literatures for natural eclogites, are used to calibrate the clinopyroxene-garnet Mg isotope thermometer. This yields a function of Δ26Mgclinopyroxene-garnet = (0.99 ± 0.06) × 106/ T 2, where T is temperature in Kelvin. The refined function not only provides the best empirically calibrated clinopyroxene-garnet Mg isotope thermometer for precise constraints of temperatures of clinopyroxene- and garnet-bearing rocks, but also has potential applications in high-temperature Mg isotope geochemistry.

Free Vibration Characteristics of Functionally Graded Pre-twisted Conical Shells under Rotation

NASA Astrophysics Data System (ADS)

Das, Apurba; Karmakar, Amit

2017-06-01

This article deals with effect of rotation and pretwist angle on free vibration characteristics of functionally graded conical shells. The dynamic equilibrium equation is derived from Lagrange's equation neglecting the Coriolis effect for moderate rotational speeds. The materials properties of conical shell are varied with a power-law distribution of the volume fractions of their constituents through its thickness. Convergence studies are performed in respect of mesh sizes, and comparisons of the present solutions and those reported in open literature are provided to substantiate the accuracy of the proposed method. Computer codes developed to obtain the numerical results for the combined effects of twist angle and rotational speed on the natural frequencies of functionally graded conical shells. The mode shapes for a typical laminate configuration under different conditions are also illustrated. Numerical results are obtained for the non-dimensional fundamental (NDFF) and second frequencies (NDSF).

Droplet size in flow: Theoretical model and application to polymer blends

NASA Astrophysics Data System (ADS)

Fortelný, Ivan; Jůza, Josef

2017-05-01

The paper is focused on prediction of the average droplet radius, R, in flowing polymer blends where the droplet size is determined by dynamic equilibrium between the droplet breakup and coalescence. Expressions for the droplet breakup frequency in systems with low and high contents of the dispersed phase are derived using available theoretical and experimental results for model blends. Dependences of the coalescence probability, Pc, on system parameters, following from recent theories, is considered and approximate equation for Pc in a system with a low polydispersity in the droplet size is proposed. Equations for R in systems with low and high contents of the dispersed phase are derived. Combination of these equations predicts realistic dependence of R on the volume fraction of dispersed droplets, φ. Theoretical prediction of the ratio of R to the critical droplet radius at breakup agrees fairly well with experimental values for steadily mixed polymer blends.

Influence of primary α-phase volume fraction on the mechanical properties of Ti-6Al-4V alloy at different strain rates and temperatures

NASA Astrophysics Data System (ADS)

Ren, Yu; Zhou, Shimeng; Luo, Wenbo; Xue, Zhiyong; Zhang, Yajing

2018-03-01

Bimodal microstructures with primary α-phase volume fractions ranging from 14.3% to 57.1% were gained in Ti-6Al-4V (Ti-64) alloy through annealed in two-phase region at various temperatures below the β-transus point. Then the influence of the primary α-phase volume fraction on the mechanical properties of Ti-64 were studied. The results show that, at room temperature and a strain rate of 10‑3 s‑1, the yield stress decreases but the fracture strain augments with added primary α-phase volume fraction. The equiaxed primary α-phase possesses stronger ability to coordinate plastic deformation, leading to the improvement of the ductile as well as degradation of the strength of Ti-64 with higher primary α-phase volume fraction. As the temperature goes up to 473 K, the quasi-static yield stress and ultimate strength decrease first and then increase with the incremental primary α-phase volume fraction, due to the interaction between the work hardening and the softening caused by the DRX and the growth of the primary α-phase. At room temperature and a strain rate of 3×103 s‑1, the varying pattern of strength with the primary α-phase volume fraction resembles that at a quasi-static strain rate. However, the flow stress significantly increases but the strain-hardening rate decreases compared to those at quasi-static strain rate due to the competition between the strain rate hardening and the thermal softening during dynamic compression process.

Pressure-dependent boron isotopic fractionation observed by column chromatography

NASA Astrophysics Data System (ADS)

Musashi, M.; Oi, T.; Matsuo, M.; Nomura, M.

2007-12-01

Boron isotopic fractionation factor ( S ) between boron taken up in strongly basic anion exchange resin and boron in aqueous solution was determined by breakthrough column chromatography at 5 and 17 MPa at 25°C, using 0.1 mmol/L boric acid solution as feed solution. The S values obtained were 1.018 and 1.012, respectively, which were smaller than the value reported by using the same chromatographic method at atmospheric pressure at 25°C with the boron concentration of 10 mmol/L, but were larger than the values at the same condition with much higher concentration of 100 and 501 mmol/L, indicating that borate-polymerization reducing the isotopic fractionation was negligible. However, calculations based on the theory of isotope distribution between two phases estimated that 21% (5MPa) and 47% (17MPa) of boron taken up in the resin phase was in the three-coordinated B(OH)3-form, instead of in the four-coordinated B(OH)4--form, at high pressures even with the very diluted solution. We discussed this discrepancy by introducing (1) hydration or (2) a partial molar volume difference between isotopic molecules. It was inferred that borate ions were partially dehydrated upon transfer from the solution phase to the resin phase at high pressures, which resulted in smaller S values compared with those at the atmospheric pressure. Alternatively, it was likely that the S value decreased with increasing pressure, because the difference of the partial isotopic molar volumes between 10B(OH)3 and 11B(OH)3 was larger than that between 10B(OH)4- and 11B(OH)4-. If either will be the case, the influence of a pressure upon the isotope effect may not be negligible for boron isotopic exchange equilibrium. This knowledge is crucial for the principle of the boron isotopic pH-metry reconstructing a chemical variation at the paleo-deep oceanic environment where the early life may have been evolved.

Do volcanic gases represent equilibrium volatile concentrations? Some insights from a model of diffusive fractionation during rapid bubble growth

NASA Astrophysics Data System (ADS)

Baker, D. R.

2012-12-01

Measurements of volcanic gas compositions are often presumed to be directly related to equilibrium compositions of fluids exsolved at depth in magmatic systems that rapidly escape into the atmosphere. In particular, changes in the ratios of volatile species concentrations in volcanic gases have been interpreted to reflect influx of new magma batches or changes in the degassing depth. However, other mechanisms can also yield changes in volcanic gas compositions. One such mechanism is diffusive fractionation during rapid bubble growth. Such fractionation can occur because radial growth rates of bubbles in magmas are estimated to be in the range of 10-6 to 10-3 m s-1 and diffusion coefficients of minor volatiles (e.g., Cl, F, S, CO2) are orders of magnitude slower, 10-12 to 10-9 m2 s-1. Thus a bubble that rapidly grows and subsequently loses its volatiles to the surface may contribute a fluid sample whose concentration is affected by the interplay between the kinetics of bubble growth and volatile diffusion in the melt. A finite difference code was developed to calculate the effects of rapid bubble growth on the concentration of minor elements in the bubble for a spherical growth geometry. The bubble is modeled with a fixed growth rate and a constant equilibrium fluid-melt partition coefficient, KD. Bubbles were modeled to grow to a radius of 50 μm, the size at which the dominant bubble growth mechanism appears to change from diffusion to coalescence. The critical variables that control the departure from equilibrium behavior are the K D and the ratio of the growth velocity, V, to the diffusivity, D. Modeling bubble growth in a magma chamber at 100 MPa demonstrates that when KD is in the range of 10 to 1000 at low V/D values (e.g., 103 m-1) the composition of the fluid is at, or near, equilibrium with the melt. However, as V/D increases the bubble composition deviates increasingly from equilibrium. For V/D ratios of 105 and equilibrium KD's of either 50 or 100 (similar to estimates for S), a bubble with a 50 μm radius will contain a fluid whose concentration was apparently determined by a KD of less than 10. These models also demonstrate that the combination of rapid bubble growth with slow diffusion can deplete the melt in the volatile species only within the immediate neighborhood, on the order of 100 μm. If bubbles are spaced further apart the melts may retain significant concentrations of dissolved volatiles, which could lead to secondary and tertiary nucleation events. These models for diffusive fractionation during rapid bubble growth suggest that changes in the ratios of minor elements in volcanic gases may be influenced by bubble growth rate changes. Volatiles with lower diffusivities and volatiles with very high or very low partition coefficients will be more influenced by this process. Diffusive fractionation may be responsible for the drop in the CO2/SO2 ratios sometimes observed prior to large eruptions of Stromboli volcano.

Application of a novel sorting system for equine mesenchymal stem cells (MSCs)

PubMed Central

Radtke, Catherine L.; Nino-Fong, Rodolfo; Esparza Gonzalez, Blanca P.; McDuffee, Laurie A.

2014-01-01

The objective of this study was to validate non-equilibrium gravitational field-flow fractionation (GrFFF), an immunotag-less method of sorting mesenchymal stem cells (MSCs) into subpopulations, for use with MSCs derived from equine muscle tissue, periosteal tissue, bone marrow, and adipose tissue. Cells were collected from 6 young, adult horses, postmortem. Cells were isolated from left semitendinosus muscle tissue, periosteal tissue from the distomedial aspect of the right tibia, bone marrow aspirates from the fourth and fifth sternebrae, and left supragluteal subcutaneous adipose tissue. Aliquots of 800 × 103 MSCs from each tissue source were separated and injected into a ribbon-like capillary device by continuous flow (GrFFF proprietary system). Cells were sorted into 6 fractions and absorbencies [optical density (OD)] were read. Six fractions from each of the 6 aliquots were then combined to provide pooled fractions that had adequate cell numbers to seed at equal concentrations into assays. Equine muscle tissue-derived, periosteal tissue-derived, bone marrow-derived, and adipose tissue-derived mesenchymal stem cells were consistently sorted into 6 fractions that remained viable for use in further assays. Fraction 1 had more cuboidal morphology in culture when compared to the other fractions. Statistical analysis of the fraction absorbencies (OD) revealed a P-value of < 0.05 when fractions 2 and 3 were compared to fractions 1, 4, 5, and 6. It was concluded that non-equilibrium GrFFF is a valid method for sorting equine muscle tissue-derived, periosteal tissue-derived, bone marrow-derived, and adipose tissue-derived mesenchymal stem cells into subpopulations that remain viable, thus securing its potential for use in equine stem cell applications and veterinary medicine. PMID:25355998

Molecular structure of liquid alcohols

NASA Astrophysics Data System (ADS)

Huyskens, P.

1983-07-01

A new thermodynamic treatment of continuous association is presented, where the various equilibria between i-mers are replaced by a single equilibrium between an OH groups in the bonded and the non-bonded states, linked in both cases to an indefinite ensemble of molecules. The treatment leads to an association constant K which differs from those considered in the theories of Kretschmer and Wiebe and of Wiehe and Bagley. For pure alcohols the association constant can be estimated from the vapor pressure of the alcohol and that of the homomorphous hydrocarbon. The fraction γ of free OH groups determined in this way is markedly smaller than those calculated from the other theories. For the normal alcohols the product K VA is approximately constant at a given temperature, VA being the molar volume. This can be expected from the increasing of the standard entropy of the non-bonded molecules when the molecular volume increases. For secondary and tertiary alcohols the product K VA is significantly lower due to steric hindrances. However for all the alcohols considered here the enthalpy of the hydrogen bond remains nearly constant — δ H being equal to 24.8 ± 2 kJ mol -1.

Modeling the Capillary Pressure for the Migration of the Liquid Phase in Granular Solid-Liquid-Vapor Systems: Application to the Control of the Composition Profile in W-Cu FGM Materials

NASA Astrophysics Data System (ADS)

Missiaen, Jean-Michel; Raharijaona, Jean-Joël; Delannay, Francis

2016-11-01

A model is developed to compute the capillary pressure for the migration of the liquid phase out or into a uniform solid-liquid-vapor system. The capillary pressure is defined as the reduction of the overall interface energy per volume increment of the transferred fluid phase. The model takes into account the particle size of the solid particle aggregate, the packing configuration (coordination number, porosity), the volume fractions of the different phases, and the values of the interface energies in the system. The model is used for analyzing the stability of the composition profile during processing of W-Cu functionally graded materials combining a composition gradient with a particle size gradient. The migration pressure is computed with the model in two stages: (1) just after the melting of copper, i.e., when sintering and shape accommodation of the W particle aggregate can still be neglected and (2) at high temperature, when the system is close to full density with equilibrium particle shape. The model predicts well the different stages of liquid-phase migration observed experimentally.

Testing the paradigms of the glass transition in colloids

NASA Astrophysics Data System (ADS)

Zia, Roseanna; Wang, Jialun; Peng, Xiaoguang; Li, Qi; McKenna, Gregory

2017-11-01

Many molecular liquids freeze upon fast enough cooling. This so-called glass state is path dependent and out of equilibrium, as measured by the Kovacs signature experiments, i.e. intrinsic isotherms, asymmetry of approach and memory effect. The reasons for this path- and time-dependence are not fully understood, due to fast molecular relaxations. Colloids provide a natural way to model such behavior, owing to disparity in colloidal versus solvent time scales that can slow dynamics. To shed light on the ambiguity of glass transition, we study via large-scale dynamic simulation of hard-sphere colloidal glass after volume-fraction jumps, where particle size increases at fixed system volume followed by protocols of the McKenna-Kovacs signature experiments. During and following each jump, the positions, velocities, and particle-phase stress are tracked and utilized to characterize relaxation time scales. The impact of both quench depth and quench rate on arrested dynamics and ``state'' variables is explored. In addition, we expand our view to various structural signatures, and rearrangement mechanism is proposed. The results provide insight into not only the existence of an ``ideal'' glass transition, but also the role of structure in such a dense amorphous system.

Thermobarometry of mafic igneous rocks based on clinopyroxene-liquid equilibria, 0 30 kbar

NASA Astrophysics Data System (ADS)

Putirka, K.; Johnson, Marie; Kinzler, Rosamond; Longhi, John; Walker, David

1996-02-01

Models for estimating the pressure and temperature of igneous rocks from co-existing clino-pyroxene and liquid compositions are calibrated from existing data and from new data obtained from experiments performed on several mafic bulk compositions (from 8 30 kbar and 1100 1475° C). The resulting geothermobarometers involve thermodynamic expressions that relate temperature and pressure to equilibrium constants. Specifically, the jadeite (Jd; NaAlSi2O6) diopside/hedenbergite (DiHd; Ca(Mg, Fe) Si2O6) exchange equilibrium between clinopyroxene and liquid is temperature sensitive. When compositional corrections are made to the calibrated equilibrium constant the resulting geothermometer is (i) 104 T=6.73-0.26* ln [Jdpx*Caliq*FmliqDiHdpx*Naliq*Alliq] -0.86* ln [MgliqMgliq+Feliq]+0.52*ln [Caliq] an expression which estimates temperature to ±27 K. Compared to (i), the equilibrium constant for jadeite formation is more sensitive to pressure resulting in a thermobarometer (ii) P=-54.3+299* T104+36.4* T104 ln [Jdpx[Siliq]2*Naliq*Alliq] +367*[Naliq*Alliq] which estimates pressure to ± 1.4 kbar. Pressure is in kbar, T is in Kelvin. Quantities such as Naliq represent the cation fraction of the given oxide (NaO0.5) in the liquid and Fm=MgO+FeO. The mole fractions of Jd and diopside+hedenbergite (DiHd) components are calculated from a normative scheme which assigns the lesser of Na or octahedral Al to form Jd; any excess AlVI forms Calcium Tschermak’s component (CaTs; CaAlAlSiO6); Ca remaining after forming CaTs and CaTiAl2O6 is taken as DiHd. Experimental data not included in the regressions were used to test models (i) and (ii). Error on predictions of T using model (i) is ±40 K. A pressure-dependent form of (i) reduces this error to ±30 K. Using model (ii) to predict pressures, the error on mean values of 10 isobaric data sets (0 25 kbar, 118 data) is ±0.3 kbar. Calculating thermodynamic properties from regression coefficients in (ii) gives VJd f of 23.4 ±1.3 cm3/mol, close to the value anticipated from bar molar volume data (23.5 cm3/mol). Applied to clinopyroxene phenocrysts from Mauna Kea, Hawaii lavas, the expressions estimate equilibration depths as great as 40 km. This result indicates that transport was sufficiently rapid that at least some phenocrysts had insufficient time to re-equilibrate at lower pressures.

Constitutive modeling of the rheological behavior of platelet suspensions

NASA Astrophysics Data System (ADS)

Sommer, Drew E.

Compression molding of chopped fiber composites is used to manufacture complex 3D geometries with high fiber volume fractions of 50-60% and long, discontinuous fibers and thermoplastic matrices. When prepreg, chopped into platelets, is used as a charge material, the individual platelets remain intact during the molding process and flow relative to one another, as experimental observations show. Heterogeneity of the platelet/resin suspension cannot be considered at the structural scale of molding simulation. Instead, the suspension should be idealized into the homogenized anisotropic and viscous system which obeys the prescribed anisotropic stress-strain rate constitutive relation. The viscosity tensor of the aforementioned constitutive law was analytically evaluated in this work through the representative volume element (RVE) based analysis. An idealized microstructure of platelets was developed to perform such an analysis. The platelets were aligned and arranged in a planar configuration with periodic boundary conditions. Analytic expressions for the effective, anisotropic viscosities were derived by micromechanical analysis for the idealized microstructure of rigid platelets. In this analysis, the load transfer mechanisms and their contribution to the viscosity of the platelet assembly were investigated. The kinematic assumption of linear velocity distributions consistent with the mechanism of shearing rate was adopted. While the platelets were assumed to be rigid, the resin was taken as an incompressible, isotropic fluid which provided for the platelet-to-platelet load transfer. Strain rate and temperature dependence were included by modeling the polymer matrix as a Carreau fluid. Shear strain in the resin was developed due to the relative motion of adjacent platelets. The resin shear strain rate was expressed in terms of the corresponding platelet velocities. Equilibrium of the platelet was used to relate the applied far-field stress to the average strain rate through the viscosity of neat resin and geometric parameters of the RVE constituents. When combined, these parameters defined the effective homogenized viscosities of an anisotropic system equivalent to the platelet/resin suspension. The expressions for the effective viscosities were found to be dependent on the platelet geometry, stack geometry, the platelet volume fraction and the viscosity of neat resin. In this study, the platelet volume fraction was defined as the volume of platelets within the RVE divided by the RVE volume and discriminated from the fiber volume fraction within a platelet. An approach using the "viscous solid analogy'' was developed to leverage structural finite element methods to predict homogenized viscosities of the platelet assembly. A finite element model was constructed to develop a comparison to the analytic expressions for rigid platelets and include the effect of deformation within the platelets. To compare with the analytic expressions, large viscosities were prescribed for the platelet to approximate rigidity. The properties of the deformable platelets were determined by an approach proposed by Pipes and co-workers. The assumption of rigidity was found to be approximate except in the case of elongation along the fiber direction. A laminate analogy was implemented as a homogenization tool to include the effect of orientation on the apparent viscosities of a multi-axial platelet assembly. The aligned platelet suspension was used to predict the `pseudo-ply' properties. Pseudo-laminates, which were assumed to approximate the microstructure, were developed. The effective `pseudo-laminate' viscosities were predicted with classical lamination theory.

Computational Characterization of Impact Induced Multi-Scale Dissipation in Reactive Solid Composites

DTIC Science & Technology

2016-07-01

Predicted variation in (a) hot-spot number density , (b) hot-spot volume fraction, and (c) hot-spot specific surface area for each ensemble with piston speed...packing density , characterized by its effective solid volume fraction φs,0, affects hot-spot statistics for pressure dominated waves corresponding to...distribution in solid volume fraction within each ensemble was nearly Gaussian, and its standard deviation decreased with increasing density . Analysis of

The dense gas mass fraction of molecular clouds in the Milky Way

DOE Office of Scientific and Technical Information (OSTI.GOV)

Battisti, Andrew J.; Heyer, Mark H., E-mail: abattist@astro.umass.edu, E-mail: heyer@astro.umass.edu

2014-01-10

The mass fraction of dense gas within giant molecular clouds (GMCs) of the Milky Way is investigated using {sup 13}CO data from the Five College Radio Astronomy Observatory Galactic Plane Surveys and the Bolocam Galactic Plane Survey (BGPS) of 1.1 mm dust continuum emission. A sample of 860 compact dust sources are selected from the BGPS catalog and kinematically linked to 344 clouds of extended (>3') {sup 13}CO J = 1-0 emission. Gas masses are tabulated for the full dust source and subregions within the dust sources with mass surface densities greater than 200 M {sub ☉} pc{sup –2}, whichmore » are assumed to be regions of enhanced volume density. Masses of the parent GMCs are calculated assuming optically thin {sup 13}CO J = 1-0 emission and local thermodynamic equilibrium conditions. The mean fractional mass of dust sources to host GMC mass is 0.11{sub −0.06}{sup +0.12}. The high column density subregions comprise 0.07{sub −0.05}{sup +0.13} of the mass of the cloud. Owing to our assumptions, these values are upper limits to the true mass fractions. The fractional mass of dense gas is independent of GMC mass and gas surface density. The low dense gas mass fraction suggests that the formation of dense structures within GMCs is the primary bottleneck for star formation. The distribution of velocity differences between the dense gas and the low density material along the line of sight is also examined. We find a strong, centrally peaked distribution centered on zero velocity displacement. This distribution of velocity differences is modeled with radially converging flows toward the dense gas position that are randomly oriented with respect to the observed line of sight. These models constrain the infall velocities to be 2-4 km s{sup –1} for various flow configurations.« less

Lamb Wave Assessment of Fiber Volume Fraction in Composites

NASA Technical Reports Server (NTRS)

Seale, Michael D.; Smith, Barry T.; Prosser, W. H.; Zalameda, Joseph N.

1998-01-01

Among the various techniques available, ultrasonic Lamb waves offer a convenient method of examining composite materials. Since the Lamb wave velocity depends on the elastic properties of a material, an effective tool exists to evaluate composites by measuring the velocity of these waves. Lamb waves can propagate over long distances and are sensitive to the desired in-plane elastic properties of the material. This paper discusses a study in which Lamb waves were used to examine fiber volume fraction variations of approximately 0.40-0.70 in composites. The Lamb wave measurements were compared to fiber volume fractions obtained from acid digestion tests. Additionally, a model to predict the fiber volume fraction from Lamb wave velocity values was evaluated.

Widely Tunable Morphologies in Block Copolymer Thin Films Through Solvent Vapor Annealing Using Mixtures of Selective Solvents

PubMed Central

Chavis, Michelle A.; Smilgies, Detlef-M.; Wiesner, Ulrich B.; Ober, Christopher K.

2015-01-01

Thin films of block copolymers are extremely attractive for nanofabrication because of their ability to form uniform and periodic nanoscale structures by microphase separation. One shortcoming of this approach is that to date the design of a desired equilibrium structure requires synthesis of a block copolymer de novo within the corresponding volume ratio of the blocks. In this work, we investigated solvent vapor annealing in supported thin films of poly(2-hydroxyethyl methacrylate)-block-poly(methyl methacrylate) [PHEMA-b-PMMA] by means of grazing incidence small angle X–ray scattering (GISAXS). A spin-coated thin film of lamellar block copolymer was solvent vapor annealed to induce microphase separation and improve the long-range order of the self-assembled pattern. Annealing in a mixture of solvent vapors using a controlled volume ratio of solvents (methanol, MeOH, and tetrahydrofuran, THF), which are chosen to be preferential for each block, enabled selective formation of ordered lamellae, gyroid, hexagonal or spherical morphologies from a single block copolymer with a fixed volume fraction. The selected microstructure was then kinetically trapped in the dry film by rapid drying. To our knowledge, this paper describes the first reported case where in-situ methods are used to study the transition of block copolymer films from one initial disordered morphology to four different ordered morphologies, covering much of the theoretical diblock copolymer phase diagram. PMID:26819574

Estimation of the fractional coverage of rainfall in climate models

NASA Technical Reports Server (NTRS)

Eltahir, E. A. B.; Bras, R. L.

1993-01-01

The fraction of the grid cell area covered by rainfall, mu, is an essential parameter in descriptions of land surface hydrology in climate models. A simple procedure is presented for estimating this fraction, based on extensive observations of storm areas and rainfall volumes. Storm area and rainfall volume are often linearly related; this relation can be used to compute the storm area from the volume of rainfall simulated by a climate model. A formula is developed for computing mu, which describes the dependence of the fractional coverage of rainfall on the season of the year, the geographical region, rainfall volume, and the spatial and temporal resolution of the model. The new formula is applied in computing mu over the Amazon region. Significant temporal variability in the fractional coverage of rainfall is demonstrated. The implications of this variability for the modeling of land surface hydrology in climate models are discussed.

Predictions and Tests of the "Late Noachian Icy Highlands" Climate Model: Can Evidence for Fluvial/Lacustrine Systems Be Reconciled?

NASA Astrophysics Data System (ADS)

Head, J. W., III

2016-12-01

Improved 3D global simulations (GCMs) of the early martian climate have found that for atmospheric pressures greater than a fraction of a bar, atmospheric-surface thermal coupling occurs and the adiabatic cooling effect (ACE) causes temperatures in the southern uplands to fall significantly below the global average. Long-term climate evolution simulations indicate that in these circumstances, water ice is transported to the highlands from low-lying regions for a wide range of obliquities. Conditions are too cold (MAT 225 K) to permit the presence of long-term surface liquid water, including streams, lakes and oceans. The LNIH equilibrium state predicts: 1) a global permafrost layer, 2) a horizontally stratified hydrological cycle/system, 3) thick ice deposits in the southern uplands, 4) an extended water ice cap on the southern pole, and 5) no rainfall, streams lakes or oceans. The majority of these predictions are in direct conflict with the observed fluvial/lacustrine geologic record. Can non-equilibrium conditions in a LNIH scenario explain these conflicts by transient heating and melting of the LNIH? As steps in the comprehensive testing of this "Late Noachian Icy Highlands" (LNIH) model we explore the predictions for geologic settings and processes in both equilibrium and non-equilibrium climate states. We assess the following sources of disequilibrium: 1) Top-down heating and melting: a) impact cratering, b) extrusive/explosive volcanism, and c) short-term emission of greenhouse gases. 2) Bottom up heating and melting: a) enhanced regional-global geothermal gradients, and b) thick ice accumulation to cause/sustain basal melting, wet-based glaciation and runoff. We assess these disequilibrium mechanisms in terms of: 1) the altitude dependence of melting, 2) melting duration, 3) volumes of meltwater produced, 4) predicted locations of meltwater production, and 6) comparison to the distribution of fluvial/lacustrine features. We find that the Late Noachian Icy Highlands climate model cannot be reconciled with observations unless punctuated non-equilibrium conditions occur. We show that the best candidates for LNIH disequilibrium conditions involve top-down heating and melting conditions chronologically summing in duration to more than tens of thousands to millions of years.

Effect of measurement protocol on organic aerosol measurements of exhaust emissions from gasoline and diesel vehicles

NASA Astrophysics Data System (ADS)

Kim, Youngseob; Sartelet, Karine; Seigneur, Christian; Charron, Aurélie; Besombes, Jean-Luc; Jaffrezo, Jean-Luc; Marchand, Nicolas; Polo, Lucie

2016-09-01

Exhaust emissions of semi-volatile organic compounds (SVOC) from passenger vehicles are usually estimated only for the particle phase via the total particulate matter measurements. However, they also need to be estimated for the gas phase, as they are semi-volatile. To better estimate SVOC emission factors of passenger vehicles, a measurement campaign using a chassis dynamometer was conducted with different instruments: (1) a constant volume sampling (CVS) system in which emissions were diluted with filtered air and sampling was performed on filters and polyurethane foams (PUF) and (2) a Dekati Fine Particle Sampler (FPS) in which emissions were diluted with purified air and sampled with on-line instruments (PTR-ToF-MS, HR-ToF-AMS, MAAP, CPC). Significant differences in the concentrations of organic carbon (OC) measured by the instruments are observed. The differences can be explained by sampling artefacts, differences between (1) the time elapsed during sampling (in the case of filter and PUF sampling) and (2) the time elapsed from emission to measurement (in the case of on-line instruments), which vary from a few seconds to 15 min, and by the different dilution factors. To relate elapsed times and measured concentrations of OC, the condensation of SVOC between the gas and particle phases is simulated with a dynamic aerosol model. The simulation results allow us to understand the relation between elapsed times and concentrations in the gas and particle phases. They indicate that the characteristic times to reach thermodynamic equilibrium between gas and particle phases may be as long as 8 min. Therefore, if the elapsed time is less than this characteristic time to reach equilibrium, gas-phase SVOC are not at equilibrium with the particle phase and a larger fraction of emitted SVOC will be in the gas phase than estimated by equilibrium theory, leading to an underestimation of emitted OC if only the particle phase is considered or if the gas-phase SVOC are estimated by equilibrium theory. Current European emission inventories for passenger cars do not yet estimate gas-phase SVOC emissions, although they may represent 60% of total emitted SVOC (gas + particle phases).

Site-specific equilibrium isotopic fractionation of oxygen, carbon and calcium in apatite

NASA Astrophysics Data System (ADS)

Aufort, Julie; Ségalen, Loïc; Gervais, Christel; Paulatto, Lorenzo; Blanchard, Marc; Balan, Etienne

2017-12-01

The stable isotope composition of biogenic apatite is an important geochemical marker that can record environmental parameters and is widely used to infer past climates, biomineralization processes, dietary preferences and habitat of vertebrates. In this study, theoretical equilibrium isotopic fractionation of oxygen, carbon and calcium in hydroxyapatite and carbonate-bearing hydroxyapatite is investigated using first-principles methods based on density-functional theory and compared to the theoretical isotopic fractionation properties of calcite, CO2 and H2O. Considering the variability of apatite crystal-chemistry, special attention is given to specific contributions of crystal sites to isotopic fractionation. Significant internal fractionation is calculated for oxygen and carbon isotopes in CO3 between the different structural sites occupied by carbonate groups in apatite (typically 7‰ for both 18O/16O and 13C/12C fractionation at 37 °C). Compared with calcite-water oxygen isotope fractionation, occurrence of A-type substitution in apatite structure, in addition to the main B-type substitution, could explain the larger temperature dependence of oxygen isotope fractionation measured at low temperature between carbonate in apatite and water. Theoretical internal fractionation of oxygen isotopes between carbonate and phosphate in B-type carbonated apatite (∼8‰ at 37 °C) is consistent with experimental values obtained from modern and well-preserved fossil bio-apatites. Concerning calcium, theoretical results suggest a small fractionation between apatite and calcite (-0.17‰ at 37 °C). Internal fractionation reaching 0.8‰ at 37 °C occurs between the two Ca sites in hydroxyapatite. Furthermore, the Ca isotopic fractionation properties of apatite are affected by the occurrence of carbonate groups, which could contribute to the variability observed on natural samples. Owing to the complexity of apatite crystal-chemistry and in light of the theoretical results, measurements of site-specific isotopic fractionation properties could improve our understanding and the interpretation of isotopic records in apatites.

Equilibrium lithium isotope fractionation in Li-rich minerals

NASA Astrophysics Data System (ADS)

Liu, S.; Li, Y.; Liu, J.

2017-12-01

Lithium is the lightest alkali metal, and only exhibits +1 valence state in minerals. It is widely distributed on the Earth, and usually substitutes for Mg in silicate minerals. Li has two stable isotopes, 6Li and 7Li, with the relative abundances of 7.52% and 92.48%, respectively. The large mass difference between 6Li and 7Li could induce significant isotope fractionation in minerals. Li isotopes can provide an important geochemical tracer for mantle processes. However, the fractionation factors for Li in most minerals remain poorly known, which makes the geochemical implications of Li isotope fractionations in minerals difficult to assess. Here, we try to use the vibrational frequencies obtained by the first-principles methods based on density-functional theory to calculate the Li isotope fractionation parameters for amblygonite (LiAlPO4F), bikitaite (LiSi2AlO7H2), eucryptite (LiAlSiO4), lithiophilite (LiMnPO4), lithiophosphate (Li3PO4), montebrasite (LiAlPO5H), and spodumene (LiAlSi2O6) in the temperature range of 0-1200 ºC. For forsterite (Mg2SiO4) and diopside (CaMgSi2O6) in which Li takes the place of Mg, the equilibrium Li isotope fractionation between them also be studied. Our preliminary calculations show that the coordination number of Li seems to play an important role in controlling Li isotope fractionation in these minerals, and concentration of Li in forsterite and diopside seems to have great effects on Li isotope fractionation factors of them.

A Harris-Todaro Agent-Based Model to Rural-Urban Migration

NASA Astrophysics Data System (ADS)

Espíndola, Aquino L.; Silveira, Jaylson J.; Penna, T. J. P.

2006-09-01

The Harris-Todaro model of the rural-urban migration process is revisited under an agent-based approach. The migration of the workers is interpreted as a process of social learning by imitation, formalized by a computational model. By simulating this model, we observe a transitional dynamics with continuous growth of the urban fraction of overall population toward an equilibrium. Such an equilibrium is characterized by stabilization of rural-urban expected wages differential (generalized Harris-Todaro equilibrium condition), urban concentration and urban unemployment. These classic results obtained originally by Harris and Todaro are emergent properties of our model.

Unconfined laminar nanofluid flow and heat transfer around a rotating circular cylinder in the steady regime

NASA Astrophysics Data System (ADS)

Bouakkaz, Rafik; Salhi, Fouzi; Khelili, Yacine; Quazzazi, Mohamed; Talbi, Kamel

2017-06-01

In this work, steady flow-field and heat transfer through a copper- water nanofluid around a rotating circular cylinder with a constant nondimensional rotation rate α varying from 0 to 5 was investigated for Reynolds numbers of 5-40. Furthermore, the range of nanoparticle volume fractions considered is 0-5%. The effect of volume fraction of nanoparticles on the fluid flow and heat transfer characteristics are carried out by using a finite-volume method based commercial computational fluid dynamics solver. The variation of the local and the average Nusselt numbers with Reynolds number, volume fractions, and rotation rate are presented for the range of conditions. The average Nusselt number is found to decrease with increasing value of the rotation rate for the fixed value of the Reynolds number and volume fraction of nanoparticles. In addition, rotation can be used as a drag reduction technique.

Numerical Investigation on Absorption Enhancement of Black Carbon Aerosols Partially Coated With Nonabsorbing Organics

NASA Astrophysics Data System (ADS)

Zhang, Xiaolin; Mao, Mao; Yin, Yan; Wang, Bin

2018-01-01

This study numerically evaluates the effects of aerosol microphysics, including coated volume fraction of black carbon (BC), shell/core ratio, and size distribution, on the absorption enhancement (Eab) of polydisperse BC aggregates partially coated by organics, which is calculated by the exact multiple-sphere T-matrix method. The coated volume fraction of BC plays a substantial role in determining the absorption enhancement of partially coated BC aggregates, which typically have an Eab in the range of 1.0-2.0 with a larger value for larger coated volume fraction of BC as the shell/core ratio, BC geometry, and size distribution are fixed. The shell/core ratio, BC geometry, and size distribution have little impact on the Eab of coated BC with small coated volume fraction of BC, while they become significant for large coated volume fraction of BC. The Eab of partially coated BC particles can be slightly less than 1.0 for the large BC in the accumulation mode exhibiting large shell/core ratio and small coated volume fraction of BC, indicating that the absorption shows even slight decrease relative to uncoated BC particles. For partially coated BC aggregates in the accumulation and coarse modes, the refractive index uncertainties of BC result in the Eab differences of less than 9% and 2%, respectively, while those of organics can induce larger variations with the maximum differences up to 22% and 18%, respectively. Our study indicates that accounting for particle coating microphysics, particularly the coated volume fraction of BC, can potentially help to understand the differences in observations of largely variable absorption enhancements over various regions.

A study on the effects of temperature and volume fraction on thermal conductivity of copper oxide nanofluid.

PubMed

Jwo, Ching-Song; Chang, Ho; Teng, Tun-Ping; Kao, Mu-Jnug; Guo, Yu-Ting

2007-06-01

By using copper oxide nanofluid fabricated by the self-made Submerged Arc Nanofluid Synthesis System (SANSS), this paper measures the thermal conductivity under different volume fractions and different temperatures by thermal properties analyzer, and analyzes the correlation among the thermal conductivity, volume fraction, and temperature of nanofluid. The CuO nanoparticles used in the experiment are needle-like, with a mean particle size of about 30 nm. They can be stably suspended in deionized water for a long time. The experimental results show that under the condition that the temperature is 40 degrees C, when the volume fraction of nanofluid increases from 0.2% to 0.8%, the thermal conductivity increment of the prepared nanofluid towards deionized water can be increased from 14.7% to 38.2%. Under the condition that the volume fraction is 0.8%, as the temperature of nanofluid rises from 5 degrees C to 40 degrees C, the thermal conductivity increment of the prepared nanofluid towards deionized water increases from 5.9% to 38.2%. Besides, the effects of temperature change are greater than the effects of volume fraction on the thermal conductivity of nanofluid. Therefore, when the self-made copper oxide nanofluid is applied to the heat exchange device under medium and high temperature, an optimal radiation effect can be acquired.

The effect of non-equilibrium metal cooling on the interstellar medium

NASA Astrophysics Data System (ADS)

Capelo, Pedro R.; Bovino, Stefano; Lupi, Alessandro; Schleicher, Dominik R. G.; Grassi, Tommaso

2018-04-01

By using a novel interface between the modern smoothed particle hydrodynamics code GASOLINE2 and the chemistry package KROME, we follow the hydrodynamical and chemical evolution of an isolated galaxy. In order to assess the relevance of different physical parameters and prescriptions, we constructed a suite of 10 simulations, in which we vary the chemical network (primordial and metal species), how metal cooling is modelled (non-equilibrium versus equilibrium; optically thin versus thick approximation), the initial gas metallicity (from 10 to 100 per cent solar), and how molecular hydrogen forms on dust. This is the first work in which metal injection from supernovae, turbulent metal diffusion, and a metal network with non-equilibrium metal cooling are self-consistently included in a galaxy simulation. We find that properly modelling the chemical evolution of several metal species and the corresponding non-equilibrium metal cooling has important effects on the thermodynamics of the gas, the chemical abundances, and the appearance of the galaxy: the gas is typically warmer, has a larger molecular-gas mass fraction, and has a smoother disc. We also conclude that, at relatively high metallicity, the choice of molecular-hydrogen formation rates on dust is not crucial. Moreover, we confirm that a higher initial metallicity produces a colder gas and a larger fraction of molecular gas, with the low-metallicity simulation best matching the observed molecular Kennicutt-Schmidt relation. Finally, our simulations agree quite well with observations that link star formation rate to metal emission lines.

Simultaneous integrated vs. sequential boost in VMAT radiotherapy of high-grade gliomas.

PubMed

Farzin, Mostafa; Molls, Michael; Astner, Sabrina; Rondak, Ina-Christine; Oechsner, Markus

2015-12-01

In 20 patients with high-grade gliomas, we compared two methods of planning for volumetric-modulated arc therapy (VMAT): simultaneous integrated boost (SIB) vs. sequential boost (SEB). The investigation focused on the analysis of dose distributions in the target volumes and the organs at risk (OARs). After contouring the target volumes [planning target volumes (PTVs) and boost volumes (BVs)] and OARs, SIB planning and SEB planning were performed. The SEB method consisted of two plans: in the first plan the PTV received 50 Gy in 25 fractions with a 2-Gy dose per fraction. In the second plan the BV received 10 Gy in 5 fractions with a dose per fraction of 2 Gy. The doses of both plans were summed up to show the total doses delivered. In the SIB method the PTV received 54 Gy in 30 fractions with a dose per fraction of 1.8 Gy, while the BV received 60 Gy in the same fraction number but with a dose per fraction of 2 Gy. All of the OARs showed higher doses (Dmax and Dmean) in the SEB method when compared with the SIB technique. The differences between the two methods were statistically significant in almost all of the OARs. Analysing the total doses of the target volumes we found dose distributions with similar homogeneities and comparable total doses. Our analysis shows that the SIB method offers advantages over the SEB method in terms of sparing OARs.

Interfacial effect on physical properties of composite media: Interfacial volume fraction with non-spherical hard-core-soft-shell-structured particles.

PubMed

Xu, Wenxiang; Duan, Qinglin; Ma, Huaifa; Chen, Wen; Chen, Huisu

2015-11-02

Interfaces are known to be crucial in a variety of fields and the interfacial volume fraction dramatically affects physical properties of composite media. However, it is an open problem with great significance how to determine the interfacial property in composite media with inclusions of complex geometry. By the stereological theory and the nearest-surface distribution functions, we first propose a theoretical framework to symmetrically present the interfacial volume fraction. In order to verify the interesting generalization, we simulate three-phase composite media by employing hard-core-soft-shell structures composed of hard mono-/polydisperse non-spherical particles, soft interfaces, and matrix. We numerically derive the interfacial volume fraction by a Monte Carlo integration scheme. With the theoretical and numerical results, we find that the interfacial volume fraction is strongly dependent on the so-called geometric size factor and sphericity characterizing the geometric shape in spite of anisotropic particle types. As a significant interfacial property, the present theoretical contribution can be further drawn into predicting the effective transport properties of composite materials.

Interfacial effect on physical properties of composite media: Interfacial volume fraction with non-spherical hard-core-soft-shell-structured particles

PubMed Central

Xu, Wenxiang; Duan, Qinglin; Ma, Huaifa; Chen, Wen; Chen, Huisu

2015-01-01

Interfaces are known to be crucial in a variety of fields and the interfacial volume fraction dramatically affects physical properties of composite media. However, it is an open problem with great significance how to determine the interfacial property in composite media with inclusions of complex geometry. By the stereological theory and the nearest-surface distribution functions, we first propose a theoretical framework to symmetrically present the interfacial volume fraction. In order to verify the interesting generalization, we simulate three-phase composite media by employing hard-core-soft-shell structures composed of hard mono-/polydisperse non-spherical particles, soft interfaces, and matrix. We numerically derive the interfacial volume fraction by a Monte Carlo integration scheme. With the theoretical and numerical results, we find that the interfacial volume fraction is strongly dependent on the so-called geometric size factor and sphericity characterizing the geometric shape in spite of anisotropic particle types. As a significant interfacial property, the present theoretical contribution can be further drawn into predicting the effective transport properties of composite materials. PMID:26522701

Experimental evidence for the absence of iron isotope fractionation between metal and silicate liquids at 1 GPa and 1250-1300 °C and its cosmochemical consequences

NASA Astrophysics Data System (ADS)

Hin, Remco C.; Schmidt, Max W.; Bourdon, Bernard

2012-09-01

Iron isotope fractionation during metal-silicate differentiation has been proposed as a cause for differences in iron isotope compositions of chondrites, iron meteorites and the bulk silicate Earth. Stable isotope fractionation, however, rapidly decreases with increasing temperature. We have thus performed liquid metal-liquid silicate equilibration experiments at 1250-1300 °C and 1 GPa to address whether Fe isotope fractionation is resolvable at the lowest possible temperatures for magmatic metal-silicate differentiation. A centrifuging piston cylinder apparatus enabled quantitative metal-silicate segregation. Elemental tin or sulphur was used in the synthetic metal-oxide mixtures to lower the melting temperature of the metal. The analyses demonstrate that eight of the 10 experimental systems equilibrated in a closed isotopic system, as was assessed by varying run durations and starting Fe isotope compositions. Statistically significant iron isotope fractionation between quenched metals and silicates was absent in nine of the 10 experiments and all 10 experiments yield an average metal-silicate fractionation factor of 0.01 ± 0.04‰, independent of whether graphite or silica glass capsules were used. This implies that Fe isotopes do not fractionate during low pressure metal-silicate segregation under magmatic conditions. In large bodies such as the Earth, fractionation between metal and high pressure (>20 GPa) silicate phases may still be a possible process for equilibrium fractionation during metal-silicate differentiation. However, the 0.07 ± 0.02‰ heavier composition of bulk magmatic iron meteorites relative to the average of bulk ordinary/carbonaceous chondrites cannot result from equilibrium Fe isotope fractionation during core segregation. The up to 0.5‰ lighter sulphide than metal fraction in iron meteorites and in one ordinary chondrite can only be explained by fractionation during subsolidus processes.

Local structure of percolating gels at very low volume fractions

NASA Astrophysics Data System (ADS)

Griffiths, Samuel; Turci, Francesco; Royall, C. Patrick

2017-01-01

The formation of colloidal gels is strongly dependent on the volume fraction of the system and the strength of the interactions between the colloids. Here we explore very dilute solutions by the means of numerical simulations and show that, in the absence of hydrodynamic interactions and for sufficiently strong interactions, percolating colloidal gels can be realised at very low values of the volume fraction. Characterising the structure of the network of the arrested material we find that, when reducing the volume fraction, the gels are dominated by low-energy local structures, analogous to the isolated clusters of the interaction potential. Changing the strength of the interaction allows us to tune the compactness of the gel as characterised by the fractal dimension, with low interaction strength favouring more chain-like structures.

Dependence of particle volume fraction on sound velocity and attenuation of EPDM composites.

PubMed

Kim, K S; Lee, K I; Kim, H Y; Yoon, S W; Hong, S H

2007-05-01

The sound velocity and the attenuation coefficient of EPDM (Ethylene-propylene Diene Monomer) composites incorporated with Silicon Carbide particles (SiCp's) of various volume fractions (0-40%) were experimentally and theoretically investigated. For the experiment a through-transmission technique was used. For the theoretical prediction, some mechanical property models such as Reuss model and Coherent Potential Approximation (CPA) model etc. were employed. The experimental results showed that the sound velocity decreased with the increase of the SiCp volume fraction up to 30% and then increased with the 40 vol% specimen. The attenuation coefficient was increased with the increasing SiCp volume fractions. The modified Reuss model with a longitudinal elastic modulus predicted most well the experimental sound velocity and elastic modulus results.

A quantitative assessment of volumetric and anatomic changes of the parotid gland during intensity-modulated radiotherapy for head and neck cancer using serial computed tomography

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ajani, Abdallah A.; Qureshi, Muhammad M.; Kovalchuk, Nataliya

To evaluate the change in volume and movement of the parotid gland measured by serial contrast-enhanced computed tomography scans in patients with head and neck cancer treated with parotid-sparing intensity-modulated radiotherapy (IMRT). A prospective study was performed on 13 patients with head and neck cancer undergoing dose-painted IMRT to 69.96 Gy in 33 fractions. Serial computed tomography scans were performed at baseline, weeks 2, 4, and 6 of radiotherapy (RT), and at 6 weeks post-RT. The parotid volume was contoured at each scan, and the movement of the medial and lateral borders was measured. The patient's body weight was recordedmore » at each corresponding week during RT. Regression analyses were performed to ascertain the rate of change during treatment as a percent change per fraction in parotid volume and distance relative to baseline. The mean parotid volume decreased by 37.3% from baseline to week 6 of RT. The overall rate of change in parotid volume during RT was−1.30% per fraction (−1.67% and−0.91% per fraction in≥31 Gy and<31 Gy mean planned parotid dose groups, respectively, p = 0.0004). The movement of parotid borders was greater in the≥31 Gy mean parotid dose group compared with the<31 Gy group (0.22% per fraction and 0.14% per fraction for the lateral border and 0.19% per fraction and 0.06% per fraction for the medial border, respectively). The median change in body weight was−7.4% (range, 0.75% to−17.5%) during RT. A positive correlation was noted between change in body weight and parotid volume during the course of RT (Spearman correlation coefficient, r = 0.66, p<0.01). Head and neck IMRT results in a volume loss of the parotid gland, which is related to the planned parotid dose, and the patient's weight loss during RT.« less

Silicon isotope fractionations in pure Si and Fe-Si systems and their geological implications

NASA Astrophysics Data System (ADS)

Zheng, X. Y.; Beard, B. L.; Reddy, T. R.; Roden, E. E.; Johnson, C.

2016-12-01

Amorphous Si or Si-bearing materials are ubiquitous in nature, and are likely precursors to various rock types, such as cherts and banded iron formations (BIFs). Si isotope exchange kinetics and fractionation factors between these materials and aqueous Si, however, are poorly constrained, preventing a mechanistic or quantitative understanding of geological δ30Si records. A series of laboratory experiments were conducted to provide better estimates on Si isotope exchange kinetics and fractionation factors. Equilibrium Si isotope fractionation factors between Fe(III)-Si gel and aqueous Si (Δ30Sigel-aq) in artificial Archean seawater (AAS), determined by a three-isotope method with a 29Si tracer, are -2.3‰ where Fe2+ is absent from the solution, and -3.2‰ where Fe2+ is present in the solution[1]. Aqueous Fe2+ catalyzes Si isotope exchange, and causes larger Si isotope fractionation due to incorporation into the solid that may have changed Si bonding. In contrast, our preliminary results show that Δ30Sigel-aq between pure Si gel and aqueous Si at equilibrium is -0.13‰. Ongoing experiments are intended to approach the isotope equilibrium from multiple directions to resolve potential kinetic effects, and to explore temperature dependence. Nonetheless, the contrast in Δ30Sigel-aq between Fe-Si and pure Si systems highlights a significant impact of Fe on Si isotope fractionations. These results have important implications for Si isotopes in Precambrian cherts and BIFs, as well as in weathering systems in general. Silicon isotope fractionation was also studied in experiments that involved dissimilatory iron reduction of Fe(III)-Si gel by Desulfuromonas acetoxidans in AAS[2], and was found to become larger with progression of Fe reduction. A Δ30Sigel-aq of -3.5‰ was observed at 32% reduction of Fe3+. This result explains lower δ30Si values in magnetite-associated quartz that those in hematite-associated quartz in some BIFs. The large Si isotope fractionation produced in the microbial experiment, even larger than that seen in our Fe(II)-bearing abiologic experiments, suggests that δ30Si can be a potential tracer for magnetite of a microbial origin, or, vice versa, for microbial activities in magnetite. [1] Zheng et al., 2016, GCA 187, 102-122. [2] Reddy et al., 2016, GCA 190, 85-99.

Change in Seroma Volume During Whole-Breast Radiation Therapy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sharma, Rajiv; Spierer, Marnee; Mutyala, Subhakar

2009-09-01

Purpose: After breast-conserving surgery, a seroma often forms in the surgical cavity. If not drained, it may affect the volume of tumor bed requiring a boost after whole-breast radiation therapy (WBRT). Our objective was to evaluate the change in seroma volume that occurs during WBRT, before boost planning. Methods and Materials: A retrospective review was performed of women receiving breast-conserving therapy with evidence of seroma at the time of WBRT planning. Computed tomography (CT) simulation was performed before WBRT and before the tumor bed boost. All patients received either a hypofractionated (42.4 Gy/16 fraction + 9.6 Gy/4 fraction boost) ormore » standard fractionated (50.4 Gy/28 fraction + 10 Gy/5 fraction boost) regimen. Seroma volumes were contoured and compared on CT at the time of WBRT simulation and tumor bed boost planning. Results: Twenty-four patients with evidence of seroma were identified and all patients received WBRT without drainage of the seroma. Mean seroma volume before WBRT and at boost planning were significantly different at 65.7 cm{sup 3} (SD, 50.5 cm{sup 3}) and 35.6 cm{sup 3} (SD, 24.8 cm{sup 3}), respectively (p < 0.001). Mean and median reduction in seroma volume during radiation were 39.6% (SD, 23.8%) and 46.2% (range, 10.7-76.7%), respectively. Fractionation schedule was not correlated with change in seroma volume. Length of time from surgery to start of radiation therapy showed an inverse correlation with change in seroma volume (Pearson correlation r = -0.53, p < 0.01). Conclusions: The volume of seroma changes significantly during WBRT. Consequently, the accuracy of breast boost planning is likely affected, as is the volume of normal breast tissue irradiated. CT-based boost planning before boost irradiation is suggested to ensure appropriate coverage.« less

Using nonequilibrium capillary electrophoresis of equilibrium mixtures (NECEEM) for simultaneous determination of concentration and equilibrium constant.

PubMed

Kanoatov, Mirzo; Galievsky, Victor A; Krylova, Svetlana M; Cherney, Leonid T; Jankowski, Hanna K; Krylov, Sergey N

2015-03-03

Nonequilibrium capillary electrophoresis of equilibrium mixtures (NECEEM) is a versatile tool for studying affinity binding. Here we describe a NECEEM-based approach for simultaneous determination of both the equilibrium constant, K(d), and the unknown concentration of a binder that we call a target, T. In essence, NECEEM is used to measure the unbound equilibrium fraction, R, for the binder with a known concentration that we call a ligand, L. The first set of experiments is performed at varying concentrations of T, prepared by serial dilution of the stock solution, but at a constant concentration of L, which is as low as its reliable quantitation allows. The value of R is plotted as a function of the dilution coefficient, and dilution corresponding to R = 0.5 is determined. This dilution of T is used in the second set of experiments in which the concentration of T is fixed but the concentration of L is varied. The experimental dependence of R on the concentration of L is fitted with a function describing their theoretical dependence. Both K(d) and the concentration of T are used as fitting parameters, and their sought values are determined as the ones that generate the best fit. We have fully validated this approach in silico by using computer-simulated NECEEM electropherograms and then applied it to experimental determination of the unknown concentration of MutS protein and K(d) of its interactions with a DNA aptamer. The general approach described here is applicable not only to NECEEM but also to any other method that can determine a fraction of unbound molecules at equilibrium.

Identification of the Centrifuged Lipoaspirate Fractions Suitable for Postgrafting Survival.

PubMed

Qiu, Lihong; Su, Yingjun; Zhang, Dongliang; Song, Yajuan; Liu, Bei; Yu, Zhou; Guo, Shuzhong; Yi, Chenggang

2016-01-01

The Coleman centrifugation procedure generates fractions with different adipocyte and progenitor cell densities. This study aimed to identify all fractions that are feasible for implantation. Human lipoaspirates were processed by Coleman centrifugation. The centrifugates were divided arbitrarily into upper, middle, and lower layers. Adipocyte viability, morphology, numbers of stromal vascular fraction cells, and adipose-derived mesenchymal stem cells of each layer were determined. The 12-week volume retention of subcutaneously implanted 0.3-ml lipoasperate of each layer was investigated in an athymic mice model. Most damaged adipocytes were located in the upper layers, whereas the intact adipocytes were distributed in the middle and lower layers. A gradient of stromal vascular fraction cell density was formed in the centrifugates. The implant volume retentions of samples from the upper, middle, and lower layers were 33.44 ± 5.9, 55.11 ± 4.4, and 71.2 ± 5.8 percent, respectively. Furthermore, the middle and lower layers contained significantly more adipose-derived stem cells than did the upper layer. The lower layer contains more viable adipocytes and stromal vascular fraction cells leading to the highest implant volume retention, whereas the most impaired cells are distributed in the upper layer, leading to the least volume retention. Although with a lower stromal vascular fraction content, the middle layer has a substantial number of intact adipocytes that are capable of retaining partial adipose tissue volume after implantation, suggesting that the middle layer may be an alternative fat source when large volumes of fat grafts are needed for transplantation.

Intra-fraction motion of larynx radiotherapy

NASA Astrophysics Data System (ADS)

Durmus, Ismail Faruk; Tas, Bora

2018-02-01

In early stage laryngeal radiotherapy, movement is an important factor. Thyroid cartilage can move from swallowing, breathing, sound and reflexes. The effects of this motion on the target volume (PTV) during treatment were examined. In our study, the target volume movement during the treatment for this purpose was examined. Thus, setup margins are re-evaluated and patient-based PTV margins are determined. Intrafraction CBCT was scanned in 246 fractions for 14 patients. During the treatment, the amount of deviation which could be lateral, vertical and longitudinal axis was determined. ≤ ± 0.1cm deviation; 237 fractions in the lateral direction, 202 fractions in the longitudinal direction, 185 fractions in the vertical direction. The maximum deviation values were found in the longitudinal direction. Intrafraction guide in laryngeal radiotherapy; we are sure of the correctness of the treatment, the target volume is to adjust the margin and dose more precisely, we control the maximum deviation of the target volume for each fraction. Although the image quality of intrafraction-CBCT scans was lower than the image quality of planning CT, they showed sufficient contrast for this work.

Performance enhancement of direct ethanol fuel cell using Nafion composites with high volume fraction of titania

NASA Astrophysics Data System (ADS)

Matos, B. R.; Isidoro, R. A.; Santiago, E. I.; Fonseca, F. C.

2014-12-01

The present study reports on the performance enhancement of direct ethanol fuel cell (DEFC) at 130 °C with Nafion-titania composite electrolytes prepared by sol-gel technique and containing high volume fractions of the ceramic phase. It is found that for high volume fractions of titania (>10 vol%) the ethanol uptake of composites is largely reduced while the proton conductivity at high-temperatures is weakly dependent on the titania content. Such tradeoff between alcohol uptake and conductivity resulted in a boost of DEFC performance at high temperatures using Nafion-titania composites with high fraction of the inorganic phase.

Response functions for computing absorbed dose to skeletal tissues from photon irradiation—an update

NASA Astrophysics Data System (ADS)

Johnson, Perry B.; Bahadori, Amir A.; Eckerman, Keith F.; Lee, Choonsik; Bolch, Wesley E.

2011-04-01

A comprehensive set of photon fluence-to-dose response functions (DRFs) is presented for two radiosensitive skeletal tissues—active and total shallow marrow—within 15 and 32 bone sites, respectively, of the ICRP reference adult male. The functions were developed using fractional skeletal masses and associated electron-absorbed fractions as reported for the UF hybrid adult male phantom, which in turn is based upon micro-CT images of trabecular spongiosa taken from a 40 year male cadaver. The new DRFs expand upon both the original set of seven functions produced in 1985, and a 2007 update calculated under the assumption of secondary electron escape from spongiosa. In this study, it is assumed that photon irradiation of the skeleton will yield charged particle equilibrium across all spongiosa regions at energies exceeding 200 keV. Kerma coefficients for active marrow, inactive marrow, trabecular bone and spongiosa at higher energies are calculated using the DRF algorithm setting the electron-absorbed fraction for self-irradiation to unity. By comparing kerma coefficients and DRF functions, dose enhancement factors and mass energy-absorption coefficient (MEAC) ratios for active marrow to spongiosa were derived. These MEAC ratios compared well with those provided by the NIST Physical Reference Data Library (mean difference of 0.8%), and the dose enhancement factors for active marrow compared favorably with values calculated in the well-known study published by King and Spiers (1985 Br. J. Radiol. 58 345-56) (mean absolute difference of 1.9 percentage points). Additionally, dose enhancement factors for active marrow were shown to correlate well with the shallow marrow volume fraction (R2 = 0.91). Dose enhancement factors for the total shallow marrow were also calculated for 32 bone sites representing the first such derivation for this target tissue.

Response functions for computing absorbed dose to skeletal tissues from photon irradiation--an update.

PubMed

Johnson, Perry B; Bahadori, Amir A; Eckerman, Keith F; Lee, Choonsik; Bolch, Wesley E

2011-04-21

A comprehensive set of photon fluence-to-dose response functions (DRFs) is presented for two radiosensitive skeletal tissues-active and total shallow marrow-within 15 and 32 bone sites, respectively, of the ICRP reference adult male. The functions were developed using fractional skeletal masses and associated electron-absorbed fractions as reported for the UF hybrid adult male phantom, which in turn is based upon micro-CT images of trabecular spongiosa taken from a 40 year male cadaver. The new DRFs expand upon both the original set of seven functions produced in 1985, and a 2007 update calculated under the assumption of secondary electron escape from spongiosa. In this study, it is assumed that photon irradiation of the skeleton will yield charged particle equilibrium across all spongiosa regions at energies exceeding 200 keV. Kerma coefficients for active marrow, inactive marrow, trabecular bone and spongiosa at higher energies are calculated using the DRF algorithm setting the electron-absorbed fraction for self-irradiation to unity. By comparing kerma coefficients and DRF functions, dose enhancement factors and mass energy-absorption coefficient (MEAC) ratios for active marrow to spongiosa were derived. These MEAC ratios compared well with those provided by the NIST Physical Reference Data Library (mean difference of 0.8%), and the dose enhancement factors for active marrow compared favorably with values calculated in the well-known study published by King and Spiers (1985 Br. J. Radiol. 58 345-56) (mean absolute difference of 1.9 percentage points). Additionally, dose enhancement factors for active marrow were shown to correlate well with the shallow marrow volume fraction (R(2) = 0.91). Dose enhancement factors for the total shallow marrow were also calculated for 32 bone sites representing the first such derivation for this target tissue.

RESPONSE FUNCTIONS FOR COMPUTING ABSORBED DOSE TO SKELETAL TISSUES FROM PHOTON IRRADIATION – AN UPDATE

PubMed Central

Johnson, Perry; Bahadori, Amir; Eckerman, Keith; Lee, Choonsik; Bolch, Wesley E.

2014-01-01

A comprehensive set of photon fluence-to-dose response functions (DRFs) are presented for two radiosensitive skeletal tissues – active and total shallow marrow – within 15 and 32 bones sites, respectively, of the ICRP reference adult male. The functions were developed using fractional skeletal masses and associated electron absorbed fractions as reported for the UF hybrid adult male phantom, which in turn is based upon microCT images of trabecular spongiosa taken from a 40-year male cadaver. The new DRFs expand upon both the original set of seven functions produced in 1985, as well as a 2007 update calculated under the assumption of secondary electron escape from spongiosa. In the present study, it is assumed that photon irradiation of the skeleton will yield charged particle equilibrium across all spongiosa regions at energies exceeding 200 keV. Kerma factors for active marrow, inactive marrow, trabecular bone, and spongiosa at higher energies are calculated using the DRF algorithm setting the electron absorbed fraction for self-irradiation to unity. By comparing kerma factors and DRF functions, dose enhancement factors and mass energy-absorption coefficient (MEAC) ratios for active marrow to spongiosa were derived. These MEAC ratios compared well with those provided by the NIST Physical Reference Data Library (mean difference of 0.8%), and the dose enhancement factors for active marrow compared favorably with values calculated in the well-known study published by King and Spiers (1985) (mean absolute difference of 1.9 percentage points). Additionally, dose enhancement factors for active marrow were shown to correlate well with the shallow marrow volume fraction (R2 = 0.91). Dose enhancement factors for the total shallow marrow were also calculated for 32 bone sites PMID:21427484

Synthesis of Silane and Silicon in a Non-equilibrium Plasma Jet

NASA Technical Reports Server (NTRS)

Calcote, H. F.

1978-01-01

The original objective of this program was to determine the feasibility of high volume, low-cost production of high purity silane or solar cell grade silicon using a non equilibrium plasma jet. The emphasis was changed near the end of the program to determine the feasibility of preparing photovoltaic amorphous silicon films directly using this method. The non equilibrium plasma jet should be further evaluated as a technique for producing high efficiency photovoltaic amorphous silicon films.

Revisiting atenolol as a low passive permeability marker.

PubMed

Chen, Xiaomei; Slättengren, Tim; de Lange, Elizabeth C M; Smith, David E; Hammarlund-Udenaes, Margareta

2017-10-31

Atenolol, a hydrophilic beta blocker, has been used as a model drug for studying passive permeability of biological membranes such as the blood-brain barrier (BBB) and the intestinal epithelium. However, the extent of S-atenolol (the active enantiomer) distribution in brain has never been evaluated, at equilibrium, to confirm that no transporters are involved in its transport at the BBB. To assess whether S-atenolol, in fact, depicts the characteristics of a low passive permeable drug at the BBB, a microdialysis study was performed in rats to monitor the unbound concentrations of S-atenolol in brain extracellular fluid (ECF) and plasma during and after intravenous infusion. A pharmacokinetic model was developed, based on the microdialysis data, to estimate the permeability clearance of S-atenolol into and out of brain. In addition, the nonspecific binding of S-atenolol in brain homogenate was evaluated using equilibrium dialysis. The steady-state ratio of unbound S-atenolol concentrations in brain ECF to that in plasma (i.e., K p,uu,brain ) was 3.5% ± 0.4%, a value much less than unity. The unbound volume of distribution in brain (V u, brain ) of S-atenolol was also calculated as 0.69 ± 0.10 mL/g brain, indicating that S-atenolol is evenly distributed within brain parenchyma. Lastly, equilibrium dialysis showed limited nonspecific binding of S-atenolol in brain homogenate with an unbound fraction (f u,brain ) of 0.88 ± 0.07. It is concluded, based on K p,uu,brain being much smaller than unity, that S-atenolol is actively effluxed at the BBB, indicating the need to re-consider S-atenolol as a model drug for passive permeability studies of BBB transport or intestinal absorption.

Numerical analysis of the air chemical non-equilibrium effect in combustion for a semi-sphere with opposing jet

NASA Astrophysics Data System (ADS)

Zhao, Fa-Ming; Wang, Jiang-Feng; Li, Long-Fei

2018-05-01

The air chemical non-equilibrium effect (ACNEE) on hydrogen-air combustion flow fields at Mach number of 10 is numerically analyzed for a semi-sphere with a sonic opposing-hydrogen jet. The 2D axisymmetric multi-components N-S equations are solved by using the central scheme with artificial dissipation and the S-A turbulence model. Numerical results show that as compared to the result without ACNEE, the ACNEE has little influence on the structure of flow field, but has a considerable impact on fluid characteristics which reduces the maximum value of mass fraction of water in the flow field and increases the maximum value of mass fraction of water on solid surface, as well as the maximum surface temperature.

Efficient estimation of diffusion during dendritic solidification

NASA Technical Reports Server (NTRS)

Yeum, K. S.; Poirier, D. R.; Laxmanan, V.

1989-01-01

A very efficient finite difference method has been developed to estimate the solute redistribution during solidification with diffusion in the solid. This method is validated by comparing the computed results with the results of an analytical solution derived by Kobayashi (1988) for the assumptions of a constant diffusion coefficient, a constant equilibrium partition ratio, and a parabolic rate of the advancement of the solid/liquid interface. The flexibility of the method is demonstrated by applying it to the dendritic solidification of a Pb-15 wt pct Sn alloy, for which the equilibrium partition ratio and diffusion coefficient vary substantially during solidification. The fraction eutectic at the end of solidification is also obtained by estimating the fraction solid, in greater resolution, where the concentration of solute in the interdendritic liquid reaches the eutectic composition of the alloy.

Pharmacokinetic evidence for improved ophthalmic drug delivery by reduction of instilled volume.

PubMed

Patton, T F

1977-07-01

The bioavailability of topically applied pilocarpine nitrate was studied as a function of instilled volume. As the instilled volume decreased, the fraction of dose absorbed increased. The relationship between fraction absorbed and instilled volume was not direct, but appropriate adjustment of instilled volume and concentration should permit substantial dosage reductions without sacrifice of drug concentration in the eye. The implications of these findings from both a therapeutic and toxicity standpoint are discussed.

Mechanistic approach for nitride fuel evolution and fission product release under irradiation

NASA Astrophysics Data System (ADS)

Dolgodvorov, A. P.; Ozrin, V. D.

2017-01-01

A model for describing uranium-plutonium mixed nitride fuel pellet burning was developed. Except fission products generating, the model includes impurities of oxygen and carbon. Nitrogen behaviour in nitride fuel was analysed and the nitrogen chemical potential in solid solution with uranium-plutonium nitride was constructed. The chemical program module was tested with the help of thermodynamic equilibrium phase distribution calculation. Results were compared with analogous data in literature, quite good agreement was achieved, especially for uranium sesquinitride, metallic species and some oxides. Calculation of a process of nitride fuel burning was also conducted. Used mechanistic approaches for fission product evolution give the opportunity to find fission gas release fractions and also volumes of intergranular secondary phases. Calculations present that the most massive secondary phases are the oxide and metallic phases. Oxide phase contain approximately 1 % wt of substance over all time of burning with slightly increasing of content. Metallic phase has considerable rising of mass and by the last stage of burning it contains about 0.6 % wt of substance. Intermetallic phase has less increasing rate than metallic phase and include from 0.1 to 0.2 % wt over all time of burning. The highest element fractions of released gaseous fission products correspond to caesium and iodide.

Characterization of the kinetic arrest of martensitic transformation in Ni45Co5Mn36.8In13.2 melt-spun ribbons

NASA Astrophysics Data System (ADS)

Lino-Zapata, F. M.; Yan, H. L.; Ríos-Jara, D.; Sánchez Llamazares, J. L.; Zhang, Y. D.; Zhao, X.; Zuo, L.

2018-01-01

The kinetic arrest (KA) of martensitic transformation (MT) observed in Ni45Co5Mn36.8In13.2 melt-spun ribbons has been studied. These alloy ribbons show an ordered columnar-like grain microstructure with the longer grain axis growing perpendicular to ribbon plane and transform martensitically from a single austenitic (AST) parent phase with the L21-type crystal structure to a monoclinic incommensurate 6 M modulated martensite (MST). Results show that the volume fraction of austenite frozen into the martensitic matrix is proportional to the applied magnetic field. A fully arrest of the structural transition is found for a magnetic field of 7 T. The metastable character of the non-equilibrium field-cooled glassy state was characterized by introducing thermal and magnetic field fluctuations or measuring the relaxation of magnetization. The relaxation of magnetization from a field-cooled kinetically arrested state at 5 and 7 T follows the Kohlrausch-Williams-Watts (KWW) stretched exponential function with a β exponent around 0.95 indicating the weak metastable nature of the system under the strong magnetic fields. The relationship between the occurrence of exchange bias and the frozen fraction of AST into the MST matrix was studied.

Fractional Relativistic Yamaleev Oscillator Model and Its Dynamical Behaviors

NASA Astrophysics Data System (ADS)

Luo, Shao-Kai; He, Jin-Man; Xu, Yan-Li; Zhang, Xiao-Tian

2016-07-01

In the paper we construct a new kind of fractional dynamical model, i.e. the fractional relativistic Yamaleev oscillator model, and explore its dynamical behaviors. We will find that the fractional relativistic Yamaleev oscillator model possesses Lie algebraic structure and satisfies generalized Poisson conservation law. We will also give the Poisson conserved quantities of the model. Further, the relation between conserved quantities and integral invariants of the model is studied and it is proved that, by using the Poisson conserved quantities, we can construct integral invariants of the model. Finally, the stability of the manifold of equilibrium states of the fractional relativistic Yamaleev oscillator model is studied. The paper provides a general method, i.e. fractional generalized Hamiltonian method, for constructing a family of fractional dynamical models of an actual dynamical system.

Quantitative assessment of fatty infiltration and muscle volume of the rotator cuff muscles using 3-dimensional 2-point Dixon magnetic resonance imaging.

PubMed

Matsumura, Noboru; Oguro, Sota; Okuda, Shigeo; Jinzaki, Masahiro; Matsumoto, Morio; Nakamura, Masaya; Nagura, Takeo

2017-10-01

In patients with rotator cuff tears, muscle degeneration is known to be a predictor of irreparable tears and poor outcomes after surgical repair. Fatty infiltration and volume of the whole muscles constituting the rotator cuff were quantitatively assessed using 3-dimensional 2-point Dixon magnetic resonance imaging. Ten shoulders with a partial-thickness tear, 10 shoulders with an isolated supraspinatus tear, and 10 shoulders with a massive tear involving supraspinatus and infraspinatus were compared with 10 control shoulders after matching age and sex. With segmentation of muscle boundaries, the fat fraction value and the volume of the whole rotator cuff muscles were computed. After reliabilities were determined, differences in fat fraction, muscle volume, and fat-free muscle volume were evaluated. Intra-rater and inter-rater reliabilities were regarded as excellent for fat fraction and muscle volume. Tendon rupture adversely increased the fat fraction value of the respective rotator cuff muscle (P < .002). In the massive tear group, muscle volume was significantly decreased in the infraspinatus (P = .035) and increased in the teres minor (P = .039). With subtraction of fat volume, a significant decrease of fat-free volume of the supraspinatus muscle became apparent with a massive tear (P = .003). Three-dimensional measurement could evaluate fatty infiltration and muscular volume with excellent reliabilities. The present study showed that chronic rupture of the tendon adversely increases the fat fraction of the respective muscle and indicates that the residual capacity of the rotator cuff muscles might be overestimated in patients with severe fatty infiltration. Copyright © 2017 Journal of Shoulder and Elbow Surgery Board of Trustees. Published by Elsevier Inc. All rights reserved.

Effect of ethanol on crystallization of the polymorphs of L-histidine

NASA Astrophysics Data System (ADS)

Wantha, Lek; Punmalee, Neeranuch; Sawaddiphol, Vanida; Flood, Adrian E.

2018-05-01

It is known that the antisolvents used for crystallization can affect the crystallization outcome and may promote the crystallization of a specific polymorph. In this study L-histidine (L-his) is used as a model substance, and ethanol was selected to be an antisolvent. The formation of the polymorphs of L-his in antisolvent crystallization as a function of supersaturation, ethanol volume fraction, and temperature was studied. The induction time for the antisolvent crystallization was also measured. The results showed that the induction time decreases with higher supersaturation and ethanol volume fraction, indicating that the nucleation rate of L-his from antisolvent crystallization (where water was used as the solvent and ethanol as the antisolvent) increases with higher supersaturation, as expected, and ethanol fraction. At all temperatures studied, the pure metastable polymorph B of L-his was obtained initially at higher ethanol volume fraction and supersaturation, while a mixture of the polymorphs A and B was obtained at lower ethanol volume fraction and supersaturation.

Photodegradation of crude oil: liquid injection and headspace solid-phase microextraction for crude oil analysis by gas chromatography with mass spectrometer detector.

PubMed

D'Auria, Maurizio; Racioppi, Rocco; Velluzzi, Vincenzina

2008-04-01

The fate of crude oil under irradiation is studied. After UV irradiation, the fraction present in the highest percentage shifts from the C8-C9 fractions to C13, using gas chromatography-mass spectrometry (GC-MS) analysis in solution. An increase of the relative amount of the C13-C25 fraction is observed, while a decrease in the relative amount of the C7-C12 fractions is present. In headspace solid-phase microextraction (HS-SPME) analysis, the C8-C10 fractions represent 53% of all the compounds detected. A decrease in the relative amount of the C8-C10 fractions is observed, while C11-C15 fractions increase. The irradiation of crude oil with a solar simulator gives a mixture the analysis of which using GC-MS in solution furnishes the same type of results: the relative amounts of linear alkanes and aromatic compounds increase, while a sharp decrease in the relative amounts of branched and cyclic alkanes is observed. In the SPME analysis, a decreased relative amount of branched alkanes and alkenes, and an increase in the relative amounts of cyclic alkanes and aromatic compounds are observed. Analysis of the distribution of the compounds in all the types of compound shows that a dynamic equilibrium between different compounds and different types of compounds is present. To confirm the presence of a dynamic equilibrium, the irradiation of methylcyclohexane in the presence of 2-methylnaphthalene shows the presence in the reaction mixture of a small amount of tetradecane.

Fractionated Mercury Isotopes in Fish: The Effects of Nuclear Mass, Spin, and Volume

NASA Astrophysics Data System (ADS)

Das, R.; Odom, A. L.

2007-12-01

Mercury is long known as a common environmental contaminant. In methylated form it is even more toxic and the methylation process is facilitated by microbial activities. Methyl mercury easily crosses cell membrane and accumulates in soft tissues of fishes and finally biomagnifies with increasing trophic levels. Natural variations in the isotopic composition of mercury have been reported and such variations have emphasized mass dependent fractionations, while theory and laboratory experiments indicate that mass-independent isotopic fractionation (MIF) effects are likely to be found as well. This study focuses on the MIF of mercury isotopes in the soft tissues of fishes. Samples include both fresh water and marine fish, from different continents and oceans. Approximately 1 gm of fish soft tissue was dissolved in 5 ml of conc. aqua regia for 24 hrs and filtered through a ¬¬¬100 μm filter paper and diluted with DI water. Hg is measured as a gaseous phase generated by reduction of the sample with SnCl2 in a continuous- flow cold-vapor generator connected to a Thermo-Finnigan Neptune MC-ICPMS. To minimize instrumental fractionation isotope ratios were measured by sample standard bracketing and reported as δ‰ relative to NIST SRM 3133 Hg standard where δAHg = [(A Hg/202Hg)sample/(A Hg/202Hg)NIST313] -1 ×1000‰. In this study we have measured the isotope ratios 198Hg/202Hg, 199Hg/202Hg, 200Hg/202Hg, 201Hg/202Hg and 204Hg/202Hg. In all the fish samples δ198Hg, δ200Hg, δ202Hg, δ204Hg define a mass- dependent fractionation sequence, where as the δ199Hg and δ201Hg depart from the mass- dependent fractionation line and indicate an excess of the odd-N isotopes. The magnitude of the deviation (ΔAHg where A=199 or 201) as obtained by difference between the measured δ199Hg and δ201Hg of the samples and the value obtained by linear scaling defined by the even-N isotopes ranges from approximately 0.2 ‰ to 3‰. The ratios of Δ199Hg /Δ201Hg range from 0.8 to 1.3, and thus more than one mass-independent isotope effect is inferred. MIF of mercury can be caused by the nuclear volume effect. Schauble, 2007 has calculated nuclear volume fractionation scaling factors for a number of common mercury chemical species in equilibrium with Hg° vapor. From his calculations the nuclear field shift effect is larger in Δ199Hg than in Δ201Hg by approximately a factor of two. The predominant mercury chemical species in fish is methylmercury cysteine. From the experimental studies of Buchachenko and others (2004) on the reaction of methylmercury chloride with creatine kinase it seems reasonable to predicted that the thiol functional groups of cysteine gets enriched in 199Hg and 201Hg. Here the magnetic isotope effect (MIE) produces a kinetic partial separation of isotopes with non-zero nuclear spin quantum numbers from the even-N isotopes. The ratio of enrichment of Δ201Hg /Δ199Hg is predicted from theory to be 1.11, which is the ratio of the magnetic moments of 199Hg and 201Hg. Because mercury possesses two odd-N isotopes, it is possible to detect and evaluate the effects of two distinct, mass-independent isotope fractionating processes. From the data obtained on fish samples, we can deconvolute the contributions of the isotope effects of nuclear mass, spin and volume. For these samples the role of spin or the magnetic isotope effect is the most dominant.

SU-E-T-480: Radiobiological Dose Comparison of Single Fraction SRS, Multi-Fraction SRT and Multi-Stage SRS of Large Target Volumes Using the Linear-Quadratic Formula

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ding, C; Hrycushko, B; Jiang, S

2014-06-01

Purpose: To compare the radiobiological effect on large tumors and surrounding normal tissues from single fraction SRS, multi-fractionated SRT, and multi-staged SRS treatment. Methods: An anthropomorphic head phantom with a centrally located large volume target (18.2 cm{sup 3}) was scanned using a 16 slice large bore CT simulator. Scans were imported to the Multiplan treatment planning system where a total prescription dose of 20Gy was used for a single, three staged and three fractionated treatment. Cyber Knife treatment plans were inversely optimized for the target volume to achieve at least 95% coverage of the prescription dose. For the multistage plan,more » the target was segmented into three subtargets having similar volume and shape. Staged plans for individual subtargets were generated based on a planning technique where the beam MUs of the original plan on the total target volume are changed by weighting the MUs based on projected beam lengths within each subtarget. Dose matrices for each plan were export in DICOM format and used to calculate equivalent dose distributions in 2Gy fractions using an alpha beta ratio of 10 for the target and 3 for normal tissue. Results: Singe fraction SRS, multi-stage plan and multi-fractionated SRT plans had an average 2Gy dose equivalent to the target of 62.89Gy, 37.91Gy and 33.68Gy, respectively. The normal tissue within 12Gy physical dose region had an average 2Gy dose equivalent of 29.55Gy, 16.08Gy and 13.93Gy, respectively. Conclusion: The single fraction SRS plan had the largest predicted biological effect for the target and the surrounding normal tissue. The multi-stage treatment provided for a more potent biologically effect on target compared to the multi-fraction SRT treatments with less biological normal tissue than single-fraction SRS treatment.« less

Mathematical modeling of impact of two metal plates using two-fluid approach

NASA Astrophysics Data System (ADS)

Utkin, P. S.; Fortova, S. V.

2018-01-01

The paper is devoted to the development of the two-fluid mathematical model and the computational algorithm for the modeling of two metal plates impact. In one-dimensional case the governing system of equations comprises seven equations: three conservation laws for each fluid and transfer equation for the volume fraction of one of the fluids. Both fluids are considered to be compressible and equilibrium on velocities. Pressures equilibrium is used as fluids interface condition. The system has hyperbolic type but could not be written in the conservative form because of nozzling terms in the right-hand side of the equations. The algorithm is based on the Harten-Lax-van Leer numerical flux function. The robust computation in the presence of the interface boundary is carried out due to the special pressure relaxation procedure. The problem is solved using stiffened gas equations of state for each fluid. The parameters in the equations of state are calibrated using the results of computations using wide-range equations of state for the metals. In simulations of metal plates impact we get two shocks after the initial impact that propagate to the free surfaces of the samples. The characteristics of shock waves are close (maximum relative error in characteristics of shocks is not greater than 7%) to the data from the wide-range equations of states computations.

Effects of finite wall thickness and sinusoidal heating on convection in nanofluid-saturated local thermal non-equilibrium porous cavity

NASA Astrophysics Data System (ADS)

Alsabery, A. I.; Chamkha, A. J.; Saleh, H.; Hashim, I.; Chanane, B.

2017-03-01

The effects of finite wall thickness and sinusoidal heating on convection in a nanofluid-saturated local thermal non-equilibrium (LTNE) porous cavity are studied numerically using the finite difference method. The finite thickness vertical wall of the cavity is maintained at a constant temperature and the right wall is heated sinusoidally. The horizontal insulated walls allow no heat transfer to the surrounding. The Darcy law is used along with the Boussinesq approximation for the flow. Water-based nanofluids with Cu nanoparticles are chosen for investigation. The results of this study are obtained for various parameters such as the Rayleigh number, periodicity parameter, nanoparticles volume fraction, thermal conductivity ratio, ratio of wall thickness to its height and the modified conductivity ratio. Explanation for the influence of the various above-mentioned parameters on the streamlines, isotherms, local Nusselt number and the weighted average heat transfer is provided with regards to the thermal conductivities of nanoparticles suspended in the pure fluid and the porous medium. It is shown that the overall heat transfer is significantly increased with the relative non-uniform heating. Further, the convection heat transfer is shown to be inhibited by the presence of the solid wall. The results have possible applications in the heat-storage fluid-saturated porous systems and the applications of the high power heat transfer.

Effect on the operation properties of DMBR with the addition of GAC

NASA Astrophysics Data System (ADS)

Lin, Jizhi; Zhang, Qian; Hong, Junming

2017-01-01

The membrane bioreactor and dynamic membrane bioreactor were used to examine the effect of granular activated carbon (GAC) on the treatment of synthetic wastewater. After the addition of different volume fractions GAC in the DMBR, the operation parameters, effluent COD, NH4 +-N, NO3 --N, TN concentrations and sludge viscosity of the bioreactor was investigated. The results showed that the addition of GAC could relieve the membrane fouling and improve the removal efficiencies of pollutants in the DMBR. The effluent concentrations of pollutants were linear correlation with the addition of volume fractions of GAC in the bioreactor. The value of R2 of each modulation was almost more than 0.9. The sludge viscosity was almost not affected by the volume fractions of GAC in the bioreactor. The best volume fractions of GAC were 20% in the DMBR.

Tissue microstructure features derived from anomalous diffusion measurements in magnetic resonance imaging.

PubMed

Yu, Qiang; Reutens, David; O'Brien, Kieran; Vegh, Viktor

2017-02-01

Tissue microstructure features, namely axon radius and volume fraction, provide important information on the function of white matter pathways. These parameters vary on the scale much smaller than imaging voxels (microscale) yet influence the magnetic resonance imaging diffusion signal at the image voxel scale (macroscale) in an anomalous manner. Researchers have already mapped anomalous diffusion parameters from magnetic resonance imaging data, but macroscopic variations have not been related to microscale influences. With the aid of a tissue model, we aimed to connect anomalous diffusion parameters to axon radius and volume fraction using diffusion-weighted magnetic resonance imaging measurements. An ex vivo human brain experiment was performed to directly validate axon radius and volume fraction measurements in the human brain. These findings were validated using electron microscopy. Additionally, we performed an in vivo study on nine healthy participants to map axon radius and volume fraction along different regions of the corpus callosum projecting into various cortical areas identified using tractography. We found a clear relationship between anomalous diffusion parameters and axon radius and volume fraction. We were also able to map accurately the trend in axon radius along the corpus callosum, and in vivo findings resembled the low-high-low-high behaviour in axon radius demonstrated previously. Axon radius and volume fraction measurements can potentially be used in brain connectivity studies and to understand the implications of white matter structure in brain diseases and disorders. Hum Brain Mapp 38:1068-1081, 2017. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Evaporation in equilibrium, in vacuum, and in hydrogen gas

NASA Technical Reports Server (NTRS)

Nagahara, Hiroko

1993-01-01

Evaporation experiments were conducted for SiO2 in three different conditions: in equilibrium, in vacuum, and in hydrogen gas. Evaporation rate in vacuum is about two orders of magnitude smaller than that in equilibrium, which is consistent with previous works. The rate in hydrogen gas changes depending on hydrogen pressure. The rate at 10 exp -7 bar of hydrogen pressure is as small as that of free evaporation, but at 10 exp -5 bar of hydrogen pressure it is larger than that in equilibrium. In equilibrium and in vacuum, the evaporation rate is limited by decomposition of SiO2 on the crystal surface, but it is limited by a diffusion process for evaporation in hydrogen gas. Therefore, evaporation rate of minerals in the solar nebula can be shown neither by that in equilibrium nor by that in vacuum. The maximum temperature of the solar nebula at the midplane at 2-3 AU where chondrites are believed to have originated is calculated to be as low as 150 K, 1500 K, or in between them. The temperature is, in any case, not high enough for total evaporation of the interstellar materials. Therefore, evaporation of interstellar materials is one of the most important processes for the origin and fractionation of solid materials. The fundamental process of evaporation of minerals has been intensively studied for these several years. Those experiments were carried out either in equilibrium or in vacuum; however, evaporation in the solar nebula is in hydrogen (and much smaller amount of helium) gas. In order to investigate evaporation rate and compositional (including isotopic) fractionation during evaporation, vaporization experiments for various minerals in various conditions are conducted. At first, SiO2 was adopted for a starting material, because thermochemical data and its nature of congruent vaporization are well known. Experiments were carried out in a vacuum furnace system.

Theoretical estimation of equilibrium sulfur isotope fractionations among aqueous sulfite species: Implications for isotope models of microbial sulfate reduction

NASA Astrophysics Data System (ADS)

Eldridge, D. L.; Farquhar, J.; Guo, W.

2015-12-01

Sulfite (sensu lato), an intermediate in a variety sulfur redox processes, plays a particularly important role in microbial sulfate reduction. It exists intracellularly as multiple species between sets of enzymatic reactions that transform sulfate to sulfide, with the exact speciation depending on pH, T, and ionic strength. However, the complex speciation of sulfite is ignored in current isotope partitioning models of microbial sulfate reduction and simplified solely to the pyramidal SO32- (sulfite sensu stricto), due to a lack of appropriate constraints. We theoretically estimated the equilibrium sulfur isotope fractionations (33S/32S, 34S/32S, 36S/32S) among all documented sulfite species in aqueous solution, including sulfite (SO32-), bisulfite isomers and dimers ((HS)O3-, (HO)SO2-, S2O52-), and SO2(aq), through first principles quantum mechanical calculations. The calculations were performed at B3LYP/6-31+G(d,p) level using cluster models with 30-40 water molecules surrounding the solute. Our calculated equilibrium fractionation factors compare well to the available experimental constraints and suggest that the minor and often-ignored tetrahedral (HS)O3- isomer of bisulfite strongly influences isotope partitioning behavior in the sulfite system under most environmentally relevant conditions, particularly fractionation magnitudes and unusual temperature dependence. For example, we predict that sulfur isotope fractionation between sulfite and bulk bisulfite in solution should have an apparent inverse temperature dependence due to the influence of (HS)O3- and its increased stability at higher temperatures. Our findings highlight the need to appropriately account for speciation/isomerization of sulfur species in sulfur isotope studies. We will also present similar calculation results of other aqueous sulfur compounds (e.g., H2S/HS-, SO42-, S2O32-, S3O62-, and poorly documented SO22- species), and discuss the implication of our results for microbial sulfate reduction models and other sulfur-redox processes in nature.

Hydrogen isotopic fractionation during crystallization of the terrestrial magma ocean

NASA Astrophysics Data System (ADS)

Pahlevan, K.; Karato, S. I.

2016-12-01

Models of the Moon-forming giant impact extensively melt and partially vaporize the silicate Earth and deliver a substantial mass of metal to the Earth's core. The subsequent evolution of the terrestrial magma ocean and overlying vapor atmosphere over the ensuing 105-6 years has been largely constrained by theoretical models with remnant signatures from this epoch proving somewhat elusive. We have calculated equilibrium hydrogen isotopic fractionation between the magma ocean and overlying steam atmosphere to determine the extent to which H isotopes trace the evolution during this epoch. By analogy with the modern silicate Earth, the magma ocean-steam atmosphere system is often assumed to be chemically oxidized (log fO2 QFM) with the dominant atmospheric vapor species taken to be water vapor. However, the terrestrial magma ocean - having held metallic droplets in suspension - may also exhibit a much more reducing character (log fO2 IW) such that equilibration with the overlying atmosphere renders molecular hydrogen the dominant H-bearing vapor species. This variable - the redox state of the magma ocean - has not been explicitly included in prior models of the coupled evolution of the magma ocean-steam atmosphere system. We find that the redox state of the magma ocean influences not only the vapor speciation and liquid-vapor partitioning of hydrogen but also the equilibrium isotopic fractionation during the crystallization epoch. The liquid-vapor isotopic fractionation of H is substantial under reducing conditions and can generate measurable D/H signatures in the crystallization products but is largely muted in an oxidizing magma ocean and steam atmosphere. We couple equilibrium isotopic fractionation with magma ocean crystallization calculations to forward model the behavior of hydrogen isotopes during this epoch and find that the distribution of H isotopes in the silicate Earth immediately following crystallization represents an oxybarometer for the terrestrial magma ocean. Whether such endogenous isotopic heterogeneity would survive as an observable signature in the modern silicate Earth is an open question.

Chemical equilibrium. [maximizing entropy of gas system to derive relations between thermodynamic variables

NASA Technical Reports Server (NTRS)

1976-01-01

The entropy of a gas system with the number of particles subject to external control is maximized to derive relations between the thermodynamic variables that obtain at equilibrium. These relations are described in terms of the chemical potential, defined as equivalent partial derivatives of entropy, energy, enthalpy, free energy, or free enthalpy. At equilibrium, the change in total chemical potential must vanish. This fact is used to derive the equilibrium constants for chemical reactions in terms of the partition functions of the species involved in the reaction. Thus the equilibrium constants can be determined accurately, just as other thermodynamic properties, from a knowledge of the energy levels and degeneracies for the gas species involved. These equilibrium constants permit one to calculate the equilibrium concentrations or partial pressures of chemically reacting species that occur in gas mixtures at any given condition of pressure and temperature or volume and temperature.

The major volume /density/ of solid oxygen in equilibrium with vapor

NASA Technical Reports Server (NTRS)

Roder, H. M.

1979-01-01

Data from the literature on the molar volume of solid oxygen have been compiled and critically analyzed. A correlated and thermodynamically consistent set of molar volumes, including the volume changes at the various solid phase transitions, is presented. Evidence for the existence of a delta-solid phase is reviewed. Uncertainties in the data and in the recommended set of values are discussed.

Long-range correlations, geometrical structure, and transport properties of macromolecular solutions. The equivalence of configurational statistics and geometrodynamics of large molecules.

PubMed

Mezzasalma, Stefano A

2007-12-04

A special theory of Brownian relativity was previously proposed to describe the universal picture arising in ideal polymer solutions. In brief, it redefines a Gaussian macromolecule in a 4-dimensional diffusive spacetime, establishing a (weak) Lorentz-Poincaré invariance between liquid and polymer Einstein's laws for Brownian movement. Here, aimed at inquiring into the effect of correlations, we deepen the extension of the special theory to a general formulation. The previous statistical equivalence, for dynamic trajectories of liquid molecules and static configurations of macromolecules, and rather obvious in uncorrelated systems, is enlarged by a more general principle of equivalence, for configurational statistics and geometrodynamics. Accordingly, the three geodesic motion, continuity, and field equations could be rewritten, and a number of scaling behaviors were recovered in a spacetime endowed with general static isotropic metric (i.e., for equilibrium polymer solutions). We also dealt with universality in the volume fraction and, unexpectedly, found that a hyperscaling relation of the form, (average size) x (diffusivity) x (viscosity)1/2 ~f(N0, phi0) is fulfilled in several regimes, both in the chain monomer number (N) and polymer volume fraction (phi). Entangled macromolecular dynamics was treated as a geodesic light deflection, entaglements acting in close analogy to the field generated by a spherically symmetric mass source, where length fluctuations of the chain primitive path behave as azimuth fluctuations of its shape. Finally, the general transformation rule for translational and diffusive frames gives a coordinate gauge invariance, suggesting a widened Lorentz-Poincaré symmetry for Brownian statistics. We expect this approach to find effective applications to solutions of arbitrarily large molecules displaying a variety of structures, where the effect of geometry is more explicit and significant in itself (e.g., surfactants, lipids, proteins).

Clinical high-resolution mapping of the proteoglycan-bound water fraction in articular cartilage of the human knee joint.

PubMed

Bouhrara, Mustapha; Reiter, David A; Sexton, Kyle W; Bergeron, Christopher M; Zukley, Linda M; Spencer, Richard G

2017-11-01

We applied our recently introduced Bayesian analytic method to achieve clinically-feasible in-vivo mapping of the proteoglycan water fraction (PgWF) of human knee cartilage with improved spatial resolution and stability as compared to existing methods. Multicomponent driven equilibrium single-pulse observation of T 1 and T 2 (mcDESPOT) datasets were acquired from the knees of two healthy young subjects and one older subject with previous knee injury. Each dataset was processed using Bayesian Monte Carlo (BMC) analysis incorporating a two-component tissue model. We assessed the performance and reproducibility of BMC and of the conventional analysis of stochastic region contraction (SRC) in the estimation of PgWF. Stability of the BMC analysis of PgWF was tested by comparing independent high-resolution (HR) datasets from each of the two young subjects. Unlike SRC, the BMC-derived maps from the two HR datasets were essentially identical. Furthermore, SRC maps showed substantial random variation in estimated PgWF, and mean values that differed from those obtained using BMC. In addition, PgWF maps derived from conventional low-resolution (LR) datasets exhibited partial volume and magnetic susceptibility effects. These artifacts were absent in HR PgWF images. Finally, our analysis showed regional variation in PgWF estimates, and substantially higher values in the younger subjects as compared to the older subject. BMC-mcDESPOT permits HR in-vivo mapping of PgWF in human knee cartilage in a clinically-feasible acquisition time. HR mapping reduces the impact of partial volume and magnetic susceptibility artifacts compared to LR mapping. Finally, BMC-mcDESPOT demonstrated excellent reproducibility in the determination of PgWF. Published by Elsevier Inc.

Quantification of local strain distributions in nanoscale strained SiGe FinFET structures

NASA Astrophysics Data System (ADS)

Mochizuki, Shogo; Murray, Conal E.; Madan, Anita; Pinto, Teresa; Wang, Yun-Yu; Li, Juntao; Weng, Weihao; Jagannathan, Hemanth; Imai, Yasuhiko; Kimura, Shigeru; Takeuchi, Shotaro; Sakai, Akira

2017-10-01

Strain within nanoscale strained SiGe FinFET structures has been investigated using a combination of X-ray diffraction and transmission electron microscopy-based nanobeam diffraction (NBD) techniques to reveal the evolution of the stress state within the FinFETs. Reciprocal space maps collected using high-resolution X-ray diffraction exhibited distinct features corresponding to the SiGe fin width, pitch, and lattice deformation and were analyzed to quantify the state of stress within the fins. Although the majority of the SiGe fin volume exhibited a uniaxial stress state due to elastic relaxation of the transverse in-plane stress, NBD measurements confirmed a small interaction region near the SOI interface that is mechanically constrained by the underlying substrate. We have quantitatively characterized the evolution of the fin stress state from biaxial to uniaxial as a function of fin aspect ratio and Ge fraction and confirmed that the fins obey elastic deformation based on a model that depends on the relative difference between the equilibrium Si and SiGe lattice constants and relative fraction of in-plane stress transverse to the SiGe fins. Spatially resolved, nanobeam X-ray diffraction measurements conducted near the SiGe fin edge indicate the presence of additional elastic relaxation from a uniaxial stress state to a fully relaxed state at the fin edge. Mapping of the lattice deformation within 500 nm of this fin edge by NBD revealed large gradients, particularly at the top corner of the fin. The values of the volume averaged lattice deformation obtained by nanoXRD and NBD are qualitatively consistent. Furthermore, the modulation of strain at the fin edge obtained by quantitative analysis of the nanoXRD results agrees with the lattice deformation profile obtained by NBD.

The roles of auxeticity and volume fraction on γ‧ precipitate microstructures in nickel-base alloys

NASA Astrophysics Data System (ADS)

Ardell, Alan J.

2017-01-01

New correlations are found between the elastic constants and late-stage precipitate microstructures in Ni-Al, Ni-Ga, Ni-Ge and Ni-Si alloys. The auxetic behaviour of Poisson's ratio, ν, measured parallel to [0 0 1] or ? in response to [1 1 0] loading, favours the amalgamation of Ni3Al and Ni3Ga precipitates into non-equilibrium shapes along cube directions when δν = (νγ‧ - νγ)/νγ‧ > 0, the superscripts referring to the γ‧ (Ni3X) and γ (Ni-X) phases, respectively. When δν < 0 amalgamation of Ni3Ge and Ni3Si precipitates does not occur and the particles retain cuboidal shapes. When δν > 0 amalgamation of Ni3Al and Ni3Ga occurs readily, primarily producing laths of both phases. The γ‧ volume fraction, f, is also shown to play a role in the late-stage microstructures of Ni-Al alloys, with an increasing tendency to form Ni3Al laths, rather than plates, as f increases. The shapes of elastically soft γ precipitates in inverse Ni-Al and Ni-Ge alloys are different; Ni-Al precipitates are lath shaped, but Ni-Ge precipitates are plate shaped. The Ni-Ge plate shape, in a non-auxetic Ni3Ge matrix (Ni3Ge being the sole non-auxetic Ni3X phase of the four studied), is the only example of persistent plates in any of the Ni-base alloys investigated to date. The combination of an elastically soft precipitate (Ni-Ge) in a non-auxetic matrix suggests a connection between auxeticity and shape.

Speciation and equilibrium relations of soluble aluminum in a headwater stream at base flow and during rain events

USGS Publications Warehouse

Burns, Douglas A.

1989-01-01

In a small watershed in the Shenandoah National Park, Virginia, the short-term dynamics of soluble aluminum in stream water sampled during rain events differed significantly from stream water sampled during base flow conditions. Three fractions of dissolved aluminum were measured. The inorganic monomeric fraction made up approximately two thirds of the total reactive aluminum at base flow, followed by the acid-soluble and organic monomeric fractions, respectively. Equilibrium modeling showed that hydroxide complexes were the most abundant form of inorganic monomeric aluminum followed by fluoride, free aluminum ion, and sulfate. The activity of inorganic monomeric aluminum at base flow appears to be in equilibrium with an Al(OH)3 phase with solubility intermediate between microcrystalline gibbsite and natural gibbsite. During two rain events, the concentration of all three aluminum fractions increased significantly. Available chemical evidence indicates that acidic soil water was the primary source of dissolved aluminum. As flow increased, the Al(OH)3 saturation index in the stream water increased significantly. The primary cause of the transient increase in the Al(OH)3 saturation index appears to have been the neutralization of excess H+ added by soil water through reaction with stream water HCO3− at a more rapid rate than excess inorganic monomeric aluminum could be removed from solution by hydroxide mineral precipitation. A soil water/stream water mixing model was developed based on measured changes of stream water alkalinity, silica concentration, and charge imbalance during the rain events. Model results indicate that a small amount of soil water (3–11%) was present in the stream at peak stage.

Turbulent forced convection of nanofluids downstream an abrupt expansion

NASA Astrophysics Data System (ADS)

Kimouche, Abdelali; Mataoui, Amina

2018-03-01

Turbulent forced convection of Nanofluids through an axisymmetric abrupt expansion is investigated numerically in the present study. The governing equations are solved by ANYS 14.0 CFD code based on the finite volume method by implementing the thermo-physical properties of each nanofluid. All results are analyzed through the evolutions of skin friction coefficient and Nusselt number. For each nanofluid, the effect of both volume fraction and Reynolds number on this type of flow configuration, are examined. An increase on average Nusselt number with the volume fraction and Reynolds number, are highlighted and correlated. Two relationships are proposed. The first one, determines the average Nusselt number versus Reynolds number, volume fraction and the ratio of densities of the solid particles to that of the base fluid ( \\overline{Nu}=f(\\operatorname{Re},φ, ρ_s/ρ_f) ). The second one varies according Reynolds number, volume fraction and the conductivities ratio of solid particle to that of the base fluid ( \\overline{Nu}=f(\\operatorname{Re},φ, k_s/k_f) ).

SU-E-T-429: Uncertainties of Cell Surviving Fractions Derived From Tumor-Volume Variation Curves

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chvetsov, A

2014-06-01

Purpose: To evaluate uncertainties of cell surviving fraction reconstructed from tumor-volume variation curves during radiation therapy using sensitivity analysis based on linear perturbation theory. Methods: The time dependent tumor-volume functions V(t) have been calculated using a twolevel cell population model which is based on the separation of entire tumor cell population in two subpopulations: oxygenated viable and lethally damaged cells. The sensitivity function is defined as S(t)=[δV(t)/V(t)]/[δx/x] where δV(t)/V(t) is the time dependent relative variation of the volume V(t) and δx/x is the relative variation of the radiobiological parameter x. The sensitivity analysis was performed using direct perturbation method wheremore » the radiobiological parameter x was changed by a certain error and the tumor-volume was recalculated to evaluate the corresponding tumor-volume variation. Tumor volume variation curves and sensitivity functions have been computed for different values of cell surviving fractions from the practically important interval S{sub 2}=0.1-0.7 using the two-level cell population model. Results: The sensitivity functions of tumor-volume to cell surviving fractions achieved a relatively large value of 2.7 for S{sub 2}=0.7 and then approached zero as S{sub 2} is approaching zero Assuming a systematic error of 3-4% we obtain that the relative error in S{sub 2} is less that 20% in the range S2=0.4-0.7. This Resultis important because the large values of S{sub 2} are associated with poor treatment outcome should be measured with relatively small uncertainties. For the very small values of S2<0.3, the relative error can be larger than 20%; however, the absolute error does not increase significantly. Conclusion: Tumor-volume curves measured during radiotherapy can be used for evaluation of cell surviving fractions usually observed in radiation therapy with conventional fractionation.« less

Long-range interacting systems in the unconstrained ensemble.

PubMed

Latella, Ivan; Pérez-Madrid, Agustín; Campa, Alessandro; Casetti, Lapo; Ruffo, Stefano

2017-01-01

Completely open systems can exchange heat, work, and matter with the environment. While energy, volume, and number of particles fluctuate under completely open conditions, the equilibrium states of the system, if they exist, can be specified using the temperature, pressure, and chemical potential as control parameters. The unconstrained ensemble is the statistical ensemble describing completely open systems and the replica energy is the appropriate free energy for these control parameters from which the thermodynamics must be derived. It turns out that macroscopic systems with short-range interactions cannot attain equilibrium configurations in the unconstrained ensemble, since temperature, pressure, and chemical potential cannot be taken as a set of independent variables in this case. In contrast, we show that systems with long-range interactions can reach states of thermodynamic equilibrium in the unconstrained ensemble. To illustrate this fact, we consider a modification of the Thirring model and compare the unconstrained ensemble with the canonical and grand-canonical ones: The more the ensemble is constrained by fixing the volume or number of particles, the larger the space of parameters defining the equilibrium configurations.

Kinetic characteristic of phenanthrene sorption in aged soil amended with biochar

NASA Astrophysics Data System (ADS)

Kim, Chanyang; Kim, Yong-Seong; Hyun, Seunghun

2015-04-01

Biochar has been recently highlighted as an amendment that affects yield of the crops by increasing pH, cation exchange capacity and water retention, and reduces the lability of contaminants by increasing sorption capacity in the soil system. Biochar's physico-chemical properties, high CEC, surfaces containing abundant micropores and macropores, and various types of functional groups, play important roles in enhancing sorption capacity of contaminants. Aging through a natural weathering process might change physico-chemical properties of biochar amended in soils, which can affect the sorption behavior of contaminants. Thus, in this study, the sorption characteristics of phenanthrene (PHE) on biochar-amended soils were studied with various types of chars depending on aging time. To do this, 1) soil was amended with sludge waste char (SWC), wood char (WC), and municipal waste char (MWC) during 0, 6, and 12 month. Chars were applied to soil at 1% and 2.5% (w/w) ratio. 2) Several batch kinetic and equilibrium studies were conducted. One-compartment first order and two-compartment first order model apportioning the fraction of fast and slow sorbing were selected for kinetic models. Where, qt is PHE concentration in biochar-amended soils at each time t, qeis PHE concentration in biochar-amended soils at equilibrium. ff is fastly sorbing fraction and (1-ff) is slowly sorbing fraction. k is sorption rate constant from one-compartment first order model, k1 and k2 are sorption rate constant from two-compartment first order model, t is time (hr). The equilibrium sorption data were fitted with Fruendlich and Langmuir equation. 3) Change in physico-chemical properties of biochar-amended soils was investigated with aging time. Batch equilibrium sorption results suggested that sorbed amount of PHE on WC was greater than SWC and MWC. The more char contents added to soil, the greater sorption capacity of PHE. Sorption equilibrium was reached after 4 hours and equilibrium pH ranged from 6.5 to 8.0. Sorption capacity was reduced with aging time. From kinetic results, two-compartment first order model was more suitable than one-compartment first order model. Fast sorption site of biochar-amended soils dominated total sorption process (i.e., Fraction of fast sorption site ranged from 0.55 to 0.96). Reduced sorption capacity with aging time could be attributed to changes in physico-chemical properties of biochar-amended soils (e.g., reduced pores and increased hydrophilic carboxyl and carbonyl functional groups). Verification is FI-IR and SSA. It is assumed that biochar is a suitable material for PHE contaminated soil in order to reduce the lability of PHE. However, aging effects would lessen biochar benefit for reducing the sorption capacity of PHE by forming hydrophilic functional group and reducing pores.

Planar measurements of soot volume fraction and OH in a JP-8 pool fire

DOE Office of Scientific and Technical Information (OSTI.GOV)

Henriksen, Tara L.; Ring, Terry A.; Eddings, Eric G.

2009-07-15

The simultaneous measurement of soot volume fraction by laser induced incandescence (LII) and qualitative imaging of OH by laser induced fluorescence (LIF) was performed in a JP-8 pool fire contained in a 152 mm diameter pan. Line of sight extinction was used to calibrate the LII system in a laminar flame, and to provide an independent method of measuring average soot volume fraction in the turbulent flame. The presence of soot in the turbulent flame was found to be approximately 50% probable, resulting in high levels of optical extinction, which increased slightly through the flame from approximately 30% near themore » base, to approximately 50% at the tip. This high soot loading pushes both techniques toward their detection limit. Nevertheless, useful accuracy was obtained, with the LII measurement of apparent extinction in the turbulent flame being approximately 21% lower than a direct measurement, consistent with the influence of signal trapping. The axial and radial distributions of soot volume fraction are presented, along with PDFs of volume fraction, and new insight into the behavior of soot sheets in pool fires are sought from the simultaneous measurements of OH and LII. (author)« less

Iron Isotopic Fractionation in Igneous Systems: Looking for Anharmonicity

NASA Astrophysics Data System (ADS)

Dauphas, N.; Roskosz, M.; Hu, M. Y.; Neuville, D. R.; Alp, E. E.; Hu, J.; Heard, A.; Zhao, J.

2017-12-01

Igneous rocks display variations in their Fe isotopic compositions that can be used to trace partial melting, magma differentiation, the origin of mineral zoning, and metasomatic processes. While tremendous progress has been made in our understanding of how iron isotopes can be fractionated at equilibrium or during diffusion, significant work remains to be done to establish equilibrium fractionation factors between phases relevant to igneous petrology. A virtue of iron isotope systematics is that iron possesses a Mössbauer isotope, 57Fe, and one can use the method of NRIXS to measure the force constant of iron bonds, from which beta-factors can be calculated. These measurements are done at a few synchrotron beamlines around the world, such as sector 3ID of the APS (Argonne). Tremendous insights have already been gained by applying this technique to Earth science materials. It was shown for instance that significant equilibrium fractionation exists between Fe2+ and Fe3+ at magmatic temperature, that the iron isotopic fractionation resulting from core formation must be small, and that iron isotopic fractionation is influenced by the polymerization of the melt. Combining NRIXS and ab initio studies, there are approximately 130 geologically-relevant solids and aqueous species for which beta-factors have been reported. A potential limitation of applying published NRIXS data to igneous petrology is that all the force constants have been measured at room temperature and the beta-factors are extrapolated to magmatic temperatures assuming that the systems are harmonic, which has never been demonstrated. One way to test this critical assumption is to measure the apparent force constant of iron bonds at various temperatures, so that the interatomic potential of iron bonds can be probed. A further virtue of NRIXS is that the data also allows us to derive the mean square displacement. If significant anharmonicity is present, it should be manifested as a decrease in the apparent force constant with increasing temperature and increasing mean square displacement. We have measured the Fe force constant of basalt glass and olivine using a wire furnace. At the conference, we will report on these experiments and will discuss some implications for igneous petrology.

Predicting Rectal and Bladder Overdose During the Course of Prostate Radiotherapy Using Dose-Volume Data From Initial Treatment Fractions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Murthy, Vedang, E-mail: vmurthy@actrec.gov.in; Shukla, Pragya; Adurkar, Pranjal

2012-09-01

Purpose: To evaluate whether information from the initial fractions can determine which patients are likely to consistently exceed their planning dose-volume constraints during the course of radiotherapy for prostate cancer. Methods and Materials: Ten patients with high-risk prostate cancer were treated with helical tomotherapy to a dose of 60 Gy in 20 fractions. The prostate, rectum, and bladder were recontoured on their daily megavoltage computed tomography scans and the dose was recalculated. The bladder and rectal volumes (in mL) receiving {>=}100% and {>=}70% of the prescribed dose in each fraction and in the original plans were recorded. A fraction formore » which the difference between planned and delivered was more than 2 mL was considered a volume failure. Similarly if the difference in the planned and delivered maximum dose (D{sub max}) was {>=}1% for the rectum and bladder, the fraction was considered a dose failure. Each patient's first 3 to 5 fractions were analyzed to determine if they correctly identified those patients who would consistently fail (i.e., {>=}20% of fractions) during the course of their radiotherapy. Results: Six parameters were studied; the rectal volume (RV) and bladder volumes (BV) (in mL) received {>=}100% and {>=}70% of the prescribed dose and maximum dose to 2 mL of the rectum and bladder. This was given by RV{sub 100}, RV{sub 70}, BV{sub 100}, BV{sub 70}, RD{sub max}, and BD{sub max}, respectively. When more than 1 of the first 3 fractions exceed the planning constraint as defined, it accurately predicts consistent failures through the course of the treatment. This method is able to correctly identify the consistent failures about 80% (RV{sub 70}, BV{sub 100}, and RV{sub 100}), 90% (BV{sub 70}), and 100% (RD{sub max} and BD{sub max}) of the times. Conclusions: This study demonstrates the feasibility of a method accurately identifying patients who are likely to consistently exceed the planning constraints during the course of their treatment, using information from the first 3 to 5 fractions.« less

An energetic scale for equilibrium H/D fractionation factors illuminates hydrogen bond free energies in proteins

PubMed Central

Cao, Zheng; Bowie, James U

2014-01-01

Equilibrium H/D fractionation factors have been extensively employed to qualitatively assess hydrogen bond strengths in protein structure, enzyme active sites, and DNA. It remains unclear how fractionation factors correlate with hydrogen bond free energies, however. Here we develop an empirical relationship between fractionation factors and free energy, allowing for the simple and quantitative measurement of hydrogen bond free energies. Applying our empirical relationship to prior fractionation factor studies in proteins, we find: [1] Within the folded state, backbone hydrogen bonds are only marginally stronger on average in α-helices compared to β-sheets by ∼0.2 kcal/mol. [2] Charge-stabilized hydrogen bonds are stronger than neutral hydrogen bonds by ∼2 kcal/mol on average, and can be as strong as –7 kcal/mol. [3] Changes in a few hydrogen bonds during an enzyme catalytic cycle can stabilize an intermediate state by –4.2 kcal/mol. [4] Backbone hydrogen bonds can make a large overall contribution to the energetics of conformational changes, possibly playing an important role in directing conformational changes. [5] Backbone hydrogen bonding becomes more uniform overall upon ligand binding, which may facilitate participation of the entire protein structure in events at the active site. Our energetic scale provides a simple method for further exploration of hydrogen bond free energies. PMID:24501090

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sugano, Yasutaka; Mizuta, Masahiro; Takao, Seishin

Purpose: Radiotherapy of solid tumors has been performed with various fractionation regimens such as multi- and hypofractionations. However, the ability to optimize the fractionation regimen considering the physical dose distribution remains insufficient. This study aims to optimize the fractionation regimen, in which the authors propose a graphical method for selecting the optimal number of fractions (n) and dose per fraction (d) based on dose–volume histograms for tumor and normal tissues of organs around the tumor. Methods: Modified linear-quadratic models were employed to estimate the radiation effects on the tumor and an organ at risk (OAR), where the repopulation of themore » tumor cells and the linearity of the dose-response curve in the high dose range of the surviving fraction were considered. The minimization problem for the damage effect on the OAR was solved under the constraint that the radiation effect on the tumor is fixed by a graphical method. Here, the damage effect on the OAR was estimated based on the dose–volume histogram. Results: It was found that the optimization of fractionation scheme incorporating the dose–volume histogram is possible by employing appropriate cell surviving models. The graphical method considering the repopulation of tumor cells and a rectilinear response in the high dose range enables them to derive the optimal number of fractions and dose per fraction. For example, in the treatment of prostate cancer, the optimal fractionation was suggested to lie in the range of 8–32 fractions with a daily dose of 2.2–6.3 Gy. Conclusions: It is possible to optimize the number of fractions and dose per fraction based on the physical dose distribution (i.e., dose–volume histogram) by the graphical method considering the effects on tumor and OARs around the tumor. This method may stipulate a new guideline to optimize the fractionation regimen for physics-guided fractionation.« less

13C 18O clumping in speleothems: Observations from natural caves and precipitation experiments

NASA Astrophysics Data System (ADS)

Daëron, M.; Guo, W.; Eiler, J.; Genty, D.; Blamart, D.; Boch, R.; Drysdale, R.; Maire, R.; Wainer, K.; Zanchetta, G.

2011-06-01

The oxygen isotope composition of speleothems is an important proxy of continental paleoenvironments, because of its sensitivity to variations in cave temperature and drip water δ 18O. Interpreting speleothem δ 18O records in terms of absolute paleotemperatures and δ 18O values of paleo-precipitation requires quantitative separation of the effects of these two parameters, and correcting for possible kinetic isotope fractionation associated with precipitation of calcite out of thermodynamic equilibrium. Carbonate clumped-isotope thermometry, based on measurements of Δ47 (a geochemical variable reflecting the statistical overabundance of 13C 18O bonds in CO 2 evolved from phosphoric acid digestion of carbonate minerals), potentially provides a method for absolute speleothem paleotemperature reconstructions independent of drip water composition. Application of this new technique to karst records is currently limited by the scarcity of published clumped-isotope studies of modern speleothems. The only modern stalagmite reported so far in the literature yielded a lower Δ47 value than expected for equilibrium precipitation, possibly due to kinetic isotope fractionation. Here we report Δ47 values measured in natural speleothems from various cave settings, in carbonate produced by cave precipitation experiments, and in synthetic stalagmite analogs precipitated in controlled laboratory conditions designed to mimic natural cave processes. All samples yield lower Δ47 and heavier δ 18O values than predicted by experimental calibrations of thermodynamic equilibrium in inorganic calcite. The amplitudes of these isotopic disequilibria vary between samples, but there is clear correlation between the amount of Δ47 disequilibrium and that of δ 18O. Even pool carbonates believed to offer excellent conditions for equilibrium precipitation of calcite display out-of-equilibrium δ 18O and Δ47 values, probably inherited from prior degassing within the cave system. In addition to these modern observations, clumped-isotope analyses of a flowstone from Villars cave (France) offer evidence that the amount of disequilibrium affecting Δ47 in a single speleothem can experience large variations at time scales of 10 kyr. Application of clumped-isotope thermometry to speleothem records calls for an improved physical understanding of DIC fractionation processes in karst waters, and for the resolution of important issues regarding equilibrium calibration of Δ47 in inorganic carbonates.

Hyperdiffusive dynamics in Newtonian nanoparticle fluids [Hyperdiffusive dynamics in equilibrated nanoparticle fluids

DOE PAGES

Srivastava, Samanvaya; Agarwal, Praveen; Mangal, Rahul; ...

2015-09-24

Hyperdiffusive relaxations in soft glassy materials are typically associated with out-of-equilibrium states, and non-equilibrium physics and aging are often invoked in explaining their origins. Here, we report on hyperdiffusive motion in a model, equilibrium soft material comprised of single-component polymer-tethered-nanoparticles. In these materials, polymer mediated interactions lead to strong nanoparticle correlations, hyperdiffusive relaxations, and unusual variations of properties with temperature. Our experimental observations complement the current hypothesis that hyperdiffusive relaxations in soft materials require the material to exist in out–of–equilibrium states capable of driving structural rearrangements. Lastly, we propose alternatively that hyperdiffusive relaxations in our materials can arise naturally frommore » volume fluctuations brought about by equilibrium thermal forces.« less

Theory of Random Copolymer Fractionation in Columns

NASA Astrophysics Data System (ADS)

Enders, Sabine

Random copolymers show polydispersity both with respect to molecular weight and with respect to chemical composition, where the physical and chemical properties depend on both polydispersities. For special applications, the two-dimensional distribution function must adjusted to the application purpose. The adjustment can be achieved by polymer fractionation. From the thermodynamic point of view, the distribution function can be adjusted by the successive establishment of liquid-liquid equilibria (LLE) for suitable solutions of the polymer to be fractionated. The fractionation column is divided into theoretical stages. Assuming an LLE on each theoretical stage, the polymer fractionation can be modeled using phase equilibrium thermodynamics. As examples, simulations of stepwise fractionation in one direction, cross-fractionation in two directions, and two different column fractionations (Baker-Williams fractionation and continuous polymer fractionation) have been investigated. The simulation delivers the distribution according the molecular weight and chemical composition in every obtained fraction, depending on the operative properties, and is able to optimize the fractionation effectively.

Universality in volume-law entanglement of scrambled pure quantum states.

PubMed

Nakagawa, Yuya O; Watanabe, Masataka; Fujita, Hiroyuki; Sugiura, Sho

2018-04-24

A pure quantum state can fully describe thermal equilibrium as long as one focuses on local observables. The thermodynamic entropy can also be recovered as the entanglement entropy of small subsystems. When the size of the subsystem increases, however, quantum correlations break the correspondence and mandate a correction to this simple volume law. The elucidation of the size dependence of the entanglement entropy is thus essentially important in linking quantum physics with thermodynamics. Here we derive an analytic formula of the entanglement entropy for a class of pure states called cTPQ states representing equilibrium. We numerically find that our formula applies universally to any sufficiently scrambled pure state representing thermal equilibrium, i.e., energy eigenstates of non-integrable models and states after quantum quenches. Our formula is exploited as diagnostics for chaotic systems; it can distinguish integrable models from non-integrable models and many-body localization phases from chaotic phases.

Matrix-array 3-dimensional echocardiographic assessment of volumes, mass, and ejection fraction in young pediatric patients with a functional single ventricle: a comparison study with cardiac magnetic resonance.

PubMed

Soriano, Brian D; Hoch, Martin; Ithuralde, Alejandro; Geva, Tal; Powell, Andrew J; Kussman, Barry D; Graham, Dionne A; Tworetzky, Wayne; Marx, Gerald R

2008-04-08

Quantitative assessment of ventricular volumes and mass in pediatric patients with single-ventricle physiology would aid clinical management, but it is difficult to obtain with 2-dimensional echocardiography. The purpose of the present study was to compare matrix-array 3-dimensional echocardiography (3DE) measurements of single-ventricle volumes, mass, and ejection fraction with those measured by cardiac magnetic resonance (CMR) in young patients. Twenty-nine patients (median age, 7 months) with a functional single ventricle undergoing CMR under general anesthesia were prospectively enrolled. The 3DE images were acquired at the conclusion of the CMR. Twenty-seven of 29 3DE data sets (93%) were optimal for 3DE assessment. Two blinded and independent observers performed 3DE measurements of volume, mass, and ejection fraction. The 3DE end-diastolic volume correlated well (r=0.96) but was smaller than CMR by 9% (P<0.01), and 3DE ejection fraction was smaller than CMR by 11% (P<0.01). There was no significant difference in measurements of end-systolic volume and mass. The 3DE interobserver differences for mass and volumes were not significant except for ejection fraction (8% difference; P<0.05). Intraobserver differences were not significant. In young pediatric patients with a functional single ventricle, matrix-array 3DE measurements of mass and volumes compare well with those obtained by CMR. 3DE will provide an important modality for the serial analysis of ventricular size and performance in young patients with functional single ventricles.

Microscale models of partially molten rocks and their macroscale physical properties

NASA Astrophysics Data System (ADS)

Rudge, J. F.

2017-12-01

Any geodynamical model of melt transport in the Earth's mantle requires constitutive laws for the rheology of partially molten rock. These constitutive laws are poorly known, and one way to make progress in our understanding is through the upscaling of microscale models which describe physics at the scale of individual mineral grains. Crucially, many upscaled physical properties (such as permeability) depend not only on how much melt is present, but on how that melt is arranged at the microscale; i.e. on the geometry of the melt network. Here I will present some new calculations of equilibrium melt network geometries around idealised tetrakaidecahedral grains. In contrast to several previous calculations of textural equilibrium, these calculations allow for a both a liquid-phase and a solid-phase topology that can tile 3D space. The calculations are based on a simple minimisation of surface energy using the finite element method. In these simple models just two parameters control the topology of the melt network: the porosity (volume fraction of melt), and the dihedral angle. The consquences of these melt geometries for upscaled properties such as permeability; electrical conductivity; and importantly, effective viscosity will be explored. Recent theoretical work [1,2] has suggested that in diffusion creep a small amount of melt may dramatically reduce the effective shear viscosity of a partially molten rock, with profound consequences for the nature of the asthenosphere. This contribution will show that this reduction in viscosity may have been significantly overestimated, so that the drop in the effective viscosity at onset of melting is more modest. [1] Takei, Y., and B. K. Holtzman (2009), Viscous constitutive relations of solid-liquid composites in terms of grain boundary contiguity: 1. Grain boundary diffusion control model, J. Geophys. Res., 114, B06205.[2] Holtzmann B. K. (2016) Questions on the existence, persistence, and mechanical effects of a very small melt fraction in the asthenosphere, Geophys. Geochem. Geosyst. 17, 470-484.

Soot volume fraction fields in unsteady axis-symmetric flames by continuous laser extinction technique.

PubMed

Kashif, Muhammad; Bonnety, Jérôme; Guibert, Philippe; Morin, Céline; Legros, Guillaume

2012-12-17

A Laser Extinction Method has been set up to provide two-dimensional soot volume fraction field time history at a tunable frequency up to 70 Hz inside an axis-symmetric diffusion flame experiencing slow unsteady phenomena preserving the symmetry. The use of a continuous wave laser as the light source enables this repetition rate, which is an incremental advance in the laser extinction technique. The technique is shown to allow a fine description of the soot volume fraction field in a flickering flame exhibiting a 12.6 Hz flickering phenomenon. Within this range of repetition rate, the technique and its subsequent post-processing require neither any method for time-domain reconstruction nor any correction for energy intrusion. Possibly complemented by such a reconstruction method, the technique should support further soot volume fraction database in oscillating flames that exhibit characteristic times relevant to the current efforts in the validation of soot processes modeling.

Feasibility of Reducing the Fiber Content in Ultra-High-Performance Fiber-Reinforced Concrete under Flexure.

PubMed

Park, Jung-Jun; Yoo, Doo-Yeol; Park, Gi-Joon; Kim, Sung-Wook

2017-01-28

In this study, the flexural behavior of ultra-high-performance fiber-reinforced concrete (UHPFRC) is examined as a function of fiber length and volume fraction. Straight steel fiber with three different lengths ( l f ) of 13, 19.5, and 30 mm and four different volume fractions ( v f ) of 0.5%, 1.0%, 1.5%, and 2.0% are considered. Test results show that post-cracking flexural properties of UHPFRC, such as flexural strength, deflection capacity, toughness, and cracking behavior, improve with increasing fiber length and volume fraction, while first-cracking properties are not significantly influenced by fiber length and volume fraction. A 0.5 vol % reduction of steel fiber content relative to commercial UHPFRC can be achieved without deterioration of flexural performance by replacing short fibers ( l f of 13 mm) with longer fibers ( l f of 19.5 mm and 30 mm).

Feasibility of Reducing the Fiber Content in Ultra-High-Performance Fiber-Reinforced Concrete under Flexure

PubMed Central

Park, Jung-Jun; Yoo, Doo-Yeol; Park, Gi-Joon; Kim, Sung-Wook

2017-01-01

In this study, the flexural behavior of ultra-high-performance fiber-reinforced concrete (UHPFRC) is examined as a function of fiber length and volume fraction. Straight steel fiber with three different lengths (lf) of 13, 19.5, and 30 mm and four different volume fractions (vf) of 0.5%, 1.0%, 1.5%, and 2.0% are considered. Test results show that post-cracking flexural properties of UHPFRC, such as flexural strength, deflection capacity, toughness, and cracking behavior, improve with increasing fiber length and volume fraction, while first-cracking properties are not significantly influenced by fiber length and volume fraction. A 0.5 vol % reduction of steel fiber content relative to commercial UHPFRC can be achieved without deterioration of flexural performance by replacing short fibers (lf of 13 mm) with longer fibers (lf of 19.5 mm and 30 mm). PMID:28772477

Effective Thermal Conductivity of an Aluminum Foam + Water Two Phase System

NASA Technical Reports Server (NTRS)

Moskito, John

1996-01-01

This study examined the effect of volume fraction and pore size on the effective thermal conductivity of an aluminum foam and water system. Nine specimens of aluminum foam representing a matrix of three volume fractions (4-8% by vol.) and three pore sizes (2-4 mm) were tested with water to determine relationships to the effective thermal conductivity. It was determined that increases in volume fraction of the aluminum phase were correlated to increases in the effective thermal conductivity. It was not statistically possible to prove that changes in pore size of the aluminum foam correlated to changes in the effective thermal conductivity. However, interaction effects between the volume fraction and pore size of the foam were statistically significant. Ten theoretical models were selected from the published literature to compare against the experimental data. Models by Asaad, Hadley, and de Vries provided effective thermal conductivity predictions within a 95% confidence interval.

Electric-field-dependent phase volume fractions and enhanced piezoelectricity near the polymorphic phase boundary of (K0.5Na0.5)1-xLixNbO3 textured ceramics

NASA Astrophysics Data System (ADS)

Ge, Wenwei; Li, Jiefang; Viehland, D.; Chang, Yunfei; Messing, Gary L.

2011-06-01

The structure, ferroelectric and piezoelectric properties of <001> textured (K0.5Na0.5)0.98Li0.02NbO3 ceramics were investigated as a function of temperature and dc bias E. X-ray diffraction revealed an orthorhombic (O) → tetragonal (T) polymorphic phase boundary (PPB). Phase coexistence was found near the PPB over a 30 °C temperature range, where the relative phase volume fractions changed with temperature. Furthermore, increasing E applied along the <001> texture direction resulted in a notable increase in the volume fraction of the T phase at the expense of the O phase, effectively shifting the O → T boundary to lower temperature. An enhancement in the piezoelectric properties was found to accompany this increase in the T volume fraction.

Laser-induced incandescence calibration via gravimetric sampling

NASA Technical Reports Server (NTRS)

Choi, M. Y.; Vander Wal, R. L.; Zhou, Z.

1996-01-01

Absolute calibration of laser-induced incandescence (LII) is demonstrated via comparison of LII signal intensities with gravimetrically determined soot volume fractions. This calibration technique does not rely upon calculated or measured optical characteristics of soot. The variation of the LII signal with gravimetrically measured soot volume fractions ranging from 0.078 to 1.1 ppm established the linearly of the calibration. With the high spatial and temporal resolution capabilities of laser-induced incandescence (LII), the spatial and temporal fluctuations of the soot field within a gravimetric chimney were characterized. Radial uniformity of the soot volume fraction, f(sub v) was demonstrated with sufficient averaging of the single laser-shot LII images of the soot field thus confirming the validity of the calibration method for imaging applications. As illustration, instantaneous soot volume fractions within a Re = 5000 ethylene/air diffusion flame measured via planar LII were established quantitatively with this calibration.

Molecular controls on Cu and Zn isotopic fractionation in Fe-Mn crusts

NASA Astrophysics Data System (ADS)

Little, S. H.; Sherman, D. M.; Vance, D.; Hein, J. R.

2014-06-01

The isotopic systems of the transition metals are increasingly being developed as oceanic tracers, due to their tendency to be fractionated by biological and/or redox-related processes. However, for many of these promising isotope systems the molecular level controls on their isotopic fractionations are only just beginning to be explored. Here we investigate the relative roles of abiotic and biotic fractionation processes in controlling modern seawater Cu and Zn isotopic compositions. Scavenging to Fe-Mn oxides represents the principal output for Cu and Zn to sediments deposited under normal marine (oxic) conditions. Using Fe-Mn crusts as an analogue for these dispersed phases, we investigate the phase association and crystal chemistry of Cu and Zn in such sediments. We present the results of an EXAFS study that demonstrate unequivocally that Cu and Zn are predominantly associated with the birnessite (δ-MnO2) phase in Fe-Mn crusts, as previously predicted from sequential leaching experiments (e.g., Koschinsky and Hein, 2003). The crystal chemistry of Cu and Zn in the crusts implies a reduction in coordination number in the sorbed phase relative to the free metal ion in seawater. Thus, theory would predict equilibrium fractionations that enrich the heavy isotope in the sorbed phase (e.g., Schauble, 2004). In natural samples, Fe-Mn crusts and nodules are indeed isotopically heavy in Zn isotopes (at ∼1‰) compared to deep seawater (at ∼0.5‰), consistent with the predicted direction of equilibrium isotopic fractionation based on our observations of the coordination environment of sorbed Zn. Further, ∼50% of inorganic Zn‧ is chloro-complexed (the other ∼50% is present as the free Zn2+ ion), and complexation by Cl- is also predicted to favour equilibrium partitioning of light Zn isotopes into the dissolved phase. The heavy Zn isotopic composition of Fe-Mn crusts and nodules relative to seawater can therefore be explained by an inorganic fractionation during uptake. However, Cu in Fe-Mn crusts is isotopically light (at ∼0.3 to 0.5‰) compared to the dissolved phase in seawater (at ∼0.9‰). We suggest that this is because dissolved Cu in the oceans is overwhelmingly complexed to strong organic ligands, which are better competitors for the heavy isotope.

Cardiac cycle-dependent left atrial dynamics: implications for catheter ablation of atrial fibrillation.

PubMed

Patel, Amit R; Fatemi, Omid; Norton, Patrick T; West, J Jason; Helms, Adam S; Kramer, Christopher M; Ferguson, John D

2008-06-01

Left atrial (LA) volume determines prognosis and response to therapy for atrial fibrillation. Integration of electroanatomic maps with three-dimensional images rendered from computed tomography and magnetic resonance imaging (MRI) is used to facilitate atrial fibrillation ablation. The purpose of this study was to measure LA volume changes and regional motion during the cardiac cycle that might affect the accuracy of image integration and to determine their relationship to standard LA volume measurements. MRI was performed in 30 patients with paroxysmal atrial fibrillation. LA time-volume curves were generated and used to divide LA ejection fraction into pumping ejection fraction and conduit ejection fraction and to determine maximum LA volume (LA(max)) and preatrial contraction volume. LA volume was measured using an MRI angiogram and traditional geometric models from echocardiography (area-length model and ellipsoid model). In-plane displacement of the pulmonary veins, anterior left atrium, mitral annulus, and LA appendage was measured. LA(max) was 107 +/- 36 mL and occurred at 42% +/- 5% of the R-R interval. Preatrial contraction volume was 86 +/- 34 mL and occurred at 81% +/- 4% of the R-R interval. LA ejection fraction was 45% +/- 10%, and pumping ejection fraction was 31% +/- 10%. LA volume measurements made from MRI angiogram, area-length model, and ellipsoid model underestimated LA(max) by 21 +/- 25 mL, 16 +/- 26 mL, and 35 +/- 22 mL, respectively. Anterior LA, mitral annulus, and LA appendage were significantly displaced during the cardiac cycle (8.8 +/- 2.0 mm, 13.2 +/- 3.8 mm, and 10.2 +/- 3.4 mm, respectively); the pulmonary veins were not displaced. LA volume changes significantly during the cardiac cycle, and substantial regional variation in LA motion exists. Standard measurements of LA volume significantly underestimate LA(max) compared to the gold standard measure of three-dimensional volumetrics.

Chemical and isotopic fractionations by evaporation and their cosmochemical implications

NASA Astrophysics Data System (ADS)

Ozawa, Kazuhito; Nagahara, Hiroko

2001-07-01

A kinetic model for evaporation of a multi-component condensed phase with a fixed rate constant of the reaction is developed. A binary system with two isotopes for one of the components undergoing simple thermal histories (e.g., isothermal heating) is investigated in order to evaluate the extent of isotopic and chemical fractionations during evaporation. Diffusion in the condensed phase and the effect of back reaction from ambient gas are taken into consideration. Chemical and isotopic fractionation factors and the Péclet number for evaporation are the three main parameters that control the fractionation. Dust enrichment factor (η), the ratio of the initial dust quantity to that required for attainment of gas-dust equilibrium, is critical when back reactions become significant. Dust does not reach equilibrium with gas at η < 1. Notable chemical and isotopic fractionations usually take place under these conditions. There are two circumstances in which isotopic fractionation of a very volatile element does not accompany chemical fractionation during isothermal heating. One is free evaporation when diffusion in the condensed phase is very slow (η = 0), and the other is evaporation in the presence of ambient gas (η > 0). In the former case, a quasi-steady state in the diffusion boundary layer is maintained for isotopic fractionation but not for chemical fractionation. In the latter case, the back reaction brings the strong isotopic fractionation generated in the earlier stage of evaporation back to a negligibly small value in the later stage before complete evaporation. The model results are applied to cosmochemical fractionation of volatile elements during evaporation from a condensed phase that can be regarded as a binary solution phase. The wide range of potassium depletion without isotopic fractionation in various types of chondrules (Alexander et al., 2000) is explained by instantaneous heating followed by cooling in a closed system with various degrees of dust enrichment (η = 0.001-10) and cooling rates of less than ˜5°C/min. The extent of decoupling between isotopic and chemical fractionations of various elements in chondrules and matrix minerals may constrain the time scale and the conditions of heating and cooling processes in the early solar nebula.

Kinetic fractionation processes recorded in the stalagmites of some limestone caves in Korea

NASA Astrophysics Data System (ADS)

Woo, K. S.; Jo, K.; Edwards, L. R.; Cheng, H.; Wang, Y.; Yoon, H.

2006-12-01

Stable isotope data (oxygen and carbon) of carbonate minerals (mostly calcite, but sometimes aragonite) in stalagmites have been the most commonly and widely used proxies for paleoclimatic research. This is based upon the assumption that carbonate minerals precipitated in isotopic equilibrium with dripping waters from stalactites, thus should reflect paleoclimatic variations. The state of equilibrium, so called "Hendy Test", has been commonly used. Hendy (1971) showed that during kinetic fractionation both oxygen and carbon isotopes behaves in a similar way due to faster degassing rate of cabon dioxide, resulting in the enrichment of both isotopes. The stalagmites from three limestone caves (Gwaneum, Eden and Daeya Caves) in Korea were investigated to understand the effects of kinetic fractionation during their growth. The stalagmites are mostly composed of columnar calcites, but contains the layers of cave coral that is composed of fibrous calcite. The cave coral layers should have grown when the supply rate of dripping water decreased significantly. Stable isotope pattern in three stalagmites do not show the same pattern of disequilibrium process. The cave corals in the Eden stalagmite show the enriched carbon and oxygen isotope values (15 and 5 per mil, respectively) that has the same bimodal pattern as suggested by Hendy (1971). However, the cave corals in the Gwaneum stalagmites show the enriched carbon, but depleted oxygen isotope values (3 and 1 per mil, respectively). Also, the calcite layer precipitated in disequilibrium in the Daeya stalagmite show more enriched carbon isotope values by up to 6 per mil, but show more or less the same oxygen isotopic values, compared to the columnar calcite which was precipitated in equilibrium. Therefore, caution should be made to determine the state of equilibrium precipitation of carbonate minerals in stalagmites. The "Hendy Test" may not be the only solution because other types of speleothems can be formed in stalagmites as the supply rate of dripping water changes. Also, different texture in stalagmites can be used as another criteria to determine the degree of equilibrium.

Investigation of Micro- and Nanosized Particle Erosion in a 90° Pipe Bend Using a Two-Phase Discrete Phase Model

PubMed Central

Safaei, M. R.; Mahian, O.; Garoosi, F.; Hooman, K.; Karimipour, A.; Kazi, S. N.; Gharehkhani, S.

2014-01-01

This paper addresses erosion prediction in 3-D, 90° elbow for two-phase (solid and liquid) turbulent flow with low volume fraction of copper. For a range of particle sizes from 10 nm to 100 microns and particle volume fractions from 0.00 to 0.04, the simulations were performed for the velocity range of 5–20 m/s. The 3-D governing differential equations were discretized using finite volume method. The influences of size and concentration of micro- and nanoparticles, shear forces, and turbulence on erosion behavior of fluid flow were studied. The model predictions are compared with the earlier studies and a good agreement is found. The results indicate that the erosion rate is directly dependent on particles' size and volume fraction as well as flow velocity. It has been observed that the maximum pressure has direct relationship with the particle volume fraction and velocity but has a reverse relationship with the particle diameter. It also has been noted that there is a threshold velocity as well as a threshold particle size, beyond which significant erosion effects kick in. The average friction factor is independent of the particle size and volume fraction at a given fluid velocity but increases with the increase of inlet velocities. PMID:25379542

Magnetic susceptibility, artifact volume in MRI, and tensile properties of swaged Zr-Ag composites for biomedical applications.

PubMed

Imai, Haruki; Tanaka, Yoji; Nomura, Naoyuki; Doi, Hisashi; Tsutsumi, Yusuke; Ono, Takashi; Hanawa, Takao

2017-02-01

Zr-Ag composites were fabricated to decrease the magnetic susceptibility by compensating for the magnetic susceptibility of their components. The Zr-Ag composites with a different Zr-Ag ratio were swaged, and their magnetic susceptibility, artifact volume, and mechanical properties were evaluated by magnetic balance, three-dimensional (3-D) artifact rendering, and a tensile test, respectively. These properties were correlated with the volume fraction of Ag using the linear rule of mixture. We successfully obtained the swaged Zr-Ag composites up to the reduction ratio of 96% for Zr-4, 16, 36, 64Ag and 86% for Zr-81Ag. However, the volume fraction of Ag after swaging tended to be lower than that before swaging, especially for Ag-rich Zr-Ag composites. The magnetic susceptibility of the composites linearly decreased with the increasing volume fraction of Ag. No artifact could be estimated with the Ag volume fraction in the range from 93.7% to 95.4% in three conditions. Young's modulus, ultimate tensile strength (UTS), and 0.2% yield strength of Zr-Ag composites showed slightly lower values compared to the estimated values using a linear rule of mixture. The decrease in magnetic susceptibility of Zr and Ag by alloying or combining would contribute to the decrease of the Ag fraction, leading to the improvement of mechanical properties. Copyright © 2016 Elsevier Ltd. All rights reserved.

Design and implementation of grid multi-scroll fractional-order chaotic attractors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Liping, E-mail: lip-chenhut@126.com; Pan, Wei; Wu, Ranchao

2016-08-15

This paper proposes a novel approach for generating multi-scroll chaotic attractors in multi-directions for fractional-order (FO) systems. The stair nonlinear function series and the saturated nonlinear function are combined to extend equilibrium points with index 2 in a new FO linear system. With the help of stability theory of FO systems, stability of its equilibrium points is analyzed, and the chaotic behaviors are validated through phase portraits, Lyapunov exponents, and Poincaré section. Choosing the order 0.96 as an example, a circuit for generating 2-D grid multiscroll chaotic attractors is designed, and 2-D 9 × 9 grid FO attractors are observed at most.more » Numerical simulations and circuit experimental results show that the method is feasible and the designed circuit is correct.« less

Multiple-collision analysis of characteristic X-rays from low-energy Ar 2+ travelling in solid targets

NASA Astrophysics Data System (ADS)

Cipolla, Sam J.; Mildebrath, Mark E.

1983-12-01

The density of atoms in a solid target fosters a multiple-collision mechanism that leads to the production of an equilibrium fraction of L-shell vacancies in an incident heavy ion. It is then possiblein a subsequent ion-atom collision in the solid for an L-vacancy to be transferred to the K-shell of a target atom via rotational coupling of the 2p π-2p σ molecular orbitals formed in the ion-atom quasimolecule. The vacancy-transfer cross section and the equilibrium fraction and lifetime of the vacancies can be found by using an appropriate multiple-collision analysis of the characteristic target and projectile X-rays. Results will be presented for 160-380 keV Ar 2+ incident of targets of Mg, Al, and Si.

31P NMR spectroscopy studies of phospholipid metabolism in human melanoma xenograft lines differing in rate of tumour cell proliferation.

PubMed

Lyng, H; Olsen, D R; Petersen, S B; Rofstad, E K

1995-04-01

The concentration of phospholipid metabolites in tumours has been hypothesized to be related to rate of cell membrane turnover and may reflect rate of cell proliferation. The purpose of the study reported here was to investigate whether 31P NMR resonance ratios involving the phosphomonoester (PME) or phosphodiester (PDE) resonance are correlated to fraction of cells in S-phase or volume-doubling time in experimental tumours. Four human melanoma xenograft lines (BEX-t, HUX-t, SAX-t, WIX-t) were included in the study. The tumours were grown subcutaneously in male BALB/c-nu/nu mice. 31P NMR spectroscopy was performed at a magnetic field strength of 4.7 T. Fraction of cells in S-phase was measured by flow cytometry. Tumour volume-doubling time was determined by Gompertzian analysis of volumetric growth data. BEX-t and SAX-t tumours differed in fraction of cells in S-phase and volume-doubling time, but showed similar 31P NMR resonance ratios. BEX-t and WIX-t tumours showed significantly different 31P NMR resonance ratios but similar fractions of cells in S-phase. The 31P NMR resonance ratios were significantly different for small and large HUX-t tumours even though fraction of cells in S-phase and volume-doubling time did not differ with tumour volume. None of the 31P NMR resonance ratios showed significant increase with increasing fraction of cells in S-phase or significant decrease with increasing tumour volume-doubling time across the four xenograft lines.(ABSTRACT TRUNCATED AT 250 WORDS)

Soot Volume Fraction Maps for Normal and Reduced Gravity Laminar Acetylene Jet Diffusion Flames

NASA Technical Reports Server (NTRS)

Greenberg, Paul S.; Ku, Jerry C.

1997-01-01

The study of soot particulate distribution inside gas jet diffusion flames is important to the understanding of fundamental soot particle and thermal radiative transport processes, as well as providing findings relevant to spacecraft fire safety, soot emissions, and radiant heat loads for combustors used in air-breathing propulsion systems. Compared to those under normal gravity (1-g) conditions, the elimination of buoyancy-induced flows is expected to significantly change the flow field in microgravity (O g) flames, resulting in taller and wider flames with longer particle residence times. Work by Bahadori and Edelman demonstrate many previously unreported qualitative and semi-quantitative results, including flame shape and radiation, for sooting laminar zas jet diffusion flames. Work by Ku et al. report soot aggregate size and morphology analyses and data and model predictions of soot volume fraction maps for various gas jet diffusion flames. In this study, we present the first 1-g and 0-g comparisons of soot volume fraction maps for laminar acetylene and nitrogen-diluted acetylene jet diffusion flames. Volume fraction is one of the most useful properties in the study of sooting diffusion flames. The amount of radiation heat transfer depends directly on the volume fraction and this parameter can be measured from line-of-sight extinction measurements. Although most Soot aggregates are submicron in size, the primary particles (20 to 50 nm in diameter) are in the Rayleigh limit, so the extinction absorption) cross section of aggregates can be accurately approximated by the Rayleigh solution as a function of incident wavelength, particles' complex refractive index, and particles' volume fraction.

A test of the significance of intermolecular vibrational coupling in isotopic fractionation

DOE PAGES

Herman, Michael F.; Currier, Robert P.; Peery, Travis B.; ...

2017-07-15

Intermolecular coupling of dipole moments is studied for a model system consisting of two diatomic molecules (AB monomers) arranged co-linearly and which can form non-covalently bound dimers. The dipolar coupling is a function of the bond length in each molecule as well as of the distance between the centers-of-mass of the two molecules. The calculations show that intermolecular coupling of the vibrations results in an isotope-dependent modification of the AB-AB intermolecular potential. This in turn alters the energies of the low-lying bound states of the dimers, producing isotope-dependent changes in the AB-AB dimer partition function. Explicit inclusion of intermolecular vibrationalmore » coupling then changes the predicted gas-dimer isotopic fractionation. In addition, a mass dependence in the intermolecular potential can also result in changes in the number of bound dimer states in an equilibrium mixture. This in turn leads to a significant dimer population shift in the model monomer-dimer equilibrium system considered here. Finally, the results suggest that intermolecular coupling terms should be considered when probing the origins of isotopic fractionation.« less

Global Mittag-Leffler stability and synchronization analysis of fractional-order quaternion-valued neural networks with linear threshold neurons.

PubMed

Yang, Xujun; Li, Chuandong; Song, Qiankun; Chen, Jiyang; Huang, Junjian

2018-05-04

This paper talks about the stability and synchronization problems of fractional-order quaternion-valued neural networks (FQVNNs) with linear threshold neurons. On account of the non-commutativity of quaternion multiplication resulting from Hamilton rules, the FQVNN models are separated into four real-valued neural network (RVNN) models. Consequently, the dynamic analysis of FQVNNs can be realized by investigating the real-valued ones. Based on the method of M-matrix, the existence and uniqueness of the equilibrium point of the FQVNNs are obtained without detailed proof. Afterwards, several sufficient criteria ensuring the global Mittag-Leffler stability for the unique equilibrium point of the FQVNNs are derived by applying the Lyapunov direct method, the theory of fractional differential equation, the theory of matrix eigenvalue, and some inequality techniques. In the meanwhile, global Mittag-Leffler synchronization for the drive-response models of the addressed FQVNNs are investigated explicitly. Finally, simulation examples are designed to verify the feasibility and availability of the theoretical results. Copyright © 2018 Elsevier Ltd. All rights reserved.

Achieving Chemical Equilibrium: The Role of Imposed Conditions in the Ammonia Formation Reaction

ERIC Educational Resources Information Center

Tellinghuisen, Joel

2006-01-01

Under conditions of constant temperature T and pressure P, chemical equilibrium occurs in a closed system (fixed mass) when the Gibbs free energy G of the reaction mixture is minimized. However, when chemical reactions occur under other conditions, other thermodynamic functions are minimized or maximized. For processes at constant T and volume V,…

Equilibrium shapes of drops on membranes

NASA Astrophysics Data System (ADS)

Sharma, Ishan; Nair, Vineet; Shankar, Viswanathan

2017-11-01

Equilibrium shapes for axisymmetric sessile and pendant drops placed on / attached to geometrically nonlinear elastic membranes, in horizontal as well as inclined configurations, are obtained. The effective contact angle of the drop with the membrane, its contact radius, the maximum membrane displacement, and the volume of the drop is investigated for various values of Bond Number and membrane tension.

[Grain Size Distribution Characteristics of Suspended Particulate Matter as Influenced by the Apparent Pollution in the Eutrophic Urban Landscape Water Body].

PubMed

Gong, Dan-yan; Pan, Yang; Huang, Yong; Bao, Wei; Li, Qian-qian

2016-03-15

Grain size distribution characteristics of suspended particulate matter (SPM) reflects the apparent polluted condition of the urban landscape water. In order to explore the internal relationship between the eutrophication of urban landscape water's apparent pollution and grain size distribution of SPM, and its influencing factors, this paper selected five representative sampling sites in Feng Jin River which is a typical eutrophication river in Suzhou City, measured the grain size distribution of SPM, sensation pollution index (SPI) and water quality index, and analyzed their correlation. The results showed that: The rich nutrient water possessed a similar characteristics in grain size distribution. The grain size distribution of SPM in water was multimodal, and the the peak position was roughly the same; the grain size distribution of SPM was composed by multiple components. It could be roughly divided into six parts with the particle size range of every group being < 1.5 µm, 1.5-8 µm, 8-35 µm, 35-186 µm, 186-516 µm, > 516 µm. The component III was superior (with an average volume fraction of 38.3%-43.2%), and its volume fraction had a significant positive relation with the SPI value and the Chl-a content. The increase of component III volume fraction was the reflection of particle size's result of increasing SPI value. The increase of component III volume fraction was mainly derived from the increasing algal content. The volume fraction of group IV + group VI + group V was significantly higher under the condition of exogenous enter. When there was no exogenous component, the volume fraction of group IV + group VI + group V had a significant negative correlation with SPI value; when there were exogenous components, the volume fraction of group IV + group VI + group V had a weak positive correlation with SPI value, but the correlation did not reach a significant level. Environmental factors (Fv/Fm and DO) and exogenous factors had an influence by functioning on the algal content which signified the polluted material, and then affected the volume fraction of particle size's components and the quality of apparent water. Hydrodynamic conditions mainly had a certain influence on the median particle size, and had no effect on the apparent polluted condition of water.

Structural and water diffusion of poly(acryl amide)/poly(vinyl alcohol) blend films: Experiment and molecular dynamics simulations.

PubMed

Wang, Yanen; Wei, Qinghua; Wang, Shuzhi; Chai, Weihong; Zhang, Yingfeng

2017-01-01

To study the effects of composition ratios and temperature on the diffusion of water molecules in PVA/PAM blend films, five simulation models of PVA/PAM with ten water molecules at different composition ratios (4/0, 3/1, 2/2, 1/3, 0/4) were constructed and simulated by using a molecular dynamics (MD) simulation. The diffusion behavior of water molecules in blends were investigated from the aspects of the diffusion coefficient, free volume, pair correlation function (PCF) and trajectories of water molecules, respectively. And the hydrophilicity of blend composite was studied based on the contact angle and equilibrium water content (EWC) of the blend films. The simulation results show that the diffusion coefficient of water molecules and fractional free volume (FFV) of blend membranes increase with the addition of PAM, and a higher temperature can also improve the diffusion of water molecules. Additionally, the analysis of PCFs reveals the main reason why the diffusion coefficient of water in blend system increases with the addition of PAM. The measurement results of contact angle and EWC of blend films indicate that the hydrophilicity of blend films decreases with the addition of PAM, but the EWC of blends increases with the addition of PAM. Copyright © 2016 Elsevier Inc. All rights reserved.

Primary Phase Field of the Pb-Doped 2223 High-Tc Superconductor in the (Bi, Pb)-Sr-Ca-Cu-O System

PubMed Central

Wong-Ng, W.; Cook, L. P.; Kearsley, A.; Greenwood, W.

1999-01-01

Both liquidus and subsolidus phase equilibrium data are of central importance for applications of high temperature superconductors in the (Bi, Pb)-Sr-Ca-Cu-O system, including material synthesis, melt processing and single crystal growth. The subsolidus equilibria of the 110 K high-Tc Pb-doped 2223 ([Bi, Pb], Sr, Ca, Cu) phase and the location of the primary phase field (crystallization field) have been determined in this study. For the quantitative determination of liquidus data, a wicking technique was developed to capture the melt for quantitative microchemical analysis. A total of 29 five-phase volumes that include the 2223 phase as a component was obtained. The initial melt compositions of these volumes range from a mole fraction of 7.3 % to 28.0 % for Bi, 11.3 % to 27.8 % for Sr, 1.2 % to 19.4 % for Pb, 9.8 % to 30.8 % for Ca, and 17.1 % to 47.0 % for Cu. Based on these data, the crystallization field for the 2223 phase was constructed using the convex hull technique. A section of this “volume” was obtained by holding two components of the composition at the median value, allowing projection on the other three axes to show the extent of the field.

Standard filtration practices may significantly distort planktonic microbial diversity estimates.

PubMed

Padilla, Cory C; Ganesh, Sangita; Gantt, Shelby; Huhman, Alex; Parris, Darren J; Sarode, Neha; Stewart, Frank J

2015-01-01

Fractionation of biomass by filtration is a standard method for sampling planktonic microbes. It is unclear how the taxonomic composition of filtered biomass changes depending on sample volume. Using seawater from a marine oxygen minimum zone, we quantified the 16S rRNA gene composition of biomass on a prefilter (1.6 μm pore-size) and a downstream 0.2 μm filter over sample volumes from 0.05 to 5 L. Significant community shifts occurred in both filter fractions, and were most dramatic in the prefilter community. Sequences matching Vibrionales decreased from ~40 to 60% of prefilter datasets at low volumes (0.05-0.5 L) to less than 5% at higher volumes, while groups such at the Chromatiales and Thiohalorhabdales followed opposite trends, increasing from minor representation to become the dominant taxa at higher volumes. Groups often associated with marine particles, including members of the Deltaproteobacteria, Planctomycetes, and Bacteroidetes, were among those showing the greatest increase with volume (4 to 27-fold). Taxon richness (97% similarity clusters) also varied significantly with volume, and in opposing directions depending on filter fraction, highlighting potential biases in community complexity estimates. These data raise concerns for studies using filter fractionation for quantitative comparisons of aquatic microbial diversity, for example between free-living and particle-associated communities.

Magnesium Isotopic Evidence for Widespread Microbial Dolomite Precipitation in the Geological Record.

NASA Astrophysics Data System (ADS)

Carder, E. A.; Galy, A.; McKenzie, J. A.; Vasconcelos, C.; Elderfield, H.

2005-12-01

The enigma surrounding the `Dolomite Problem' is the relative abundance of dolomite in the geological record versus its very rare occurrence on the surface of the modern Earth despite a particularly favourable modern seawater chemistry. Recent studies of modern dolomite from hypersaline coastal lagoons in Brazil and Pleistocene dolomite from ODP cores collected during ODP Leg 201 on the Peru Margin suggest microbial mediation is an important factor [1]. Indeed, cultures of sulfate-reducing bacteria isolated from the lagoons mediate dolomite precipitation in the laboratory [2, 3]. In this study we report magnesium isotopic analyses of these modern microbial associated dolomites and ancient dolomites of a range of geological ages and environments. The application of stable magnesium isotopes to study dolomite formation and the nature of the processes involved represents a new frontier in isotope geochemistry. Highly accurate determination of the magnesium isotopic composition allows us to distinguish between kinetic and equilibrium isotope fractionation on the basis of the excess of 25Mg. A significant kinetic isotope fractionation is observed in laboratory cultures and surfical microbial mats from the Brazilian lagoons. Older dolomites (<3000 yrs.) taken from cores recovered from the lagoon are much closer to equilibrium. We interpret our data as evidencing an initial microbial mediated nucleation of dolomite that is a kinetic process and a subsequent inorganic addition of dolomite overprinting an equilibrium signature. This is in agreement with a previous major element and crystallographic study of the Brazilian dolomites [1]. The ancient dolomites analysed range in age from Neoproterozoic to Pleistocene and come from diverse geological environments including submarine diagenetic zones, platform carbonates and lagoonal environments. Magnesium isotopic analysis shows evidence of a varying component of kinetic fractionation, smaller than the kinetic end member as typified by the laboratory cultures. The ancient dolomites appear to evidence the same initial kinetic nucleation and subsequent equilibrium growth as the modern. In contrast, hydrothermal dolomite exhibits only equilibrium fractionation. Taken together, our results argue for a strong biological role in magnesium fixation into sedimentary dolomite in both the ancient and modern and suggest microbial processes are important in resolving the `Dolomite Problem'. References [1] Vasconcelos, C. and McKenzie, J.A., (1997), J. Sed. Res., 67, 378-390. [2] Vasconcelos, C., McKenzie, J.A., Bernasconi, S., Grujic, D. and Tien, A.J., (1995), Nature 377, 220-222. [3] Warthmann R., van Lith Y., Vasconcelos C., McKenzie J.A. and Karpoff A.M., (2000), Geology 28, 1091-1094.

A sub-grid, mixture-fraction-based thermodynamic equilibrium model for gas phase combustion in FIRETEC: development and results

Treesearch

M. M. Clark; T. H. Fletcher; R. R. Linn

2010-01-01

The chemical processes of gas phase combustion in wildland fires are complex and occur at length-scales that are not resolved in computational fluid dynamics (CFD) models of landscape-scale wildland fire. A new approach for modelling fire chemistry in HIGRAD/FIRETEC (a landscape-scale CFD wildfire model) applies a mixture– fraction model relying on thermodynamic...

Oxygen isotope fractionation in the siderite-water system between 8.5 and 62 °C

NASA Astrophysics Data System (ADS)

van Dijk, Joep; Fernandez, Alvaro; Müller, Inigo A.; Lever, Mark; Bernasconi, Stefano M.

2018-01-01

The oxygen isotope composition of siderites can be used to deduce the temperature and/or oxygen isotope composition of the fluids from which they precipitated. Previous siderite-water oxygen isotope fractionation calibrations are not well constrained at temperatures below 33 °C where most of the siderite forms at the Earth's surface. Moreover, the few experimental low temperature calibration points available are possibly inaccurate as the corresponding siderites may not have formed in equilibrium with the solution. In this study, we synthesized siderite in the laboratory from 8.5 to 62 °C, using both active-degassing experiments and microbial cultures. We used the enzyme carbonic anhydrase, which significantly reduces the equilibration time of oxygen isotopes among all dissolved inorganic carbon (DIC) species and water to minimize siderite formation out of equilibrium. Our calibration is based on many more data points than previous calibrations and significantly reduces the uncertainty in siderite-water oxygen isotope fractionation in natural siderites formed at low temperatures. The best fit equation is 1000 * ln α = 19.67 ± 0.42(103/T) -36.27 ± 1.34 where α (1000+δ18Osiderite/1000+δ18Owater) is the fractionation factor and T is the temperature in Kelvin.

Can Fractional Crystallization of a Lunar Magma Ocean Produce the Lunar Crust?

NASA Technical Reports Server (NTRS)

Rapp, Jennifer F.; Draper, David S.

2013-01-01

New techniques enable the study of Apollo samples and lunar meteorites in unprecedented detail, and recent orbital spectral data reveal more about the lunar farside than ever before, raising new questions about the supposed simplicity of lunar geology. Nevertheless, crystallization of a global-scale magma ocean remains the best model to account for known lunar lithologies. Crystallization of a lunar magma ocean (LMO) is modeled to proceed by two end-member processes - fractional crystallization from (mostly) the bottom up, or initial equilibrium crystallization as the magma is vigorously convecting and crystals remain entrained, followed by crystal settling and a final period of fractional crystallization [1]. Physical models of magma viscosity and convection at this scale suggest that both processes are possible. We have been carrying out high-fidelity experimental simulations of LMO crystallization using two bulk compositions that can be regarded as end-members in the likely relevant range: Taylor Whole Moon (TWM) [2] and Lunar Primitive Upper Mantle (LPUM) [3]. TWM is enriched in refractory elements by 1.5 times relative to Earth, whereas LPUM is similar to the terrestrial primitive upper mantle, with adjustments made for the depletion of volatile alkalis observed on the Moon. Here we extend our earlier equilibrium-crystallization experiments [4] with runs simulating full fractional crystallization

Implementation of Radiation, Ablation, and Free Energy Minimization Modules for Coupled Simulations of Hypersonic Flow

NASA Technical Reports Server (NTRS)

Gnoffo, Peter A.; Johnston, Christopher O.; Thompson, Richard A.

2009-01-01

A description of models and boundary conditions required for coupling radiation and ablation physics to a hypersonic flow simulation is provided. Chemical equilibrium routines for varying elemental mass fraction are required in the flow solver to integrate with the equilibrium chemistry assumption employed in the ablation models. The capability also enables an equilibrium catalytic wall boundary condition in the non-ablating case. The paper focuses on numerical implementation issues using FIRE II, Mars return, and Apollo 4 applications to provide context for discussion. Variable relaxation factors applied to the Jacobian elements of partial equilibrium relations required for convergence are defined. Challenges of strong radiation coupling in a shock capturing algorithm are addressed. Results are presented to show how the current suite of models responds to a wide variety of conditions involving coupled radiation and ablation.

Formation of Minor Phases in a Nickel-Based Disk Superalloy

NASA Technical Reports Server (NTRS)

Gabb, T. P.; Garg, A.; Miller, D. R.; Sudbrack, C. K.; Hull, D. R.; Johnson, D.; Rogers, R. B.; Gayda, J.; Semiatin, S. L.

2012-01-01

The minor phases of powder metallurgy disk superalloy LSHR were studied. Samples were consistently heat treated at three different temperatures for long times to approximate equilibrium. Additional heat treatments were also performed for shorter times, to then assess non-equilibrium conditions. Minor phases including MC carbides, M23C6 carbides, M3B2 borides, and sigma were identified. Their transformation temperatures, lattice parameters, compositions, average sizes and total area fractions were determined, and compared to estimates of an existing phase prediction software package. Parameters measured at equilibrium sometimes agreed reasonably well with software model estimates, with potential for further improvements. Results for shorter times representing non-equilibrium indicated significant potential for further extension of the software to such conditions, which are more commonly observed during heat treatments and service at high temperatures for disk applications.

On the adaptive sliding mode controller for a hyperchaotic fractional-order financial system

NASA Astrophysics Data System (ADS)

Hajipour, Ahamad; Hajipour, Mojtaba; Baleanu, Dumitru

2018-05-01

This manuscript mainly focuses on the construction, dynamic analysis and control of a new fractional-order financial system. The basic dynamical behaviors of the proposed system are studied such as the equilibrium points and their stability, Lyapunov exponents, bifurcation diagrams, phase portraits of state variables and the intervals of system parameters. It is shown that the system exhibits hyperchaotic behavior for a number of system parameters and fractional-order values. To stabilize the proposed hyperchaotic fractional system with uncertain dynamics and disturbances, an efficient adaptive sliding mode controller technique is developed. Using the proposed technique, two hyperchaotic fractional-order financial systems are also synchronized. Numerical simulations are presented to verify the successful performance of the designed controllers.

Analytical functions for beta and gamma absorbed fractions of iodine-131 in spherical and ellipsoidal volumes.

PubMed

Mowlavi, Ali Asghar; Fornasier, Maria Rossa; Mirzaei, Mohammd; Bregant, Paola; de Denaro, Mario

2014-10-01

The beta and gamma absorbed fractions in organs and tissues are the important key factors of radionuclide internal dosimetry based on Medical Internal Radiation Dose (MIRD) approach. The aim of this study is to find suitable analytical functions for beta and gamma absorbed fractions in spherical and ellipsoidal volumes with a uniform distribution of iodine-131 radionuclide. MCNPX code has been used to calculate the energy absorption from beta and gamma rays of iodine-131 uniformly distributed inside different ellipsoids and spheres, and then the absorbed fractions have been evaluated. We have found the fit parameters of a suitable analytical function for the beta absorbed fraction, depending on a generalized radius for ellipsoid based on the radius of sphere, and a linear fit function for the gamma absorbed fraction. The analytical functions that we obtained from fitting process in Monte Carlo data can be used for obtaining the absorbed fractions of iodine-131 beta and gamma rays for any volume of the thyroid lobe. Moreover, our results for the spheres are in good agreement with the results of MIRD and other scientific literatures.

Spreading of a pendant liquid drop underneath a textured substrate

NASA Astrophysics Data System (ADS)

Mistry, Aashutosh; Muralidhar, K.

2018-04-01

A pendant drop spreading underneath a partially wetting surface from an initial shape to its final equilibrium configuration and contact angle is studied. A mathematical formulation that quantifies spreading behavior of liquid drops over textured surfaces is discussed. The drop volume and the equilibrium contact angle are treated as parameters in the study. The unbalanced force at the three-phase contact line is modeled as being proportional to the degree of departure from the equilibrium state. Model predictions are verified against the available experimental data in the literature. Results show that the flow dynamics is strongly influenced by the fluid properties, drop volume, and contact angle of the liquid with the partially wetting surface. The drop exhibits rich dynamical behavior including inertial oscillations and gravitational instability, given that gravity tries to detach the drop against wetting contributions. Flow characteristics of drop motion, namely, the radius of the footprint, slip length, and dynamic contact angle in the pendant configuration are presented. Given the interplay among the competing time-dependent forces, a spreading drop can momentarily be destabilized and not achieve a stable equilibrium shape. Instability is then controlled by the initial drop shape as well. The spreading model is used to delineate stable and unstable regimes in the parameter space. Predictions of the drop volume based on the Young-Laplace equation are seen to be conservative relative to the estimates of the dynamical model discussed in the present study.

Oxygen isotope geochemistry of the amphiboles: isotope effects of cation substitutions in minerals

NASA Astrophysics Data System (ADS)

Kohn, Matthew J.; Valley, John W.

1998-06-01

The occurrence of coexisting amphiboles in rocks and the likelihood of concurrent isotope closure allows equilibrium oxygen isotope fractionations among the amphiboles to be recovered from natural samples. Oxygen isotope analyses of mineral separates using laser fluorination show that coexisting amphiboles increasingly partition 18O in the order: hornblende ≪ gedrite < cummingtonite ≤ anthophyllite. The observed fractionations at ˜575°C are: Δ(Ged-Hbl) = 0.8‰, Δ(Cum-Hbl) = 0.9, Δ(Cum-Ged) = 0.2, Δ(Ath-Ged) = 0.3, and Δ(Ath-Hbl) > 0.9. Previously published data for hornblende, actinolite, glaucophane, and garnet show that Δ(Act-Hbl) ˜ 0.2, Δ(Gln-Grt) ≫ 1, and Δ(Hbl-Grt) ˜ 0. Thus, glaucophane strongly partitions 18O relative to the calcic amphiboles. The fractionation between two amphiboles of arbitrary composition can be predicted from the known fractionations for mica endmembers, pyroxene endmembers, and exchange components such as CaAl(NaSi) -1, NaAl(CaMg) -1, CaMg -1, MgFe -1, FeMn -1, KNa -1, KAl( Si) -1, and Fe 3+Al -1. Applications of the exchange component method reproduce measured amphibole fractionations to within ±0.1 to ±0.2‰, whereas other predictive methods cause misfit for typical metamorphic hornblende of ≥0.5‰ at 575°C. Although the isotope effects of cation exchanges may be small at high-T, they magnify dramatically for minerals formed in surficial, diagenetic, and low-T metamorphic environments. Different composition clays are predicted to have equilibrium δ 18O differences of 2-9‰. If the isotope fractionation can be determined for one mineral endmember, then calibrated exchanges allow accurate prediction of the isotope fractionations for intermediate compositions of most ortho-, ring-, chain-, and sheet-silicates.

Fractionation of Cu and Zn isotopes during adsorption onto amorphous Fe(III) oxyhydroxide: Experimental mixing of acid rock drainage and ambient river water

USGS Publications Warehouse

Balistrieri, L.S.; Borrok, D.M.; Wanty, R.B.; Ridley, W.I.

2008-01-01

Fractionation of Cu and Zn isotopes during adsorption onto amorphous ferric oxyhydroxide is examined in experimental mixtures of metal-rich acid rock drainage and relatively pure river water and during batch adsorption experiments using synthetic ferrihydrite. A diverse set of Cu- and Zn-bearing solutions was examined, including natural waters, complex synthetic acid rock drainage, and simple NaNO3 electrolyte. Metal adsorption data are combined with isotopic measurements of dissolved Cu (65Cu/63Cu) and Zn (66Zn/64Zn) in each of the experiments. Fractionation of Cu and Zn isotopes occurs during adsorption of the metal onto amorphous ferric oxyhydroxide. The adsorption data are modeled successfully using the diffuse double layer model in PHREEQC. The isotopic data are best described by a closed system, equilibrium exchange model. The fractionation factors (??soln-solid) are 0.99927 ?? 0.00008 for Cu and 0.99948 ?? 0.00004 for Zn or, alternately, the separation factors (??soln-solid) are -0.73 ?? 0.08??? for Cu and -0.52 ?? 0.04??? for Zn. These factors indicate that the heavier isotope preferentially adsorbs onto the oxyhydroxide surface, which is consistent with shorter metal-oxygen bonds and lower coordination number for the metal at the surface relative to the aqueous ion. Fractionation of Cu isotopes also is greater than that for Zn isotopes. Limited isotopic data for adsorption of Cu, Fe(II), and Zn onto amorphous ferric oxyhydroxide suggest that isotopic fractionation is related to the intrinsic equilibrium constants that define aqueous metal interactions with oxyhydroxide surface sites. Greater isotopic fractionation occurs with stronger metal binding by the oxyhydroxide with Cu > Zn > Fe(II).

Equilibrium β-limits in classical stellarators

DOE Office of Scientific and Technical Information (OSTI.GOV)

Loizu, Joaquim; Hudson, S. R.; Nuhrenberg, C.

Here, a numerical investigation is carried out to understand the equilibrium β-limit in a classical stellarator. The stepped-pressure equilibrium code is used in order to assess whether or not magnetic islands and stochastic field-lines can emerge at high β. Two modes of operation are considered: a zero-net-current stellarator and a fixed-iota stellarator. Despite the fact that relaxation is allowed, the former is shown to maintain good flux surfaces up to the equilibrium β-limit predicted by ideal-magnetohydrodynamics (MHD), above which a separatrix forms. The latter, which has no ideal equilibrium β-limit, is shown to develop regions of magnetic islands and chaosmore » at sufficiently high β, thereby providing a ‘non-ideal β-limit’. Perhaps surprisingly, however, the value of β at which the Shafranov shift of the axis reaches a fraction of the minor radius follows in all cases the scaling laws predicted by ideal-MHD. We compare our results to the High-Beta-Stellarator theory of Freidberg and derive a new prediction for the non-ideal equilibrium β-limit above which chaos emerges.« less

Equilibrium β-limits in classical stellarators

DOE PAGES

Loizu, Joaquim; Hudson, S. R.; Nuhrenberg, C.; ...

2017-11-17

Here, a numerical investigation is carried out to understand the equilibrium β-limit in a classical stellarator. The stepped-pressure equilibrium code is used in order to assess whether or not magnetic islands and stochastic field-lines can emerge at high β. Two modes of operation are considered: a zero-net-current stellarator and a fixed-iota stellarator. Despite the fact that relaxation is allowed, the former is shown to maintain good flux surfaces up to the equilibrium β-limit predicted by ideal-magnetohydrodynamics (MHD), above which a separatrix forms. The latter, which has no ideal equilibrium β-limit, is shown to develop regions of magnetic islands and chaosmore » at sufficiently high β, thereby providing a ‘non-ideal β-limit’. Perhaps surprisingly, however, the value of β at which the Shafranov shift of the axis reaches a fraction of the minor radius follows in all cases the scaling laws predicted by ideal-MHD. We compare our results to the High-Beta-Stellarator theory of Freidberg and derive a new prediction for the non-ideal equilibrium β-limit above which chaos emerges.« less

Analytical investigation for Lorentz forces effect on nanofluid Marangoni boundary layer hydrothermal behavior using HAM

NASA Astrophysics Data System (ADS)

Sheikholeslami, M.; Ganji, D. D.

2017-12-01

In this paper, semi analytical approach is applied to investigate nanofluid Marangoni convection in presence of magnetic field. Koo-Kleinstreuer-Li model is taken into account to simulate nanofluid properties. Homotopy analysis method is utilized to solve the final ordinary equations which are obtained from similarity transformation. Roles of Hartmann number and nanofluid volume fraction are presented graphically. Results show that temperature augments with rise of nanofluid volume fraction. Impact of nanofluid volume fraction on normal velocity is more than tangential velocity. Temperature gradient enhances with rise of magnetic number.

Visualization of the hot chocolate sound effect by spectrograms

NASA Astrophysics Data System (ADS)

Trávníček, Z.; Fedorchenko, A. I.; Pavelka, M.; Hrubý, J.

2012-12-01

We present an experimental and a theoretical analysis of the hot chocolate effect. The sound effect is evaluated using time-frequency signal processing, resulting in a quantitative visualization by spectrograms. This method allows us to capture the whole phenomenon, namely to quantify the dynamics of the rising pitch. A general form of the time dependence volume fraction of the bubbles is proposed. We show that the effect occurs due to the nonlinear dependence of the speed of sound in the gas/liquid mixture on the volume fraction of the bubbles and the nonlinear time dependence of the volume fraction of the bubbles.

Simulation of hydrodynamics using large eddy simulation-second-order moment model in circulating fluidized beds

NASA Astrophysics Data System (ADS)

Juhui, Chen; Yanjia, Tang; Dan, Li; Pengfei, Xu; Huilin, Lu

2013-07-01

Flow behavior of gas and particles is predicted by the large eddy simulation of gas-second order moment of solid model (LES-SOM model) in the simulation of flow behavior in CFB. This study shows that the simulated solid volume fractions along height using a two-dimensional model are in agreement with experiments. The velocity, volume fraction and second-order moments of particles are computed. The second-order moments of clusters are calculated. The solid volume fraction, velocity and second order moments are compared at the three different model constants.

Application of artificial neural networks for the prediction of volume fraction using spectra of gamma rays backscattered by three-phase flows

NASA Astrophysics Data System (ADS)

Gholipour Peyvandi, R.; Islami Rad, S. Z.

2017-12-01

The determination of the volume fraction percentage of the different phases flowing in vessels using transmission gamma rays is a conventional method in petroleum and oil industries. In some cases, with access only to the one side of the vessels, attention was drawn toward backscattered gamma rays as a desirable choice. In this research, the volume fraction percentage was measured precisely in water-gasoil-air three-phase flows by using the backscatter gamma ray technique andthe multilayer perceptron (MLP) neural network. The volume fraction determination in three-phase flows requires two gamma radioactive sources or a dual-energy source (with different energies) while in this study, we used just a 137Cs source (with the single energy) and a NaI detector to analyze backscattered gamma rays. The experimental set-up provides the required data for training and testing the network. Using the presented method, the volume fraction was predicted with a mean relative error percentage less than 6.47%. Also, the root mean square error was calculated as 1.60. The presented set-up is applicable in some industries with limited access. Also, using this technique, the cost, radiation safety and shielding requirements are minimized toward the other proposed methods.

Origins of microstructural transformations in charged vesicle suspensions: the crowding hypothesis.

PubMed

Seth, Mansi; Ramachandran, Arun; Murch, Bruce P; Leal, L Gary

2014-09-02

It is observed that charged unilamellar vesicles in a suspension can spontaneously deflate and subsequently transition to form bilamellar vesicles, even in the absence of externally applied triggers such as salt or temperature gradients. We provide strong evidence that the driving force for this deflation-induced transition is the repulsive electrostatic pressure between charged vesicles in concentrated suspensions, above a critical effective volume fraction. We use volume fraction measurements and cryogenic transmission electron microscopy imaging to quantitatively follow both the macroscopic and microstructural time-evolution of cationic diC18:1 DEEDMAC vesicle suspensions at different surfactant and salt concentrations. A simple model is developed to estimate the extent of deflation of unilamellar vesicles caused by electrostatic interactions with neighboring vesicles. It is determined that when the effective volume fraction of the suspension exceeds a critical value, charged vesicles in a suspension can experience "crowding" due to overlap of their electrical double layers, which can result in deflation and subsequent microstructural transformations to reduce the effective volume fraction of the suspension. Ordinarily in polydisperse colloidal suspensions, particles interacting via a repulsive potential transform into a glassy state above a critical volume fraction. The behavior of charged vesicle suspensions reported in this paper thus represents a new mechanism for the relaxation of repulsive interactions in crowded situations.

Crystallization of sheared hard spheres at 64.5% volume fraction

NASA Astrophysics Data System (ADS)

Swinney, H. L.; Rietz, F.; Schroeter, M.; Radin, C.

2017-11-01

A classic experiment by G.D. Scott Nature 188, 908, 1960) showed that pouring balls into a rigid container filled the volume to an upper limit of 64% of the container volume, which is well below the 74% volume fraction filled by spheres in a hexagonal close packed (HCP) or face center cubic (FCC) lattice. Subsequent experiments have confirmed a ``random closed packed'' (RCP) fraction of about 64%. However, the physics of the RCP limit has remained a mystery. Our experiment on a cubical box filled with 49400 weakly sheared glass spheres reveals a first order phase transition from a disordered to an ordered state at a volume fraction of 64.5%. The ordered state consists of crystallites of mixed FCC and HCP symmetry that coexist with the amorphous bulk. The transition is initiated by homogeneous nucleation: in the shearing process small crystallites with about ten or fewer spheres dissolve, while larger crystallites grow. A movie illustrates the crystallization process. German Academic Exchange Service (DAAD), German Research Foundation (DFG), NSF DMS, and R.A. Welch Foundation.

Cryogenic separation of an oxygen-argon mixture in natural air samples for the determination of isotope and molecular ratios.

PubMed

Keedakkadan, Habeeb Rahman; Abe, Osamu

2015-04-30

The separation and purification of oxygen-argon mixtures are critical in the high-precision analysis of Δ(17) O and δ(O2 /Ar) for geochemical applications. At present, chromatographic methods are used for the separation and purification of oxygen-argon mixtures or pure oxygen, but these methods require the use of high-purity helium as a carrier gas. Considerable interest has been expressed in the development of a helium-free cryogenic separation of oxygen-argon mixtures in natural air samples. The precise and simplified cryogenic separation of oxygen-argon mixtures from natural air samples presented here was made possible using a single 5A (30/60 mesh) molecular sieve column. The method involves the trapping of eluted gases using molecular sieves at liquid nitrogen temperature, which is associated with isotopic fractionation. We tested the proposed method for the determination of isotopic fractionations during the gas exchange between water and atmospheric air at equilibrium. The dependency of fractionation was studied at different water temperatures and for different methods of equilibration (bubbling and stirring). Isotopic and molecular fractionations during gas desorption from molecular sieves were studied for different amounts and types of molecular sieves. Repeated measurements of atmospheric air yielded a reproducibility (±SD) of 0.021 ‰, 0.044 ‰, 15 per meg and 1.9 ‰ for δ(17) O, δ(18) O, Δ(17) O and δ(O2 /Ar) values, respectively. We applied the method to determine equilibrium isotope fractionation during gas exchange between air and water. Consistent δ(18) O and Δ(17) O results were obtained with the latest two studies, whereas there was a significant difference in δ(18) O values between seawater and deionized water. We have revised a helium-free, cryogenic separation of oxygen-argon mixtures in natural air samples for isotopic and molecular ratio analysis. The use of a single 13X (1/8" pellet) molecular sieve yielded the smallest isotopic and molecular fractionations, and this fractionation by molecular sieves can be corrected by the amount of molecular sieve used in the experiment. The reproducibility of the method was tested by the measurement of the oxygen isotope ratios of dissolved oxygen at equilibrium with atmospheric air. We confirmed that the choice of methods for making air-equilibrated water was not related to the magnitude of isotope fractionation, whereas there was a difference between seawater and deionized water. Copyright © 2015 John Wiley & Sons, Ltd.

Assessment of left atrial volume and function: a comparative study between echocardiography, magnetic resonance imaging and multi slice computed tomography.

PubMed

Kühl, J Tobias; Lønborg, Jacob; Fuchs, Andreas; Andersen, Mads J; Vejlstrup, Niels; Kelbæk, Henning; Engstrøm, Thomas; Møller, Jacob E; Kofoed, Klaus F

2012-06-01

Measurement of left atrial (LA) maximal volume (LA(max)) using two-dimensional transthoracic echocardiography (TTE) provides prognostic information in several cardiac diseases. However, the relationship between LA(max) and LA function is poorly understood and TTE is less well suited for measuring dynamic LA volume changes. Conversely, cardiac magnetic resonance imaging (CMR) and multi-slice computed tomography (MSCT) appears more appropriate for such measures. We sought to determine the relationship between LA size assessed with TTE and LA size and function assessed with CMR and MSCT. Fifty-four patients were examined 3 months post myocardial infarction with echocardiography, CMR and MSCT. Left atrial volumes and LA reservoir function were assessed by TTE. LA time-volume curves were determined and LA reservoir function (cyclic change and fractional change), passive emptying function (reservoir volume) and pump function (left atrial ejection fraction-LAEF) were derived using CMR and MSCT. Left atrial fractional change and left atrial ejection fraction (LAEF) determined with CMR and MSCT were unrelated to LA(max) enlargement by echocardiography (P = NS). There was an overall good agreement between CMR and MSCT, with a small to moderate bias in LA(max) (4.9 ± 10.4 ml), CC (3.1 ± 9.1 ml) and reservoir volume (3.4 ± 9.1 ml). TTE underestimates LA(max) with up to 32% compared with CMR and MSCT (P < 0.001). Left atrial function assessed with MSCT and CMR as LA fractional change and LAEF is not significantly related to LA(max) measured by TTE. TTE systematically underestimated LA volumes, whereas there are good agreements between MSCT and CMR for volumetric and functional properties.

Pancreas volume and fat fraction in children with Type 1 diabetes.

PubMed

Regnell, S E; Peterson, P; Trinh, L; Broberg, P; Leander, P; Lernmark, Å; Månsson, S; Elding Larsson, H

2016-10-01

People with Type 1 diabetes have smaller pancreases than healthy individuals. Several diseases causing pancreatic atrophy are associated with pancreatic steatosis, but pancreatic fat in Type 1 diabetes has not been measured. This cross-sectional study aimed to compare pancreas size and fat fraction in children with Type 1 diabetes and controls. The volume and fat fraction of the pancreases of 22 children with Type 1 diabetes and 29 controls were determined using magnetic resonance imaging. Pancreas volume was 27% smaller in children with diabetes (median 34.9 cm(3) ) than in controls (47.8 cm(3) ; P < 0.001). Pancreas volume correlated positively with age in controls (P = 0.033), but not in children with diabetes (P = 0.649). Pancreas volume did not correlate with diabetes duration, but it did correlate positively with units of insulin/kg body weight/day (P = 0.048). A linear model of pancreas volume as influenced by age, body surface area and insulin units/kg body weight/day found that insulin dosage correlated with pancreas volume after controlling for both age and body surface area (P = 0.009). Pancreatic fat fraction was not significantly different between the two groups (1.34% vs. 1.57%; P = 0.891). Our findings do not indicate that pancreatic atrophy in Type 1 diabetes is associated with an increased pancreatic fat fraction, unlike some other diseases featuring reduced pancreatic volume. We speculate that our results may support the hypotheses that much of pancreatic atrophy in Type 1 diabetes occurs before the clinical onset of the disease and that exogenous insulin administration decelerates pancreatic atrophy after diabetes onset. © 2016 Diabetes UK.

Thermodynamic and transport combustion properties of hydrocarbons with air. Part 2: Compositions corresponding to Kelvin temperature schedules in part 1

NASA Technical Reports Server (NTRS)

Gordon, S.

1982-01-01

The equilibrium compositions that correspond to the thermodynamic and transport combustion properties for a wide range of conditions for the reaction of hydrocarbons with air are presented. Initially 55 gaseous species and 3 coin condensed species were considered in the calculations. Only 17 of these 55 gaseous species had equilibrium mole fractions greater than 0.000005 for any of the conditions studied and therefore these were the only ones retained in the final tables.

Understanding the mechanisms of amorphous creep through molecular simulation

NASA Astrophysics Data System (ADS)

Cao, Penghui; Short, Michael P.; Yip, Sidney

2017-12-01

Molecular processes of creep in metallic glass thin films are simulated at experimental timescales using a metadynamics-based atomistic method. Space-time evolutions of the atomic strains and nonaffine atom displacements are analyzed to reveal details of the atomic-level deformation and flow processes of amorphous creep in response to stress and thermal activations. From the simulation results, resolved spatially on the nanoscale and temporally over time increments of fractions of a second, we derive a mechanistic explanation of the well-known variation of creep rate with stress. We also construct a deformation map delineating the predominant regimes of diffusional creep at low stress and high temperature and deformational creep at high stress. Our findings validate the relevance of two original models of the mechanisms of amorphous plasticity: one focusing on atomic diffusion via free volume and the other focusing on stress-induced shear deformation. These processes are found to be nonlinearly coupled through dynamically heterogeneous fluctuations that characterize the slow dynamics of systems out of equilibrium.

Microgravity Diode Laser Spectroscopy Measurements in a Reacting Vortex Ring

NASA Technical Reports Server (NTRS)

Chen, Shin-Juh; Dahm, Werner J. A.; Silver, Joel A.; Piltch, Nancy D.; VanderWal, R. (Technical Monitor)

2001-01-01

The technique of Diode Laser Spectroscopy (DLS) with wavelength modulation is utilized to measure the concentration of methane in reacting vortex rings under microgravity conditions. From the measured concentration of methane, other major species such as water, carbon dioxide, nitrogen, and oxygen can be easily computed under the assumption of equilibrium chemistry with an iterative method called ITAC (Iterative Temperature with Assumed Chemistry). The conserved scalar approach in modelling the coupling between fluid dynamics and combustion is utilized to represent the unknown variables in terms of the mixture fraction and scalar dissipation rate in conjunction with ITAC. Post-processing of the DLS and the method used to compute the species concentration are discussed. From the flame luminosity results, ring circulation appears to increase the fuel consumption rate inside the reacting vortex ring and the flame height for cases with similar fuel volumes but different ring circulations. The concentrations of methane, water, and carbon dioxide agree well with available results from numerical simulations.

Understanding arsenic mobilization using reactive transport modeling of groundwater hydrochemistry in the Datong basin study plot, China.

PubMed

Mapoma, Harold Wilson Tumwitike; Xie, Xianjun; Pi, Kunfu; Liu, Yaqing; Zhu, Yapeng

2016-03-01

This paper discusses the reactive transport and evolution of arsenic along a selected flow path in a study plot within the central part of Datong basin. The simulation used the TOUGHREACT code. The spatial and temporal trends in hydrochemistry and mineral volume fraction along a flow path were observed. Furthermore, initial simulation of major ions and pH fits closely to the measured data. The study shows that equilibrium conditions may be attained at different stress periods for each parameter simulated. It is noted that the variations in ionic chemistry have a greater impact on arsenic distribution while reducing conditions drive the mobilization of arsenic. The study concluded that the reduction of Fe(iii) and As(v) and probably SO4/HS cycling are significant factors affecting localized mobilization of arsenic. Besides cation exchange and water-rock interaction, incongruent dissolution of silicates is also a significant control mechanism of general chemistry of the Datong basin aquifer.

SOA formation by biogenic and carbonyl compounds: data evaluation and application.

PubMed

Ervens, Barbara; Kreidenweis, Sonia M

2007-06-01

The organic fraction of atmospheric aerosols affects the physical and chemical properties of the particles and their role in the climate system. Current models greatly underpredict secondary organic aerosol (SOA) mass. Based on a compilation of literature studies that address SOA formation, we discuss different parameters that affect the SOA formation efficiency of biogenic compounds (alpha-pinene, isoprene) and aliphatic aldehydes (glyoxal, hexanal, octanal, hexadienal). Applying a simple model, we find that the estimated SOA mass after one week of aerosol processing under typical atmospheric conditions is increased by a few microg m(-3) (low NO(x) conditions). Acid-catalyzed reactions can create > 50% more SOA mass than processes under neutral conditions; however, other parameters such as the concentration ratio of organics/NO(x), relative humidity, and absorbing mass are more significant. The assumption of irreversible SOA formation not limited by equilibrium in the particle phase or by depletion of the precursor leads to unrealistically high SOA masses for some of the assumptions we made (surface vs volume controlled processes).

Current Status in Cavitation Modeling

NASA Technical Reports Server (NTRS)

Singhal, Ashok K.; Avva, Ram K.

1993-01-01

Cavitation is a common problem for many engineering devices in which the main working fluid is in liquid state. In turbomachinery applications, cavitation generally occurs on the inlet side of pumps. The deleterious effects of cavitation include: lowered performance, load asymmetry, erosion and pitting of blade surfaces, vibration and noise, and reduction of the overall machine life. Cavitation models in use today range from rather crude approximations to sophisticated bubble dynamics models. Details about bubble inception, growth and collapse are relevant to the prediction of blade erosion, but are not necessary to predict the performance of pumps. An engineering model of cavitation is proposed to predict the extent of cavitation and performance. The vapor volume fraction is used as an indicator variable to quantify cavitation. A two-phase flow approach is employed with the assumption of the thermal equilibrium between liquid and vapor. At present velocity slip between the two phases is selected. Preliminary analyses of 2D flows shows qualitatively correct results.

Effect of Ag and Pb Addition on Microstructural and Mechanical Properties of SAC 105 Solders

NASA Astrophysics Data System (ADS)

Molnar, Aliz; Janovszky, Dora; Kardos, Ibolya; Molnar, Istvan; Gacsi, Zoltan

2015-10-01

Melting and crystallization processes of lead-free and lead-contaminated alloys in near-equilibrium state were investigated. In addition, the effect of silver content up to 4 wt.% on the microstructure of Sn-Ag-Cu alloys was studied. The volume fraction of β-Sn decreased by half owing to 4 wt.% Ag content. Furthermore, contamination by lead strongly influences the properties of the solidified microstructure. The Pb grains appear as a result of two processes when the Pb content is equal to 0.5 wt.% or higher: Pb phase solidifies in the quaternary eutectic at 176°C, and Pb grains precipitate from the primary β-Sn solid solution grain during a solid state reaction. The freezing range enlarges to 51°C due to 2 wt.% Pb content owing to quaternary eutectic. Above 1 wt.% Pb content, the mechanical properties also improve due to grains of quaternary eutectic Pb and precipitated Pb grains with a size <1 μm.

Dynamic compaction of granular materials

PubMed Central

Favrie, N.; Gavrilyuk, S.

2013-01-01

An Eulerian hyperbolic multiphase flow model for dynamic and irreversible compaction of granular materials is constructed. The reversible model is first constructed on the basis of the classical Hertz theory. The irreversible model is then derived in accordance with the following two basic principles. First, the entropy inequality is satisfied by the model. Second, the corresponding ‘intergranular stress’ coming from elastic energy owing to contact between grains decreases in time (the granular media behave as Maxwell-type materials). The irreversible model admits an equilibrium state corresponding to von Mises-type yield limit. The yield limit depends on the volume fraction of the solid. The sound velocity at the yield surface is smaller than that in the reversible model. The last one is smaller than the sound velocity in the irreversible model. Such an embedded model structure assures a thermodynamically correct formulation of the model of granular materials. The model is validated on quasi-static experiments on loading–unloading cycles. The experimentally observed hysteresis phenomena were numerically confirmed with a good accuracy by the proposed model. PMID:24353466

Volume fractions of DCE-MRI parameter as early predictor of histologic response in soft tissue sarcoma: A feasibility study.

PubMed

Xia, Wei; Yan, Zhuangzhi; Gao, Xin

2017-10-01

To find early predictors of histologic response in soft tissue sarcoma through volume transfer constant (K trans ) analysis based on dynamic contrast-enhanced magnetic resonance imaging (DCE-MRI). 11 Patients with soft tissue sarcoma of the lower extremity that underwent preoperative chemoradiotherapy followed by limb salvage surgery were included in this retrospective study. For each patient, DCE-MRI data sets were collected before and two weeks after therapy initiation, and histologic tumor cell necrosis rate (TCNR) was reported at surgery. The DCE-MRI volumes were aligned by registration. Then, the aligned volumes were used to obtain the K trans variation map. Accordingly, three sub-volumes (with increased, decreased or unchanged K trans ) were defined and identified, and fractions of the sub-volumes, denoted as F + , F - and F 0 , respectively, were calculated. The predictive ability of volume fractions was determined by using area under a receiver operating characteristic curve (AUC). Linear regression analysis was performed to investigate the relationship between TCNR and volume fractions. In addition, the K trans values of the sub-volumes were compared. The AUC for F - (0.896) and F 0 (0.833) were larger than that for change of tumor longest diameter ΔD (0.625) and the change of mean K trans ΔK trans ¯ (0.792). Moreover, the regression results indicated that TCNR was directly proportional to F 0 (R 2 =0.75, P=0.0003), while it was inversely proportional to F - (R 2 =0.77, P=0.0002). However, TCNR had relatively weak linear relationship with ΔK trans ¯ (R 2 =0.64, P=0.0018). Additionally, TCNR did not have linear relationship with DD (R 2 =0.16, P=0.1246). The volume fraction F - and F 0 have potential as early predictors of soft tissue sarcoma histologic response. Copyright © 2017 Elsevier B.V. All rights reserved.

Competitive Cyber-Insurance and Internet Security

NASA Astrophysics Data System (ADS)

Shetty, Nikhil; Schwartz, Galina; Felegyhazi, Mark; Walrand, Jean

This paper investigates how competitive cyber-insurers affect network security and welfare of the networked society. In our model, a user's probability to incur damage (from being attacked) depends on both his security and the network security, with the latter taken by individual users as given. First, we consider cyberinsurers who cannot observe (and thus, affect) individual user security. This asymmetric information causes moral hazard. Then, for most parameters, no equilibrium exists: the insurance market is missing. Even if an equilibrium exists, the insurance contract covers only a minor fraction of the damage; network security worsens relative to the no-insurance equilibrium. Second, we consider insurers with perfect information about their users' security. Here, user security is perfectly enforceable (zero cost); each insurance contract stipulates the required user security. The unique equilibrium contract covers the entire user damage. Still, for most parameters, network security worsens relative to the no-insurance equilibrium. Although cyber-insurance improves user welfare, in general, competitive cyber-insurers fail to improve network security.

Brown Adipose Tissue Quantification in Human Neonates Using Water-Fat Separated MRI

PubMed Central

Rasmussen, Jerod M.; Entringer, Sonja; Nguyen, Annie; van Erp, Theo G. M.; Guijarro, Ana; Oveisi, Fariba; Swanson, James M.; Piomelli, Daniele; Wadhwa, Pathik D.

2013-01-01

There is a major resurgence of interest in brown adipose tissue (BAT) biology, particularly regarding its determinants and consequences in newborns and infants. Reliable methods for non-invasive BAT measurement in human infants have yet to be demonstrated. The current study first validates methods for quantitative BAT imaging of rodents post mortem followed by BAT excision and re-imaging of excised tissues. Identical methods are then employed in a cohort of in vivo infants to establish the reliability of these measures and provide normative statistics for BAT depot volume and fat fraction. Using multi-echo water-fat MRI, fat- and water-based images of rodents and neonates were acquired and ratios of fat to the combined signal from fat and water (fat signal fraction) were calculated. Neonatal scans (n = 22) were acquired during natural sleep to quantify BAT and WAT deposits for depot volume and fat fraction. Acquisition repeatability was assessed based on multiple scans from the same neonate. Intra- and inter-rater measures of reliability in regional BAT depot volume and fat fraction quantification were determined based on multiple segmentations by two raters. Rodent BAT was characterized as having significantly higher water content than WAT in both in situ as well as ex vivo imaging assessments. Human neonate deposits indicative of bilateral BAT in spinal, supraclavicular and axillary regions were observed. Pairwise, WAT fat fraction was significantly greater than BAT fat fraction throughout the sample (ΔWAT-BAT = 38%, p<10−4). Repeated scans demonstrated a high voxelwise correlation for fat fraction (Rall = 0.99). BAT depot volume and fat fraction measurements showed high intra-rater (ICCBAT,VOL = 0.93, ICCBAT,FF = 0.93) and inter-rater reliability (ICCBAT,VOL = 0.86, ICCBAT,FF = 0.93). This study demonstrates the reliability of using multi-echo water-fat MRI in human neonates for quantification throughout the torso of BAT depot volume and fat fraction measurements. PMID:24205024

Low-temperature, non-stoichiometric oxygen isotope exchange coupled to Fe(II)-goethite interactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Frierdich, Andrew J.; Beard, Brian L.; Rosso, Kevin M.

2015-07-01

The oxygen isotope composition of natural iron oxide minerals has been widely used as a paleoclimate proxy. Interpretation of their stable isotope compositions, however, requires accurate knowledge of isotopic fractionation factors and an understanding of their isotopic exchange kinetics, the latter of which informs us how diagenetic processes may alter their isotopic compositions. Prior work has demonstrated that crystalline iron oxides do not significantly exchange oxygen isotopes with pure water at low temperature, which has restricted studies of isotopic fractionation factors to precipitation experiments or theoretical calculations. Using a double three-isotope method (¹⁸O-¹⁷O-¹⁶O and ⁵⁷Fe-⁵⁶Fe-⁵⁴Fe) we compare O and Femore » isotope exchange kinetics, and demonstrate, for the first time, that O isotope exchange between structural O in crystalline goethite and water occurs in the presence of aqueous Fe(II) (Fe(II) aq) at ambient temperature (i.e., 22–50 °C). The three-isotope method was used to extrapolate partial exchange results to infer the equilibrium, mass-dependent isotope fractionations between goethite and water. In addition, this was combined with a reversal approach to equilibrium by reacting goethite in two unique waters that vary in composition by about 16‰ in ¹⁸O/¹⁶O ratios. Our results show that interactions between Fe(II) aq and goethite catalyzes O isotope exchange between the mineral and bulk fluid; no exchange (within error) is observed when goethite is suspended in ¹⁷O-enriched water in the absence of Fe(II) aq. In contrast, Fe(II)-catalyzed O isotope exchange is accompanied by significant changes in ¹⁸O/¹⁶O ratios. Despite significant O exchange, however, we observed disproportionate amounts of Fe versus O exchange, where Fe isotope exchange in goethite was roughly three times that of O. This disparity provides novel insight into the reactivity of oxide minerals in aqueous solutions, but presents a challenge for utilizing such an approach to determine equilibrium isotope fractionation factors. Despite the uncertainty from extrapolation, there is consistency in goethite-water fractionation factors for our reversal approach to equilibrium, with final weighted average fractionation factor values of Δ¹⁸O Gth-wate r = 0.2 (±0.9‰) and 3.0 (±2.5‰) at 22 °C and -1.6 (±0.8‰) and 1.9 (±1.5‰) at 50 °C for micron-sized and nano-particulate goethite, respectively (errors at 2σ level). Reaction of ferrihydrite with Fe(II) aq in two distinct waters resulted in a quantitative conversion to goethite and complete O isotope exchange in each case, and similar fractionation factors were observed for experiments using the two waters. Comparison of our results with previous studies of O isotope fractionation between goethite and water suggests that particle size may be a contributing factor to the disparity among experimental studies.« less

Stability of high-speed boundary layers in oxygen including chemical non-equilibrium effects

NASA Astrophysics Data System (ADS)

Klentzman, Jill; Tumin, Anatoli

2013-11-01

The stability of high-speed boundary layers in chemical non-equilibrium is examined. A parametric study varying the edge temperature and the wall conditions is conducted for boundary layers in oxygen. The edge Mach number and enthalpy ranges considered are relevant to the flight conditions of reusable hypersonic cruise vehicles. Both viscous and inviscid stability formulations are used and the results compared to gain insight into the effects of viscosity and thermal conductivity on the stability. It is found that viscous effects have a strong impact on the temperature and mass fraction perturbations in the critical layer and in the viscous sublayer near the wall. Outside of these areas, the perturbations closely match in the viscous and inviscid models. The impact of chemical non-equilibrium on the stability is investigated by analyzing the effects of the chemical source term in the stability equations. The chemical source term is found to influence the growth rate of the second Mack mode instability but not have much of an effect on the mass fraction eigenfunction for the flow parameters considered. This work was supported by the AFOSR/NASA/National Center for Hypersonic Laminar-Turbulent Transition Research.

An Experimental Investigation of the Laminar Flamelet Concept for Soot Properties

NASA Technical Reports Server (NTRS)

Diez, F. J.; Aalburg, C.; Sunderland, P. B.; Urban, D. L.; Yuan, Z.-G.; Faeth, G. M.

2007-01-01

The soot properties of round, nonbuoyant, laminar jet diffusion flames are described, based on experiments at microgravity carried out on orbit during three flights of the Space Shuttle Columbia, (Flights STS-83, 94 and 107). Experimental conditions included ethylene- and propane-fueled flames burning in still air at an ambient temperature of 300 K and ambient pressures of 35-100 kPa. Measurements included soot volume fraction distributions using deconvoluted laser extinction imaging, and soot temperature distributions using deconvoluted multiline emission imaging. Flowfield modeling based on the work of Spalding is presented. The present work explores whether soot properties of these flames are universal functions of mixture fraction, i.e., whether they satisfy soot state relationships. Measurements are presented, including radiative emissions and distributions of soot temperature and soot volume fraction. It is shown that most of the volume of these flames is bounded by the dividing streamline and thus should follow residence time state relationships. Most streamlines from the fuel supply to the surroundings are found to exhibit nearly the same maximum soot volume fraction and temperature. The radiation intensity along internal streamlines also is found to have relatively uniform values. Finally, soot state relationships were observed, i.e., soot volume fraction was found to correlate with estimated mixture fraction for each fuel/pressure selection. These results support the existence of soot property state relationships for steady nonbuoyant laminar diffusion flames, and thus in a large class of practical turbulent diffusion flames through the application of the laminar flamelet concept.

Experimental and theoretical investigation of thermal conductivity of ethylene glycol containing functionalized single walled carbon nanotubes

NASA Astrophysics Data System (ADS)

Hemmat Esfe, Mohammad; Firouzi, Masoumeh; Afrand, Masoud

2018-01-01

In this paper, functionalized single walled carbon nanotubes (FSWCNTs) were suspended in Ethylene Glycol (EG) at different volume fractions. A KD2 pro thermal conductivity meter was used to measure the thermal conductivity in the temperature range from 30 to 50 °C. Nanofluids were prepared in solid volume fraction of 0.02, 0.05, 0.075, 0.1, 0.25, 0.5 and, 0.75%. Experimental results revealed that the thermal conductivity of the nanofluid is a non-linear function of temperature and SWCNTs volume fraction in the range of this investigation. Thermal conductivity increases with temperature and nanoparticles volume fraction as usual for this type of nanofluid. Maximum increment in thermal conductivity of the nanofluids was found to be about 45% at 0.75 vol fractions loading at 50 °C. Finally, a new correlation based on artificial neural network (ANN) approach has been proposed for SWCNT-EG thermal conductivity in terms of nanoparticles volume fraction and temperature using the experimental data. Used ANN approach has estimated the experimental values of thermal conductivity with the absolute average relative deviation lower than 0.9%, mean square error of 3.67 × 10-5 and regression coefficient of 0.9989. Comparison between the suggested techniques with various used correlation in the literatures established that the ANN approach is better to other presented methods and therefore can be proposed as a useful means for predicting of the nanofluids thermal conductivity.

Phase Equilibrium Investigation on 2-Phenylethanol in Binary and Ternary Systems: Influence of High Pressure on Density and Solid-Liquid Phase Equilibrium.

PubMed

Domańska, Urszula; Królikowski, Marek; Wlazło, Michał; Więckowski, Mikołaj

2018-05-30

Ionic liquids (ILs) are important new solvents proposed for applications in different separation processes. Herein, an idea of possible use of high pressure in a general strategy of production of 2-phenylethanol (PEA) is discussed. In this work, we present the influence of pressure on the density in binary systems of {1-hexyl-1-methylpyrrolidynium bis{(trifluoromethyl)sulfonyl}imide, [HMPYR][NTf 2 ], or 1-dodecyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}imide, [DoMIM][NTf 2 ] + PEA} in a wide range of temperatures (298.15-348.15 K) and pressures (0.1-40 MPa). The densities at ambient and high pressures are measured to present the physicochemical properties of the ILs used in the process of separation of PEA from aqueous phase. The Tait equation was used for the correlation of density of one-component and two-component systems as a function of mole fraction, temperature, and pressure. The influence of pressure is not significant. These systems exhibit mainly negative molar excess volumes, V E . The solid-liquid phase equilibrium (SLE) of [DoMIM][NTf 2 ] in PEA at atmospheric pressure was measured and compared to the SLE high-pressure results. Additionally, the ternary liquid-liquid phase equilibrium (LLE) at ambient pressure in the {[DoMIM][NTf 2 ] (1) + PEA (2) + water (3)} at temperature T = 308.15 K was investigated. The solubility of water in the [DoMIM][NTf 2 ] is quite high in comparison with that measured by us earlier for ILs ( x 3 = 0.403) at T = 308.15 K, which results in not very successful average selectivity of extraction of PEA from the aqueous phase. The [DoMIM][NTf 2 ] has shown strong interaction with PEA without the immiscibility region. The ternary system revealed Treybal's type phase equilibrium in which two partially miscible binaries ([DoMIM][NTf 2 ] + water) and (PEA + water) exist. From the results of LLE in the ternary system, the selectivity and the solute distribution ratio of separation of water/PEA were calculated and compared to the results obtained for the ILs measured earlier by us. The popular NRTL model was used to correlate the experimental tie-lines in ternary LLE. These results may help in a new technological project of "in situ" extraction of PEA from aqueous phase during the biosynthesis.

Heavy ion beam probe operation in time varying equilibria of improved confinement reversed field pinch discharges.

PubMed

Demers, D R; Chen, X; Schoch, P M; Fimognari, P J

2010-10-01

Operation of a heavy ion beam probe (HIBP) on a reversed field pinch is unique from other toroidal applications because the magnetic field is more temporal and largely produced by plasma current. Improved confinement, produced through the transient application of a poloidal electric field which leads to a reduction of dynamo activity, exhibits gradual changes in equilibrium plasma quantities. A consequence of this is sweeping of the HIBP trajectories by the dynamic magnetic field, resulting in motion of the sample volume. In addition, the plasma potential evolves with the magnetic equilibrium. Measurement of the potential as a function of time is thus a combination of temporal changes of the equilibrium and motion of the sample volume. A frequent additional complication is a nonideal balance of ion current on the detectors resulting from changes in the beam trajectory (magnetic field) and energy (plasma potential). This necessitates use of data selection criteria. Nevertheless, the HIBP on the Madison Symmetric Torus has acquired measurements as a function of time throughout improved confinement. A technique developed to infer the potential in the improved confinement reversed field pinch from HIBP data in light of the time varying plasma equilibrium will be discussed.

Abnormal brain white matter microstructure is associated with both pre-hypertension and hypertension

PubMed Central

Gao, He; Bai, Wenjia; Evangelou, Evangelos; Glocker, Ben; O’Regan, Declan P.; Elliott, Paul; Matthews, Paul M.

2017-01-01

Objectives To characterize effects of chronically elevated blood pressure on the brain, we tested for brain white matter microstructural differences associated with normotension, pre-hypertension and hypertension in recently available brain magnetic resonance imaging data from 4659 participants without known neurological or psychiatric disease (62.3±7.4 yrs, 47.0% male) in UK Biobank. Methods For assessment of white matter microstructure, we used measures derived from neurite orientation dispersion and density imaging (NODDI) including the intracellular volume fraction (an estimate of neurite density) and isotropic volume fraction (an index of the relative extra-cellular water diffusion). To estimate differences associated specifically with blood pressure, we applied propensity score matching based on age, sex, educational level, body mass index, and history of smoking, diabetes mellitus and cardiovascular disease to perform separate contrasts of non-hypertensive (normotensive or pre-hypertensive, N = 2332) and hypertensive (N = 2337) individuals and of normotensive (N = 741) and pre-hypertensive (N = 1581) individuals (p<0.05 after Bonferroni correction). Results The brain white matter intracellular volume fraction was significantly lower, and isotropic volume fraction was higher in hypertensive relative to non-hypertensive individuals (N = 1559, each). The white matter isotropic volume fraction also was higher in pre-hypertensive than in normotensive individuals (N = 694, each) in the right superior longitudinal fasciculus and the right superior thalamic radiation, where the lower intracellular volume fraction was observed in the hypertensives relative to the non-hypertensive group. Significance Pathological processes associated with chronically elevated blood pressure are associated with imaging differences suggesting chronic alterations of white matter axonal structure that may affect cognitive functions even with pre-hypertension. PMID:29145428

Accelerated Gray and White Matter Deterioration With Age in Schizophrenia.

PubMed

Cropley, Vanessa L; Klauser, Paul; Lenroot, Rhoshel K; Bruggemann, Jason; Sundram, Suresh; Bousman, Chad; Pereira, Avril; Di Biase, Maria A; Weickert, Thomas W; Weickert, Cynthia Shannon; Pantelis, Christos; Zalesky, Andrew

2017-03-01

Although brain changes in schizophrenia have been proposed to mirror those found with advancing age, the trajectory of gray matter and white matter changes during the disease course remains unclear. The authors sought to measure whether these changes in individuals with schizophrenia remain stable, are accelerated, or are diminished with age. Gray matter volume and fractional anisotropy were mapped in 326 individuals diagnosed with schizophrenia or schizoaffective disorder and in 197 healthy comparison subjects aged 20-65 years. Polynomial regression was used to model the influence of age on gray matter volume and fractional anisotropy at a whole-brain and voxel level. Between-group differences in gray matter volume and fractional anisotropy were regionally localized across the lifespan using permutation testing and cluster-based inference. Significant loss of gray matter volume was evident in schizophrenia, progressively worsening with age to a maximal loss of 8% in the seventh decade of life. The inferred rate of gray matter volume loss was significantly accelerated in schizophrenia up to middle age and plateaued thereafter. In contrast, significant reductions in fractional anisotropy emerged in schizophrenia only after age 35, and the rate of fractional anisotropy deterioration with age was constant and best modeled with a straight line. The slope of this line was 60% steeper in schizophrenia relative to comparison subjects, indicating a significantly faster rate of white matter deterioration with age. The rates of reduction of gray matter volume and fractional anisotropy were significantly faster in males than in females, but an interaction between sex and diagnosis was not evident. The findings suggest that schizophrenia is characterized by an initial, rapid rate of gray matter loss that slows in middle life, followed by the emergence of a deficit in white matter that progressively worsens with age at a constant rate.

The Effect of Microstructure and Pre-strain on the Change in Apparent Young's Modulus of a Dual-Phase Steel

NASA Astrophysics Data System (ADS)

Kupke, A.; Hodgson, P. D.; Weiss, M.

2017-07-01

The elastic recovery in dual-phase (DP) steels is not a linear process and changes with plastic deformation. The level of change in the apparent Young's modulus has been reported to depend on material composition and microstructure, but most previous experimental studies were limited to industrial DP steels and led to contradicting results. This work represents a first fundamental study that investigates the separate and combined effect of phase volume fraction and hardness on the change in apparent Young's modulus in DP steel. A common automotive DP steel (DP780) is heat treated to obtain seven different combinations of martensite and ferrite volume fraction and hardness while keeping the chemical composition as well as the shape of the martensite and ferrite phases unchanged. Loading-unloading tests were performed to analyze the chord modulus at various levels of pre-strain. The results suggest that the point of saturation of the chord modulus with pre-strain depends on the morphology of the microstructure, occurring earlier for microstructures consisting of ferrite grains surrounded by martensite laths. It is further revealed that the reduction of the apparent Young's modulus, which is the difference between the material's initial Young's modulus and the chord modulus, increases with martensite hardness if the martensite volume fraction is kept constant. A higher martensite volume fraction initially elevates the reduction of the apparent Young's modulus. After a critical volume fraction of martensite phase of 35%, a decrease in apparent Young's modulus reduction was observed. A comparison of the plastic unloading strain suggests that the mechanisms leading to a reduction in apparent Young's modulus are strongest for the microstructure consisting of 35% martensite volume fraction.

Polymorphism in the two-locus Levene model with nonepistatic directional selection.

PubMed

Bürger, Reinhard

2009-11-01

For the Levene model with soft selection in two demes, the maintenance of polymorphism at two diallelic loci is studied. Selection is nonepistatic and dominance is intermediate. Thus, there is directional selection in every deme and at every locus. We assume that selection is in opposite directions in the two demes because otherwise no polymorphism is possible. If at one locus there is no dominance, then a complete analysis of the dynamical and equilibrium properties is performed. In particular, a simple necessary and sufficient condition for the existence of an internal equilibrium and sufficient conditions for global asymptotic stability are obtained. These results are extended to deme-independent degree of dominance at one locus. A perturbation analysis establishes structural stability within the full parameter space. In the absence of genotype-environment interaction, which requires deme-independent dominance at both loci, nongeneric equilibrium behavior occurs, and the introduction of arbitrarily small genotype-environment interaction changes the equilibrium structure and may destroy stable polymorphism. The volume of the parameter space for which a (stable) two-locus polymorphism is maintained is computed numerically. It is investigated how this volume depends on the strength of selection and on the dominance relations. If the favorable allele is (partially) dominant in its deme, more than 20% of all parameter combinations lead to a globally asymptotically stable, fully polymorphic equilibrium.

Modern Chemical Technology, Volume 7.

ERIC Educational Resources Information Center

Pecsok, Robert L.; Chapman, Kenneth

This volume is one of the series for the Chemical Technician Curriculum Project (ChemTeC) of the American Chemical Society funded by the National Science Foundation. It consists of discussions, exercises, and experiments on the following topics: the nature of reversible processes, equilibrium constants, variable reaction tendencies, practical…

The Abundance of Molecular Hydrogen and Its Correlation with Midplane Pressure in Galaxies: Non-equilibrium, Turbulent, Chemical Models

NASA Astrophysics Data System (ADS)

Mac Low, Mordecai-Mark; Glover, Simon C. O.

2012-02-01

Observations of spiral galaxies show a strong linear correlation between the ratio of molecular to atomic hydrogen surface density R mol and midplane pressure. To explain this, we simulate three-dimensional, magnetized turbulence, including simplified treatments of non-equilibrium chemistry and the propagation of dissociating radiation, to follow the formation of H2 from cold atomic gas. The formation timescale for H2 is sufficiently long that equilibrium is not reached within the 20-30 Myr lifetimes of molecular clouds. The equilibrium balance between radiative dissociation and H2 formation on dust grains fails to predict the time-dependent molecular fractions we find. A simple, time-dependent model of H2 formation can reproduce the gross behavior, although turbulent density perturbations increase molecular fractions by a factor of few above it. In contradiction to equilibrium models, radiative dissociation of molecules plays little role in our model for diffuse radiation fields with strengths less than 10 times that of the solar neighborhood, because of the effective self-shielding of H2. The observed correlation of R mol with pressure corresponds to a correlation with local gas density if the effective temperature in the cold neutral medium of galactic disks is roughly constant. We indeed find such a correlation of R mol with density. If we examine the value of R mol in our local models after a free-fall time at their average density, as expected for models of molecular cloud formation by large-scale gravitational instability, our models reproduce the observed correlation over more than an order-of-magnitude range in density.

Model of DNA topology simplification has come full (supercoiled) circle after two decades of research. Comment on "Disentangling DNA molecules" by Alexander Vologodskii

NASA Astrophysics Data System (ADS)

Stasiak, Andrzej

2016-09-01

Being a geek of DNA topology, I remember very well the stir caused by 1997 Science paper showing that DNA topoisomerases have the ability to simplify DNA topology below the topological equilibrium values [1]. In their seminal experiments Rybenkov et al. [1] started with linear double-stranded DNA molecules with cohesive ends. The mutual cohesiveness of DNA ends was due to mutual complementarity of single-stranded extensions at both ends of linear double-stranded DNA molecules. When such DNA molecules were heated up and then slowly cooled down the single-stranded ends eventually annealed with each other causing DNA circularization. This experimental protocol permitted the authors to establish topological/thermodynamic equilibrium within samples of circularized DNA molecules. Among simple unknotted circles one also observed knotted and catenated DNA molecules. The fraction of knotted molecules in DNA samples at topological equilibrium was increasing with the length of DNA molecules undergoing slow circularization. The fraction of catenated molecules was increasing with the length and the concentration of the molecules undergoing slow circularization. Rybenkov et al. incubated then such equilibrated DNA samples with type II DNA topoisomerases, which pass DNA duplex regions through each other, and observed that as the result of it the fraction of knotted and catenated DNA molecules was dramatically decreased (up to 80-fold). This elegant experiment indicated for the first time that type II DNA topoisomerases acting on knotted or catenated DNA molecules have the ability to select among many potential sites of DNA-DNA passages these that result in DNA unknotting or decatenation. Without such a selection topoisomerases could only maintain the original topological equilibrium obtained during the slow cyclization. The big question was how DNA topoisomerases can be directed to do DNA-DNA passages that preferentially result in DNA unknotting and decatenation.

Cobalt and scandium partitioning versus iron content for crystalline phases in ultramafic nodules

USGS Publications Warehouse

Glassley, W.E.; Piper, D.Z.

1978-01-01

Fractionation of Co and Sc between garnets, olivines, and clino- and orthopyroxenes, separated from a suite of Salt Lake Crater ultramafic nodules that equilibrated at the same T and P, is strongly dependent on Fe contents. This observation suggests that petrogenetic equilibrium models of partial melting and crystal fractionation must take into account effects of magma composition, if they are to describe quantitatively geochemical evolutionary trends. ?? 1978.

Effects of the aging temperature and stress relaxation conditions on γ‧ precipitation in Inconel X-750

NASA Astrophysics Data System (ADS)

Ha, Jeong Won; Seong, Baek Seok; Jeong, Hi Won; Choi, Yoon Suk; Kang, Namhyun

2015-02-01

Inconel X-750 is a Ni-based precipitation-hardened superalloy typically used in springs designed for high-temperature applications such as the hold-down springs in nuclear power plants. γ‧ is a major precipitate in X-750 alloys which affects the strength, creep resistance, and stress relaxation properties of the spring. In this study, a solution-treated X-750 wire coiled into a spring was used that was aged at various temperatures and submitted to stress relaxation tests with and without loading. Small angle neutron scattering was employed to quantify the size and volume fraction of γ‧ phase in the springs as a function of the aging temperature and the application of a load during stress relaxation. The volume fraction of γ‧ precipitates increased in the specimen aged at 732 °C following stress relaxation at 500 °C for 300 h. However, the mean size of the precipitates in the samples was not affected by stress relaxation. The specimen aged at the lower temperature (620 °C) contained a smaller γ‧ volume fraction and gained a smaller fraction of γ‧ during stress relaxation compared with the sample aged at the higher temperature (732 °C). The smaller increase in the γ‧ volume fraction for the sample aged at 620 °C was associated with a larger increase in the M23C6 secondary carbide content during relaxation. The Cr depletion zone around the secondary carbides raises the solubility of γ‧ thereby decreasing the volume fraction of γ‧ precipitates in Inconel X-750. In terms of stress relaxation, a larger increase in the γ‧ volume fraction was measured with loading rather than without. This is probably associated with the dislocation accumulation generated under loading that facilitate the nucleation and growth of heterogeneous γ‧ phase due to enhanced diffusion.

Oxygen isotope fractionation in the CaCO3-DIC-H2O system

NASA Astrophysics Data System (ADS)

Devriendt, Laurent S.; Watkins, James M.; McGregor, Helen V.

2017-10-01

The oxygen isotope ratio (δ18O) of inorganic and biogenic carbonates is widely used to reconstruct past environments. However, the oxygen isotope exchange between CaCO3 and H2O rarely reaches equilibrium and kinetic isotope effects (KIE) commonly complicate paleoclimate reconstructions. We present a comprehensive model of kinetic and equilibrium oxygen isotope fractionation between CaCO3 and water (αc/w) that accounts for fractionation between both (a) CaCO3 and the CO32- pool (α c / CO32-) , and (b) CO32- and water (α CO32- / w) , as a function of temperature, pH, salinity, calcite saturation state (Ω), the residence time of the dissolved inorganic carbon (DIC) in solution, and the activity of the enzyme carbonic anhydrase. The model results suggest that: (1) The equilibrium αc/w is only approached in solutions with low Ω (i.e. close to 1) and low ionic strength such as in the cave system of Devils Hole, Nevada. (2) The sensitivity of αc/w to the solution pH and/or the mineral growth rate depends on the level of isotopic equilibration between the CO32- pool and water. When the CO32- pool approaches isotopic equilibrium with water, small negative pH and/or growth rate effects on αc/w of about 1-2‰ occur where these parameters covary with Ω. In contrast, isotopic disequilibrium between CO32- and water leads to strong (>2‰) positive or negative pH and growth rate effects on α CO32-/ w (and αc/w) due to the isotopic imprint of oxygen atoms derived from HCO3-, CO2, H2O and/or OH-. (3) The temperature sensitivity of αc/w originates from the negative effect of temperature on α CO32-/ w and is expected to deviate from the commonly accepted value (-0.22 ± 0.02‰/°C between 0 and 30 °C; Kim and O'Neil, 1997) when the CO32- pool is not in isotopic equilibrium with water. (4) The model suggests that the δ18O of planktic and benthic foraminifers reflects a quantitative precipitation of DIC in isotopic equilibrium with a high-pH calcifying fluid, leading to a relatively constant foraminifer calcite δ18O-temperature relationship (-0.21 ± 0.01‰/°C). The lower average coral δ18O data relative to foraminifers and other calcifiers is best explained by the precipitation of internal DIC derived from hydrated CO2 in a high-pH calcifying fluid and minimal subsequent DIC-H2O isotopic equilibration. This leads to a reduced and variable coral aragonite δ18O-temperature relationship (-0.11 to -0.22‰/°C). Together, the model presented here reconciles observations of oxygen isotope fractionation over a range of CaCO3-DIC-H2O systems.

Effects of temperature and particles concentration on the dynamic viscosity of MgO-MWCNT/ethylene glycol hybrid nanofluid: Experimental study

NASA Astrophysics Data System (ADS)

Soltani, Omid; Akbari, Mohammad

2016-10-01

In this paper, the effects of temperature and particles concentration on the dynamic viscosity of MgO-MWCNT/ethylene glycol hybrid nanofluid is examined. The experiments carried out in the solid volume fraction range of 0 to 1.0% under the temperature ranging from 30 °C to 60 °C. The results showed that the hybrid nanofluid behaves as a Newtonian fluid for all solid volume fractions and temperatures considered. The measurements also indicated that the dynamic viscosity increases with increasing the solid volume fraction and decreases with the temperature rising. The relative viscosity revealed that when the solid volume fraction enhances from 0.1 to 1%, the dynamic viscosity increases up to 168%. Finally, using experimental data, in order to predict the dynamic viscosity of MgO-MWCNT/ethylene glycol hybrid nanofluids, a new correlation has been suggested. The comparisons between the correlation outputs and experimental results showed that the suggested correlation has an acceptable accuracy.

Size distribution and volume fraction of T(1) phase precipitates from TEM images: Direct measurements and related correction.

PubMed

Dorin, Thomas; Donnadieu, Patricia; Chaix, Jean-Marc; Lefebvre, Williams; Geuser, Frédéric De; Deschamps, Alexis

2015-11-01

Transmission Electron Microscopy (TEM) can be used to measure the size distribution and volume fraction of fine scale precipitates in metallic systems. However, such measurements suffer from a number of artefacts that need to be accounted for, related to the finite thickness of the TEM foil and to the projected observation in two dimensions of the microstructure. We present a correction procedure to describe the 3D distribution of disc-like particles and apply this method to the plate-like T1 precipitates in an Al-Li-Cu alloy in two ageing conditions showing different particle morphologies. The precipitates were imaged in a High-Angular Annular Dark Field Microscope (HAADF-STEM). The corrected size distribution is further used to determine the precipitate volume fraction. Atom probe tomography (APT) is finally utilised as an alternative way to measure the precipitate volume fraction and test the validity of the electron microscopy results. Copyright © 2015 Elsevier Ltd. All rights reserved.

Computer Simulation of Spatial Arrangement and Connectivity of Particles in Three-Dimensional Microstructure: Application to Model Electrical Conductivity of Polymer Matrix Composite

NASA Technical Reports Server (NTRS)

Louis, P.; Gokhale, A. M.

1996-01-01

Computer simulation is a powerful tool for analyzing the geometry of three-dimensional microstructure. A computer simulation model is developed to represent the three-dimensional microstructure of a two-phase particulate composite where particles may be in contact with one another but do not overlap significantly. The model is used to quantify the "connectedness" of the particulate phase of a polymer matrix composite containing hollow carbon particles in a dielectric polymer resin matrix. The simulations are utilized to estimate the morphological percolation volume fraction for electrical conduction, and the effective volume fraction of the particles that actually take part in the electrical conduction. The calculated values of the effective volume fraction are used as an input for a self-consistent physical model for electrical conductivity. The predicted values of electrical conductivity are in very good agreement with the corresponding experimental data on a series of specimens having different particulate volume fraction.

Anharmonic 1D actuator model including electrostatic and Casimir forces with fractional damping perturbed by an external force

NASA Astrophysics Data System (ADS)

Mansoori Kermani, Maryam; Dehestani, Maryam

2018-06-01

We modeled a one-dimensional actuator including the Casimir and electrostatic forces perturbed by an external force with fractional damping. The movable electrode was assumed to oscillate by an anharmonic elastic force originated from Murrell-Mottram or Lippincott potential. The nonlinear equations have been solved via the Adomian decomposition method. The behavior of the displacement of the electrode from equilibrium position, its velocity and acceleration were described versus time. Also, the changes of the displacement have been investigated according to the frequency of the external force and the voltage of the electrostatic force. The convergence of the Adomian method and the effect of the orders of expansion on the displacement versus time, frequency, and voltage were discussed. The pull-in parameter was obtained and compared with the other models in the literature. This parameter was described versus the equilibrium position and anharmonicity constant.

Resonant behavior of MHD waves on magnetic flux tubes. IV - Total resonant absorption and MHD radiating eigenmodes

NASA Technical Reports Server (NTRS)

Goossens, Marcel; Hollweg, Joseph V.

1993-01-01

Resonant absorption of MHD waves on a nonuniform flux tube is investigated as a driven problem for a 1D cylindrical equilibrium. The variation of the fractional absorption is studied as a function of the frequency and its relation to the eigenvalue problem of the MHD radiating eigenmodes of the nonuniform flux tube is established. The optimal frequencies producing maximal fractional absorption are determined and the condition for total absorption is obtained. This condition defines an impedance matching and is fulfilled for an equilibrium that is fine tuned with respect to the incoming wave. The variation of the spatial wave solutions with respect to the frequency is explained as due to the variation of the real and imaginary parts of the dispersion relation of the MHD radiating eigenmodes with respect to the real driving frequency.

The equilibrium sedimentation of hyaluronic acid and of two synthetic polymers

PubMed Central

Nichol, L. W.; Ogston, A. G.; Preston, B. N.

1967-01-01

1. The method of equilibrium sedimentation has been investigated as an alternative to osmotic-pressure measurement for determining thermodynamic properties of polymer solutions at relatively high concentrations. 2. The simplifications that must be made in the theoretical treatment are discussed. 3. Measurements have been made on samples of polyethylene glycol, neutralized polymethacrylic acid and hyaluronic acid. With the first and third, values of the `non-ideality coefficients' have been obtained that agree with those obtained from osmotic measurements on the same materials. 4. Evidence has been obtained of the presence in hyaluronic acid preparations of a fraction that has either a lower degree of thermodynamic non-ideality or a higher density increment than the bulk of the sample. This fraction is not protein. ImagesFig. 3.Fig. 4.Fig. 5.Fig. 7.Fig. 8.Fig. 9.Fig. 11.Fig. 12.Fig. 13.Fig. 14. PMID:6029600

Bethe lattice approach and relaxation dynamics study of spin-crossover materials

NASA Astrophysics Data System (ADS)

Oke, Toussaint Djidjoho; Hontinfinde, Félix; Boukheddaden, Kamel

2015-07-01

Dynamical properties of Prussian blue analogs and spin-crossover materials are investigated in the framework of a Blume-Emery-Griffiths (BEG) spin-1 model, where states ±1 and 0 represent the high-spin (HS) state and the low-spin state, respectively. The quadrupolar interaction depends on the temperature in the form . Magnetic interactions are controlled by a factor such that for (), magnetic ordering is not expected. The model is exactly solved using the Bethe lattice approach for the equilibrium properties. The results are closer to those calculated by numerical simulations with suitable Arrhenius-type transition rates. The study of relaxation processes of non-equilibrium HS states revealed one-step nonlinear sigmoidal relaxation curves of the HS fraction at low temperatures. We found that increasing the magnetic interactions leads to the appearance of a plateau in the thermal hysteresis as well as in the relaxation curves of the HS fraction at low temperature.

Anharmonic 1D actuator model including electrostatic and Casimir forces with fractional damping perturbed by an external force

NASA Astrophysics Data System (ADS)

Mansoori Kermani, Maryam; Dehestani, Maryam

2018-03-01

We modeled a one-dimensional actuator including the Casimir and electrostatic forces perturbed by an external force with fractional damping. The movable electrode was assumed to oscillate by an anharmonic elastic force originated from Murrell-Mottram or Lippincott potential. The nonlinear equations have been solved via the Adomian decomposition method. The behavior of the displacement of the electrode from equilibrium position, its velocity and acceleration were described versus time. Also, the changes of the displacement have been investigated according to the frequency of the external force and the voltage of the electrostatic force. The convergence of the Adomian method and the effect of the orders of expansion on the displacement versus time, frequency, and voltage were discussed. The pull-in parameter was obtained and compared with the other models in the literature. This parameter was described versus the equilibrium position and anharmonicity constant.

Dynamic stability analysis of fractional order leaky integrator echo state neural networks

NASA Astrophysics Data System (ADS)

Pahnehkolaei, Seyed Mehdi Abedi; Alfi, Alireza; Tenreiro Machado, J. A.

2017-06-01

The Leaky integrator echo state neural network (Leaky-ESN) is an improved model of the recurrent neural network (RNN) and adopts an interconnected recurrent grid of processing neurons. This paper presents a new proof for the convergence of a Lyapunov candidate function to zero when time tends to infinity by means of the Caputo fractional derivative with order lying in the range (0, 1). The stability of Fractional-Order Leaky-ESN (FO Leaky-ESN) is then analyzed, and the existence, uniqueness and stability of the equilibrium point are provided. A numerical example demonstrates the feasibility of the proposed method.

An image-based skeletal model for the ICRP reference adult male—specific absorbed fractions for neutron-generated recoil protons

NASA Astrophysics Data System (ADS)

Jokisch, D. W.; Rajon, D. A.; Bahadori, A. A.; Bolch, W. E.

2011-11-01

Recoiling hydrogen nuclei are a principle mechanism for energy deposition from incident neutrons. For neutrons incident on the human skeleton, the small sizes of two contrasting media (trabecular bone and marrow) present unique problems due to a lack of charged-particle (protons) equilibrium. Specific absorbed fractions have been computed for protons originating in the human skeletal tissues for use in computing neutron dose response functions. The proton specific absorbed fractions were computed using a pathlength-based range-energy calculation in trabecular skeletal samples of a 40 year old male cadaver.

A study of fiber volume fraction effects in notched unidirectional SCS-6/Ti-15V-3Cr-3Al-3Sn composite. Ph.D. Thesis Final Report

NASA Technical Reports Server (NTRS)

Covey, Steven J.

1993-01-01

Notched unidirectional SCS-6/Ti-15-3 composite of three different fiber volume fractions (vf = 0.15, 0.37, and 0.41) was investigated for various room temperature microstructural and material properties including: fatigue crack initiation, fatigue crack growth, and fracture toughness. While the matrix hardness is similar for all fiber volume fractions, the fiber/matrix interfacial shear strength and matrix residual stress increases with fiber volume fraction. The composite fatigue crack initiation stress is shown to be matrix controlled and occurs when the net maximum matrix stress approaches the endurance limit stress of the matrix. A model is presented which includes residual stresses and presents the composite initiation stress as a function of fiber volume fraction. This model predicts a maximum composite initiation stress at vf approximately 0.15 which agrees with the experimental data. The applied composite stress levels were increased as necessary for continued crack growth. The applied Delta(K) values at crack arrest increase with fiber volume fraction by an amount better approximated using an energy based formulation rather than when scaled linear with modulus. After crack arrest, the crack growth rate exponents for vf37 and vf41 were much lower and toughness much higher, when compared to the unreinforced matrix, because of the bridged region which parades with the propagating fatigue crack. However, the vf15 material exhibited a higher crack growth rate exponent and lower toughness than the unreinforced matrix because once the bridged fibers nearest the crack mouth broke, the stress redistribution broke all bridged fibers, leaving an unbridged crack. Degraded, unbridged behavior is modeled using the residual stress state in the matrix ahead of the crack tip. Plastic zone sizes were directly measured using a metallographic technique and allow prediction of an effective matrix stress intensity which agrees with the fiber pressure model if residual stresses are considered. The sophisticated macro/micro finite element models of the 0.15 and 0.37 fiber volume fractions presented show good agreement with experimental data and the fiber pressure model when an estimated effective fiber/matrix debond length is used.

Analysis of Hydrogen Generation through Thermochemical Gasification of Coconut Shell Using Thermodynamic Equilibrium Model Considering Char and Tar

PubMed Central

Rupesh, Shanmughom; Muraleedharan, Chandrasekharan; Arun, Palatel

2014-01-01

This work investigates the potential of coconut shell for air-steam gasification using thermodynamic equilibrium model. A thermodynamic equilibrium model considering tar and realistic char conversion was developed using MATLAB software to predict the product gas composition. After comparing it with experimental results the prediction capability of the model is enhanced by multiplying equilibrium constants with suitable coefficients. The modified model is used to study the effect of key process parameters like temperature, steam to biomass ratio, and equivalence ratio on product gas yield, composition, and heating value of syngas along with gasification efficiency. For a steam to biomass ratio of unity, the maximum mole fraction of hydrogen in the product gas is found to be 36.14% with a lower heating value of 7.49 MJ/Nm3 at a gasification temperature of 1500 K and equivalence ratio of 0.15. PMID:27433487

Analysis of Hydrogen Generation through Thermochemical Gasification of Coconut Shell Using Thermodynamic Equilibrium Model Considering Char and Tar.

PubMed

Rupesh, Shanmughom; Muraleedharan, Chandrasekharan; Arun, Palatel

2014-01-01

This work investigates the potential of coconut shell for air-steam gasification using thermodynamic equilibrium model. A thermodynamic equilibrium model considering tar and realistic char conversion was developed using MATLAB software to predict the product gas composition. After comparing it with experimental results the prediction capability of the model is enhanced by multiplying equilibrium constants with suitable coefficients. The modified model is used to study the effect of key process parameters like temperature, steam to biomass ratio, and equivalence ratio on product gas yield, composition, and heating value of syngas along with gasification efficiency. For a steam to biomass ratio of unity, the maximum mole fraction of hydrogen in the product gas is found to be 36.14% with a lower heating value of 7.49 MJ/Nm(3) at a gasification temperature of 1500 K and equivalence ratio of 0.15.

A comparative study of the adsorption equilibrium of progesterone by a carbon black and a commercial activated carbon

NASA Astrophysics Data System (ADS)

Valenzuela-Calahorro, Cristóbal; Navarrete-Guijosa, Antonio; Stitou, Mostafa; Cuerda-Correa, Eduardo M.

2007-04-01

In this paper the adsorption process of a natural steroid hormone (progesterone) by a carbon black and a commercial activated carbon has been studied. The corresponding equilibrium isotherms have been analyzed according to a previously proposed model which establishes a kinetic law satisfactorily fitting the C versus t isotherms. The analysis of the experimental data points out the existence of two well-defined sections in the equilibrium isotherms. A general equation including these two processes has been proposed, the global adsorption process being fitted to such equation. From the values of the kinetic equilibrium constant so obtained, values of standard average adsorption enthalpy ( ΔH°) and entropy ( ΔS°) have been calculated. Finally, information related to variations of differential adsorption enthalpy ( ΔH) and entropy ( ΔS) with the surface coverage fraction ( θ) was obtained by using the corresponding Clausius-Clapeyron equations.

Effects of laser fluence non-uniformity on ambient-temperature soot measurements using the auto-compensating laser-induced incandescence technique

NASA Astrophysics Data System (ADS)

Liu, Fengshan; Rogak, Steven; Snelling, David R.; Saffaripour, Meghdad; Thomson, Kevin A.; Smallwood, Gregory J.

2016-11-01

Multimode pulsed Nd:YAG lasers are commonly used in auto-compensating laser-induced incandescence (AC-LII) measurements of soot in flames and engine exhaust as well as black carbon in the atmosphere. Such lasers possess a certain degree of fluence non-uniformity across the laser beam even with the use of beam shaping optics. Recent research showed that the measured volume fraction of ambient-temperature soot using AC-LII increases significantly, by about a factor of 5-8, with increasing the laser fluence in the low-fluence regime from a very low fluence to a relatively high fluence of near sublimation. The causes of this so-called soot volume fraction anomaly are currently not understood. The effects of laser fluence non-uniformity on the measured soot volume fraction using AC-LII were investigated. Three sets of LII experiments were conducted in the exhaust of a MiniCAST soot generator under conditions of high elemental carbon using Nd:YAG lasers operated at 1064 nm. The laser beams were shaped and relay imaged to achieve a relatively uniform fluence distribution in the measurement volume. To further homogenize the laser fluence, one set of LII experiments was conducted by using a diffractive optical element. The measured soot volume fractions in all three sets of LII experiments increase strongly with increasing the laser fluence before a peak value is reached and then start to decrease at higher fluences. Numerical calculations were conducted using the experimental laser fluence histograms. Laser fluence non-uniformity is found partially responsible for the soot volume fraction anomaly, but is insufficient to explain the degree of soot volume fraction anomaly observed experimentally. Representing the laser fluence variations by a histogram derived from high-resolution images of the laser beam energy profile gives a more accurate definition of inhomogeneity than a simple averaged linear profile across the laser beam.

A partition-limited model for the plant uptake of organic contaminants from soil and water

USGS Publications Warehouse

Chiou, C.T.; Sheng, G.; Manes, M.

2001-01-01

In dealing with the passive transport of organic contaminants from soils to plants (including crops), a partition-limited model is proposed in which (i) the maximum (equilibrium) concentration of a contaminant in any location in the plant is determined by partition equilibrium with its concentration in the soil interstitial water, which in turn is determined essentially by the concentration in the soil organic matter (SOM) and (ii) the extent of approach to partition equilibrium, as measured by the ratio of the contaminant concentrations in plant water and soil interstitial water, ??pt (??? 1), depends on the transport rate of the contaminant in soil water into the plant and the volume of soil water solution that is required for the plant contaminant level to reach equilibrium with the external soil-water phase. Through reasonable estimates of plant organic-water compositions and of contaminant partition coefficients with various plant components, the model accounts for calculated values of ??pt in several published crop-contamination studies, including near-equilibrium values (i.e., ??pt ??? 1) for relatively water-soluble contaminants and lower values for much less soluble contaminants; the differences are attributed to the much higher partition coefficients of the less soluble compounds between plant lipids and plant water, which necessitates much larger volumes of the plant water transport for achieving the equilibrium capacities. The model analysis indicates that for plants with high water contents the plant-water phase acts as the major reservoir for highly water-soluble contaminants. By contrast, the lipid in a plant, even at small amounts, is usually the major reservoir for highly water-insoluble contaminants.

Free volume of mixed cation borosilicate glass sealants elucidated by positron annihilation lifetime spectroscopy and its correlation with glass properties

NASA Astrophysics Data System (ADS)

Ojha, Prasanta K.; Rath, Sangram K.; Sharma, Sandeep K.; Sudarshan, Kathi; Pujari, Pradeep K.; Chongdar, Tapas K.; Gokhale, Nitin M.

2015-01-01

The role of La+3/Sr+2 ratios, which is varied from 0.08 to 5.09, on density, molar volume, packing fraction, free volume, thermal and electrical properties in strontium lanthanum aluminoborosilicate based glass sealants intended for solid oxide fuel cell (SOFC) applications is evaluated. The studies reveal expansion of the glass network evident from increasing molar volume and decreasing packing fraction of glasses with progressive La+3 substitutions. The molecular origin of these macroscopic structural features can be accounted for by the free volume parameters measured from positron annihilation lifetime spectroscopy (PALS). The La+3 induced expanded glass networks show increased number of subnanoscopic voids with larger sizes, as revealed from the ortho-positronium (o-Ps) lifetime and its intensity. A remarkably direct correspondence between the molar volume and fractional free volume trend is established with progressive La2O3 substitution in the glasses. The effect of these structural changes on the glass transition temperature, softening temperature, coefficient of thermal expansion, thermal stability as well as electrical conductivity has been studied.

Protein Stability in Mixed Solvents: A Balance of Contact Interaction and Excluded Volume

PubMed Central

Schellman, John A.

2003-01-01

Changes in excluded volume and contact interaction with the surface of a protein have been suggested as mechanisms for the changes in stability induced by cosolvents. The aim of the present paper is to present an analysis that combines both effects in a quantitative manner. The result is that both processes are present in both stabilizing and destabilizing interactions and neither can be ignored. Excluded volume was estimated using accessible surface area calculations of the kind introduced by Lee and Richards. The change in excluded volume on unfolding, ΔX, is quite large. For example, ΔX for ribonuclease is 6.7 L in urea and ∼16 L in sucrose. The latter number is greater than the molar volume of the protein. Direct interaction with the protein is represented as the solvent exchange mechanism, which differs from ordinary association theory because of the weakness of the interaction and the high concentrations of cosolvents. The balance between the two effects and their contribution to overall stability are most simply presented as bar diagrams as in Fig. 3. Our finding for five proteins is that excluded volume contributes to the stabilization of the native structure and that contact interaction contributes to destabilization. This is true for five proteins and four cosolvents including both denaturants and osmolytes. Whether a substance stabilizes a protein or destabilizes it depends on the relative size of these two contributions. The constant for the cosolvent contact with the protein is remarkably uniform for four of the proteins, indicating a similarity of groups exposed during unfolding. One protein, staphylococcus nuclease, is anomalous in almost all respects. In general, the strength of the interaction with guanidinium is about twice that of urea, which is about twice that of trimethylamine-N-oxide and sucrose. Arguments are presented for the use of volume fractions in equilibrium equations and the ignoring of activity coefficients of the cosolvent. It is shown in the Appendix that both the excluded volume and the direct interaction can be extracted in a unified way from the McMillan-Mayer formula for the second virial coefficient. PMID:12829469

A Solar Volumetric Receiver: Influence of Absorbing Cells Configuration on Device Thermal Performance

NASA Astrophysics Data System (ADS)

Yilbas, B. S.; Shuja, S. Z.

2017-01-01

Thermal performance of a solar volumetric receiver incorporating the different cell geometric configurations is investigated. Triangular, hexagonal, and rectangular absorbing cells are incorporated in the analysis. The fluid volume fraction, which is the ratio of the volume of the working fluid over the total volume of solar volumetric receiver, is introduced to assess the effect of cell size on the heat transfer rates in the receiver. In this case, reducing the fluid volume fraction corresponds to increasing cell size in the receiver. SiC is considered as the cell material, and air is used as the working fluid in the receiver. The Lambert's Beer law is incorporated to account for the solar absorption in the receiver. A finite element method is used to solve the governing equation of flow and heat transfer. It is found that the fluid volume fraction has significant effect on the flow field in the solar volumetric receiver, which also modifies thermal field in the working fluid. The triangular absorbing cell gives rise to improved effectiveness of the receiver and then follows the hexagonal and rectangular cells. The second law efficiency of the receiver remains high when hexagonal cells are used. This occurs for the fluid volume fraction ratio of 0.5.

FRAC-IN-THE-BOX utilization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Collins, D.G.; West, J.T.

FRAC-IN-THE-BOX is a computer code developed to calculate the fractions of rectangular parallelepiped mesh cell volumes that are intersected by combinatorial geometry type zones. The geometry description used in the code is a subset of the combinatorial geometry used in SABRINA. The input file may be read into SABRINA and three dimensional plots made of the input geometry. The volume fractions for those portions of the geometry that are too complicated to describe with the geometry routines provided in FRAC-IN-THE-BOX may be calculated in SABRINA and merged with the volume fractions computed for the remainder of the geometry. 21 figs.,more » 1 tab.« less

The effect of different fibre volume fraction on mechanical properties of banana/pineapple leaf (PaLF)/glass hybrid composite

NASA Astrophysics Data System (ADS)

Hanafee, Z. M.; Khalina, A.; Norkhairunnisa, M.; Syams, Z. Edi; Liew, K. E.

2017-09-01

This paper investigates the effect of fibre volume fraction on mechanical properties of banana-pineapple leaf (PaLF)-glass reinforced epoxy resin under tensile loading. Uniaxial tensile tests were carried out on specimens with different fibre contents (30%, 40%, 50% in weight). The composite specimens consists of 13 different combinations. The effect of hybridisation between synthetic and natural fibre onto tensile properties was determined and the optimum fibre volume fraction was obtained at 50% for both banana and PaLF composites. Additional 1 layer of woven glass fibre increased the tensile strength of banana-PaLF composite up to 85%.

Crystal structure optimisation using an auxiliary equation of state

NASA Astrophysics Data System (ADS)

Jackson, Adam J.; Skelton, Jonathan M.; Hendon, Christopher H.; Butler, Keith T.; Walsh, Aron

2015-11-01

Standard procedures for local crystal-structure optimisation involve numerous energy and force calculations. It is common to calculate an energy-volume curve, fitting an equation of state around the equilibrium cell volume. This is a computationally intensive process, in particular, for low-symmetry crystal structures where each isochoric optimisation involves energy minimisation over many degrees of freedom. Such procedures can be prohibitive for non-local exchange-correlation functionals or other "beyond" density functional theory electronic structure techniques, particularly where analytical gradients are not available. We present a simple approach for efficient optimisation of crystal structures based on a known equation of state. The equilibrium volume can be predicted from one single-point calculation and refined with successive calculations if required. The approach is validated for PbS, PbTe, ZnS, and ZnTe using nine density functionals and applied to the quaternary semiconductor Cu2ZnSnS4 and the magnetic metal-organic framework HKUST-1.

Network Aggregation in Transportation Planning : Volume II : A Fixed Point Method for Treating Traffic Equilibria

DOT National Transportation Integrated Search

1978-04-01

Volume 2 defines a new algorithm for the network equilibrium model that works in the space of path flows and is based on the theory of fixed point method. The goals of the study were broadly defined as the identification of aggregation practices and ...

Enthalpy versus entropy: What drives hard-particle ordering in condensed phases?

DOE PAGES

Anthamatten, Mitchell; Ou, Jane J.; Weinfeld, Jeffrey A.; ...

2016-07-27

In support of mesoscopic-scale materials processing, spontaneous hard-particle ordering has been actively pursued for over a half-century. The generally accepted view that entropy alone can drive hard particle ordering is evaluated. Furthermore, a thermodynamic analysis of hard particle ordering was conducted and shown to agree with existing computations and experiments. Conclusions are that (i) hard particle ordering transitions between states in equilibrium are forbidden at constant volume but are allowed at constant pressure; (ii) spontaneous ordering transitions at constant pressure are driven by enthalpy, and (iii) ordering under constant volume necessarily involves a non-equilibrium initial state which has yet tomore » be rigorously defined.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, S.; Yang, M.; Song, X.L.

The Laves phase precipitation process was characterised by means of field emission scanning electron microscopy to demonstrate its effect on creep rupture strength of steels with a fully ferritic matrix. To eliminate the effects of carbide and carbonitride precipitations so that the creep rupture data can be analysed exclusively in relation to the Laves phase precipitation process, an alloy Fe–9Cr–3Co–3W (wt.%) without C and N additions was used for the study. Creep rupture strengths were measured and volume fraction and particle size of Laves phase precipitates in the ruptured specimens were analysed. It was found that the creep rupture strengthmore » started to collapse (or decrease more rapidly) long before the Laves phase precipitation reached equilibrium fraction. This was related to the onset of the coarsening of Laves phase particles, which precipitated only on grain boundaries and hence contributed little to precipitation strengthening. Creep deformation had no effect either on the precipitation kinetics or on the growth kinetics of Laves phase particles. - Highlights: • Laves phase precipitation at 650 °C was characterised for Fe–9Cr–3W–3Co alloy. • Laves phase precipitated predominantly on grain boundaries. • Creep deformation had no effect on Laves phase precipitation and growth kinetics. • Creep strength started to collapse long before Laves phase precipitation is ended. • Collapse of creep strength was attributed to the coarsening of Laves phase particles.« less

Equilibrium swelling of elastomeric materials in solvent environments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Green, P.F.

1990-03-01

The equilibrium swelling of silicones, fluorosilicones, VITON and ethylene-propylene-diene (EPDM) elastomers in an environment of the jet fuel JP4 was investigated. The volume of silicone and DPDM elastomers increased by approximately 100% when they were placed in a saturated environment of JP4. Conversely, the volume of the fluorosilicone elastomer increased by approximately 15% and that of VITON less than 1%. In acetone, a commonly used solvent, the equilibrium swelling of VITON and the fluorosilicone elastomer was excessive, on the order of 100%, wheras the silicone and EPDM elastomers exhibited small changes in dimensions. Reasons for these observations are discussed inmore » detail. We also present a simple scheme by which one may, qualitatively, determine the dimensional stability of these elastomers in different solvents if the cohesive energy density of the solvent, which is readily available in a number of handbooks, is known. We also evaluated the vulnerability of some commonly used engineering thermoplastics to JP4. The results are tabulated. 13 refs., 6 figs., 3 tab.« less

Carbon isotope constraints on degassing of carbon dioxide from Kilauea Volcano

USGS Publications Warehouse

Gerlach, T.M.; Taylor, B.E.

1990-01-01

We examine models for batch-equilibrium and fractional-equilibrium degassing of CO2 from magma at Kilauea Volcano. The models are based on 1. (1) the concept of two-stage degassing of CO2 from magma supplied to the summit chamber, 2. (2) C isotope data for CO2 in eruptive and noneruptive (quiescent) gases from Kilauea and 3. (3) data for the isotopic fractionation of C between CO2 and C dissolved in tholeiitic basalt melt. The results of our study indicate that 1. (1) both eruptive and noneruptive degassing of CO2 most closely approach a batch equilibrium process, 2. (2) the ??13C of parental magma supplied to the summit chamber is in the range -4.1 to-3.4??? and 3. (3) the ??13C of melt after summit chamber degassing is in the range -7 to -8???, depending upon the depth of equilibration. We also present ??13C data for CO2 in eruptive gases from the current East Rift Zone eruption. These are the first C isotope data for CO2 in high-temperature (>900??C) eruptive gases from Kilauea; they have a mean ??13C value of -7.82 ?? 0.24??? and are similar to those predicted for the melt after summit chamber degassing. The minor role played by fractional degassing of ascending magma at Kilauea means that exsolved CO2 tends to remain entrained in and coherent with its host melt during ascent from both mantle source regions and crustal magma reservoirs. This has important implications for magma dynamics at Kilauea. ?? 1990.

New constraints on kinetic isotope effects during CO2(aq) hydration and hydroxylation: Revisiting theoretical and experimental data

NASA Astrophysics Data System (ADS)

Sade, Ziv; Halevy, Itay

2017-10-01

CO2 (de)hydration (i.e., CO2 hydration/HCO3- dehydration) and (de)hydroxylation (i.e., CO2 hydroxylation/HCO3- dehydroxylation) are key reactions in the dissolved inorganic carbon (DIC) system. Kinetic isotope effects (KIEs) during these reactions are likely to be expressed in the DIC and recorded in carbonate minerals formed during CO2 degassing or dissolution of gaseous CO2. Thus, a better understanding of KIEs during CO2 (de)hydration and (de)hydroxylation would improve interpretations of disequilibrium compositions in carbonate minerals. To date, the literature lacks direct experimental constraints on most of the oxygen KIEs associated with these reactions. In addition, theoretical estimates describe oxygen KIEs during separate individual reactions. The KIEs of the related reverse reactions were neither derived directly nor calculated from a link to the equilibrium fractionation. Consequently, KIE estimates of experimental and theoretical studies have been difficult to compare. Here we revisit experimental and theoretical data to provide new constraints on oxygen KIEs during CO2 (de)hydration and (de)hydroxylation. For this purpose, we provide a clearer definition of the KIEs and relate them both to isotopic rate constants and equilibrium fractionations. Such relations are well founded in studies of single isotope source/sink reactions, but they have not been established for reactions that involve dual isotopic sources/sinks, such as CO2 (de)hydration and (de)hydroxylation. We apply the new quantitative constraints on the KIEs to investigate fractionations during simultaneous CaCO3 precipitation and HCO3- dehydration far from equilibrium.

Rheological study of two-dimensional very anisometric colloidal particle suspensions: from shear-induced orientation to viscous dissipation.

PubMed

Philippe, A M; Baravian, C; Bezuglyy, V; Angilella, J R; Meneau, F; Bihannic, I; Michot, L J

2013-04-30

In the present study, we investigate the evolution with shear of the viscosity of aqueous suspensions of size-selected natural swelling clay minerals for volume fractions extending from isotropic liquids to weak nematic gels. Such suspensions are strongly shear-thinning, a feature that is systematically observed for suspensions of nonspherical particles and that is linked to their orientational properties. We then combined our rheological measurements with small-angle X-ray scattering experiments that, after appropriate treatment, provide the orientational field of the particles. Whatever the clay nature, particle size, and volume fraction, this orientational field was shown to depend only on a nondimensional Péclet number (Pe) defined for one isolated particle as the ratio between hydrodynamic energy and Brownian thermal energy. The measured orientational fields were then directly compared to those obtained for infinitely thin disks through a numerical computation of the Fokker-Plank equation. Even in cases where multiple hydrodynamic interactions dominate, qualitative agreement between both orientational fields is observed, especially at high Péclet number. We have then used an effective approach to assess the viscosity of these suspensions through the definition of an effective volume fraction. Using such an approach, we have been able to transform the relationship between viscosity and volume fraction (ηr = f(φ)) into a relationship that links viscosity with both flow and volume fraction (ηr = f(φ, Pe)).

The effect of latent adenovirus 5 infection on cigarette smoke-induced lung inflammation.

PubMed

Vitalis, T Z; Kern, I; Croome, A; Behzad, H; Hayashi, S; Hogg, J C

1998-03-01

The aim of this study was to test the hypothesis that latent adenovirus (Ad) 5 infection increases the lung inflammation that follows a single acute exposure to cigarette smoke. A recently developed model of latent adenoviral infection in guinea-pigs was used. Twelve animals were infected with Ad5 (10(8) plaque-forming units) and 12 animals were sham-infected. Thirty five days later six Ad5-infected and six sham-infected animals were exposed to the smoke from five cigarettes. The remaining animals were used as controls for both infection and smoking. As markers of inflammation, the volume fraction of macrophages, T-lymphocytes, neutrophils and eosinophils were measured by quantitative histology. We found that latent Ad5-infection alone, doubled the number of macrophages in the lung parenchyma and that smoking alone, doubled the volume fraction of neutrophils in the airway wall and the volume fraction of macrophages in the lung parenchyma. Neither viral infection nor smoking, alone, had an effect on T-lymphocytes or eosinophils. However, the combination of viral infection and smoking doubled the T-lymphocyte helper cells and quadrupled the volume fraction of macrophages in the lung parenchyma. We conclude that in guinea-pigs, latent adenovirus 5 infection increases the inflammation that follows a single acute exposure to cigarette smoke, by increasing the volume fraction of macrophages and T-lymphocyte helper cells.

Universal scaling of permeability through the granular-to-continuum transition

NASA Astrophysics Data System (ADS)

Wadsworth, F. B.; Scheu, B.; Heap, M. J.; Kendrick, J. E.; Vasseur, J.; Lavallée, Y.; Dingwell, D. B.

2015-12-01

Magmas fragment forming a transiently granular material, which can weld back to a fluid-continuum. This process results in dramatic changes in the gas-volume fraction of the material, which impacts the gas permeability. We collate published data for the gas-volume fraction and permeability of volcanic and synthetic materials which have undergone this process to different amounts and note that in all cases there exists a discontinuity in the relationship between these two properties. By discriminating data for which good microstructural information are provided, we use simple scaling arguments to collapse the data in both the still-granular, high gas-volume fraction regime and the fluid-continuum low gas-volume fraction regime such that a universal description can be achieved. We use this to argue for the microstructural meaning of the well-described discontinuity between gas-permeability and gas-volume fraction and to infer the controls on the position of this transition between dominantly granular and dominantly fluid-continuum material descriptions. As a specific application, we consider the transiently granular magma transported through and deposited in fractures in more-coherent magmas, thought to be a primary degassing pathway in high viscosity systems. We propose that our scaling coupled with constitutive laws for densification can provide insights into the longevity of such degassing channels, informing sub-surface pressure modelling at such volcanoes.

Applications for carbon fibre recovered from composites

NASA Astrophysics Data System (ADS)

Pickering; Liu, Z.; Turner, TA; Wong, KH

2016-07-01

Commercial operations to recover carbon fibre from waste composites are now developing and as more recovered fibre becomes available new applications for recovered fibre are required. Opportunities to use recovered carbon fibre as a structural reinforcement are considered involving the use of wet lay processes to produce nonwoven mats. Mats with random in-plane fibre orientation can readily be produced using existing commercial processes. However, the fibre volume fraction, and hence the mechanical properties that can be achieved, result in composites with limited mechanical properties. Fibre volume fractions of 40% can be achieved with high moulding pressures of over 100 bar, however, moulding at these pressures results in substantial fibre breakage which reduces the mean fibre length and the properties of the composite manufactured. Nonwoven mats made from aligned, short carbon fibres can achieve higher fibre volume fractions with lower fibre breakage even at high moulding pressure. A process for aligning short fibres is described and a composite of over 60% fibre volume fraction has been manufactured at a pressures up to 100 bar with low fibre breakage. Further developments of the alignment process have been undertaken and a composite of 46% fibre volume fraction has been produced moulded at a pressure of 7 bar in an autoclave, exhibiting good mechanical properties that compete with higher grade materials. This demonstrates the potential for high value applications for recovered carbon fibre by fibre alignment.

Predicting the apparent viscosity and yield stress of mixtures of primary, secondary and anaerobically digested sewage sludge: Simulating anaerobic digesters.

PubMed

Markis, Flora; Baudez, Jean-Christophe; Parthasarathy, Rajarathinam; Slatter, Paul; Eshtiaghi, Nicky

2016-09-01

Predicting the flow behaviour, most notably, the apparent viscosity and yield stress of sludge mixtures inside the anaerobic digester is essential because it helps optimize the mixing system in digesters. This paper investigates the rheology of sludge mixtures as a function of digested sludge volume fraction. Sludge mixtures exhibited non-Newtonian, shear thinning, yield stress behaviour. The apparent viscosity and yield stress of sludge mixtures prepared at the same total solids concentration was influenced by the interactions within the digested sludge and increased with the volume fraction of digested sludge - highlighted using shear compliance and shear modulus of sludge mixtures. However, when a thickened primary - secondary sludge mixture was mixed with dilute digested sludge, the apparent viscosity and yield stress decreased with increasing the volume fraction of digested sludge. This was caused by the dilution effect leading to a reduction in the hydrodynamic and non-hydrodynamic interactions when dilute digested sludge was added. Correlations were developed to predict the apparent viscosity and yield stress of the mixtures as a function of the digested sludge volume fraction and total solids concentration of the mixtures. The parameters of correlations can be estimated using pH of sludge. The shear and complex modulus were also modelled and they followed an exponential relationship with increasing digested sludge volume fraction. Copyright © 2016 Elsevier Ltd. All rights reserved.

Doubly labeled water method: in vivo oxygen and hydrogen isotope fractionation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schoeller, D.A.; Leitch, C.A.; Brown, C.

The accuracy and precision of the doubly labeled water method for measuring energy expenditure are influenced by isotope fractionation during evaporative water loss and CO/sub 2/ excretion. To characterize in vivo isotope fractionation, we collected and isotopically analyzed physiological fluids and gases. Breath and transcutaneous water vapor were isotopically fractionated. The degree of fractionation indicated that the former was fractionated under equilibrium control at 37/sup 0/C, and the latter was kinetically fractionated. Sweat and urine were unfractionated. By use of isotopic balance models, the fraction of water lost via fractionating routes was estimated from the isotopic abundances of body water,more » local drinking water, and dietary solids. Fractionated water loss averaged 23% (SD = 10%) of water turnover, which agreed with our previous estimates based on metabolic rate, but there was a systematic difference between the results based on O/sub 2/ and hydrogen. Corrections for isotopic fractionation of water lost in breath and (nonsweat) transcutaneous loss should be made when using labeled water to measure water turnover or CO/sub 2/ production.« less

Molecular simulation of dispersion and mechanical stability of organically modified layered silicates in polymer matrices

NASA Astrophysics Data System (ADS)

Fu, Yao-Tsung

The experimental analysis of nanometer-scale separation processes and mechanical properties at buried interfaces in nanocomposites has remained difficult. We have employed molecular dynamics simulation in relation to available experimental data to alleviate such limitations and gain insight into the dispersion and mechanical stability of organically modified layered silicates in hydrophobic polymer matrices. We analyzed cleavage energies of various organically modified silicates as a function of the cation exchange capacity, surfactant head group chemistry, and chain length using MD simulations with the PCFF-PHYLLOSILICATE force field. The range of the cleavage energy is between 25 and 210 mJ/m2 upon the molecular structures and packing of surfactants. As a function of chain length, the cleavage energy indicates local minima for interlayer structures comprised of loosely packed layers of alkyl chains and local maxima for interlayer structures comprised of densely packed layers of alkyl chains between the layers. In addition, the distribution of cationic head groups between the layers in the equilibrium state determines whether large increases in cleavage energy due to Coulomb attraction. We have also examined mechanical bending and failure mechanisms of layered silicates on the nanometer scale using molecular dynamics simulation in comparison to a library of TEM data of polymer nanocomposites. We investigated the energy of single clay lamellae as a function of bending radius and different cation density. The layer energy increases particularly for bending radii below 20 nm and is largely independent of cation exchange capacity. The analysis of TEM images of agglomerated and exfoliated aluminosilicates of different CEC in polymer matrices at small volume fractions showed bending radii in excess of 100 nm due to free volumes in the polymer matrix. At a volume fraction >5%, however, bent clay layers were found with bending radii <20 nm and kinks as a failure mechanism in good agreement with simulation results. We have examined thermal conductivity of organically modified layered silicates using molecular dynamics simulation in comparison to experimental results by laser measurement. The thermal conductivity slightly increased from 0.08 to 0.14 Wm-1K-1 with increasing chain length, related to the gallery spacing and interlayer density of the organic material.

Numerical simulation of convective heat transfer of nonhomogeneous nanofluid using Buongiorno model

NASA Astrophysics Data System (ADS)

Sayyar, Ramin Onsor; Saghafian, Mohsen

2017-08-01

The aim is to study the assessment of the flow and convective heat transfer of laminar developing flow of Al2O3-water nanofluid inside a vertical tube. A finite volume method procedure on a structured grid was used to solve the governing partial differential equations. The adopted model (Buongiorno model) assumes that the nanofluid is a mixture of a base fluid and nanoparticles, with the relative motion caused by Brownian motion and thermophoretic diffusion. The results showed the distribution of nanoparticles remained almost uniform except in a region near the hot wall where nanoparticles volume fraction were reduced as a result of thermophoresis. The simulation results also indicated there is an optimal volume fraction about 1-2% of the nanoparticles at each Reynolds number for which the maximum performance evaluation criteria can be obtained. The difference between Nusselt number and nondimensional pressure drop calculated based on two phase model and the one calculated based on single phase model was less than 5% at all nanoparticles volume fractions and can be neglected. In natural convection, for 4% of nanoparticles volume fraction, in Gr = 10 more than 15% enhancement of Nusselt number was achieved but in Gr = 300 it was less than 1%.

Prediction of a Densely Loaded Particle-Laden Jet using a Euler-Lagrange Dense Spray Model

NASA Astrophysics Data System (ADS)

Pakseresht, Pedram; Apte, Sourabh V.

2017-11-01

Modeling of a dense spray regime using an Euler-Lagrange discrete-element approach is challenging because of local high volume loading. A subgrid cluster of droplets can lead to locally high void fractions for the disperse phase. Under these conditions, spatio-temporal changes in the carrier phase volume fractions, which are commonly neglected in spray simulations in an Euler-Lagrange two-way coupling model, could become important. Accounting for the carrier phase volume fraction variations, leads to zero-Mach number, variable density governing equations. Using pressure-based solvers, this gives rise to a source term in the pressure Poisson equation and a non-divergence free velocity field. To test the validity and predictive capability of such an approach, a round jet laden with solid particles is investigated using Direct Numerical Simulation and compared with available experimental data for different loadings. Various volume fractions spanning from dilute to dense regimes are investigated with and without taking into account the volume displacement effects. The predictions of the two approaches are compared and analyzed to investigate the effectiveness of the dense spray model. Financial support was provided by National Aeronautics and Space Administration (NASA).

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vercher, E.; Pena, M.P.; Martinez-Andreu, A.

Isobaric experimental data of vapor-liquid equilibrium for the ethanol-water-strontium bromide system at different mole fractions of strontium bromide have been measured at 100.6 kPa. Data were correlated by Jaques and Furter's method. Thermodynamic consistency was checked by Herington's method with satisfactory results.

Unique strain history during ejection in canine left ventricle.

PubMed

Douglas, A S; Rodriguez, E K; O'Dell, W; Hunter, W C

1991-05-01

Understanding the relationship between structure and function in the heart requires a knowledge of the connection between the local behavior of the myocardium (e.g., shortening) and the pumping action of the left ventricle. We asked the question, how do changes in preload and afterload affect the relationship between local myocardial deformation and ventricular volume? To study this, a set of small radiopaque beads was implanted in approximately 1 cm3 of the isolated canine heart left ventricular free wall. Using biplane cineradiography, we tracked the motion of these markers through various cardiac cycles (controlling pre- and afterload) using the relative motion of six markers to quantify the local three dimensional Lagrangian strain. Two different reference states (used to define the strains) were considered. First, we used the configuration of the heart at end diastole for that particular cardiac cycle to define the individual strains (which gave the local "shortening fraction") and the ejection fraction. Second, we used a single reference state for all cardiac cycles i.e., the end-diastolic state at maximum volume, to define absolute strains (which gave local fractional length) and the volume fraction. The individual strain versus ejection fraction trajectories were dependent on preload and afterload. For any one heart, however, each component of absolute strain was more tightly correlated to volume fraction. Around each linear regression, the individual measurements of absolute strain scattered with standard errors that averaged less than 7% of their range. Thus the canine hearts examined had a preferred kinematic (shape) history during ejection, different from the kinematics of filling and independent or pre-or afterload and of stroke volume.

Equilibrium mass-dependent fractionation relationships for triple oxygen isotopes

NASA Astrophysics Data System (ADS)

Cao, Xiaobin; Liu, Yun

2011-12-01

With a growing interest in small 17O-anomaly, there is a pressing need for the precise ratio, ln 17α/ln 18α, for a particular mass-dependent fractionation process (MDFP) (e.g., for an equilibrium isotope exchange reaction). This ratio (also denoted as " θ") can be determined experimentally, however, such efforts suffer from the demand of well-defined process or a set of processes in addition to high precision analytical capabilities. Here, we present a theoretical approach from which high-precision ratios for MDFPs can be obtained. This approach will complement and serve as a benchmark for experimental studies. We use oxygen isotope exchanges in equilibrium processes as an example. We propose that the ratio at equilibrium, θE ≡ ln 17α/ln 18α, can be calculated through the equation below: θa-bE=κa+(κa-κb){ln18βb}/{ln18α} where 18βb is the fractionation factor between a compound "b" and the mono-atomic ideal reference material "O", 18αa-b is the fractionation factor between a and b and it equals to 18βa/ 18βb and κ is a new concept defined in this study as κ ≡ ln 17β/ln 18β. The relationship between θ and κ is similar to that between α and β. The advantages of using κ include the convenience in documenting a large number of θ values for MDFPs and in estimating any θ values using a small data set due to the fact that κ values are similar among O-bearing compounds with similar chemical groups. Frequency scaling factor, anharmonic corrections and clumped isotope effects are found insignificant to the κ value calculation. However, the employment of the rule of geometric mean (RGM) can significantly affect the κ value. There are only small differences in κ values among carbonates and the structural effect is smaller than that of chemical compositions. We provide κ values for most O-bearing compounds, and we argue that κ values for Mg-bearing and S-bearing compounds should be close to their high temperature limitation (i.e., 0.5210 for Mg and 0.5159 for S). We also provide θ values for CO 2(g)-water, quartz-water and calcite-water oxygen isotope exchange reactions at temperature from 0 to 100 °C.

Enhanced explosive sensing based on bis(methyltetraphenyl)silole nanoaggregate

NASA Astrophysics Data System (ADS)

Shin, Bomina; Sohn, Honglae

2018-01-01

New photoluminescent bis(methyltetraphenyl)silole nanoaggregates for the detection of trinitrotoluene (TNT) were developed by using aggregation-induced emission property. Bis(methyltetraphenyl)silole nanoaggregates exhibited that photoluminescence (PL) intensity was increased when the water fraction was increased to 90% by volume. Relative PL efficiency of bis(methyltetraphenyl)silole nanoaggregates was exponentially increased to the percent of water fraction and particle diameter was dependent on solvent composition. Particle size of bis(methyltetraphenyl)silole nanoaggregates was tuned by controlling the water fraction by volume. Absolute quantum yield of bis(methyltetraphenyl)silole nanoaggregates in 90% water volume fraction were 32.4%, which increases by about 40 times. Detection of TNT was achieved from the quenching PL measurement of bis(methyltetraphenyl)silole nanoaggregates by adding the TNT. A linear Stern-Volmer relationship was observed for the detection of TNT.

Novel Technology for Enrichment of Biomolecules from Cell-Free Body Fluids and Subsequent DNA Sizing.

PubMed

Patel, Vipulkumar; Celec, Peter; Grunt, Magdalena; Schwarzenbach, Heidi; Jenneckens, Ingo; Hillebrand, Timo

2016-01-01

Circulating cell-free DNA (ccfDNA) is a promising diagnostic tool and its size fractionation is of interest. However, kits for isolation of ccfDNA available on the market are designed for small volumes hence processing large sample volumes is laborious. We have tested a new method that enables enrichment of ccfDNA from large volumes of plasma and subsequently allows size-fractionation of isolated ccfDNA into two fractions with individually established cut-off levels of ccfDNA length. This method allows isolation of low-abundant DNA as well as separation of long and short DNA molecules. This procedure may be important e.g., in prenatal diagnostics and cancer research that have been already confirmed by our primary experiments. Here, we report the results of selective separation of 200- and 500-bp long synthetic DNA fragments spiked in plasma samples. Furthermore, we size-fractionated ccfDNA from the plasma of pregnant women and verified the prevalence of fetal ccfDNA in all fractions.

Evolution of volume fractions and droplet sizes by analysis of electrical conductance curves during destabilization of oil-in-water emulsions.

PubMed

Kostoglou, M; Varka, E-M; Kalogianni, E P; Karapantsios, T D

2010-09-01

Destabilization of hexane-in-water emulsions is studied by a continuous, non-intrusive, multi-probe, electrical conductance technique. Emulsions made of different oil fractions and surfactant (C(10)E(5)) concentrations are prepared in a stirred vessel using a Rushton turbine to break and agitate droplets. During the separation of phases, electrical signals from pairs of ring electrodes mounted at different heights onto the vessel wall, are recorded. The evolution of the local water volume fractions at the locations of the electrodes is estimated from these signals. It is found that in the absence of coalescence, the water fraction evolution curve from the bottom pair of electrodes is compatible with a bidisperse oil droplet size distribution. The sizes and volume fractions of the two droplet modes are estimated using theoretical arguments. The electrically determined droplet sizes are compared to data from microscopy image analysis. Results are discussed in detail. Copyright 2010 Elsevier Inc. All rights reserved.

Efficient Application of Continuous Fractional Component Monte Carlo in the Reaction Ensemble

PubMed Central

2017-01-01

A new formulation of the Reaction Ensemble Monte Carlo technique (RxMC) combined with the Continuous Fractional Component Monte Carlo method is presented. This method is denoted by serial Rx/CFC. The key ingredient is that fractional molecules of either reactants or reaction products are present and that chemical reactions always involve fractional molecules. Serial Rx/CFC has the following advantages compared to other approaches: (1) One directly obtains chemical potentials of all reactants and reaction products. Obtained chemical potentials can be used directly as an independent check to ensure that chemical equilibrium is achieved. (2) Independent biasing is applied to the fractional molecules of reactants and reaction products. Therefore, the efficiency of the algorithm is significantly increased, compared to the other approaches. (3) Changes in the maximum scaling parameter of intermolecular interactions can be chosen differently for reactants and reaction products. (4) The number of fractional molecules is reduced. As a proof of principle, our method is tested for Lennard-Jones systems at various pressures and for various chemical reactions. Excellent agreement was found both for average densities and equilibrium mixture compositions computed using serial Rx/CFC, RxMC/CFCMC previously introduced by Rosch and Maginn (Journal of Chemical Theory and Computation, 2011, 7, 269–279), and the conventional RxMC approach. The serial Rx/CFC approach is also tested for the reaction of ammonia synthesis at various temperatures and pressures. Excellent agreement was found between results obtained from serial Rx/CFC, experimental results from literature, and thermodynamic modeling using the Peng–Robinson equation of state. The efficiency of reaction trial moves is improved by a factor of 2 to 3 (depending on the system) compared to the RxMC/CFCMC formulation by Rosch and Maginn. PMID:28737933

Characterization of calcium isotopes in natural and synthetic barite

USGS Publications Warehouse

Griffith, E.M.; Schauble, E.A.; Bullen, T.D.; Paytan, A.

2008-01-01

The mineral barite (BaSO4) accommodates calcium in its crystal lattice, providing an archive of Ca-isotopes in the highly stable sulfate mineral. Holocene marine (pelagic) barite samples from the major ocean basins are isotopically indistinguishable from each other (??44/40Ca = -2.01 ?? 0.15???) but are different from hydrothermal and cold seep barite samples (??44/40Ca = -4.13 to -2.72???). Laboratory precipitated (synthetic) barite samples are more depleted in the heavy Ca-isotopes than pelagic marine barite and span a range of Ca-isotope compositions, ??44/40Ca = -3.42 to -2.40???. Temperature, saturation state, a Ba2 + / a SO42 -, and aCa2+/aBa2+ each influence the fractionation of Ca-isotopes in synthetic barite; however, the fractionation in marine barite samples is not strongly related to any measured environmental parameter. First-principles lattice dynamical modeling predicts that at equilibrium Ca-substituted barite will have much lower 44Ca/40Ca than calcite, by -9??? at 0 ??C and -8??? at 25 ??C. Based on this model, none of the measured barite samples appear to be in isotopic equilibrium with their parent solutions, although as predicted they do record lower ??44/40Ca values than seawater and calcite. Kinetic fractionation processes therefore most likely control the extent of isotopic fractionation exhibited in barite. Potential fractionation mechanisms include factors influencing Ca2+ substitution for Ba2+ in barite (e.g. ionic strength and trace element concentration of the solution, competing complexation reactions, precipitation or growth rate, temperature, pressure, and saturation state) as well as nucleation and crystal growth rates. These factors should be considered when investigating controls on isotopic fractionation of Ca2+ and other elements in inorganic and biogenic minerals. ?? 2008 Elsevier Ltd.

Thermodynamics of impurity-enhanced vacancy formation in metals

NASA Astrophysics Data System (ADS)

Bukonte, Laura; Ahlgren, Tommy; Heinola, Kalle

2017-01-01

Hydrogen induced vacancy formation in metals and metal alloys has been of great interest during the past couple of decades. The main reason for this phenomenon, often referred to as the superabundant vacancy formation, is the lowering of vacancy formation energy due to the trapping of hydrogen. By means of thermodynamics, we study the equilibrium vacancy formation in fcc metals (Pd, Ni, Co, and Fe) in correlation with the H amounts. The results of this study are compared and found to be in good agreement with experiments. For the accurate description of the total energy of the metal-hydrogen system, we take into account the binding energies of each trapped impurity, the vibrational entropy of defects, and the thermodynamics of divacancy formation. We demonstrate the effect of vacancy formation energy, the hydrogen binding, and the divacancy binding energy on the total equilibrium vacancy concentration. We show that the divacancy fraction gives the major contribution to the total vacancy fraction at high H fractions and cannot be neglected when studying superabundant vacancies. Our results lead to a novel conclusion that at high hydrogen fractions, superabundant vacancy formation takes place regardless of the binding energy between vacancies and hydrogen. We also propose the reason of superabundant vacancy formation mainly in the fcc phase. The equations obtained within this work can be used for any metal-impurity system, if the impurity occupies an interstitial site in the lattice.

Regenerable biocide delivery unit, volume 2

NASA Technical Reports Server (NTRS)

Atwater, James E.; Wheeler, Richard R., Jr.

1992-01-01

Source code for programs dealing with the following topics are presented: (1) life cycle test stand-parametric test stand control (in BASIC); (2) simultaneous aqueous iodine equilibria-true equilibrium (in C); (3) simultaneous aqueous iodine equilibria-pseudo-equilibrium (in C); (4) pseudo-(fast)-equilibrium with iodide initially present (in C); (5) solution of simultaneous iodine rate expressions (Mathematica); (6) 2nd order kinetics of I2-formic acid in humidity condensate (Mathematica); (7) prototype RMCV onboard microcontroller (CAMBASIC); (8) prototype RAM data dump to PC (in BASIC); and (9) prototype real time data transfer to PC (in BASIC).

Femtosecond optical reflectivity measurements of lattice-mediated spin repulsions in photoexcited LaCoO3 thin films

NASA Astrophysics Data System (ADS)

Bielecki, J.; Rata, A. D.; Börjesson, L.

2014-01-01

We present results on the temperature dependence of ultrafast electron and lattice dynamics, measured with pump-probe transient reflectivity experiments, of an epitaxially grown LaCoO3 thin film under tensile strain. Probing spin-polarized transitions into the antibonding eg band provides a measure of the low-spin fraction, both as a function of temperature and time after photoexcitation. It is observed that femtosecond laser pulses destabilize the constant low-spin fraction (˜63%-64%) in equilibrium into a thermally activated state, driven by a subpicosecond change in spin gap Δ. From the time evolution of the low-spin fraction, it is possible to disentangle the thermal and lattice contributions to the spin state. A lattice mediated spin repulsion, identified as the governing factor determining the equilibrium spin state in thin-film LaCoO3, is observed. These results suggests that time-resolved spectroscopy is a sensitive probe of the spin state in LaCoO3 thin films, with the potential to bring forward quantitative insight into the complicated interplay between structure and spin state in LaCoO3.

Use of system code to estimate equilibrium tritium inventory in fusion DT machines, such as ARIES-AT and components testing facilities

DOE Office of Scientific and Technical Information (OSTI.GOV)

C.P.C. Wong; B. Merrill

2014-10-01

ITER is under construction and will begin operation in 2020. This is the first 500 MWfusion class DT device, and since it is not going to breed tritium, it will consume most of the limited supply of tritium resources in the world. Yet, in parallel, DT fusion nuclear component testing machines will be needed to provide technical data for the design of DEMO. It becomes necessary to estimate the tritium burn-up fraction and corresponding initial tritium inventory and the doubling time of these machines for the planning of future supply and utilization of tritium. With the use of a systemmore » code, tritium burn-up fraction and initial tritium inventory for steady state DT machines can be estimated. Estimated tritium burn-up fractions of FNSF-AT, CFETR-R and ARIES-AT are in the range of 1–2.8%. Corresponding total equilibrium tritium inventories of the plasma flow and tritium processing system, and with the DCLL blanket option are 7.6 kg, 6.1 kg, and 5.2 kg for ARIES-AT, CFETR-R and FNSF-AT, respectively.« less

Equilibrium 𝛽-limits in classical stellarators

NASA Astrophysics Data System (ADS)

Loizu, J.; Hudson, S. R.; Nührenberg, C.; Geiger, J.; Helander, P.

2017-12-01

A numerical investigation is carried out to understand the equilibrium -limit in a classical stellarator. The stepped-pressure equilibrium code (Hudson et al., Phys. Plasmas, vol. 19 (11), 2012) is used in order to assess whether or not magnetic islands and stochastic field-lines can emerge at high . Two modes of operation are considered: a zero-net-current stellarator and a fixed-iota stellarator. Despite the fact that relaxation is allowed (Taylor, Rev. Mod. Phys., vol. 58 (3), 1986, pp. 741-763), the former is shown to maintain good flux surfaces up to the equilibrium -limit predicted by ideal-magnetohydrodynamics (MHD), above which a separatrix forms. The latter, which has no ideal equilibrium -limit, is shown to develop regions of magnetic islands and chaos at sufficiently high , thereby providing a `non-ideal -limit'. Perhaps surprisingly, however, the value of at which the Shafranov shift of the axis reaches a fraction of the minor radius follows in all cases the scaling laws predicted by ideal-MHD. We compare our results to the High-Beta-Stellarator theory of Freidberg (Ideal MHD, 2014, Cambridge University Press) and derive a new prediction for the non-ideal equilibrium -limit above which chaos emerges.

Controlling species richness in spin-glass model ecosystems

NASA Astrophysics Data System (ADS)

Poderoso, Fábio C.; Fontanari, José F.

2006-11-01

Within the framework of the random replicator model of ecosystems, we use equilibrium statistical mechanics tools to study the effect of manipulating the ecosystem so as to guarantee that a fixed fraction of the surviving species at equilibrium display a predefined set of characters (e.g., characters of economic value). Provided that the intraspecies competition is not too weak, we find that the consequence of such intervention on the ecosystem composition is a significant increase on the number of species that become extinct, and so the impoverishment of the ecosystem.

Selectivity and stoichiometry boosting of beta-cyclodextrin in cationic/anionic surfactant systems: when host-guest equilibrium meets biased aggregation equilibrium.

PubMed

Jiang, Lingxiang; Yu, Caifang; Deng, Manli; Jin, Changwen; Wang, Yilin; Yan, Yun; Huang, Jianbin

2010-02-18

Cationic surfactant/anionic surfactant/beta-CD ternary aqueous systems provide a platform for the coexistence of the host-guest (beta-CD/surfactant) equilibrium and the biased aggregation (monomeric/aggregated surfactants) equilibrium. We report here that the interplay between the two equilibria dominates the systems as follows. (1) The biased aggregation equilibrium imposes an apparent selectivity on the host-guest equilibrium, namely, beta-CD has to always selectively bind the major surfactant (molar fraction > 0.5) even if binding constants of beta-CD to the pair of surfactants are quite similar. (2) In return, the host-guest equilibrium amplifies the bias of the aggregation equilibrium, that is, the selective binding partly removes the major surfactant from the aggregates and leaves the aggregate composition approaching the electroneutral mixing stoichiometry. (3) This composition variation enhances electrostatic attractions between oppositely charged surfactant head groups, thus resulting in less-curved aggregates. In particular, the present apparent host-guest selectivity is of remarkably high values, and the selectivity stems from the bias of the aggregation equilibrium rather than the difference in binding constants. Moreover, beta-CD is defined as a "stoichiometry booster" for the whole class of cationic/anionic surfactant systems, which provides an additional degree of freedom to directly adjust aggregate compositions of the systems. The stoichiometry boosting of the compositions can in turn affect or even determine microstructures and macroproperties of the systems.

Dose fractionated gamma knife radiosurgery for large arteriovenous malformations on daily or alternate day schedule outside the linear quadratic model: Proof of concept and early results. A substitute to volume fractionation.

PubMed

Mukherjee, Kanchan Kumar; Kumar, Narendra; Tripathi, Manjul; Oinam, Arun S; Ahuja, Chirag K; Dhandapani, Sivashanmugam; Kapoor, Rakesh; Ghoshal, Sushmita; Kaur, Rupinder; Bhatt, Sandeep

2017-01-01

To evaluate the feasibility, safety and efficacy of dose fractionated gamma knife radiosurgery (DFGKRS) on a daily schedule beyond the linear quadratic (LQ) model, for large volume arteriovenous malformations (AVMs). Between 2012-16, 14 patients of large AVMs (median volume 26.5 cc) unsuitable for surgery or embolization were treated in 2-3 of DFGKRS sessions. The Leksell G frame was kept in situ during the whole procedure. 86% (n = 12) patients had radiologic evidence of bleed, and 43% (n = 6) had presented with a history of seizures. 57% (n = 8) patients received a daily treatment for 3 days and 43% (n = 6) were on an alternate day (2 fractions) regimen. The marginal dose was split into 2 or 3 fractions of the ideal prescription dose of a single fraction of 23-25 Gy. The median follow up period was 35.6 months (8-57 months). In the three-fraction scheme, the marginal dose ranged from 8.9-11.5 Gy, while in the two-fraction scheme, the marginal dose ranged from 11.3-15 Gy at 50% per fraction. Headache (43%, n = 6) was the most common early postoperative complication, which was controlled with short course steroids. Follow up evaluation of at least three years was achieved in seven patients, who have shown complete nidus obliteration in 43% patients while the obliteration has been in the range of 50-99% in rest of the patients. Overall, there was a 67.8% reduction in the AVM volume at 3 years. Nidus obliteration at 3 years showed a significant rank order correlation with the cumulative prescription dose (p 0.95, P value 0.01), with attainment of near-total (more than 95%) obliteration rates beyond 29 Gy of the cumulative prescription dose. No patient receiving a cumulative prescription dose of less than 31 Gy had any severe adverse reaction. In co-variate adjusted ordinal regression, only the cumulative prescription dose had a significant correlation with common terminology criteria for adverse events (CTCAE) severity (P value 0.04), independent of age, AVM volume, number of fractions and volume of brain receiving atleast 8 Gy of radiation. DFGKRS is feasible for large AVMs with a fair nidus obliteration rate and acceptable toxicity. Cumulative prescription dose seems to be the most significant independent predictor for outcome following DFGKRS with 29-30 Gy resulting in a fair nidus obliteration with least adverse events.

Shear-induced structural transitions in Newtonian non-Newtonian two-phase flow

NASA Astrophysics Data System (ADS)

Cristobal, G.; Rouch, J.; Colin, A.; Panizza, P.

2000-09-01

We show the existence under shear flow of steady states in a two-phase region of a brine-surfactant system in which lyotropic dilute lamellar (non-Newtonian) and sponge (Newtonian) phases are coexisting. At high shear rates and low sponge phase-volume fractions, we report on the existence of a dynamic transition corresponding to the formation of a colloidal crystal of multilamellar vesicles (or ``onions'') immersed in the sponge matrix. As the sponge phase-volume fraction increases, this transition exhibits a hysteresis loop leading to a structural bistability of the two-phase flow. Contrary to single phase lamellar systems where it is always 100%, the onion volume fraction can be monitored continuously from 0 to 100 %.

SORPTION KINETICS OF PAHS IN METHANOL-WATER SYSTEMS

EPA Science Inventory

The objectives of this study were to evaluate the relationships between the equilibrium sorption constant (Kp), the first-order desorption rate coefficient (k2), and the volumetric fraction of water miscible solvent (fc); and to utilize SPARC-calculated (SPARC Performs Automatic ...

Lipid immiscibility and biophysical properties: Molecular order within and among unit cell volumes

USDA-ARS?s Scientific Manuscript database

Saturated and unsaturated fatty acids clearly have a discrete chemical structure in the solid state. In a saturated solution, the solid state and solution state are in chemical equilibrium. The lipid stearic acid packs in unit cell volumes in the liquid state as well as in the solid state. Normal...

Measuring P-V-T Phase Behavior with a Variable Volume View Cell

ERIC Educational Resources Information Center

Hoffmann, Markus M.; Salter, Jason D.

2004-01-01

An experiment using a variable volume cell is presented where students actively control and directly observe the phase equilibrium inside the view cell. Measuring and exploring P-V-T phase behavior through dielectric constant measurements conveys the important concept that solvent behavior can be changed continuously in the sc fluid state.

Mechanistic information from the first volume profile analysis for a reversible intermolecular electron-transfer reaction involving pentaammine(isonicotinamide)ruthenium and cytochrome c

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baensch, B.; Meier, M.; Martinez, P.

1994-10-12

The reversible intermolecular electron-transfer reaction between pentaammine(isonicotinamide)ruthenium(II/III) and horse-heart cytochrome c iron(III/II) was subjected to a detailed kinetic and thermodynamic study as a function of temperature and pressure. Theoretical calculations based on the Marcus-Hush theory were employed to predict all rate and equilibrium constants as well as activation parameters. There is an excellent agreement between the kinetically and thermodynamically determined equilibrium constants and associated pressure parameters. These data are used to construct a volume profile for the overall process, from which it follows that the transition state lies halfway between the reactant and product states on a volume basis. Themore » reorganization in the transition state has reached a similar degree in both directions of the electron-transfer process and corresponds to a {lambda}{sup {double_dagger}} value of 0.44 for this reversible reaction. This is the first complete volume profile analysis for a reversible intermolecular electron-transfer reaction.« less

Magnesium isotopic evidence for chemical disequilibrium among cumulus minerals in layered mafic intrusion

NASA Astrophysics Data System (ADS)

Chen, Lie-Meng; Teng, Fang-Zhen; Song, Xie-Yan; Hu, Rui-Zhong; Yu, Song-Yue; Zhu, Dan; Kang, Jian

2018-04-01

Magnesium isotopic compositions of olivine, clinopyroxene, and ilmenite from the Baima intrusion, SW China, for the first time, are investigated to constrain the magnitude and mechanisms of Mg isotope fractionation among cumulus minerals in layered mafic intrusions and to evaluate their geological implications. Olivine and clinopyroxene have limited Mg isotope variations, with δ26Mg ranging from -0.33 to +0.05‰ and from -0.29 to -0.13‰, respectively, similar to those of mantle xenolithic peridotites. By contrast, ilmenites display extremely large Mg isotopic variation, with δ26Mg ranging from -0.50 to +1.90‰. The large inter-mineral fractionations of Mg isotopes between ilmenite and silicates may reflect both equilibrium and kinetic processes. A few ilmenites have lighter Mg isotopic compositions than coexisting silicates and contain high MgO contents without compositional zoning, indicating equilibrium fractionation. The implication is that the light Mg isotopic compositions of lunar high-Ti basalts may result from an isotopically light source enriched in cumulate ilmenites. On the other hand, most ilmenites have heavy Mg isotopic compositions, coupled with high MgO concentration and chemical zoning, which can be quantitatively modeled by kinetic Mg isotope fractionations induced by subsolidus Mg-Fe exchange between ilmenite and ferromagnesian silicates during the cooling of the Baima intrusion. The extensive occurrence of kinetic Mg isotope fractionation in ilmenites implies the possibility of widespread compositional disequilibrium among igneous minerals in magma chambers. Consequently, disequilibrium effects need to be considered in studies of basaltic magma evolution, magma chamber processes, and magmatic Fe-Ti oxide ore genesis.

Comparative stereology of the mouse and finch left ventricle.

PubMed

Bossen, E H; Sommer, J R; Waugh, R A

1978-01-01

The volume fractions and surface per unit cell volume of some subcellular components of the left ventricles of the finch and mouse were quantitated by stereologic techniques. These species were chosen for study because they have similar heart rates but differ morphologically in some respects: fiber diameter is larger in the mouse; the mouse has transverse tubules while the finch does not; and the finch has a form of junctional sarcoplasmic reticulum (JSR), extended JSR (EJSR), located in the cell interior with no direct plasmalemmal contact, while the mouse interior JSR (IJSR) abuts on transverse tubules. Our data show that the volume fraction (Vv) and surface area per unit cell volume (Sv) of total SR, and free SR (FSR) are similar. The volume fractions of mitochondria, myofibrils, and total junctional SR were also similar. The Sv of the cell surface of the finch was similar to the Sv of the cell surface of the mouse (Sv-plasmalemma plus Sv of the transverse tubules). The principal difference was in the distribution of JSR; the mouse peripheral JSR (PJSR) represents only 9% of the total JSR, while the finch PJSR accounts for 24% of the bird's JSR. The similar volume fractions of total junctional SR (PJSR + EJSR in the finch; PJSR + IJSR in the mouse) suggest that the EJSR is not an embryologic remnant, and raises the possibility that some function of JSR is independent of plasmalemmal contact.

A note on AB INITIO semiconductor band structures

NASA Astrophysics Data System (ADS)

Fiorentini, Vincenzo

1992-09-01

We point out that only the internal features of the DFT ab initio theoretical picture of a crystal should be used in a consistent ab initio calculation of the band structure. As a consequence, we show that ground-state band structure calculations should be performed for the system in equilibrium at zero pressure, i.e. at the computed equilibrium cell volume ω th. Examples of consequences of this attitude are considered.

Lead free Bi0.5Na0.5TiO3 (BNT) and polyvinylidene fluoride (PVDF) based nanocomposite for energy storage applications

NASA Astrophysics Data System (ADS)

Pradhan, Lagen Kumar; Pandey, Rabichandra; Kumar, Sunil; Kar, Manoranjan

2018-05-01

Novel ceramic-polymer nanocomposites have great potential for electrical energy storage applications due to its high energy storage density. In the present work, BNT and PVDF based flexible polymer nanocomposites (BNT-PVDF) with different volume fraction (ϕ = 0, 5, 10, 15) were fabricated by solution casting method. Enhancement in beta phase of PVDF polymer matrix with the volume fraction (ϕ = 5, 10, 15) of BNT has been confirmed by X-ray diffraction (XRD) technique as well as Fourier transform infrared (FTIR) spectroscopy analysis. The enhancement of β phase increases as compared to (α) phases with volume fraction (ϕ) of nanofiller (BNT) in the matrix (PVDF) due to internal stress at the interface as well as structural modification of PVDF matrix. BNT-PVDF nanocomposites (with ϕ=10) showed a high dielectric constant (ɛr ≈ 78) relative to pure PVDF (ɛr ≈ 10) at 100 Hz. In addition to this, it exhibits relaxor type ferroelectric behavior with energy storage efficiency up to 77% for the volume fraction (ϕ) of 10.

Twinning and martensite in a 304 austenitic stainless steel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shen, Yongfeng; Li, Xi; Sun, Xin

2012-08-30

The microstructure characteristics and deformation behavior of 304L stainless steel during tensile deformation at two different strain rates have been investigated by means of interrupted tensile tests, electron-backscatter-diffraction (EBSD) and transmission electron microscopy (TEM) techniques. The volume fractions of transformed martensite and deformation twins at different stages of the deformation process were measured using X-ray diffraction method and TEM observations. It is found that the volume fraction of martensite monotonically increases with increasing strain but decreases with increasing strain rate. On the other hand, the volume fraction of twins increases with increasing strain for strain level less than 57%. Beyondmore » that, the volume fraction of twins decreases with increasing strain. Careful TEM observations show that stacking faults (SFs) and twins preferentially occur before the nucleation of martensite. Meanwhile, both {var_epsilon}-martensite and {alpha}{prime}-martensite are observed in the deformation microstructures, indicating the co-existence of stress induced- transformation and strain-induced-transformation. We also discussed the effects of twinning and martensite transformation on work-hardening as well as the relationship between stacking faults, twinning and martensite transformation.« less

Strengthening and Improving Yield Asymmetry of Magnesium Alloys by Second Phase Particle Refinement Under the Guidance of Integrated Computational Materials Engineering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Dongsheng; Lavender, Curt

2015-05-08

Improving yield strength and asymmetry is critical to expand applications of magnesium alloys in industry for higher fuel efficiency and lower CO 2 production. Grain refinement is an efficient method for strengthening low symmetry magnesium alloys, achievable by precipitate refinement. This study provides guidance on how precipitate engineering will improve mechanical properties through grain refinement. Precipitate refinement for improving yield strengths and asymmetry is simulated quantitatively by coupling a stochastic second phase grain refinement model and a modified polycrystalline crystal viscoplasticity φ-model. Using the stochastic second phase grain refinement model, grain size is quantitatively determined from the precipitate size andmore » volume fraction. Yield strengths, yield asymmetry, and deformation behavior are calculated from the modified φ-model. If the precipitate shape and size remain constant, grain size decreases with increasing precipitate volume fraction. If the precipitate volume fraction is kept constant, grain size decreases with decreasing precipitate size during precipitate refinement. Yield strengths increase and asymmetry approves to one with decreasing grain size, contributed by increasing precipitate volume fraction or decreasing precipitate size.« less

Gyroid Structures at Highly Asymmetric Volume Fractions by Blending of ABC Triblock Terpolymer and AB Diblock Copolymer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ahn, Seonghyeon; Kwak, Jongheon; Choi, Chungryong

Here, we investigated, via small angle X-ray scattering and transmission electron microscopy, the morphologies of binary blend of polyisoprene- b-polystyrene- b-poly(2-vinylpyridine) (ISP) triblock terpolymer and polyisoprene-b-polystyrene (IS) diblock copolymer. An asymmetric ISP with volume fractions ( f) of 0.12, 0.75, and 0.13 for PI, PS, and P2VP blocks, respectively, showed a new morphology: Coexistence of spheres and cylinders with tetragonal packing. Asymmetric IS with f I = 0.11 and f S =0.89 showed conventional body-centered cubic spherical microdomains. Very interestingly, a binary blend of ISP and IS with overall volume fractions of f I = 0.12, f S = 0.79,more » and f P = 0.09 exhibited core-shell double gyroid (CSG: Q 230 space group), where PI consists of thin core and PS forms thick shell, while P2VP becomes thin matrix. It is very unusual to form highly asymmetric CSG with the matrix having very small volume fraction (0.09).« less

Gyroid Structures at Highly Asymmetric Volume Fractions by Blending of ABC Triblock Terpolymer and AB Diblock Copolymer

DOE PAGES

Ahn, Seonghyeon; Kwak, Jongheon; Choi, Chungryong; ...

2017-11-08

Here, we investigated, via small angle X-ray scattering and transmission electron microscopy, the morphologies of binary blend of polyisoprene- b-polystyrene- b-poly(2-vinylpyridine) (ISP) triblock terpolymer and polyisoprene-b-polystyrene (IS) diblock copolymer. An asymmetric ISP with volume fractions ( f) of 0.12, 0.75, and 0.13 for PI, PS, and P2VP blocks, respectively, showed a new morphology: Coexistence of spheres and cylinders with tetragonal packing. Asymmetric IS with f I = 0.11 and f S =0.89 showed conventional body-centered cubic spherical microdomains. Very interestingly, a binary blend of ISP and IS with overall volume fractions of f I = 0.12, f S = 0.79,more » and f P = 0.09 exhibited core-shell double gyroid (CSG: Q 230 space group), where PI consists of thin core and PS forms thick shell, while P2VP becomes thin matrix. It is very unusual to form highly asymmetric CSG with the matrix having very small volume fraction (0.09).« less

Modeling Equilibrium Fe Isotope Fractionation in Fe-Organic Complexes: Implications for the use of Fe Isotopes as a Biomarker and Trends Based on the Properties of Bound Ligands

NASA Astrophysics Data System (ADS)

Domagal-Goldman, S.; Kubicki, J. D.

2006-05-01

Fe Isotopes have been proposed as a useful tracer of biological and geochemical processes. Key to understanding the effects these various processes have on Fe isotopes is accurate modeling of the reactions responsible for the isotope fractionations. In this study, we examined the theoretical basis for the claims that Fe isotopes can be used as a biomarker. This was done by using molecular orbital/density functional theory (MO/DFT) calculations to predict the equilibrium fractionation of Fe isotopes due to changes in the redox state and the bonding environment of Fe. Specifically, we predicted vibrational frequencies for iron desferrioxamine (Fe-DFOB), iron triscatechol (Fe(cat)3), iron trisoxalate (Fe(ox)3), and hexaaquo iron (Fe(H2O)6) for complexes containing both ferrous (Fe2+) and ferric (Fe3+) iron. Using these vibrational frequencies, we then predicted fractionation factors between these six complexes. The predicted fractionation factors resulting from changes in the redox state of Fe fell in the range 2.5- 3.5‰. The fractionation factors resulting from changes in the bonding environment of Fe ranged from 0.2 to 1.4‰. These results indicate that changes in the bonding strength of Fe ligands are less important to Fe isotope fractionation processes than are changes to the redox state of Fe. The implications for use of Fe as a tracer of biological processes is clear: abiological redox changes must be ruled out in a sample before Fe isotopes are considered as a potential biomarker. Furthermore, the use of Fe isotopes to measure the redox state of the Earths surface environment through time is supported by this work, since changes in the redox state of Fe appear to be the more important driver of isotopic fractionations. In addition to the large differences between redox-driven fractionations and ligand-driven fractionations, we will also show general trends in the demand for heavy Fe isotopes as a function of properties of the bound ligand. This will help the future analysis of Fe isotope fractionation. Future directions in the theoretical study of metal isotope fractionations will also be discussed, including the modeling of reactions on mineral surfaces.

Theory of activated glassy dynamics in randomly pinned fluids.

PubMed

Phan, Anh D; Schweizer, Kenneth S

2018-02-07

We generalize the force-level, microscopic, Nonlinear Langevin Equation (NLE) theory and its elastically collective generalization [elastically collective nonlinear Langevin equation (ECNLE) theory] of activated dynamics in bulk spherical particle liquids to address the influence of random particle pinning on structural relaxation. The simplest neutral confinement model is analyzed for hard spheres where there is no change of the equilibrium pair structure upon particle pinning. As the pinned fraction grows, cage scale dynamical constraints are intensified in a manner that increases with density. This results in the mobile particles becoming more transiently localized, with increases of the jump distance, cage scale barrier, and NLE theory mean hopping time; subtle changes of the dynamic shear modulus are predicted. The results are contrasted with recent simulations. Similarities in relaxation behavior are identified in the dynamic precursor regime, including a roughly exponential, or weakly supra-exponential, growth of the alpha time with pinning fraction and a reduction of dynamic fragility. However, the increase of the alpha time with pinning predicted by the local NLE theory is too small and severely so at very high volume fractions. The strong deviations are argued to be due to the longer range collective elasticity aspect of the problem which is expected to be modified by random pinning in a complex manner. A qualitative physical scenario is offered for how the three distinct aspects that quantify the elastic barrier may change with pinning. ECNLE theory calculations of the alpha time are then presented based on the simplest effective-medium-like treatment for how random pinning modifies the elastic barrier. The results appear to be consistent with most, but not all, trends seen in recent simulations. Key open problems are discussed with regard to both theory and simulation.

Theory of activated glassy dynamics in randomly pinned fluids

NASA Astrophysics Data System (ADS)

Phan, Anh D.; Schweizer, Kenneth S.

2018-02-01

We generalize the force-level, microscopic, Nonlinear Langevin Equation (NLE) theory and its elastically collective generalization [elastically collective nonlinear Langevin equation (ECNLE) theory] of activated dynamics in bulk spherical particle liquids to address the influence of random particle pinning on structural relaxation. The simplest neutral confinement model is analyzed for hard spheres where there is no change of the equilibrium pair structure upon particle pinning. As the pinned fraction grows, cage scale dynamical constraints are intensified in a manner that increases with density. This results in the mobile particles becoming more transiently localized, with increases of the jump distance, cage scale barrier, and NLE theory mean hopping time; subtle changes of the dynamic shear modulus are predicted. The results are contrasted with recent simulations. Similarities in relaxation behavior are identified in the dynamic precursor regime, including a roughly exponential, or weakly supra-exponential, growth of the alpha time with pinning fraction and a reduction of dynamic fragility. However, the increase of the alpha time with pinning predicted by the local NLE theory is too small and severely so at very high volume fractions. The strong deviations are argued to be due to the longer range collective elasticity aspect of the problem which is expected to be modified by random pinning in a complex manner. A qualitative physical scenario is offered for how the three distinct aspects that quantify the elastic barrier may change with pinning. ECNLE theory calculations of the alpha time are then presented based on the simplest effective-medium-like treatment for how random pinning modifies the elastic barrier. The results appear to be consistent with most, but not all, trends seen in recent simulations. Key open problems are discussed with regard to both theory and simulation.

Global Mittag-Leffler stability analysis of fractional-order impulsive neural networks with one-side Lipschitz condition.

PubMed

Zhang, Xinxin; Niu, Peifeng; Ma, Yunpeng; Wei, Yanqiao; Li, Guoqiang

2017-10-01

This paper is concerned with the stability analysis issue of fractional-order impulsive neural networks. Under the one-side Lipschitz condition or the linear growth condition of activation function, the existence of solution is analyzed respectively. In addition, the existence, uniqueness and global Mittag-Leffler stability of equilibrium point of the fractional-order impulsive neural networks with one-side Lipschitz condition are investigated by the means of contraction mapping principle and Lyapunov direct method. Finally, an example with numerical simulation is given to illustrate the validity and feasibility of the proposed results. Copyright © 2017 Elsevier Ltd. All rights reserved.

Optimization of radioactive sources to achieve the highest precision in three-phase flow meters using Jaya algorithm.

PubMed

Roshani, G H; Karami, A; Khazaei, A; Olfateh, A; Nazemi, E; Omidi, M

2018-05-17

Gamma ray source has very important role in precision of multi-phase flow metering. In this study, different combination of gamma ray sources (( 133 Ba- 137 Cs), ( 133 Ba- 60 Co), ( 241 Am- 137 Cs), ( 241 Am- 60 Co), ( 133 Ba- 241 Am) and ( 60 Co- 137 Cs)) were investigated in order to optimize the three-phase flow meter. Three phases were water, oil and gas and the regime was considered annular. The required data was numerically generated using MCNP-X code which is a Monte-Carlo code. Indeed, the present study devotes to forecast the volume fractions in the annular three-phase flow, based on a multi energy metering system including various radiation sources and also one NaI detector, using a hybrid model of artificial neural network and Jaya Optimization algorithm. Since the summation of volume fractions is constant, a constraint modeling problem exists, meaning that the hybrid model must forecast only two volume fractions. Six hybrid models associated with the number of used radiation sources are designed. The models are employed to forecast the gas and water volume fractions. The next step is to train the hybrid models based on numerically obtained data. The results show that, the best forecast results are obtained for the gas and water volume fractions of the system including the ( 241 Am- 137 Cs) as the radiation source. Copyright © 2018 Elsevier Ltd. All rights reserved.

Non-Newtonian behavior of plagioclase-bearing basaltic magma: Subliquidus viscosity measurement of the 1707 basalt of Fuji volcano, Japan

NASA Astrophysics Data System (ADS)

Ishibashi, Hidemi

2009-03-01

Laboratory measurements of viscosity were done for basalt erupted in 1707 AD from Fuji volcano, Japan, using a concentric cylinder rotational viscometer at temperatures of 1297-1157 °C, 1 atm pressure, and fO 2 near the Ni-NiO buffer. On cooling, elongated plagioclase crystals with a mean length/width ratio of ca. 8.5 appeared at 1237 °C, followed by olivine at 1157 °C. At progressively lower temperatures, the total crystal volume fraction increased monotonously to ca. 0.25; viscosity increased from 38.9 to 765 Pa s at a shear strain rate of 1 s - 1 . This basalt magma behaves as a Newtonian fluid at temperatures greater than 1217 °C, but shear-thinning behavior occurs at temperatures less than 1197 °C because of the suspended plagioclase crystals. This behavior is well approximated as a power law fluid. At the onset of shear thinning, the crystal volume fraction was between 0.06 and 0.13, which is attributed to the pronounced lath-shape of plagioclase crystals. The relative viscosity increases monotonously with increase of crystal volume fraction at a constant shear strain rate, and with decrease of shear strain rate at a constant crystal volume fraction. A modified form of the Krieger-Dougherty equation is introduced herein. It enables us to describe the dependencies of relative viscosity on both the crystal volume fraction and shear strain rate, and consequently the onset of shear-thinning behavior.

Shoulder muscle volume and fat content in healthy adult volunteers: quantification with DIXON MRI to determine the influence of demographics and handedness.

PubMed

Kälin, Pascal S; Crawford, Rebecca J; Marcon, Magda; Manoliu, Andrei; Bouaicha, Samy; Fischer, Michael A; Ulbrich, Erika J

2018-04-23

We aimed to provide mean values for fat-fraction and volume for full-length bilateral rotator cuff and deltoid muscles in asymptomatic adults selected on the basis of their good musculoskeletal and systemic health, and to understand the influence of gender, age, and arm dominance. Seventy-six volunteers aged 20 to 60 years who were screened for normal BMI and high general health were included in the study. MRI was performed at 3 Tesla using three-point DIXON sequences. Volume and fat-signal fraction of the rotator cuff muscles and the deltoid muscle were determined with semi-automated segmentation of entire muscle lengths. Differences according to age, gender, and handedness per muscle were evaluated. Fat-signal fractions were comparable between genders (mean ± 2 SD, 95% CI, women 7.0 ± 3.0; 6.8-7.2%, men 6.8 ± 2.7; 6.7-7.0%) but did not show convincing changes with age. Higher shoulder muscle volume and lower fat-signal fraction in the dominant arm were shown for teres minor and deltoid (p < 0.01) with similar trends shown for the other rotator cuff muscles. Bilateral fat-signal fractions and volumes based on entire length shoulder muscles in asymptomatic 20-60 year old adults may provide reference for clinicians. Differences shown according to arm dominance should be considered and may rationalize the need for bilateral imaging in determining appropriate management.

Analyzing near infrared scattering from human skin to monitor changes in hematocrit

NASA Astrophysics Data System (ADS)

Chaiken, Joseph; Deng, Bin; Goodisman, Jerry; Shaheen, George; Bussjager, R. J.

2012-01-01

The leading preventable cause of death, world-wide, civilian or military, for all people between the ages of 18-45 is undetected internal hemorrhage. Autonomic compensation mechanisms mask changes such as e.g. hematocrit fluctuations that could give early warning if only they could be monitored continuously with reasonable degrees of precision and relative accuracy. Probing tissue with near infrared radiation (NIR) simultaneously produces remitted fluorescence and Raman scattering (IE) plus Rayleigh/Mie light scattering (EE) that noninvasively give chemical and physical information about the materials and objects within. We model tissue as a three-phase system: plasma and red blood cell (RBC) phases that are mobile and a static tissue phase. In vivo, any volume of tissue naturally experiences spatial and temporal fluctuations of blood plasma and RBC content. Plasma and RBC fractions may be discriminated from each other on the basis of their physical, chemical and optical properties. Thus IE and EE from NIR probing yield information about these fractions. Assuming there is no void volume in viable tissue, or that void volume is constant, changes in plasma and RBC volume fractions may be calculated from simultaneous measurements of the two observables, EE and IE. In a previously published analysis we showed the underlying phenomenology but did not provide an algorithm for calculating volume fractions from experimental data. Here we present a simple analysis that allows continuous monitoring of fluid fraction and hematocrit (Hct) changes by measuring IE and EE, and apply it to some experimental in vivo measurements.

Quantitative measurement for the microstructural parameters of nano-precipitates in Al-Mg-Si-Cu alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Kai

Size, number density and volume fraction of nano-precipitates are important microstructural parameters controlling the strengthening of materials. In this work a widely accessible, convenient, moderately time efficient method with acceptable accuracy and precision has been provided for measurement of volume fraction of nano-precipitates in crystalline materials. The method is based on the traditional but highly accurate technique of measuring foil thickness via convergent beam electron diffraction. A new equation is proposed and verified with the aid of 3-dimensional atom probe (3DAP) analysis, to compensate for the additional error resulted from the hardly distinguishable contrast of too short incomplete precipitates cutmore » by the foil surface. The method can be performed on a regular foil specimen with a modern LaB{sub 6} or field-emission-gun transmission electron microscope. Precisions around ± 16% have been obtained for precipitate volume fractions of needle-like β″/C and Q precipitates in an aged Al-Mg-Si-Cu alloy. The measured number density is close to that directly obtained using 3DAP analysis by a misfit of 4.5%, and the estimated precision for number density measurement is about ± 11%. The limitations of the method are also discussed. - Highlights: •A facile method for measuring volume fraction of nano-precipitates based on CBED •An equation to compensate for small invisible precipitates, with 3DAP verification •Precisions around ± 16% for volume fraction and ± 11% for number density.« less

Cardiac Magnetic Resonance-Measured Left Atrial Volume and Function and Incident Atrial Fibrillation: Results From MESA (Multi-Ethnic Study of Atherosclerosis).

PubMed

Habibi, Mohammadali; Samiei, Sanaz; Ambale Venkatesh, Bharath; Opdahl, Anders; Helle-Valle, Thomas M; Zareian, Mytra; Almeida, Andre L C; Choi, Eui-Young; Wu, Colin; Alonso, Alvaro; Heckbert, Susan R; Bluemke, David A; Lima, João A C

2016-08-01

Early detection of structural changes in left atrium (LA) before atrial fibrillation (AF) development could be helpful in identification of those at higher risk for AF. Using cardiac magnetic resonance imaging, we examined the association of LA volume and function, and incident AF in a multiethnic population free of clinical cardiovascular diseases. In a case-cohort study embedded in MESA (Multi-Ethnic Study of Atherosclerosis), baseline LA size and function assessed by cardiac magnetic resonance feature-tracking were compared between 197 participants with incident AF and 322 participants randomly selected from the whole MESA cohort. Participants were followed up for 8 years. Incident AF cases had a larger LA volume and decreased passive, active, and total LA emptying fractions and peak global LA longitudinal strain (peak LA strain) at baseline. In multivariable analysis, elevated LA maximum volume index (hazard ratio, 1.38 per SD; 95% confidence interval, 1.01-1.89) and decreased peak LA strain (hazard ratio, 0.68 per SD; 95% confidence interval, 0.48-0.96), and passive and total LA emptying fractions (hazard ratio for passive LA emptying fractions, 0.55 per SD; 95% confidence interval, 0.40-0.75 and hazard ratio for active LA emptying fractions, 0.70 per SD; 95% confidence interval, 0.52-0.95), but not active LA emptying fraction, were associated with incident AF. Elevated LA volumes and decreased passive and total LA emptying fractions were independently associated with incident AF in an asymptomatic multiethnic population. Including LA functional variables along with other risk factors of AF may help to better risk stratify individuals at risk of AF development. © 2016 American Heart Association, Inc.

Improved understanding of the acoustophoretic focusing of dense suspensions in a microchannel

NASA Astrophysics Data System (ADS)

Karthick, S.; Sen, A. K.

2017-11-01

We provide improved understanding of acoustophoretic focusing of a dense suspension (volume fraction φ >10 % ) in a microchannel subjected to an acoustic standing wave using a proposed theoretical model and experiments. The model is based on the theory of interacting continua and utilizes a momentum transport equation for the mixture, continuity equation, and transport equation for the solid phase. The model demonstrates the interplay between acoustic radiation and shear-induced diffusion (SID) forces that is critical in the focusing of dense suspensions. The shear-induced particle migration model of Leighton and Acrivos, coupled with the acoustic radiation force, is employed to simulate the continuum behavior of particles. In the literature, various closures for the diffusion coefficient Dφ* are available for rigid spheres at high concentrations and nonspherical deformable particles [e.g., red blood cells (RBCs)] at low concentrations. Here we propose a closure for Dφ* for dense suspension of RBCs and validate the proposed model with experimental data. While the available closures for Dφ* fail to predict the acoustic focusing of a dense suspension of nonspherical deformable particles like RBCs, the predictions of the proposed model match experimental data within 15%. Both the model and experiments reveal a competition between acoustic radiation and SID forces that gives rise to an equilibrium width w* of a focused stream of particles at some distance Leq* along the flow direction. Using different shear rates, acoustic energy densities, and particle concentrations, we show that the equilibrium width is governed by Péclet number Pe and Strouhal number Stas w*=1.4(PeSt) -0.5 while the length required to obtain the equilibrium-focused width depends on St as Leq*=3.8 /(St)0.6 . The proposed model and correlations would find significance in the design of microchannels for acoustic focusing of dense suspensions such as undiluted blood.

Microstructures and hydrogen absorption/desorption properties of La-Ni alloys in the composition range of La-77.8--83.2 at.% Ni

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yamamoto, T.; Inui, H.; Yamaguchi, M.

1997-12-01

Alloys based on the intermetallic phase, LaNi{sub 5} have been used as negative electrode materials of rechargeable nickel-metal hydride (Ni-MH) batteries because of their fast activation, high storage-capacity, long cycle-life and excellent electrochemical charge/discharge kinetics. Here, microstructure and hydrogen absorption/desorption properties of La-Ni alloys have been investigated as a function of alloy composition in the range of La-77.8 {approximately} 83.2 at.% Ni, which corresponds to compositions between two intermetallic phases, La{sub 2}Ni{sub 7} and LaNi{sub 5}. The intermetallic phase, La{sub 5}Ni{sub 19} of the Ce{sub 5}Co{sub 19}-type is found for the first time to exist as an equilibrium phase atmore » a composition between La{sub 2}Ni{sub 7} and LaNi{sub 5}. This phase is stable at high temperatures around 1,000 C but decomposes into La{sub 2}Ni{sub 7} and LaNi{sub 5} below 900 C. Hydrogen absorption/desorption properties described in terms of pressure-composition isotherms decline with decreasing Ni content (i.e. with increasing volume fraction of intermetallic phases other than LaNi{sub 5}). In particular, the plateau at the equilibrium pressure corresponding to the hydrogen absorption in the LaNi{sub 5} phase is narrowed with decreasing Ni content and additional plateaus with higher equilibrium pressures come into existence. The degradation becomes more pronounced in the presence of La{sub 2}Ni{sub 7} than La{sub 5}Ni{sub 19}. This can be understood in terms of the ratio of the number of LaNi{sub 2} (Laves) unit layers to that of LaNi{sub 5} unit layers in the unit cell of the two intermetallic phases.« less

Single-coil properties and concentration effects for polyelectrolyte-like wormlike micelles: a Monte Carlo study

NASA Astrophysics Data System (ADS)

Cannavacciuolo, Luigi; Skov Pedersen, Jan; Schurtenberger, Peter

2002-03-01

Results of an extensive Monte Carlo (MC) study on both single and many semiflexible charged chains with excluded volume (EV) are summarized. The model employed has been tailored to mimic wormlike micelles in solution. Simulations have been performed at different ionic strengths of added salt, charge densities, chain lengths and volume fractions Φ, covering the dilute to concentrated regime. At infinite dilution the scattering functions can be fitted by the same fitting functions as for uncharged semiflexible chains with EV, provided that an electrostatic contribution bel is added to the bare Kuhn length. The scaling of bel is found to be more complex than the Odijk-Skolnick-Fixman predictions, and qualitatively compatible with more recent variational calculations. Universality in the scaling of the radius of gyration is found if all lengths are rescaled by the total Kuhn length. At finite concentrations, the simple model used is able to reproduce the structural peak in the scattering function S(q) observed in many experiments, as well as other properties of polyelectrolytes (PELs) in solution. Universal behaviour of the forward scattering S(0) is established after a rescaling of Φ. MC data are found to be in very good agreement with experimental scattering measurements with equilibrium PELs, which are giant wormlike micelles formed in mixtures of nonionic and ionic surfactants in dilute aqueous solution, with added salt.

Determination of the partition coefficient between dissolved organic carbon and seawater using differential equilibrium kinetics.

PubMed

Kim, Du Yung; Kwon, Jung-Hwan

2018-05-04

Because the freely dissolved fraction of highly hydrophobic organic chemicals is bioavailable, knowing the partition coefficient between dissolved organic carbon and water (K DOCw ) is crucial to estimate the freely dissolved fraction from the total concentration. A kinetic method was developed to obtain K DOCw that required a shorter experimental time than equilibrium methods. The equilibrium partition coefficients of four polychlorinated biphenyls (PCBs) (2,4,4'-trichlorobiphenyl (PCB 28), 2,2',3,5'-tetrachlorobiphenyl (PCB 44), 2,2',4,5,5'-pentachlorobiphenyl (PCB 101), and 2,2',4,4',5,5'-hexachlorobiphenyl (PCB 153)) between dissolved organic carbon and seawater (K DOCsw ) were determined using seawater samples from the Korean coast. The log K DOCsw values of PCB 28 were measured by equilibrating PCB 28, the least hydrophobic congener, with seawater samples, and the values ranged from 6.60 to 7.20. For the more hydrophobic PCBs (PCB 44, PCB 101, and PCB 153), kinetic experiments were conducted to determine the sorption rate constants (k 2 ) and their log K DOCsw values were obtained by comparing their k 2 with that of PCB 28. The calculated log K DOCsw values were 6.57-7.35 for PCB 44, 6.23-7.44 for PCB 101, and 6.35-7.73 for PCB 153. The validity of the proposed method was further confirmed using three less hydrophobic polycyclic aromatic hydrocarbons. This kinetic method shortened the experimental time to obtain the K DOCsw values of the more hydrophobic PCBs, which did not reach phase equilibrium. Copyright © 2018 Elsevier Ltd. All rights reserved.

Gallium isotope fractionation during Ga adsorption on calcite and goethite

NASA Astrophysics Data System (ADS)

Yuan, Wei; Saldi, Giuseppe D.; Chen, JiuBin; Vetuschi Zuccolini, Marino; Birck, Jean-Louis; Liu, Yujie; Schott, Jacques

2018-02-01

Gallium (Ga) isotopic fractionation during its adsorption on calcite and goethite was investigated at 20 °C as a function of the solution pH, Ga aqueous concentration and speciation, and the solid to solution ratio. In all experiments Ga was found to be enriched in light isotopes at the solid surface with isotope fractionation △71Gasolid-solution up to -1.27‰ and -0.89‰ for calcite and goethite, respectively. Comparison of Ga isotopic data of this study with predictions for 'closed system' equilibrium and 'Rayleigh fractionation' models indicates that the experimental data are consistent with a 'closed system' equilibrium exchange between the fluid and the solid. The results of this study can be interpreted based on Ga aqueous speciation and the structure of Ga complexes formed at the solid surfaces. For calcite, Ga isotope fractionation is mainly triggered by increased Ga coordination and Ga-O bond length, which vary respectively from 4 and 1.84 Å in Ga(OH)4- to 6 and 1.94 Å in the >Ca-O-GaOH(OH2)4+ surface complex. For goethite, despite the formation of Ga hexa-coordinated >FeOGa(OH)20 surface complexes (Ga-O distances of 1.96-1.98 Å) both at acid and alkaline pH, a similar extent of isotope fractionation was found at acid and alkaline pH, suggesting that Ga(OH)4- is preferentially adsorbed on goethite for all investigated pH conditions. In addition, the observed decrease of Ga isotope fractionation magnitude observed with increasing Ga surface coverage for both calcite and goethite is likely related to the formation of Ga surface polymers and/or hydroxides with reduced Ga-O distances. This first study of Ga isotope fractionation during solid-fluid interactions suggests that the adsorption of Ga by oxides, carbonates or clay minerals could yield significant Ga isotope fractionation between secondary minerals and surficial fluids including seawater. Ga isotopes thus should help to better characterize the surficial biogeochemical cycles of gallium and its geochemical analog aluminum.

Quantification of Labile Soil Mercury by Stable Isotope Dilution Techniques

NASA Astrophysics Data System (ADS)

Shetaya, Waleed; Huang, Jen-How; Osterwalder, Stefan; Alewell, Christine

2016-04-01

Mercury (Hg) is a toxic element that can cause severe health problems to humans. Mercury is emitted to the atmosphere from both natural and anthropogenic sources and can be transported over long distances before it is deposited to aquatic and terrestrial environments. Aside from accumulation in soil solid phases, Hg deposited in soils may migrate to surface- and ground-water or enter the food chain, depending on its lability. There are many operationally-defined extraction methods proposed to quantify soil labile metals. However, these methods are by definition prone to inaccuracies such as non-selectivity, underestimation or overestimation of the labile metal pool. The isotopic dilution technique (ID) is currently the most promising method for discrimination between labile and non-labile metal fractions in soil with a minimum disturbance to soil-solid phases. ID assesses the reactive metal pool in soil by defining the fraction of metal both in solid and solution phases that is isotopically-exchangeable known as the 'E-value'. The 'E-value' represents the metal fraction in a dynamic equilibrium with the solution phase and is potentially accessible to plants. This is carried out by addition of an enriched metal isotope to soil suspensions and quantifying the fraction of metal that is able to freely exchange with the added isotope by measuring the equilibrium isotopic ratio by ICP-MS. E-value (mg kg-1) is then calculated as follows: E-Value = (Msoil/ W) (CspikeVspike/ Mspike) (Iso1IAspike -Iso2IAspikeRss / Iso2IAsoil Rss - Iso1IAsoil) where M is the average atomic mass of the metal in the soil or the spike, W is the mass of soil (kg), Cspike is the concentration of the metal in the spike (mg L-1), Vspike is the volume of spike (L), IA is isotopic abundance, and Rss is the equilibrium ratio of isotopic abundances (Iso1:Iso2). Isotopic dilution has been successfully applied to determine E-values for several elements. However, to our knowledge, this method has not yet been applied to estimate the labile pool of mercury in contaminated soils. We performed a series of soil incubations spiked with 196Hg2+aiming at measuring and modelling the progressive assimilation of Hg ions into less labile forms. Soils with a wide range of characteristics are taken for our research purpose, inclusive of Hg concentrations ranging from 0.1 to 390 mg kg-1, pH between 3.5 - 7.5 and total organic carbon (TOC) between 2.5 - 8 %. In parallel, the labile pool of Hg estimated using ID will be compared with that determined using conventional extraction methods, e.g. sequential extraction procedures. These altogether allows us to answer (1) how the E-value of Hg in soils is comparable to those estimated based on selective extraction methods, (2) how the labile Hg correlates with the total soil Hg, soil pH and TOC, and (3) how the solubility of added Hg (e.g. via rainfall) decreased in soils of different properties during aging. The obtained results fills the knowledge gap concerning Hg biogeochemistry in the terrestrial environment and serves as a basis for estimating (and predicting) the risk of soil Hg diffusion from a point source to the adjacent environments.

Experimental determination of the Mo isotope fractionation factor between metal and silicate liquids

NASA Astrophysics Data System (ADS)

Hin, R. C.; Burkhardt, C.; Schmidt, M. W.; Bourdon, B.

2011-12-01

The conditions and chemical consequences of core formation have mainly been reconstructed from experimentally determined element partition coefficients between metal and silicate liquids. However, first order questions such as the mode of core formation or the nature of the light element(s) in the Earth's core are still debated [1]. In addition, the geocentric design of most experimental studies leaves the conditions of core formation on other terrestrial planets and asteroids even more uncertain than for Earth. Through mass spectrometry, records of mass-dependent stable isotope fractionation during high-temperature processes such as metal-silicate segregation are detectable. Stable isotope fractionation may thus yield additional constrains on core formation conditions and its consequences for the chemical evolution of planetary objects. Experimental investigations of equilibrium mass-dependent stable isotope fractionation have shown that Si isotopes fractionate between metal and silicate liquids at temperatures of 1800°C and pressures of 1 GPa, while Fe isotopes leave no resolvable traces of core formation processes [2,3]. Molybdenum is a refractory and siderophile trace element in the Earth, and thus much less prone to complications arising from mass balancing core and mantle and from potential volatile behaviour than other elements. To determine equilibrium mass-dependent Mo isotope fractionation during metal-silicate segregation, we have designed piston cylinder experiments with a basaltic silicate composition and an iron based metal with ~8 wt% Mo, using both graphite and MgO capsules. Metal and silicate phases are completely segregated by the use of a centrifuging piston cylinder at ETH Zurich, thus preventing analysis of mixed metal and silicate signatures. Molybdenum isotope compositions were measured using a Nu Instruments 1700 MC-ICP-MS at ETH Zurich. To ensure an accurate correction of analytical mass fractionation a 100Mo-97Mo double spike was admixed before chemical purification. Initial results provide an equilibrium 98Mo/95Mo isotope fractionation factor between metal and silicate liquids of -0.18±0.10% (2σ) at 1400°C and 1 GPa. Although the relative mass difference of these Mo isotopes is smaller than for Fe isotopes, this result implies that metal-silicate segregation may have led to mass-dependent stable Mo isotope fractionation, as opposed to Fe isotopes. A possible explanation is that the bonding environment of Mo may counterbalance its relatively small mass separation. At reducing conditions, Mo occurs in 4+ valence state in silicates [4] and thus its bond strength difference between metal and silicate may be more similar to that of Si than Fe. Stable Mo isotopes may thus become an important tool for constraining the conditions of core formation in asteroids and terrestrial planets. [1] Rubie et al. (2011) EPSL 301, 31-42. [2] Shahar et al. (2009) EPSL 288, 228-234. [3] Poitrasson et al. (2009) EPSL 278, 376-385. [4] Farges et al. (2006) Can. Min. 44, 731-753.

The determination of density and molecular weight distributions of lipoproteins by sedimentation equilibrium.

PubMed

Jeffrey, P D; Nichol, L W; Smith, G D

1975-01-25

A method is presented by which an experimental record of total concentration as a function of radial distance, obtained in a sedimentation equilibrium experiment conducted with a noninteracting mixture in the absence of a density gradient, may be analyzed to obtain the unimodal distributions of molecular weight and of partial molar volume when these vary concomitantly and continuously. Particular attention is given to the caracterization of classes of lipoproteins exhibiting Gaussian distributions of these quantities, although the analysis is applicable to other types of unimodal distribution. Equations are also formulated permitting the definition of the corresponding distributions of partial specific volume and of density. The analysis procedure is based on a method (employing Laplace transforms) developed previously, but differs from it in that it avoids the necessity of differentiating experimental results, which introduces error. The method offers certain advantages over other procedures used to characterize and compare lipoprotein samples (exhibiting unimodal distributions) with regard to the duration of the experiment, economy of the sample, and, particularly, the ability to define in principle all of the relevant distributions from one sedimentation equilibrium experiment and an external measurement of the weight average partial specific volume. These points and the steps in the analysis procedure are illustrated with experimental results obtained in the sedimentation equilibrium of a sample of human serum low density lipoprotein. The experimental parameters (such as solution density, column height, and angular velocity) used in the conduction of these experiments were selected on the basis of computer-simulated examples, which are also presented. These provide a guide for other workers interested in characterizing lipoproteins of this class.

First-principles Calculations of Equilibrium Calcium Isotope Fractionation among Ca-bearing Minerals

NASA Astrophysics Data System (ADS)

Zhou, C.; Wang, W.; Kang, J.; Wu, Z.; Huang, F.

2016-12-01

Calcium isotope fractionation factors of Ca-bearing minerals are investigated with the first principle calculations based on density functional theory (DFT). The sequence of heavy Ca isotope enrichment is forsterite > grossular > butschliite > lime > fluorite > tremolite diopside > anhydrite dolomite titanite > anorthite > perovskite gehlenite aragonite richterite > akermanite > oldhamite. This order is consistent with variation of Ca-O bond lengths, indicating that Ca-O bond energy plays an overwhelming role on the fractionations of Ca isotopes. Our study provides important insights into the Ca isotopic data of meteorites. Our calculation predicts that oldhamites (CaS) are enriched in light Ca isotopes relative to silicate phase if they are in equilibrium, contrast with the observations in Valdes et al (2014). Therefore, oldhamite and silicate phase in the meteorites should be in disequilibrium for Ca isotopes. Our results can also be used to understand Ca isotopic composition of the Moon. Δ44/40Ca between olivine (with CaO content of 2.48 wt%) and diopside is up to 0.41‰ and Δ44/40Cagrossular-diopside is 0.26‰ at 1500K. Feng et al. (2014) calculated that Δ44/40Ca between opx with CaO content of 1.74 wt% and cpx is about 0.27‰ at 1500 K. According to the Lunar Magma Ocean (LMO) model, the modern Moon is chemically stratified (Snyder et al., 1992; Elardo et al., 2011). Assuming that the lower cumulate and upper residual melt are in isotopic equilibrium during the evolution of Lunar Magma Ocean where the cumulate may be mainly composed of olivine and orthopyroxene or garnet/spinel, δ44/40Ca of the Moon could be underestimated by 0.05‰ to 0.25‰ if the shallow lunar samples are used to represent the bulk Moon.

Protein binding and its potential for eliciting minimal systemic side effects with a novel inhaled corticosteroid, ciclesonide.

PubMed

Rohatagi, Shashank; Luo, Yongyi; Shen, Liduo; Guo, Zuyu; Schemm, Christina; Huang, Yongqing; Chen, Kelly; David, Michael; Nave, Ruediger; King, S Peter

2005-01-01

Freely circulating, protein unbound, active inhaled corticosteroid (ICS) can cause systemic adverse effects. Desisobutyryl-ciclesonide (des-CIC) is the active metabolite of ciclesonide, an effective, novel ICS for persistent asthma. This study examines the free fraction of ciclesonide and des-CIC and determines whether the presence of other agents or disease states affects protein binding. Protein binding of des-CIC (0.5, 5.0, 25, 100, and 500 ng/mL) was determined, using both equilibrium dialysis and ultrafiltration, in plasma from humans (healthy and either renally or hepatically impaired) and several animal species and in the presence of either salicylates or warfarin. Dialyzed samples were analyzed by liquid chromatography with tandem mass spectroscopy to determine both free and bound concentrations of des-CIC. After ultrafiltration, spiked plasma plus H-des-CIC was separated into free and bound fractions by centrifugation and quantified by scintillation counting. Additionally, in another study, protein binding of ciclesonide was determined by equilibrium dialysis. For equilibrium dialysis, the mean percentages of des-CIC (0.5-500 ng/mL) plasma protein binding across species were high, approximately 99%, and no apparent saturation of protein binding was observed. Results were similar for ultrafiltration analysis. Protein binding of des-CIC did not change in the presence of warfarin or salicylates or in the plasma of renally or hepatically impaired patients. The protein binding of ciclesonide was 99.4% in human serum. The very low fraction of unbound des-CIC in the systemic circulation suggests minimal systemic exposure of unbound des-CIC, thus suggesting a low potential for systemic adverse effects after administration of inhaled ciclesonide.

Unveiling the relationships among the viscosity equations of glass liquids and colloidal suspensions for obtaining universal equations with the generic free volume concept.

PubMed

Hao, Tian

2015-09-14

The underlying relationships among viscosity equations of glass liquids and colloidal suspensions are explored with the aid of free volume concept. Viscosity equations of glass liquids available in literature are focused and found to have a same physical basis but different mathematical expressions for the free volume. The glass transitions induced by temperatures in glass liquids and the percolation transition induced by particle volume fractions in colloidal suspensions essentially are a second order phase transition: both those two transitions could induce the free volume changes, which in turn determines how the viscosities are going to change with temperatures and/or particle volume fractions. Unified correlations of the free volume to both temperatures and particle volume fractions are thus proposed. The resulted viscosity equations are reducible to many popular viscosity equations currently widely used in literature; those equations should be able to cover many different types of materials over a wide temperature range. For demonstration purpose, one of the simplified versions of those newly developed equations is compared with popular viscosity equations and the experimental data: it can well fit the experimental data over a wide temperature range. The current work reveals common physical grounds among various viscosity equations, deepening our understanding on viscosity and unifying the free volume theory across many different systems.

Rheological Characterization of Polyoxyethylene (POE) and Carboxymethyl Cellulose (CMC) Suspensions with Added Solids

NASA Astrophysics Data System (ADS)

Mora, A.; Skurtys, O.; Osorio, F.

2015-04-01

The rheological properties of high molecular weight POE and CMC suspensions by adding micro-metric solid particles such as fibers or spheres were studied. The volume fraction, Φ, was varied between 0 and 0.4. Their rheological properties were obtained after fitting a Cross model. For POE suspending fluid with spherical particle, the behavior of the normalized steady shear viscosity, μ/μ0, as function of the fraction volume followed a Thomas model. However, for CMC suspensions, μ/μ0 seems to be lineal with Φ. For a pure fluid or a suspension with Φ = 0; 2, the suspension presented an elastic behavior whereas it was observed a viscous behavior when the volume fraction was increased.

Morphometric analysis of abdominal organs and rib cage: Implication for risk of solid organ injuries in children.

PubMed

Harbaugh, Calista M; Shlykov, Maksim A; Tsuchida, Ryan E; Holcombe, Sven A; Hirschl, Jake; Wang, Stewart C; Ehrlich, Peter F

2015-06-01

Motor vehicle crashes are the leading cause of injury-related mortality in children, with a higher rate of multiorgan injuries than in adults. This may be related to increased solid organ volume relative to abdominal cavity and decreased protection of an underdeveloped cartilaginous rib cage in young children. To date, these anatomic relationships have not been fully described. Our study used analytic morphomics to obtain precise measures of the pediatric liver, spleen, kidneys, and ribs. This pilot study included 215 trauma patients (aged 0-18 years) with anonymized computed tomography (CT) scans. Liver, spleen, and kidney volumes were modeled using semiautomatic algorithms (MATLAB 2013a, MathWorks Inc., Natick, MA). Thirty-one scans were adequate to model the rib cage. Pearson's r was used to correlate absolute organ volume, fractional organ volume, and organ exposure with age and weight. Spleen, right and left kidney, and liver volumes increased with age and weight (p < 0.01). Right/left kidney and liver fractional volumes decreased with age (p < 0.01), whereas spleen fractional volume remained relatively constant. Exposed surface area of the liver only significantly decreased with age in the anterior (p < 0.01), right (p < 0.01), and posterior views (p = 0.02). With this study, we have demonstrated the ability to model solid organ and rib cage anatomy of children using cross-sectional imaging. In younger children, there may be a decrease in fractional organ volume and increase in liver surface exposure, although analysis of a larger sample size is warranted. In the future, this information may be used to improve the design of safety restraints in motor vehicles.

Contrasting Effects of Carbon and Sulfur on Fe-Isotope Fractionation between Metal and Silicate Melt during Planetary Core Formation

NASA Astrophysics Data System (ADS)

Elardo, S. M.; Shahar, A.

2015-12-01

There are numerous studies that show well-resolved Fe isotope fractionations in igneous materials from different planetary bodies. Potential explanations for these fractionations include a non-chondritic bulk planetary Fe isotopic composition, and equilibrium fractionation between Fe-alloys or minerals and silicate melts during planetary differentiation, mantle melting, or fractional crystallization. This is further complicated by the fact that these processes are not mutually exclusive, making the interpretation of Fe isotope data a complex task. Here we present new experimental results investigating the effect of C on Fe isotope fractionation between molten peridotite and an Fe-alloy. Experiments were conducted at 1 GPa and 1850° C for 0.5 - 3 hours on a mixture of an 54Fe-spiked peridotite and Fe-metal with and without Ni metal in an end-loaded piston cylinder at the Geophysical Laboratory. Carbon saturation was achieved with a graphite capsule, and resulted in C contents of the Fe-alloy in our experiments ranging from 3.8 - 4.9 wt. %. The metal and silicate phases from half of each experiment were separated manually and dissolved in concentrated acids. Iron was separated from matrix elements by anion exchange chromatagraphy. Iron-isotopic compositions were determined with the Nu Plasma II MC-ICP-MS at GL. The other half of each experiment was used for quantitative microbeam analysis. Equilibrium was assessed with a time series and the three-isotope exchange method. The Ni-free experiments resulted in no resolvable Fe isotope fractionation between the Fe-C-alloy and molten silicate. This is in contrast to the results of Shahar et al. (2015) which showed a fractionation for Δ57Fe of ~0.18 ‰ between a peridotite and an Fe-alloy with a similar S abundance to C in these experiments. The one experiment thus far that contained Ni (~4 wt. % in the alloy) showed a resolvable fractionation between the Fe-Ni-C alloy and silicate of ~0.10 ‰. Shahar et al. found a similar magnitude fractionation to our Ni bearing experiment in experiments with no C or S. The difference in temperature (1650° C in Shahar et al. vs. 1850° C here) may be partially responsible for these discrepancies. Ongoing experiments will further investigate the effects of C and other light elements on Fe isotope fractionation during core segregation.

The Role of Transcytolemmal Water Exchange in Magnetic Resonance Measurements of Diffuse Myocardial Fibrosis in Hypertensive Heart Disease

PubMed Central

Coelho-Filho, Otavio R.; Mongeon, François-Pierre; Mitchell, Richard; Moreno, Heitor; Nadruz, Wilson; Kwong, Raymond; Jerosch-Herold, Michael

2013-01-01

Background The myocardial extracellular volume fraction (MECVF) has been used to detect diffuse fibrosis. Estimation of MECVF relies quantification of the T1 relaxation time after contrast enhancement, which can be sensitive to equilibrium transcytolemmal water exchange. We hypothesized that MECVF, quantified with a parsimonious 2-space water-exchange model, correlates positively with the connective tissue volume fraction (CTVF) in a rodent model of hypertensive heart disease, while the widely used analysis based on assuming fast transcytolemmal water exchange could result in a significant underestimate of MECVF. Methods and Results Nω–nitro-L-arginine-metyl-ester (L-NAME) or placebo was administered to 22 and 15 wild-type mice, respectively. MECVF was measured at baseline and 7-week follow-up by pre- and post-contrast T1 CMR imaging at 4.7 T, using a 2-space water-exchange model. CTVF was quantified, using Masson’s trichrome stain. L-NAME induced hypertrophy (weight-indexed LV mass 2.2±0.3 vs. 4.1±0.4 µg/g, p<0.001), and increased CTVF (8.6%±1.5 vs. 2.58%±0.6, p<0.001), compared to controls. MECVF was higher in L-NAME-treated animals (0.43±0.09 vs, 0.26±0.03, p<0.001), and correlated with CTVF and weight-indexed LV mass (r=0.842 and r=0.737 respectively, both P<0.0001). Neglecting transcytolemmal water-exchange caused a significant underestimate of MECVF changes. Ten patients with history of hypertension had significantly higher MECVF (0.446±0.063) compared to healthy controls 0.307±0.030, p<0.001). Conclusions CMR allowed detection of myocardial extracellular matrix expansion in a mouse model, and in patients with a history of hypertension. Accounting for the effects of transcytolemmal water exchange can result in a substantial difference of MECVF, compared to assuming fast transcytolemmal water exchange. PMID:23159497

Linking hygroscopicity and the surface microstructure of model inorganic salts, simple and complex carbohydrates, and authentic sea spray aerosol particles.

PubMed

Estillore, Armando D; Morris, Holly S; Or, Victor W; Lee, Hansol D; Alves, Michael R; Marciano, Meagan A; Laskina, Olga; Qin, Zhen; Tivanski, Alexei V; Grassian, Vicki H

2017-08-09

Individual airborne sea spray aerosol (SSA) particles show diversity in their morphologies and water uptake properties that are highly dependent on the biological, chemical, and physical processes within the sea subsurface and the sea surface microlayer. In this study, hygroscopicity data for model systems of organic compounds of marine origin mixed with NaCl are compared to data for authentic SSA samples collected in an ocean-atmosphere facility providing insights into the SSA particle growth, phase transitions and interactions with water vapor in the atmosphere. In particular, we combine single particle morphology analyses using atomic force microscopy (AFM) with hygroscopic growth measurements in order to provide important insights into particle hygroscopicity and the surface microstructure. For model systems, a range of simple and complex carbohydrates were studied including glucose, maltose, sucrose, laminarin, sodium alginate, and lipopolysaccharides. The measured hygroscopic growth was compared with predictions from the Extended-Aerosol Inorganics Model (E-AIM). It is shown here that the E-AIM model describes well the deliquescence transition and hygroscopic growth at low mass ratios but not as well for high ratios, most likely due to a high organic volume fraction. AFM imaging reveals that the equilibrium morphology of these single-component organic particles is amorphous. When NaCl is mixed with the organics, the particles adopt a core-shell morphology with a cubic NaCl core and the organics forming a shell similar to what is observed for the authentic SSA samples. The observation of such core-shell morphologies is found to be highly dependent on the salt to organic ratio and varies depending on the nature and solubility of the organic component. Additionally, single particle organic volume fraction AFM analysis of NaCl : glucose and NaCl : laminarin mixtures shows that the ratio of salt to organics in solution does not correspond exactly for individual particles - showing diversity within the ensemble of particles produced even for a simple two component system.

Influence of a depletion interaction on dynamical heterogeneity in a dense quasi-two-dimensional colloid liquid.

PubMed

Ho, Hau My; Cui, Bianxiao; Repel, Stephen; Lin, Binhua; Rice, Stuart A

2004-11-01

We report the results of digital video microscopy studies of the large particle displacements in a quasi-two-dimensional binary mixture of large (L) and small (S) colloid particles with diameter ratio sigma(L)/sigma(S)=4.65, as a function of the large and small colloid particle densities. As in the case of the one-component quasi-two-dimensional colloid system, the binary mixtures exhibit structural and dynamical heterogeneity. The distribution of large particle displacements over the time scale examined provides evidence for (at least) two different mechanisms of motion, one associated with particles in locally ordered regions and the other associated with particles in locally disordered regions. When rhoL*=Npisigma(L) (2)/4A< or =0.35, the addition of small colloid particles leads to a monotonic decrease in the large particle diffusion coefficient with increasing small particle volume fraction. When rhoL* > or =0.35 the addition of small colloid particles to a dense system of large colloid particles at first leads to an increase in the large particle diffusion coefficient, which is then followed by the expected decrease of the large particle diffusion coefficient with increasing small colloid particle volume fraction. The mode coupling theory of the ideal glass transition in three-dimensional systems makes a qualitative prediction that agrees with the initial increase in the large particle diffusion coefficient with increasing small particle density. Nevertheless, because the structural and dynamical heterogeneities of the quasi-two-dimensional colloid liquid occur within the field of equilibrium states, and the fluctuations generate locally ordered domains rather than just disordered regions of higher and lower density, it is suggested that mode coupling theory does not account for all classes of relevant fluctuations in a quasi-two-dimensional liquid. (c) 2004 American Institute of Physics.

Mercury adsorption properties of sulfur-impregnated adsorbents

USGS Publications Warehouse

Hsi, N.-C.; Rood, M.J.; Rostam-Abadi, M.; Chen, S.; Chang, R.

2002-01-01

Carbonaceous and noncarbonaceous adsorbents were impregnated with elemental sulfur to evaluate the chemical and physical properties of the adsorbents and their equilibrium mercury adsorption capacities. Simulated coal combustion flue gas conditions were used to determine the equilibrium adsorption capacities for Hg0 and HgCl2 gases to better understand how to remove mercury from gas streams generated by coal-fired utility power plants. Sulfur was deposited onto the adsorbents by monolayer surface deposition or volume pore filling. Sulfur impregnation increased the total sulfur content and decreased the total and micropore surface areas and pore volumes for all of the adsorbents tested. Adsorbents with sufficient amounts of active adsorption sites and sufficient microporous structure had mercury adsorption capacities up to 4,509 ??g Hg/g adsorbent. Elemental sulfur, organic sulfur, and sulfate were formed on the adsorbents during sulfur impregnation. Correlations were established with R2>0.92 between the equilibrium Hg0/HgCl2 adsorption capacities and the mass concentrations of elemental and organic sulfur. This result indicates that elemental and organic sulfur are important active adsorption sites for Hg0 and HgCl2.

Vibrational and thermodynamic properties of β-HMX: a first-principles investigation.

PubMed

Wu, Zhongqing; Kalia, Rajiv K; Nakano, Aiichiro; Vashishta, Priya

2011-05-28

Thermodynamic properties of β-HMX crystal are investigated using the quasi-harmonic approximation and density functional theory within the local density approximation (LDA), generalized gradient approximation (GGA), and GGA + empirical van der Waals (vdW) correction. It is found that GGA well describes the thermal expansion coefficient and heat capacity but fails to produce correct bulk modulus and equilibrium volume. The vdW correction improves the bulk modulus and volume, but worsens the thermal expansion coefficient and heat capacity. In contrast, LDA describes all thermodynamic properties with reasonable accuracy, and overall is a good exchange-correlation functional for β-HMX molecular crystal. The results also demonstrate significant contributions of phonons to the equation of state. The static calculation of equilibrium volume for β-HMX differs from the room-temperature value incorporating lattice vibrations by over 5%. Therefore, for molecular crystals, it is essential to include phonon contributions when calculated equation of state is compared with experimental data at ambient condition. © 2011 American Institute of Physics

Equilibrium distribution of rare earth elements between molten KCl-LiCl eutectic salt and liquid cadmium

NASA Astrophysics Data System (ADS)

Sakata, Masahiro; Kurata, Masaki; Hijikata, Takatoshi; Inoue, Tadashi

1991-11-01

Distribution experiments for several rare earth elements (La, Ce, Pr, Nd and Y) between molten KCl-LiCl eutectic salt and liquid Cd were carried out at 450, 500 and 600°C. The material balance of rare earth elements after reaching the equilibrium and their distribution and chemical states in a Cd sample frozen after the experiment were examined. The results suggested the formation of solid intermetallic compounds at the lower concentrations of rare earth metals dissolved in liquid Cd than those solubilities measured in the binary alloy system. The distribution coefficients of rare earth elements between two phases (mole fraction in the Cd phase divided by mole fraction in the salt phase) were determined at each temperature. These distribution coefficients were explained satisfactorily by using the activity coefficients of chlorides and metals in salt and Cd. Both the activity coefficients of metal and chloride caused a much smaller distribution coefficient of Y relative to those of other elements.

Collisional Ionization Equilibrium for Optically Thin Plasmas

NASA Technical Reports Server (NTRS)

Bryans, P.; Mitthumsiri, W.; Savin, D. W.; Badnell, N. R.; Gorczyca, T. W.; Laming, J. M.

2006-01-01

Reliably interpreting spectra from electron-ionized cosmic plasmas requires accurate ionization balance calculations for the plasma in question. However, much of the atomic data needed for these calculations have not been generated using modern theoretical methods and their reliability are often highly suspect. We have utilized state-of-the-art calculations of dielectronic recombination (DR) rate coefficients for the hydrogenic through Na-like ions of all elements from He to Zn. We have also utilized state-of-the-art radiative recombination (RR) rate coefficient calculations for the bare through Na-like ions of all elements from H to Zn. Using our data and the recommended electron impact ionization data of Mazzotta et al. (1998), we have calculated improved collisional ionization equilibrium calculations. We compare our calculated fractional ionic abundances using these data with those presented by Mazzotta et al. (1998) for all elements from H to Ni, and with the fractional abundances derived from the modern DR and RR calculations of Gu (2003a,b, 2004) for Mg, Si, S, Ar, Ca, Fe, and Ni.

Solute induced relaxation in glassy polymers: Experimental measurements and nonequilibrium thermodynamic model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Minelli, Matteo; Doghieri, Ferruccio

2014-05-15

Data for kinetics of mass uptake from vapor sorption experiments in thin glassy polymer samples are here interpreted in terms of relaxation times for volume dilation. To this result, both models from non-equilibrium thermodynamics and from mechanics of volume relaxation contribute. Different kind of sorption experiments have been considered in order to facilitate the direct comparison between kinetics of solute induced volume dilation and corresponding data from process driven by pressure or temperature jumps.

Lack of Evidence for Onshore Sediment Transport from Deep Water at Decadal Time Scales: Fire Island, New York

DTIC Science & Technology

2011-01-01

the net volume change within the cell.  Qsource includes net longshore transport, net onshore transport, and contributions from bluff or dune erosion...in restoration of the downcoast beach at Westhampton Dunes (Daley et al., 2000; Terchunian and Merkert, 1994) and after the Westhampton groin...nourishment, backshore dune erosion added to the control volume, and overwash losses out of the control volume or losses due to equilibrium profile

The Impact of Nonequilibrium and Equilibrium Fractionation on Two Different Deuterium Excess Definitions

NASA Astrophysics Data System (ADS)

Dütsch, Marina; Pfahl, Stephan; Sodemann, Harald

2017-12-01

The deuterium excess (d) is a useful measure for nonequilibrium effects of isotopic fractionation and can therefore provide information about the meteorological conditions in evaporation regions or during ice cloud formation. In addition to nonequilibrium fractionation, two other effects can change d during phase transitions. The first is the dependence of the equilibrium fractionation factors on temperature, and the second is the nonlinearity of the δ scale on which d is defined. The second effect can be avoided by using an alternative definition that is based on the logarithmic scale. However, in this case d is not conserved when air parcels mix, which can lead to changes without phase transitions. Here we provide a systematic analysis of the benefits and limitations of both deuterium excess definitions by separately quantifying the impact of the nonequilibrium effect, the temperature effect, the δ-scale effect, and the mixing effect in a simple Rayleigh model simulating the isotopic composition of air parcels during moist adiabatic ascent. The δ-scale effect is important in depleted air parcels, for which it can change the sign of the traditional deuterium excess in the remaining vapor from negative to positive. The alternative definition mainly reflects the nonequilibrium and temperature effect, while the mixing effect is about 2 orders of magnitude smaller. Thus, the alternative deuterium excess definition appears to be a more accurate measure for nonequilibrium effects in situations where moisture is depleted and the δ-scale effect is large, for instance, at high latitudes or altitudes.

Chronic corticosterone affects brain weight, and mitochondrial, but not glial volume fraction in hippocampal area CA3.

PubMed

Coburn-Litvak, P S; Tata, D A; Gorby, H E; McCloskey, D P; Richardson, G; Anderson, B J

2004-01-01

Corticosterone (CORT), the predominant glucocorticoid in rodents, is known to damage hippocampal area CA3. Here we investigate how that damage is represented at the cellular and ultrastructural level of analyses. Rats were injected with CORT (26.8 mg/kg, s.c.) or vehicle for 56 days. Cell counts were estimated with the physical disector method. Glial and mitochondrial volume fractions were obtained from electron micrographs. The effectiveness of the CORT dose used was demonstrated in two ways. First, CORT significantly inhibited body weight gain relative to vehicles. Second, CORT significantly reduced adrenal gland, heart and gastrocnemius muscle weight. Both the adrenal and gastrocnemius muscle weight to body weight ratios were also significantly reduced. Although absolute brain weight was reduced, the brain to body weight ratio was higher in the CORT group relative to vehicles, suggesting that the brain is more resistant to the effects of CORT than many peripheral organs and muscles. Consistent with that interpretation, CORT did not alter CA3 cell density, cell layer volume, or apical dendritic neuropil volume. Likewise, CORT did not significantly alter glial volume fraction, but did reduce mitochondrial volume fraction. These findings highlight the need for ultrastructural analyses in addition to cellular level analyses before conclusions can be drawn about the damaging effects of prolonged CORT elevations. The relative reduction in mitochondria may indicate a reduction in bioenergetic capacity that, in turn, could render CA3 vulnerable to metabolic challenges.

Dynamic wetting and spreading and the role of topography.

PubMed

McHale, Glen; Newton, Michael I; Shirtcliffe, Neil J

2009-11-18

The spreading of a droplet of a liquid on a smooth solid surface is often described by the Hoffman-de Gennes law, which relates the edge speed, v(e), to the dynamic and equilibrium contact angles θ and θ(e) through [Formula: see text]. When the liquid wets the surface completely and the equilibrium contact angle vanishes, the edge speed is proportional to the cube of the dynamic contact angle. When the droplets are non-volatile this law gives rise to simple power laws with time for the contact angle and other parameters in both the capillary and gravity dominated regimes. On a textured surface, the equilibrium state of a droplet is strongly modified due to the amplification of the surface chemistry induced tendencies by the topography. The most common example is the conversion of hydrophobicity into superhydrophobicity. However, when the surface chemistry favors partial wetting, topography can result in a droplet spreading completely. A further, frequently overlooked consequence of topography is that the rate at which an out-of-equilibrium droplet spreads should also be modified. In this report, we review ideas related to the idea of topography induced wetting and consider how this may relate to dynamic wetting and the rate of droplet spreading. We consider the effect of the Wenzel and Cassie-Baxter equations on the driving forces and discuss how these may modify power laws for spreading. We relate the ideas to both the hydrodynamic viscous dissipation model and the molecular-kinetic theory of spreading. This suggests roughness and solid surface fraction modified Hoffman-de Gennes laws relating the edge speed to the dynamic and equilibrium contact angle. We also consider the spreading of small droplets and stripes of non-volatile liquids in the capillary regime and large droplets in the gravity regime. In the case of small non-volatile droplets spreading completely, a roughness modified Tanner's law giving the dependence of dynamic contact angle on time is presented. We review existing data for the spreading of small droplets of polydimethylsiloxane oil on surfaces decorated with micro-posts. On these surfaces, the initial droplet spreads with an approximately constant volume and the edge speed-dynamic contact angle relationship follows a power law [Formula: see text]. As the surface texture becomes stronger the exponent goes from p = 3 towards p = 1 in agreement with a Wenzel roughness driven spreading and a roughness modified Hoffman-de Gennes power law. Finally, we suggest that when a droplet spreads to a final partial wetting state on a rough surface, it approaches its Wenzel equilibrium contact angle in an exponential manner with a time constant dependent on roughness.

Effect of neutrino rest mass on ionization equilibrium freeze-out

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grohs, Evan Bradley; Fuller, George M.; Kishimoto, Chad T.

2015-12-23

We show how small neutrino rest masses can increase the expansion rate near the photon decoupling epoch in the early Universe, causing an earlier, higher temperature freeze-out for ionization equilibrium compared to the massless neutrino case. This yields a larger free-electron fraction, thereby affecting the photon diffusion length differently than the sound horizon at photon decoupling. This neutrino-mass and recombination effect depends strongly on the neutrino rest masses. Ultimately, though below current sensitivity, this effect could be probed by next-generation cosmic microwave background experiments, giving another observational handle on neutrino rest mass.

Global Dynamics of Certain Homogeneous Second-Order Quadratic Fractional Difference Equation

PubMed Central

Garić-Demirović, M.; Kulenović, M. R. S.; Nurkanović, M.

2013-01-01

We investigate the basins of attraction of equilibrium points and minimal period-two solutions of the difference equation of the form x n+1 = x n−1 2/(ax n 2 + bx n x n−1 + cx n−1 2), n = 0,1, 2,…, where the parameters a,  b, and  c are positive numbers and the initial conditions x −1 and x 0 are arbitrary nonnegative numbers. The unique feature of this equation is the coexistence of an equilibrium solution and the minimal period-two solution both of which are locally asymptotically stable. PMID:24369451

Steps toward identifying a biogeochemical signal in non-equilibrium methane clumped isotope measurements

NASA Astrophysics Data System (ADS)

Douglas, P. M.; Eiler, J. M.; Sessions, A. L.; Dawson, K.; Walter Anthony, K. M.; Smith, D. A.; Lloyd, M. K.; Yanay, E.

2016-12-01

Microbially produced methane is a globally important greenhouse gas, energy source, and biological substrate. Methane clumped isotope measurements have recently been developed as a new analytical tool for understanding the source of methane in different environments. When methane forms in isotopic equilibrium clumped isotope values are determined by formation temperature, but in many cases microbial methane clumped isotope values deviate strongly from expected equilibrium values. Indeed, we observe a very wide range of clumped isotope values in microbial methane, which are likely strongly influenced by kinetic isotope effects, but thus far the biological and environmental parameters controlling this variability are not understood. We will present data from both culture experiments and natural environments to explore patterns of variability in non-equilibrium clumped isotope values on temporal and spatial scales. In methanogen batch cultures sampled at different time points along a growth curve we observe significant variability in clumped isotope values, with values decreasing from early to late exponential growth. Clumped isotope values then increase during stationary growth. This result is consistent with previous work suggesting that differences in the reversibility of methanogenesis related to metabolic rates control non-equilibrium clumped isotope values. Within single lakes in Alaska and Sweden we observe substantial variability in clumped isotope values on the order of 5‰. Lower clumped isotope values are associated with larger 2H isotopic fractionation between water and methane, which is also consistent with a kinetic isotope effect determined by the reversibility of methanogenesis. Finally, we analyzed a time-series clumped isotope compositions of methane emitted from two seeps in an Alaskan lake over several months. Temporal variability in these seeps is on the order of 2‰, which is much less than the observed spatial variability within the lake. Comparing carbon isotope fractionation between CO2 and CH4 with clumped isotope data suggests the temporal variability may result from changes in methane oxidation.

A Virtual Mixture Approach to the Study of Multistate Equilibrium: Application to Constant pH Simulation in Explicit Water

PubMed Central

Wu, Xiongwu; Brooks, Bernard R.

2015-01-01

Chemical and thermodynamic equilibrium of multiple states is a fundamental phenomenon in biology systems and has been the focus of many experimental and computational studies. This work presents a simulation method to directly study the equilibrium of multiple states. This method constructs a virtual mixture of multiple states (VMMS) to sample the conformational space of all chemical states simultaneously. The VMMS system consists of multiple subsystems, one for each state. The subsystem contains a solute and a solvent environment. The solute molecules in all subsystems share the same conformation but have their own solvent environments. Transition between states is implicated by the change of their molar fractions. Simulation of a VMMS system allows efficient calculation of relative free energies of all states, which in turn determine their equilibrium molar fractions. For systems with a large number of state transition sites, an implicit site approximation is introduced to minimize the cost of simulation. A direct application of the VMMS method is for constant pH simulation to study protonation equilibrium. Applying the VMMS method to a heptapeptide of 3 ionizable residues, we calculated the pKas of those residues both with all explicit states and with implicit sites and obtained consistent results. For mouse epidermal growth factor of 9 ionizable groups, our VMMS simulations with implicit sites produced pKas of all 9 ionizable groups and the results agree qualitatively with NMR measurement. This example demonstrates the VMMS method can be applied to systems of a large number of ionizable groups and the computational cost scales linearly with the number of ionizable groups. For one of the most challenging systems in constant pH calculation, SNase Δ+PHS/V66K, our VMMS simulation shows that it is the state-dependent water penetration that causes the large deviation in lysine66’s pKa. PMID:26506245

A Virtual Mixture Approach to the Study of Multistate Equilibrium: Application to Constant pH Simulation in Explicit Water.

PubMed

Wu, Xiongwu; Brooks, Bernard R

2015-10-01

Chemical and thermodynamic equilibrium of multiple states is a fundamental phenomenon in biology systems and has been the focus of many experimental and computational studies. This work presents a simulation method to directly study the equilibrium of multiple states. This method constructs a virtual mixture of multiple states (VMMS) to sample the conformational space of all chemical states simultaneously. The VMMS system consists of multiple subsystems, one for each state. The subsystem contains a solute and a solvent environment. The solute molecules in all subsystems share the same conformation but have their own solvent environments. Transition between states is implicated by the change of their molar fractions. Simulation of a VMMS system allows efficient calculation of relative free energies of all states, which in turn determine their equilibrium molar fractions. For systems with a large number of state transition sites, an implicit site approximation is introduced to minimize the cost of simulation. A direct application of the VMMS method is for constant pH simulation to study protonation equilibrium. Applying the VMMS method to a heptapeptide of 3 ionizable residues, we calculated the pKas of those residues both with all explicit states and with implicit sites and obtained consistent results. For mouse epidermal growth factor of 9 ionizable groups, our VMMS simulations with implicit sites produced pKas of all 9 ionizable groups and the results agree qualitatively with NMR measurement. This example demonstrates the VMMS method can be applied to systems of a large number of ionizable groups and the computational cost scales linearly with the number of ionizable groups. For one of the most challenging systems in constant pH calculation, SNase Δ+PHS/V66K, our VMMS simulation shows that it is the state-dependent water penetration that causes the large deviation in lysine66's pKa.

A Model of Thermal Conductivity for Planetary Soils. 2; Theory for Cemented Soils

NASA Technical Reports Server (NTRS)

Piqueux, S.; Christensen, P. R.

2009-01-01

A numerical model of heat conduction through particulate media made of spherical grains cemented by various bonding agents is presented. The pore-filling gas conductivity, volume fraction, and thermal conductivity of the cementing phase are tunable parameters. Cement fractions <0.001-0.01% in volume have small effects on the soil bulk thermal conductivity. A significant conductivity increase (factor 3-8) is observed for bond fractions of 0.01 to 1% in volume. In the 1 to 15% bond fraction domain, the conductivity increases continuously but less intensely (25-100% conductivity increase compared to a 1% bond system). Beyond 15% of cements, the conductivity increases vigorously and the bulk conductivity rapidly approaches that of bedrock. The composition of the cements (i.e. conductivity) has little influence on the bulk thermal inertia of the soil, especially if the volume of bond <10%. These results indicate that temperature measurements are sufficient to detect cemented soils and quantify the amount of cementing phase, but the mineralogical nature of the bonds and the typical grain size are unlikely to be determined from orbit. On Mars, a widespread surface unit characterized by a medium albedo (0.19-0.26) and medium/high thermal inertia (200-600 J s(0.5)/sq m/K) has long been hypothesized to be associated with a duricrust. The fraction of cement required to fit the thermal data is less than approx.1-5% by volume. This small amount of material is consistent with orbital observations, confirming that soil cementation is an important factor controlling the thermal inertia of the Martian surface

A model of thermal conductivity for planetary soils: 2. Theory for cemented soils

NASA Astrophysics Data System (ADS)

Piqueux, S.; Christensen, P. R.

2009-09-01

A numerical model of heat conduction through particulate media made of spherical grains cemented by various bonding agents is presented. The pore-filling gas conductivity, volume fraction, and thermal conductivity of the cementing phase are tunable parameters. Cement fractions <0.001-0.01% in volume have small effects on the soil bulk thermal conductivity. A significant conductivity increase (factor 3-8) is observed for bond fractions of 0.01 to 1% in volume. In the 1 to 15% bond fraction domain, the conductivity increases continuously but less intensely (25-100% conductivity increase compared to a 1% bond system). Beyond 15% of cements, the conductivity increases vigorously and the bulk conductivity rapidly approaches that of bedrock. The composition of the cements (i.e. conductivity) has little influence on the bulk thermal inertia of the soil, especially if the volume of bond <10%. These results indicate that temperature measurements are sufficient to detect cemented soils and quantify the amount of cementing phase, but the mineralogical nature of the bonds and the typical grain size are unlikely to be determined from orbit. On Mars, a widespread surface unit characterized by a medium albedo (0.19-0.26) and medium/high thermal inertia (200-600 J s-0.5 m-2 K-1) has long been hypothesized to be associated with a duricrust. The fraction of cement required to fit the thermal data is less than ˜1-5% by volume. This small amount of material is consistent with orbital observations, confirming that soil cementation is an important factor controlling the thermal inertia of the Martian surface.

Metal matrix-metal nanoparticle composites with tunable melting temperature and high thermal conductivity for phase-change thermal storage.

PubMed

Liu, Minglu; Ma, Yuanyu; Wu, Hsinwei; Wang, Robert Y

2015-02-24

Phase-change materials (PCMs) are of broad interest for thermal storage and management applications. For energy-dense storage with fast thermal charging/discharging rates, a PCM should have a suitable melting temperature, large enthalpy of fusion, and high thermal conductivity. To simultaneously accomplish these traits, we custom design nanocomposites consisting of phase-change Bi nanoparticles embedded in an Ag matrix. We precisely control nanoparticle size, shape, and volume fraction in the composite by separating the nanoparticle synthesis and nanocomposite formation steps. We demonstrate a 50-100% thermal energy density improvement relative to common organic PCMs with equivalent volume fraction. We also tune the melting temperature from 236-252 °C by varying nanoparticle diameter from 8.1-14.9 nm. Importantly, the silver matrix successfully prevents nanoparticle coalescence, and no melting changes are observed during 100 melt-freeze cycles. The nanocomposite's Ag matrix also leads to very high thermal conductivities. For example, the thermal conductivity of a composite with a 10% volume fraction of 13 nm Bi nanoparticles is 128 ± 23 W/m-K, which is several orders of magnitude higher than typical thermal storage materials. We complement these measurements with calculations using a modified effective medium approximation for nanoscale thermal transport. These calculations predict that the thermal conductivity of composites with 13 nm Bi nanoparticles varies from 142 to 47 W/m-K as the nanoparticle volume fraction changes from 10 to 35%. Larger nanoparticle diameters and/or smaller nanoparticle volume fractions lead to larger thermal conductivities.

Thermal Dose Fractionation Affects Tumor Physiologic Response

PubMed Central

Thrall, Donald E; Maccarini, Paolo; Stauffer, Paul; MacFall, James; Hauck, Marlene; Snyder, Stacey; Case, Beth; Linder, Keith; Lan, Lan; McCall, Linda; Dewhirst, Mark W.

2013-01-01

Purpose It is unknown whether a thermal dose should be administered using a few large fractions with higher temperatures or a larger number of fractions with lower temperatures. To evaluate this, we assessed the effect of administering the same total thermal dose, approximately 30 CEM43T90, in 1 versus 3–4 fractions per week, over 5 weeks. Materials and Methods Canine sarcomas were randomized to receive one of the hyperthermia fractionation schemes along with fractionated radiotherapy. Tumor response was based on changes in tumor volume, oxygenation, water diffusion quantified using MRI, and a panel of histologic and immunohistochemical endpoints. Results There was a greater reduction in tumor volume and water diffusion at the end of therapy In tumors receiving 1 hyperthermia fraction per week. There was a weak but significant association between improved tumor oxygenation 24 hours after the first hyperthermia treatment and extent of volume reduction at the end of therapy. Finally, the direction of change of HIF 1α and CA IX immunoreactivity after the first hyperthermia fraction was similar and there was an inverse relationship between temperature and the direction of change of CA IX. There were no significant changes in interstitial fluid pressure, VEGF, wVf, apoptosis or necrosis as a function of treatment group or temperature. Conclusions We did not identify an advantage to a 3–4/week hyperthermia prescription and response data pointed to a 1/week prescription being superior. PMID:22804741

Fabrication of magnetic macroporous chitosan-g-poly (acrylic acid) hydrogel for removal of Cd2+ and Pb2.

PubMed

Zhu, Yongfeng; Zheng, Yian; Wang, Feng; Wang, Aiqin

2016-12-01

A novel macroporous magnetic macroporous chitosan-g-poly (acrylic acid) hydrogel adsorbent was fabricated from the Pickering high internal emulsions template stabilized by modified Fe 3 O 4 nanoparticles. The structure and composition of modified Fe 3 O 4 and macroporous magnetic hydrogel were characterized by TEM, XRD, TG and SEM techniques. The characterization results suggest that the Fe 3 O 4 nanoparticles have been modified successfully with organosilane of 3-aminopropyltrimethoxysilane (APTES), and the porous structure of the macroporous hydrogel can be tuned with the amount of stabilized particles, volume fraction of dispersed phase and the amount of the cosurfactant. Adsorption experiments indicate that the adsorption equilibrium was rapidly reached within 20min and the maximal adsorption capacities were determined to be 308.84mg/g for Cd 2+ and 695.22mg/g for Pb 2+ . After five adsorption-desorption cycles, the adsorbent can retain its high adsorption capacity. The introduction of Fe 3 O 4 is beneficial to the recycle of adsorbent after usage. Copyright © 2016 Elsevier B.V. All rights reserved.

Chasing Extreme Polymer Morphologies with Ed

NASA Astrophysics Data System (ADS)

Fredrickson, Glenn

I was privileged to have a seventeen year friendship and scientific collaboration with Edward J. Kramer that produced 55 papers and countless student and postdoc co-advisements. This talk will discuss our last project together; an ongoing research program to achieve thermoplastic polymer materials that are uniquely hard, tough, and elastic, with moduli greater than 100 MPa and elastic recovery greater than 0.9 at strains of 1 or more. The targeted materials are based on an A(BA')n mikto-arm block copolymer architecture, and alloys of these molecules with A homopolymer. The molecular design of the miktopolymer was optimized using self-consistent field theory and the materials realized in a polystyrene (A)-polyisoprene (B) system. TEM, SAXS, and tensile mechanical tests were used to validate the designs and probe microstructure/mechanics relationships. An unexpected discovery was the emergence of a new structured disordered phase - the bricks and mortar phase -in which the A domains remain discrete at up to a volume fraction of 0.7. Field-theoretic simulations have been used to understand the origins of this new fluctuation-stabilized equilibrium phase, which has no precedent in the polymer physics literature.

Laser-induced reversion of δ' precipitates in an Al-Li alloy: Study on temperature rise in pulsed laser atom probe.

PubMed

Khushaim, Muna; Gemma, Ryota; Al-Kassab, Talaat

2016-08-01

The influence of tuning the laser pulse energy during the analyses on the resulting microstructure in a specimen utilizing an ultra-fast laser assisted atom probe was demonstrated by a case study of a binary Al-Li alloy. The decomposition parameters, such as the size, number density, volume fraction, and composition of δ' precipitates, were carefully monitored after each analysis. A simple model was employed to estimate the corresponding specimen temperature for each value of the laser energy. The results indicated that the corresponding temperatures for the laser pulse energy in the range of 10 to 80 pJ are located inside the miscibility gap of the binary Al-Li phase diagram and fall into the metastable equilibrium field. In addition, the corresponding temperature for a laser pulse energy of 100 pJ was in fairly good agreement with reported range of  δ' solvus temperature, suggesting a result of reversion upon heating due to laser pulsing. Microsc. Res. Tech. 79:727-737, 2016. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Prediction of Proper Temperatures for the Hot Stamping Process Based on the Kinetics Models

NASA Astrophysics Data System (ADS)

Samadian, P.; Parsa, M. H.; Mirzadeh, H.

2015-02-01

Nowadays, the application of kinetics models for predicting microstructures of steels subjected to thermo-mechanical treatments has increased to minimize direct experimentation, which is costly and time consuming. In the current work, the final microstructures of AISI 4140 steel sheets after the hot stamping process were predicted using the Kirkaldy and Li kinetics models combined with new thermodynamically based models in order for the determination of the appropriate process temperatures. In this way, the effect of deformation during hot stamping on the Ae3, Acm, and Ae1 temperatures was considered, and then the equilibrium volume fractions of phases at different temperatures were calculated. Moreover, the ferrite transformation rate equations of the Kirkaldy and Li models were modified by a term proposed by Åkerström to consider the influence of plastic deformation. Results showed that the modified Kirkaldy model is satisfactory for the determination of appropriate austenitization temperatures for the hot stamping process of AISI 4140 steel sheets because of agreeable microstructure predictions in comparison with the experimental observations.

Microgravity Diode Laser Spectroscopy Measurements in a Reacting Vortex Ring

NASA Technical Reports Server (NTRS)

Chen, Shin-Juh; Dahm, Werner J. A.; Silver, Joel A.; Piltch, Nancy D.

2001-01-01

The technique of Diode Laser Spectroscopy (DLS) with wavelength modulation is utilized to measure the concentration of methane in reacting vortex rings under microgravity conditions. From the measured concentration of methane, other major species such as water, carbon dioxide, nitrogen, and oxygen can be easily computed under the assumption of equilibrium chemistry with the method of Interactive Temperature with Assumed Chemistry (ITAC). The conserved scalar approach in modelling the coupling between fluid dynamics and combustion is utilized to represent the unknown variables in terms of the mixture fraction and scalar dissipation rate in conjunction with ITAC. Post-processing of the DLS measurements and the method of ITAC used in computing the species concentration are discussed. From the flame luminosity results, the increase in ring circulation appears to increase the fuel consumption rate inside the reacting vortex ring and the flame height for cases with similar fuel volumes. Preliminary results and application of ITAC show some potential capabilities of ITAC in DLS. The measured concentration of methane, and computed concentrations of water and carbon dioxide agree well with available results from numerical simulations.

Large-scale model of flow in heterogeneous and hierarchical porous media

NASA Astrophysics Data System (ADS)

Chabanon, Morgan; Valdés-Parada, Francisco J.; Ochoa-Tapia, J. Alberto; Goyeau, Benoît

2017-11-01

Heterogeneous porous structures are very often encountered in natural environments, bioremediation processes among many others. Reliable models for momentum transport are crucial whenever mass transport or convective heat occurs in these systems. In this work, we derive a large-scale average model for incompressible single-phase flow in heterogeneous and hierarchical soil porous media composed of two distinct porous regions embedding a solid impermeable structure. The model, based on the local mechanical equilibrium assumption between the porous regions, results in a unique momentum transport equation where the global effective permeability naturally depends on the permeabilities at the intermediate mesoscopic scales and therefore includes the complex hierarchical structure of the soil. The associated closure problem is numerically solved for various configurations and properties of the heterogeneous medium. The results clearly show that the effective permeability increases with the volume fraction of the most permeable porous region. It is also shown that the effective permeability is sensitive to the dimensionality spatial arrangement of the porous regions and in particular depends on the contact between the impermeable solid and the two porous regions.

Stable mercury isotope ratios as tracers for Hg cycling at the inoperative New Idria Hg mine, California

NASA Astrophysics Data System (ADS)

Wiederhold, J. G.; Jew, A. D.; Brown, G. E.; Bourdon, B.; Kretzschmar, R.

2010-12-01

The seven stable isotopes of Hg are fractionated in the environment as a result of mass-dependent (MDF) and mass-independent (MIF) fractionation processes that can be studied in parallel by analyzing the ratios of even and odd mass Hg isotopes. MDF and MIF Hg isotope signatures of natural samples may provide a new tool to trace sources and transformations in environmental Hg cycling. However, the mechanisms controlling the extent of kinetic and equilibrium Hg isotope fractionations are still only partially understood. Thus, development of this promising tracer requires experimental calibration of relevant fractionation factors as well as assessment of natural variations of Hg isotope ratios under different environmental conditions. The inoperative Hg mine in New Idria (California, USA) represents an ideal case study to explore Hg isotope fractionation during Hg transformation and transport processes. More than a century of Hg mining and on-site thermal refining to obtain elemental Hg until 1972 produced large volumes of contaminated mine wastes which now represent sources of Hg pollution for the surrounding ecosystems. Here, we present Hg isotope data from various materials collected at New Idria using Cold-Vapor-MC-ICPMS with a long-term δ202Hg reproducibility of ±0.1‰ (2SD). Uncalcined mine waste samples were isotopically similar to NIST-3133 and did not exhibit any MIF signatures. In contrast, calcine samples, which represent the residue of the thermal ore processing at 700°C, had significantly heavier δ202Hg values of up to +1.5‰. In addition, we observed small negative MIF anomalies of the odd-mass Hg isotopes in the calcine samples, which could be caused either by nuclear volume fractionation or a magnetic isotope effect during or after the roasting process. The mass-dependent enrichment of heavy Hg isotopes in the calcine materials indicates that light Hg isotopes were preferentially removed during the roasting process, in agreement with a previous study by Stetson et al. (ES&T, 2009, 43:7331-7336). In order to further elucidate the Hg isotope signatures of the New Idria samples, we performed a three-step sequential extraction procedure to separate different Hg pools. The calcine samples exhibited a higher proportion of leachable Hg phases compared with the unrefined ore waste samples. The most soluble Hg pool (HAc/HCl, pH 2) had a significantly heavier MDF and more negative MIF signature than the bulk calcine samples, suggesting that the dissolution of more soluble Hg phases from calcine materials results in an enhanced flux of leached Hg which is isotopically distinct from the original ore. Moreover, this finding demonstrates that the Hg isotope fractionation during the ore roasting cannot be solely explained by a kinetic Rayleigh-type process which removes light Hg isotopes, but must additionally involve the formation of isotopically heavy secondary Hg phases in the calcine. The analysis of additional samples will enable us to test this hypothesis and to gain further insights into the applicability of stable Hg isotope ratios as source and process tracers in Hg-contaminated environments.

Finite element solution of low bond number sloshing

NASA Technical Reports Server (NTRS)

Wohlen, R. L.; Park, A. C.; Warner, D. M.

1975-01-01

The dynamics of liquid propellant in a low Bond number environment which are critical to the design of spacecraft systems with respect to orbital propellant transfer and attitude control system were investigated. Digital computer programs were developed for the determination of liquid free surface equilibrium shape, lateral slosh natural vibration mode shapes, and frequencies for a liquid in a container of arbitrary axisymmetric shape with surface tension forces the same order of magnitude as acceleration forces. A finite volume element representation of the liquid was used for the vibration analysis. The liquid free surface equilibrium shapes were computed for several tanks at various contact angles and ullage volumes. A configuration was selected for vibration analysis and lateral slosh mode shapes and natural frequencies were obtained. Results are documented.

Analysis of histological and immunohistochemical patterns of benign and malignant adrenocortical tumors by computerized morphometry.

PubMed

Dalino Ciaramella, Paolo; Vertemati, Maurizio; Petrella, Duccio; Bonacina, Edgardo; Grossrubatscher, Erika; Duregon, Eleonora; Volante, Marco; Papotti, Mauro; Loli, Paola

2017-07-01

Diagnosis of benign and purely localized malignant adrenocortical lesions is still a complex issue. Moreover, histology-based diagnosis may suffer of a moment of subjectivity due to inter- and intra-individual variations. The aim of the present study was to assess, by computerized morphometry, the morphological features in benign and malignant adrenocortical neoplasms. Eleven adrenocortical adenomas (ACA) were compared with 18 adrenocortical cancers (ACC). All specimens were stained with H&E, cellular proliferation marker Ki-67 and reticulin. We generated a morphometric model based on the analysis of volume fractions occupied by Ki-67 positive and negative cells (nuclei and cytoplasm), vascular and inflammatory compartment; we also analyzed the surface fraction occupied by reticulin. We compared the quantitative data of Ki-67 obtained by morphometry with the quantification resulting from pathologist's visual reading. The volume fraction of Ki-67 positive cells in ACCs was higher than in ACAs. The volume fraction of nuclei in unit volume and the nuclear/cytoplasmic ratio in both Ki-67 negative cells and Ki-67 positive cells were prominent in ACCs. The surface fraction of reticulin was considerably lower in ACCs. Our computerized morphometric model is simple, reproducible and can be used by the pathologist in the histological workup of adrenocortical tumors to achieve precise and reader-independent quantification of several morphological characteristics of adrenocortical tumors. Copyright © 2017 Elsevier GmbH. All rights reserved.