Structure of ternary additive hard-sphere fluid mixtures
NASA Astrophysics Data System (ADS)
Malijevský, Alexander; Malijevský, Anatol; Yuste, Santos B.; Santos, Andrés; López de Haro, Mariano
2002-12-01
Monte Carlo simulations on the structural properties of ternary fluid mixtures of additive hard spheres are reported. The results are compared with those obtained from a recent analytical approximation [S. B. Yuste, A. Santos, and M. López de Haro, J. Chem. Phys. 108, 3683 (1998)] to the radial distribution functions of hard-sphere mixtures and with the results derived from the solution of the Ornstein-Zernike integral equation with both the Martynov-Sarkisov and the Percus-Yevick closures. Very good agreement between the results of the first two approaches and simulation is observed, with a noticeable improvement over the Percus-Yevick predictions especially near contact.
NASA Astrophysics Data System (ADS)
Barrio, C.; Solana, J. R.
2006-07-01
We have analyzed the rate of convergence of a series expansion, in terms of the density, of the ratio of the excess compressibility factor of fluid mixtures of additive hard spheres to that of a pure hard-sphere fluid with the same reduced density. The terms in the series can be obtained from the virial coefficients. We have found that the series converges quickly, so that frequently the knowledge of the first two terms of the series, that can be obtained from the second and third virial coefficients which are known analytically, is sufficient to provide an accurate equation of state.
López de Haro, Mariano; Tejero, Carlos F; Santos, Andrés
2013-04-28
The problem of demixing in a binary fluid mixture of highly asymmetric additive hard spheres is revisited. A comparison is presented between the results derived previously using truncated virial expansions for three finite size ratios with those that one obtains with the same approach in the extreme case in which one of the components consists of point particles. Since this latter system is known not to exhibit fluid-fluid segregation, the similarity observed for the behavior of the critical constants arising in the truncated series in all instances, while not being conclusive, may cast serious doubts as to the actual existence of a demixing fluid-fluid transition in disparate-sized binary additive hard-sphere mixtures.
NASA Astrophysics Data System (ADS)
Barrio, C.; Solana, J. R.
2003-08-01
Density expansions of the contact pair correlation functions for binary mixtures of additive hard spheres are obtained from the virial expansion of the equation of state. The procedure is based on the use consistency conditions. The resulting expansions are exact up to first order in the density. This corresponds to the third virial coefficient which is exactly known for these mixtures. Analytical expressions for the second and third order terms are obtained on the basis of very accurate approximate analytical expressions for the fourth and fifth virial coefficients. It is found that the series converge slowly, but the convergency can be accelerated by means of a resummation procedure.
A new analytical equation of state for additive hard sphere fluid mixtures
NASA Astrophysics Data System (ADS)
Barrio, C.; Solana, J. R.
A study has been made of the relation between the equation of state of additive binary hard sphere fluid mixtures and the equation of state of a pure hard sphere fluid for the same packing fraction. An analysis of the existing simulation data for a wide variety of compositions of the mixture and diameter ratios up to 1/0.2 makes it possible to conclude that the ratio of the excess compressibility factor of the mixture to that of the pure fluid is, to a very good approximation, a linear function of the packing fraction. This suggests the possibility of deriving the equation of state of the mixture from that of the pure fluid by using the second and third virial coefficients of the mixture, which are known analytically, to reproduce the linear relation mentioned above. When a suitable equation of state is chosen for the pure fluid, the results from the equation of state of the mixture thus obtained are in excellent agreement with simulation data. The predictions for the fourth and fifth virial coefficients also are very accurate compared with known numerical data.
Consistency conditions and equation of state for additive hard-sphere fluid mixtures
NASA Astrophysics Data System (ADS)
Barrio, C.; Solana, J. R.
2000-12-01
A number of consistency conditions for the contact values gij(σij) of the pair correlation function of species i and j in an additive hard-sphere fluid mixture are discussed. It is shown that most of the theoretically-based expressions, as well as other more empirical in character, existing for these functions, fail to satisfy at least one of the conditions. It is suggested that one could improve the performance of the expressions for gij(σij) and the equation of state by using the consistency conditions. This is illustrated by modifying the Boublı´k-Mansoori-Carnahan-Starling-Leland expressions for gij(σij), which results in better predictions for these functions as well as for the compressibility factor and the fourth and fifth virial coefficients.
NASA Astrophysics Data System (ADS)
Barrio, C.; Solana, J. R.
2003-01-01
Approximate expressions for the fourth and fifth virial coefficients of binary hard-sphere fluid mixtures are derived. The procedure used to obtain these expressions is based on that previously proposed by Wheatley [J. chem. Phys., 111, 5455 (1999)], but slightly modified. Wheatley's procedure starts from a prescribed general analytical form of the virial coefficients, from which the particular expression for each virial coefficient is obtained by imposing to the general form a number of limiting conditions. Here, we propose an alternative general expression of the virial coefficients and derive one more condition. This condition is satisfied when the fourth and fifth virial coefficients are expressed in the form we propose, but not when they are expressed in Wheatley's form. The agreement of the proposed analytical expressions with exact numerical data is excellent. The procedure can be extended to higher virial coefficients, although the lack of exact numerical data prevents any comparison.
Mapping a hard-sphere fluid mixture onto a single component hard-sphere fluid
NASA Astrophysics Data System (ADS)
Barrio, C.; Solana, J. R.
2005-06-01
The possibility of obtaining the thermodynamic and structural properties of a binary additive hard-sphere fluid mixture on the basis of the corresponding properties of a suitable single-component hard-sphere fluid is analyzed. To this end, Monte Carlo simulations have been performed for binary mixtures of hard spheres for different densities, compositions and diameter ratios in order to obtain the compressibility factor Z and the partial radial distribution functions gij(r) for pairs ij of the mixtures. These data are used to test the reliability of different proposals available in the literature for mapping the thermodynamic and structural properties of conformal mixtures onto those of a single-component fluid. It is found that, while the averaged radial distribution function and the equation of state of the mixture can be reasonably well reproduced by means of those of an equivalent single-component fluid, the partial radial distribution functions cannot be obtained with enough accuracy from the radial distribution function of the equivalent fluid. A possible explanation for this fact is suggested.
Equation of state for fluid mixtures of hard spheres and linear homonuclear fused hard spheres
NASA Astrophysics Data System (ADS)
Largo, J.; Solana, J. R.
1998-08-01
This paper develops a theoretically based equation of state for fluid mixtures consisting of hard spheres and linear homonuclear fused hard spheres. The procedure is based on the equation of state previously developed for monocomponent athermal fluids. The equation of state only requires two parameters, namely the averaged effective molecular volume of the molecules in the mixture and the corresponding effective nonsphericity parameter. These parameters can be obtained from the geometry of the molecules forming the mixture. The results are in excellent agreement with simulation data and compare favorably with those obtained from other theories for athermal fluid mixtures.
Equation of state for fused-hard-sphere fluid mixtures
NASA Astrophysics Data System (ADS)
Largo, J.; Solana, J. R.
This paper develops a theoretically-based equation of state for fused-hard-sphere fluid mixtures on the basis of an equation of state previously derived for hard-convex-body fluid mixtures. The equation uses as a reference the equation of state for an equivalent hard-sphere fluid mixture in which each component has the same molecular volume as the effective molecular volume of one of the components of the fused-hard-sphere mixture. The two parameters required by the theory, namely the averaged effective molecular volume of the molecules in the mixture and the corresponding effective non-sphericity parameter, are obtained from the geometrical characteristics of the molecules that form the mixture. The results are, on the whole, in closer agreement with simulation data than those obtained with other theories developed for this kind of mixture.
Demixing in binary mixtures of apolar and dipolar hard spheres
NASA Astrophysics Data System (ADS)
Almarza, N. G.; Lomba, E.; Martín, C.; Gallardo, A.
2008-12-01
We study the demixing transition of mixtures of equal size hard spheres and dipolar hard spheres using computer simulation and integral equation theories. Calculations are carried out at constant pressure, and it is found that there is a strong correlation between the total density and the composition. The critical temperature and the critical total density are found to increase with pressure. The critical mole fraction of the dipolar component on the contrary decreases as pressure is augmented. These qualitative trends are reproduced by the theoretical approaches that on the other hand overestimate by far the value of the critical temperature. Interestingly, the critical parameters for the liquid-vapor equilibrium extrapolated from the mixture results in the limit of vanishing neutral hard sphere concentration agree rather well with recent estimates based on the extrapolation of charged hard dumbbell phase equilibria when dumbbell elongation shrinks to zero [G. Ganzenmüller and P. J. Camp, J. Chem. Phys. 126, 191104 (2007)].
Hard-sphere kinetic models for inert and reactive mixtures.
Polewczak, Jacek
2016-10-19
I consider stochastic variants of a simple reacting sphere (SRS) kinetic model (Xystris and Dahler 1978 J. Chem. Phys. 68 387-401, Qin and Dahler 1995 J. Chem. Phys. 103 725-50, Dahler and Qin 2003 J. Chem. Phys. 118 8396-404) for dense reacting mixtures. In contrast to the line-of-center models of chemical reactive models, in the SRS kinetic model, the microscopic reversibility (detailed balance) can be easily shown to be satisfied, and thus all mathematical aspects of the model can be fully justified. In the SRS model, the molecules behave as if they were single mass points with two internal states. Collisions may alter the internal states of the molecules, and this occurs when the kinetic energy associated with the reactive motion exceeds the activation energy. Reactive and non-reactive collision events are considered to be hard sphere-like. I consider a four component mixture A, B, A (*), B (*), in which the chemical reactions are of the type [Formula: see text], with A (*) and B (*) being distinct species from A and B. This work extends the joined works with George Stell to the kinetic models of dense inert and reactive mixtures. The idea of introducing smearing-type effect in the collisional process results in a new class of stochastic kinetic models for both inert and reactive mixtures. In this paper the important new mathematical properties of such systems of kinetic equations are proven. The new results for stochastic revised Enskog system for inert mixtures are also provided. PMID:27545341
Hard-sphere kinetic models for inert and reactive mixtures
NASA Astrophysics Data System (ADS)
Polewczak, Jacek
2016-10-01
I consider stochastic variants of a simple reacting sphere (SRS) kinetic model (Xystris and Dahler 1978 J. Chem. Phys. 68 387-401, Qin and Dahler 1995 J. Chem. Phys. 103 725-50, Dahler and Qin 2003 J. Chem. Phys. 118 8396-404) for dense reacting mixtures. In contrast to the line-of-center models of chemical reactive models, in the SRS kinetic model, the microscopic reversibility (detailed balance) can be easily shown to be satisfied, and thus all mathematical aspects of the model can be fully justified. In the SRS model, the molecules behave as if they were single mass points with two internal states. Collisions may alter the internal states of the molecules, and this occurs when the kinetic energy associated with the reactive motion exceeds the activation energy. Reactive and non-reactive collision events are considered to be hard sphere-like. I consider a four component mixture A, B, A *, B *, in which the chemical reactions are of the type A+B\\rightleftharpoons {{A}\\ast}+{{B}\\ast} , with A * and B * being distinct species from A and B. This work extends the joined works with George Stell to the kinetic models of dense inert and reactive mixtures. The idea of introducing smearing-type effect in the collisional process results in a new class of stochastic kinetic models for both inert and reactive mixtures. In this paper the important new mathematical properties of such systems of kinetic equations are proven. The new results for stochastic revised Enskog system for inert mixtures are also provided.
Hard-sphere kinetic models for inert and reactive mixtures.
Polewczak, Jacek
2016-10-19
I consider stochastic variants of a simple reacting sphere (SRS) kinetic model (Xystris and Dahler 1978 J. Chem. Phys. 68 387-401, Qin and Dahler 1995 J. Chem. Phys. 103 725-50, Dahler and Qin 2003 J. Chem. Phys. 118 8396-404) for dense reacting mixtures. In contrast to the line-of-center models of chemical reactive models, in the SRS kinetic model, the microscopic reversibility (detailed balance) can be easily shown to be satisfied, and thus all mathematical aspects of the model can be fully justified. In the SRS model, the molecules behave as if they were single mass points with two internal states. Collisions may alter the internal states of the molecules, and this occurs when the kinetic energy associated with the reactive motion exceeds the activation energy. Reactive and non-reactive collision events are considered to be hard sphere-like. I consider a four component mixture A, B, A (*), B (*), in which the chemical reactions are of the type [Formula: see text], with A (*) and B (*) being distinct species from A and B. This work extends the joined works with George Stell to the kinetic models of dense inert and reactive mixtures. The idea of introducing smearing-type effect in the collisional process results in a new class of stochastic kinetic models for both inert and reactive mixtures. In this paper the important new mathematical properties of such systems of kinetic equations are proven. The new results for stochastic revised Enskog system for inert mixtures are also provided.
Equation of state of nonadditive d-dimensional hard-sphere mixtures
NASA Astrophysics Data System (ADS)
Santos, A.; López de Haro, M.; Yuste, S. B.
2005-01-01
An equation of state for a multicomponent mixture of nonadditive hard spheres in d dimensions is proposed. It yields a rather simple density dependence and constitutes a natural extension of the equation of state for additive hard spheres proposed by us [A. Santos, S. B. Yuste, and M. López de Haro, Mol. Phys. 96, 1 (1999)]. The proposal relies on the known exact second and third virial coefficients and requires as input the compressibility factor of the one-component system. A comparison is carried out both with another recent theoretical proposal based on a similar philosophy and with the available exact results and simulation data in d=1, 2, and 3. Good general agreement with the reported values of the virial coefficients and of the compressibility factor of binary mixtures is observed, especially for high asymmetries and/or positive nonadditivities.
Brandani, V.; Prausnitz, J. M.
1982-01-01
This paper is the second of three describing a two-fluid theory of binary liquid mixtures. The general theory presented in the preceding paper is used to derive a model for calculating thermodynamic properties of hard-sphere mixtures. Calculations indicate that desirable boundary conditions are satisfied. PMID:16593220
NASA Astrophysics Data System (ADS)
Santos, A.; Yuste, S. B.; López de Haro, M.
The composition-independent virial coefficients of a d-dimensional binary mixture of (additive) hard hyperspheres following from a recent proposal for the equation of state of the mixture (SANTOS, A., YUSTE, S. B., and LÓPEZ DE HARO, M., 1999, Molec. Phys., 96 , 1) are examined. Good agreement between theoretical estimates and available exact or numerical results is found for d = 2, 3, 4 and 5, except for mixtures whose components are very disparate in size. A slight modification that remedies this deficiency is introduced and the resummation of the associated virial series is carried out, leading to a new proposal for the equation of state. The case of binary hard sphere mixtures (d = 3) is analysed in some detail.
Sedov, I A; Magsumov, T I
2015-07-16
Thermodynamic solvation properties of mixtures of water with tetrahydrofuran at 298 K are studied. The Gibbs free energies and enthalpies of solvation of n-octane and toluene are determined experimentally. For molecular dynamics simulations of the binary solvent, we have modified a TraPPE-UA model for tetrahydrofuran and combined it with the SPC/E potential for water. The excess thermodynamic functions of neon, xenon, and hard spheres with two different radii are calculated using the particle insertion method. Simulated and real systems share the same characteristic trends for the thermodynamic functions. A maximum is present on dependencies of the enthalpy of solvation from the composition of solvent at 70-90 mol % water, making it higher than in both of the cosolvents. It is caused by a high enthalpy of cavity formation in the mixtures rich with water due to solvent reorganization around the cavity, which is shown by calculation of the enthalpy of solvation of hard spheres. Addition of relatively small amounts of tetrahydrofuran to water effectively suppresses the hydrophobic effect, leading to a quick increase of both the entropy and enthalpy of cavity formation and solvation of low polar molecules. PMID:26115405
Equation of state for fluid mixtures of hard spheres and heteronuclear hard dumbbells
NASA Astrophysics Data System (ADS)
Barrio, C.; Solana, J. R.
1999-09-01
A theoretically founded equation of state is developed for mixtures of hard spheres with heteronuclear hard dumbbells. It is based on a model previously developed for hard-convex-body fluid mixtures, and further extended to fluid mixtures of homonuclear hard dumbbells. The equation scales the excess compressibility factor for an equivalent hard-sphere fluid mixture to obtain that corresponding to the true mixture. The equivalent mixture is one in which the averaged volume of a sphere is the same as the effective molecular volume of a molecule in the real mixture. Thus, the theory requires two parameters, namely the averaged effective molecular volume of the molecules in the mixture and the scaling factor, which is the effective nonsphericity parameter. Expressions to determine these parameters are derived in terms of the geometrical characteristics of the molecules that form the mixture. The overall results are in closer agreement with simulation data than those obtained with other theories developed for these kinds of mixtures.
Random sequential addition of hard spheres in high Euclidean dimensions
NASA Astrophysics Data System (ADS)
Torquato, S.; Uche, O. U.; Stillinger, F. H.
2006-12-01
Sphere packings in high dimensions have been the subject of recent theoretical interest. Employing numerical and theoretical methods, we investigate the structural characteristics of random sequential addition (RSA) of congruent spheres in d -dimensional Euclidean space Rd in the infinite-time or saturation limit for the first six space dimensions (1≤d≤6) . Specifically, we determine the saturation density, pair correlation function, cumulative coordination number and the structure factor in each of these dimensions. We find that for 2≤d≤6 , the saturation density ϕs scales with dimension as ϕs=c1/2d+c2d/2d , where c1=0.202048 and c2=0.973872 . We also show analytically that the same density scaling is expected to persist in the high-dimensional limit, albeit with different coefficients. A byproduct of this high-dimensional analysis is a relatively sharp lower bound on the saturation density for any d given by ϕs≥(d+2)(1-S0)/2d+1 , where S0ɛ[0,1] is the structure factor at k=0 (i.e., infinite-wavelength number variance) in the high-dimensional limit. We demonstrate that a Palàsti-type conjecture (the saturation density in Rd is equal to that of the one-dimensional problem raised to the d th power) cannot be true for RSA hyperspheres. We show that the structure factor S(k) must be analytic at k=0 and that RSA packings for 1≤d≤6 are nearly “hyperuniform.” Consistent with the recent “decorrelation principle,” we find that pair correlations markedly diminish as the space dimension increases up to six. We also obtain kissing (contact) number statistics for saturated RSA configurations on the surface of a d -dimensional sphere for dimensions 2≤d≤5 and compare to the maximal kissing numbers in these dimensions. We determine the structure factor exactly for the related “ghost” RSA packing in Rd and demonstrate that its distance from “hyperuniformity” increases as the space dimension increases, approaching a constant asymptotic value
NASA Astrophysics Data System (ADS)
Hlushak, Stepan
2015-09-01
An analytical expression for the Laplace transform of the radial distribution function of a mixture of hard-sphere chains of arbitrary segment size and chain length is used to rigorously formulate the first-order Barker-Henderson perturbation theory for the contribution of the segment-segment dispersive interactions into thermodynamics of the Lennard-Jones chain mixtures. Based on this approximation, a simple variant of the statistical associating fluid theory is proposed and used to predict properties of several mixtures of chains of different lengths and segment sizes. The theory treats the dispersive interactions more rigorously than the conventional theories and provides means for more accurate description of dispersive interactions in the mixtures of highly asymmetric components.
Hlushak, Stepan
2015-09-28
An analytical expression for the Laplace transform of the radial distribution function of a mixture of hard-sphere chains of arbitrary segment size and chain length is used to rigorously formulate the first-order Barker-Henderson perturbation theory for the contribution of the segment-segment dispersive interactions into thermodynamics of the Lennard-Jones chain mixtures. Based on this approximation, a simple variant of the statistical associating fluid theory is proposed and used to predict properties of several mixtures of chains of different lengths and segment sizes. The theory treats the dispersive interactions more rigorously than the conventional theories and provides means for more accurate description of dispersive interactions in the mixtures of highly asymmetric components.
NASA Astrophysics Data System (ADS)
Ashton, Douglas J.; Wilding, Nigel B.; Roth, Roland; Evans, Robert
2011-12-01
We report a detailed study, using state-of-the-art simulation and theoretical methods, of the effective (depletion) potential between a pair of big hard spheres immersed in a reservoir of much smaller hard spheres, the size disparity being measured by the ratio of diameters q≡σs/σb. Small particles are treated grand canonically, their influence being parameterized in terms of their packing fraction in the reservoir ηsr. Two Monte Carlo simulation schemes—the geometrical cluster algorithm, and staged particle insertion—are deployed to obtain accurate depletion potentials for a number of combinations of q⩽0.1 and ηsr. After applying corrections for simulation finite-size effects, the depletion potentials are compared with the prediction of new density functional theory (DFT) calculations based on the insertion trick using the Rosenfeld functional and several subsequent modifications. While agreement between the DFT and simulation is generally good, significant discrepancies are evident at the largest reservoir packing fraction accessible to our simulation methods, namely, ηsr=0.35. These discrepancies are, however, small compared to those between simulation and the much poorer predictions of the Derjaguin approximation at this ηsr. The recently proposed morphometric approximation performs better than Derjaguin but is somewhat poorer than DFT for the size ratios and small-sphere packing fractions that we consider. The effective potentials from simulation, DFT, and the morphometric approximation were used to compute the second virial coefficient B2 as a function of ηsr. Comparison of the results enables an assessment of the extent to which DFT can be expected to correctly predict the propensity toward fluid-fluid phase separation in additive binary hard-sphere mixtures with q⩽0.1. In all, the new simulation results provide a fully quantitative benchmark for assessing the relative accuracy of theoretical approaches for calculating depletion potentials
Depletion effects in smectic phases of hard-rod-hard-sphere mixtures.
Martínez-Ratón, Y; Cinacchi, G; Velasco, E; Mederos, L
2006-10-01
It is known that when hard spheres are added to a pure system of hard rods the stability of the smectic phase may be greatly enhanced, and that this effect can be rationalised in terms of depletion forces. In the present paper we first study the effect of orientational order on depletion forces in this particular binary system, comparing our results with those obtained adopting the usual approximation of considering the rods parallel and their orientations frozen. We consider mixtures with rods of different aspect ratios and spheres of different diameters, and we treat them within Onsager theory. Our results indicate that depletion effects, and consequently smectic stability, decrease significantly as a result of orientational disorder in the smectic phase when compared with corresponding data based on the frozen-orientation approximation. These results are discussed in terms of the tau parameter, which has been proposed as a convenient measure of depletion strength. We present closed expressions for tau, and show that it is intimately connected with the depletion potential. We then analyse the effect of particle geometry by comparing results pertaining to systems of parallel rods of different shapes (spherocylinders, cylinders and parallelepipeds). We finally provide results based on the Zwanzig approximation of a fundamental-measure density-functional theory applied to mixtures of parallelepipeds and cubes of different sizes. In this case, we show that the tau parameter exhibits a linear asymptotic behaviour in the limit of large values of the hard-rod aspect ratio, in conformity with Onsager theory, as well as in the limit of large values of the ratio of rod breadth to cube side length, d, in contrast to Onsager approximation, which predicts tau approximately d (3). Based on both this result and the Percus-Yevick approximation for the direct correlation function for a hard-sphere binary mixture in the same limit of infinite asymmetry, we speculate that, for
Doubled heterogeneous crystal nucleation in sediments of hard sphere binary-mass mixtures.
Löwen, Hartmut; Allahyarov, Elshad
2011-10-01
Crystallization during the sedimentation process of a binary colloidal hard spheres mixture is explored by Brownian dynamics computer simulations. The two species are different in buoyant mass but have the same interaction diameter. Starting from a completely mixed system in a finite container, gravity is suddenly turned on, and the crystallization process in the sample is monitored. If the Peclet numbers of the two species are both not too large, crystalline layers are formed at the bottom of the cell. The composition of lighter particles in the sedimented crystal is non-monotonic in the altitude: it is first increasing, then decreasing, and then increasing again. If one Peclet number is large and the other is small, we observe the occurrence of a doubled heterogeneous crystal nucleation process. First, crystalline layers are formed at the bottom container wall which are separated from an amorphous sediment. At the amorphous-fluid interface, a secondary crystal nucleation of layers is identified. This doubled heterogeneous nucleation can be verified in real-space experiments on colloidal mixtures.
NASA Astrophysics Data System (ADS)
Ogarko, Vitaliy; Luding, Stefan
2013-03-01
Polydisperse hard sphere mixtures have equilibrium properties which essentially depend on the number density and a reduced number K of moments of the size distribution function. Such systems are equivalent to other systems with different size distributions if the K moments are matched. In particular, a small number s of components, such that 2 s - 1 = K is sufficient to mimic systems with continuous size distributions. For most of the fluid phase K = 3 moments (s = 2 components) are enough to define an equivalent system, while in the glassy states one needs K = 5 moments (s = 3 components) to achieve good agreement between the polydisperse and its maximally-equivalent tridisperse system. With K = 5 matched moments they are also close in number- and volume-fractions of rattlers. Finally, also the jamming density of maximally-equivalent jammed packings is very close, where the tiny differences can be explained by the distribution of rattlers. This research is supported by the Dutch Technology Foundation STW, which is the applied science division of NWO, and the Technology Programme of the Ministry of Economic Affairs, project Nr. STW-MUST 10120.
NASA Astrophysics Data System (ADS)
Ni, Ran; Smallenburg, Frank; Filion, Laura; Dijkstra, Marjolein
2011-03-01
We study crystal nucleation in a binary mixture of hard spheres and investigate the composition and size of the (non)critical clusters using Monte Carlo simulations. In order to study nucleation of a crystal phase in computer simulations, a one-dimensional order parameter is usually defined to identify the solid phase from the supersaturated fluid phase. We show that the choice of order parameter can strongly influence the composition of noncritical clusters due to the projection of the Gibbs free-energy landscape in the two-dimensional composition plane onto a one-dimensional order parameter. On the other hand, the critical cluster is independent of the choice of the order parameter, due to the geometrical properties of the saddle point in the free-energy landscape, which is invariant under coordinate transformation. We investigate the effect of the order parameter on the cluster composition for nucleation of a substitutional solid solution in a simple toy model of identical hard spheres but tagged with different colours and for nucleation of an interstitial solid solution in a binary hard-sphere mixture with a diameter ratio q = 0.3. In both cases, we find that the composition of noncritical clusters depends on the order parameter choice, but are well explained by the predictions from classical nucleation theory. More importantly, we find that the properties of the critical cluster do not depend on the order parameter choice.
Odriozola, Gerardo; Berthier, Ludovic
2011-02-01
We use replica exchange Monte Carlo simulations to measure the equilibrium equation of state of the disordered fluid state for a binary hard sphere mixture up to very large densities where standard Monte Carlo simulations do not easily reach thermal equilibrium. For the moderate system sizes we use (up to N = 100), we find no sign of a pressure discontinuity near the location of dynamic glass singularities extrapolated using either algebraic or simple exponential divergences, suggesting they do not correspond to genuine thermodynamic glass transitions. Several scenarios are proposed for the fate of the fluid state in the thermodynamic limit.
NASA Astrophysics Data System (ADS)
López-Sánchez, Erik; Estrada-Álvarez, César D.; Pérez-Ángel, Gabriel; Méndez-Alcaraz, José Miguel; González-Mozuelos, Pedro; Castañeda-Priego, Ramón
2013-09-01
Asymmetric binary mixtures of hard-spheres exhibit several interesting thermodynamic phenomena, such as multiple kinds of glassy states. When the degrees of freedom of the small spheres are integrated out from the description, their effects are incorporated into an effective pair interaction between large spheres known as the depletion potential. The latter has been widely used to study both the phase behavior and dynamic arrest of the big particles. Depletion forces can be accounted for by a contraction of the description in the multicomponent Ornstein-Zernike equation [R. Castañeda-Priego, A. Rodríguez-López, and J. M. Méndez-Alcaraz, Phys. Rev. E 73, 051404 (2006)], 10.1103/PhysRevE.73.051404. Within this theoretical scheme, an approximation for the difference between the effective and bare bridge functions is needed. In the limit of infinite dilution, this difference is irrelevant and the typical Asakura-Osawa depletion potential is recovered. At higher particle concentrations, however, this difference becomes important, especially where the shell of first neighbors is formed, and, as shown here, cannot be simply neglected. In this work, we use a variant of the Verlet expression for the bridge functions to highlight their importance in the calculation of the depletion potential at high densities and close to the spinodal decomposition. We demonstrate that the modified Verlet closure predicts demixing in binary mixtures of hard spheres for different size ratios and compare its predictions with both liquid state and density functional theories, computer simulations, and experiments. We also show that it provides accurate correlation functions even near the thermodynamic instability; this is explicitly corroborated with results of molecular dynamics simulations of the whole mixture. Particularly, our findings point toward a possible universal behavior of the depletion potential around the spinodal line.
NASA Astrophysics Data System (ADS)
Wolf, A. S.; Asimow, P. D.; Stevenson, D. J.
2015-12-01
Recent first-principles calculations (e.g. Stixrude, 2009; de Koker, 2013), shock-wave experiments (Mosenfelder, 2009), and diamond-anvil cell investigations (Sanloup, 2013) indicate that silicate melts undergo complex structural evolution at high pressure. The observed increase in cation-coordination (e.g. Karki, 2006; 2007) induces higher compressibilities and lower adiabatic thermal gradients in melts as compared with their solid counterparts. These properties are crucial for understanding the evolution of impact-generated magma oceans, which are dominated by the poorly understood behavior of silicates at mantle pressures and temperatures (e.g. Stixrude et al. 2009). Probing these conditions is difficult for both theory and experiment, especially given the large compositional space (MgO-SiO2-FeO-Al2O3-etc). We develop a new model to understand and predict the behavior of oxide and silicate melts at extreme P-T conditions (Wolf et al., 2015). The Coordinated Hard Sphere Mixture (CHaSM) extends the Hard Sphere mixture model, accounting for the range of coordination states for each cation in the liquid. Using approximate analytic expressions for the hard sphere model, this fast statistical method compliments classical and first-principles methods, providing accurate thermodynamic and structural property predictions for melts. This framework is applied to the MgO system, where model parameters are trained on a collection of crystal polymorphs, producing realistic predictions of coordination evolution and the equation of state of MgO melt over a wide P-T range. Typical Mg-coordination numbers are predicted to evolve continuously from 5.25 (0 GPa) to 8.5 (250 GPa), comparing favorably with first-principles Molecular Dynamics (MD) simulations. We begin extending the model to a simplified mantle chemistry using empirical potentials (generally accurate over moderate pressure ranges, <~30 GPa), yielding predictions rooted in statistical representations of melt structure
Direct observation in 3d of structural crossover in binary hard sphere mixtures
NASA Astrophysics Data System (ADS)
Statt, Antonia; Pinchaipat, Rattachai; Turci, Francesco; Evans, Robert; Royall, C. Patrick
2016-04-01
For binary fluid mixtures of spherical particles in which the two species are sufficiently different in size, the dominant wavelength of oscillations of the pair correlation functions is predicted to change from roughly the diameter of the large species to that of the small species along a sharp crossover line in the phase diagram [C. Grodon et al., J. Chem. Phys. 121, 7869 (2004)]. Using particle-resolved colloid experiments in 3d we demonstrate that crossover exists and that its location in the phase diagram is in quantitative agreement with the results of both theory and our Monte-Carlo simulations. In contrast with previous work [J. Baumgartl et al., Phys. Rev. Lett. 98, 198303 (2007)], where a correspondence was drawn between crossover and percolation of both species, in our 3d study we find that structural crossover is unrelated to percolation.
NASA Astrophysics Data System (ADS)
van Westen, Thijs; Vlugt, Thijs J. H.; Gross, Joachim
2014-01-01
An analytical equation of state (EoS) is derived to describe the isotropic (I) and nematic (N) phase of linear- and partially flexible tangent hard-sphere chain fluids and their mixtures. The EoS is based on an extension of Onsager's second virial theory that was developed in our previous work [T. van Westen, B. Oyarzún, T. J. H. Vlugt, and J. Gross, J. Chem. Phys. 139, 034505 (2013)]. Higher virial coefficients are calculated using a Vega-Lago rescaling procedure, which is hereby generalized to mixtures. The EoS is used to study (1) the effect of length bidispersity on the I-N and N-N phase behavior of binary linear tangent hard-sphere chain fluid mixtures, (2) the effect of partial molecular flexibility on the binary phase diagram, and (3) the solubility of hard-sphere solutes in I- and N tangent hard-sphere chain fluids. By changing the length bidispersity, two types of phase diagrams were found. The first type is characterized by an I-N region at low pressure and a N-N demixed region at higher pressure that starts from an I-N-N triphase equilibrium. The second type does not show the I-N-N equilibrium. Instead, the N-N region starts from a lower critical point at a pressure above the I-N region. The results for the I-N region are in excellent agreement with the results from molecular simulations. It is shown that the N-N demixing is driven both by orientational and configurational/excluded volume entropy. By making the chains partially flexible, it is shown that the driving force resulting from the configurational entropy is reduced (due to a less anisotropic pair-excluded volume), resulting in a shift of the N-N demixed region to higher pressure. Compared to linear chains, no topological differences in the phase diagram were found. We show that the solubility of hard-sphere solutes decreases across the I-N phase transition. Furthermore, it is shown that by using a liquid crystal mixture as the solvent, the solubility difference can by maximized by tuning the
Prediction of binary hard-sphere crystal structures.
Filion, Laura; Dijkstra, Marjolein
2009-04-01
We present a method based on a combination of a genetic algorithm and Monte Carlo simulations to predict close-packed crystal structures in hard-core systems. We employ this method to predict the binary crystal structures in a mixture of large and small hard spheres with various stoichiometries and diameter ratios between 0.4 and 0.84. In addition to known binary hard-sphere crystal structures similar to NaCl and AlB2, we predict additional crystal structures with the symmetry of CrB, gammaCuTi, alphaIrV, HgBr2, AuTe2, Ag2Se, and various structures for which an atomic analog was not found. In order to determine the crystal structures at infinite pressures, we calculate the maximum packing density as a function of size ratio for the crystal structures predicted by our GA using a simulated annealing approach. PMID:19518387
Clustering and gelation of hard spheres induced by the Pickering effect
NASA Astrophysics Data System (ADS)
Fortini, Andrea
2012-04-01
A mixture of hard-sphere particles and model emulsion droplets is studied with a Brownian dynamics simulation. We find that the addition of nonwetting emulsion droplets to a suspension of pure hard spheres can lead to both gas-liquid and fluid-solid phase separations. Furthermore, we find a stable fluid of hard-sphere clusters. The stability is due to the saturation of the attraction that occurs when the surface of the droplets is completely covered with colloidal particles. At larger emulsion droplet densities a percolation transition is observed. The resulting networks of colloidal particles show dynamical and mechanical properties typical of a colloidal gel. The results of the model are in good qualitative agreement with recent experimental findings [E. Koos and N. Willenbacher, ScienceSCIEAS0036-807510.1126/science.1199243 331, 897 (2011)] in a mixture of colloidal particles and two immiscible fluids.
Segregation of Fluidized Binary Hard-Sphere Systems Under Gravity
NASA Astrophysics Data System (ADS)
Kim, Soon-Chul
We have derived an analytic expression for the contact value of the local density of binary hard-sphere systems under gravity. We have obtained the crossover conditions for the Brazil-nut type segregation of binary hard-sphere mixtures and binary hard-sphere chain mixtures from the segregation criterion, where the segregation occurs when the density (or the pressure) of the small spheres at the bottom is higher than that of the large spheres, or vice versa. For the binary hard-sphere chain mixtures, the crossover condition for the segregation depends on the number of monomers composed of hard-sphere chains as well as the mass and the diameter of each species. The fundamental-measure theories (FMTs) and local density approximation (LDA) are employed to examine the crossover condition for the segregation of the gravity-induced hard-sphere mixtures. The calculated results show that the LDA does not explain the density oscillation near the bottom, whereas the modified fundamental-measure theory (MFMT) compares with molecular dynamics simulations.
Edison, John R; Dasgupta, Tonnishtha; Dijkstra, Marjolein
2016-08-01
We study the phase behaviour of a binary mixture of colloidal hard spheres and freely jointed chains of beads using Monte Carlo simulations. Recently Panagiotopoulos and co-workers predicted [Nat. Commun. 5, 4472 (2014)] that the hexagonal close packed (HCP) structure of hard spheres can be stabilized in such a mixture due to the interplay between polymer and the void structure in the crystal phase. Their predictions were based on estimates of the free-energy penalty for adding a single hard polymer chain in the HCP and the competing face centered cubic (FCC) phase. Here we calculate the phase diagram using free-energy calculations of the full binary mixture and find a broad fluid-solid coexistence region and a metastable gas-liquid coexistence region. For the colloid-monomer size ratio considered in this work, we find that the HCP phase is only stable in a small window at relatively high polymer reservoir packing fractions, where the coexisting HCP phase is nearly close packed. Additionally we investigate the structure and dynamic behaviour of these mixtures. PMID:27497577
NASA Astrophysics Data System (ADS)
Edison, John R.; Dasgupta, Tonnishtha; Dijkstra, Marjolein
2016-08-01
We study the phase behaviour of a binary mixture of colloidal hard spheres and freely jointed chains of beads using Monte Carlo simulations. Recently Panagiotopoulos and co-workers predicted [Nat. Commun. 5, 4472 (2014)] that the hexagonal close packed (HCP) structure of hard spheres can be stabilized in such a mixture due to the interplay between polymer and the void structure in the crystal phase. Their predictions were based on estimates of the free-energy penalty for adding a single hard polymer chain in the HCP and the competing face centered cubic (FCC) phase. Here we calculate the phase diagram using free-energy calculations of the full binary mixture and find a broad fluid-solid coexistence region and a metastable gas-liquid coexistence region. For the colloid-monomer size ratio considered in this work, we find that the HCP phase is only stable in a small window at relatively high polymer reservoir packing fractions, where the coexisting HCP phase is nearly close packed. Additionally we investigate the structure and dynamic behaviour of these mixtures.
Zhang, Kai; Fan, Meng; Liu, Yanhui; Schroers, Jan; Shattuck, Mark D; O'Hern, Corey S
2015-11-14
When a liquid is cooled well below its melting temperature at a rate that exceeds the critical cooling rate Rc, the crystalline state is bypassed and a metastable, amorphous glassy state forms instead. Rc (or the corresponding critical casting thickness dc) characterizes the glass-forming ability (GFA) of each material. While silica is an excellent glass-former with small Rc < 10(-2) K/s, pure metals and most alloys are typically poor glass-formers with large Rc > 10(10) K/s. Only in the past thirty years have bulk metallic glasses (BMGs) been identified with Rc approaching that for silica. Recent simulations have shown that simple, hard-sphere models are able to identify the atomic size ratio and number fraction regime where BMGs exist with critical cooling rates more than 13 orders of magnitude smaller than those for pure metals. However, there are a number of other features of interatomic potentials beyond hard-core interactions. How do these other features affect the glass-forming ability of BMGs? In this manuscript, we perform molecular dynamics simulations to determine how variations in the softness and non-additivity of the repulsive core and form of the interatomic pair potential at intermediate distances affect the GFA of binary alloys. These variations in the interatomic pair potential allow us to introduce geometric frustration and change the crystal phases that compete with glass formation. We also investigate the effect of tuning the strength of the many-body interactions from zero to the full embedded atom model on the GFA for pure metals. We then employ the full embedded atom model for binary BMGs and show that hard-core interactions play the dominant role in setting the GFA of alloys, while other features of the interatomic potential only change the GFA by one to two orders of magnitude. Despite their perturbative effect, understanding the detailed form of the intermetallic potential is important for designing BMGs with cm or greater casting
NASA Astrophysics Data System (ADS)
Zhang, Kai; Fan, Meng; Liu, Yanhui; Schroers, Jan; Shattuck, Mark D.; O'Hern, Corey S.
2015-11-01
When a liquid is cooled well below its melting temperature at a rate that exceeds the critical cooling rate Rc, the crystalline state is bypassed and a metastable, amorphous glassy state forms instead. Rc (or the corresponding critical casting thickness dc) characterizes the glass-forming ability (GFA) of each material. While silica is an excellent glass-former with small Rc < 10-2 K/s, pure metals and most alloys are typically poor glass-formers with large Rc > 1010 K/s. Only in the past thirty years have bulk metallic glasses (BMGs) been identified with Rc approaching that for silica. Recent simulations have shown that simple, hard-sphere models are able to identify the atomic size ratio and number fraction regime where BMGs exist with critical cooling rates more than 13 orders of magnitude smaller than those for pure metals. However, there are a number of other features of interatomic potentials beyond hard-core interactions. How do these other features affect the glass-forming ability of BMGs? In this manuscript, we perform molecular dynamics simulations to determine how variations in the softness and non-additivity of the repulsive core and form of the interatomic pair potential at intermediate distances affect the GFA of binary alloys. These variations in the interatomic pair potential allow us to introduce geometric frustration and change the crystal phases that compete with glass formation. We also investigate the effect of tuning the strength of the many-body interactions from zero to the full embedded atom model on the GFA for pure metals. We then employ the full embedded atom model for binary BMGs and show that hard-core interactions play the dominant role in setting the GFA of alloys, while other features of the interatomic potential only change the GFA by one to two orders of magnitude. Despite their perturbative effect, understanding the detailed form of the intermetallic potential is important for designing BMGs with cm or greater casting thickness.
Zhang, Kai; Fan, Meng; Liu, Yanhui; Schroers, Jan; Shattuck, Mark D.; O’Hern, Corey S.
2015-11-14
When a liquid is cooled well below its melting temperature at a rate that exceeds the critical cooling rate R{sub c}, the crystalline state is bypassed and a metastable, amorphous glassy state forms instead. R{sub c} (or the corresponding critical casting thickness d{sub c}) characterizes the glass-forming ability (GFA) of each material. While silica is an excellent glass-former with small R{sub c} < 10{sup −2} K/s, pure metals and most alloys are typically poor glass-formers with large R{sub c} > 10{sup 10} K/s. Only in the past thirty years have bulk metallic glasses (BMGs) been identified with R{sub c} approaching that for silica. Recent simulations have shown that simple, hard-sphere models are able to identify the atomic size ratio and number fraction regime where BMGs exist with critical cooling rates more than 13 orders of magnitude smaller than those for pure metals. However, there are a number of other features of interatomic potentials beyond hard-core interactions. How do these other features affect the glass-forming ability of BMGs? In this manuscript, we perform molecular dynamics simulations to determine how variations in the softness and non-additivity of the repulsive core and form of the interatomic pair potential at intermediate distances affect the GFA of binary alloys. These variations in the interatomic pair potential allow us to introduce geometric frustration and change the crystal phases that compete with glass formation. We also investigate the effect of tuning the strength of the many-body interactions from zero to the full embedded atom model on the GFA for pure metals. We then employ the full embedded atom model for binary BMGs and show that hard-core interactions play the dominant role in setting the GFA of alloys, while other features of the interatomic potential only change the GFA by one to two orders of magnitude. Despite their perturbative effect, understanding the detailed form of the intermetallic potential is important for
Contact pair correlation functions and equation of state for additive hard disk fluid mixtures
NASA Astrophysics Data System (ADS)
Barrio, C.; Solana, J. R.
2001-10-01
The contact pair correlation functions and the equation of state for a binary mixture of additive hard disks is obtained using a procedure similar to that leading to the Boublı´k-Mansoori-Carnahan-Starling-Leland equation of state for mixtures of additive hard spheres. The results from the derived equations are tested against new Monte Carlo data obtained for several diameter ratios and mole fractions. The overall agreement is excellent. The equation of state reproduces exactly the second virial coefficient of the mixture and the third with great accuracy. Predicted values of the fourth and fifth virial coefficients are also in very good agreement with numerical data.
Aging dynamics of colloidal hard sphere glasses.
Martinez, V A; Bryant, G; van Megen, W
2010-09-21
We report the results of dynamic light scattering measurements of the coherent intermediate scattering function (ISF) of glasses of colloidal hard spheres for several volume fractions and a range of scattering vectors around the primary peak of the static structure factor. The ISF shows a clear crossover from an initial fast decay to a slower nonstationary decay. Aging is quantified in several different ways. However, regardless of the method chosen, the perfect "aged" glass is approached in a power law fashion. In particular the coupling between the fast and slow decays, as measured by the degree of stretching of the ISF at the crossover, also decreases algebraically with waiting time. The nonstationarity of this coupling implies that even the fastest detectable processes are themselves nonstationary. PMID:20866156
Replica exchange Monte Carlo applied to hard spheres.
Odriozola, Gerardo
2009-10-14
In this work a replica exchange Monte Carlo scheme which considers an extended isobaric-isothermal ensemble with respect to pressure is applied to study hard spheres (HSs). The idea behind the proposal is expanding volume instead of increasing temperature to let crowded systems characterized by dominant repulsive interactions to unblock, and so, to produce sampling from disjoint configurations. The method produces, in a single parallel run, the complete HS equation of state. Thus, the first order fluid-solid transition is captured. The obtained results well agree with previous calculations. This approach seems particularly useful to treat purely entropy-driven systems such as hard body and nonadditive hard mixtures, where temperature plays a trivial role.
Equations of state for fused-hard-sphere fluids
NASA Astrophysics Data System (ADS)
Maeso, M. J.; Solana, J. R.
1993-09-01
Analytical equations of state for fused-hard-sphere fluids are developed from a generalization of the Carnahan-Starling method for obtaining the equation of state of the hard-sphere fluid. The results are in good agreement with existing simulation data.
Dynamics of hard sphere colloidal dispersions
NASA Technical Reports Server (NTRS)
Zhu, J. X.; Chaikin, Paul M.; Phan, S.-E.; Russel, W. B.
1994-01-01
Our objective is to perform on homogeneous, fully equilibrated dispersions the full set of experiments characterizing the transition from fluid to solid and the properties of the crystalline and glassy solid. These include measurements quantifying the nucleation and growth of crystallites, the structure of the initial fluid and the fully crystalline solid, and Brownian motion of particles within the crystal, and the elasticity of the crystal and the glass. Experiments are being built and tested for ideal microgravity environment. Here we describe the ground based effort, which exploits a fluidized bed to create a homogeneous, steady dispersion for the studies. The differences between the microgravity environment and the fluidized bed is gauged by the Peclet number Pe, which measures the rate of convection/sedimentation relative to Brownian motion. We have designed our experiment to accomplish three types of measurements on hard sphere suspensions in a fluidized bed: the static scattering intensity as a function of angle to determine the structure factor, the temporal autocorrelation function at all scattering angles to probe the dynamics, and the amplitude of the response to an oscillatory forcing to deduce the low frequency viscoelasticity. Thus the scattering instrument and the colloidal dispersion were chosen such as that the important features of each physical property lie within the detectable range for each measurement.
Chaudhari, Mangesh I.; Holleran, Sinead A.; Ashbaugh, Henry S.; Pratt, Lawrence R.
2013-01-01
The osmotic second virial coefficients, B2, for atomic-sized hard spheres in water are attractive (B2 < 0) and become more attractive with increasing temperature (ΔB2/ΔT < 0) in the temperature range 300 K ≤ T ≤ 360 K. Thus, these hydrophobic interactions are attractive and endothermic at moderate temperatures. Hydrophobic interactions between atomic-sized hard spheres in water are more attractive than predicted by the available statistical mechanical theory. These results constitute an initial step toward detailed molecular theory of additional intermolecular interaction features, specifically, attractive interactions associated with hydrophobic solutes. PMID:24297918
Collisional statistics of the hard-sphere gas.
Visco, Paolo; van Wijland, Frédéric; Trizac, Emmanuel
2008-04-01
We investigate the probability distribution functions of the free flight time and of the number of collisions in a hard-sphere gas at equilibrium. At variance with naive expectation, the latter quantity does not follow Poissonian statistics, even in the dilute limit, which is the focus of the present analysis. The corresponding deviations are addressed both numerically and analytically. In writing an equation for the generating function of the cumulants of the number of collisions, we came across a perfect mapping between our problem and a previously introduced model: the probabilistic ballistic annihilation process [Coppex, Phys. Rev. E 69, 11303 (2004)]. We exploit this analogy to construct a Monte Carlo-like algorithm able to investigate the asymptotically large time behavior of the collisional statistics within a reasonable computational time. In addition, our predictions are compared with the results of molecular dynamics simulations and the direct simulation Monte Carlo technique. An excellent agreement is reported. PMID:18517588
NASA Astrophysics Data System (ADS)
Astillero, Antonio; Santos, Andrés
2005-09-01
In the preceding paper, we have conjectured that the main transport properties of a dilute gas of inelastic hard spheres (IHSs) can be satisfactorily captured by an equivalent gas of elastic hard spheres (EHSs), provided that the latter are under the action of an effective drag force and their collision rate is reduced by a factor (1+α)/2 (where α is the constant coefficient of normal restitution). In this paper we test the above expectation in a paradigmatic nonequilibrium state, namely, the simple or uniform shear flow, by performing Monte Carlo computer simulations of the Boltzmann equation for both classes of dissipative gases with a dissipation range 0.5⩽α⩽0.95 and two values of the imposed shear rate a . It is observed that the evolution toward the steady state proceeds in two stages: a short kinetic stage (strongly dependent on the initial preparation of the system) followed by a slower hydrodynamic regime that becomes increasingly less dependent on the initial state. Once conveniently scaled, the intrinsic quantities in the hydrodynamic regime depend on time, at a given value of α , only through the reduced shear rate a*(t)∝a/T(t) , until a steady state, independent of the imposed shear rate and of the initial preparation, is reached. The distortion of the steady-state velocity distribution from the local equilibrium state is measured by the shear stress, the normal stress differences, the cooling rate, the fourth and sixth cumulants, and the shape of the distribution itself. In particular, the simulation results seem to be consistent with an exponential overpopulation of the high-velocity tail. These properties are common to both the IHS and EHS systems. In addition, the EHS results are in general hardly distinguishable from the IHS ones if α≳0.7 , so that the distinct signature of the IHS gas (higher anisotropy and overpopulation) only manifests itself at relatively high dissipations.
Simple effective rule to estimate the jamming packing fraction of polydisperse hard spheres.
Santos, Andrés; Yuste, Santos B; López de Haro, Mariano; Odriozola, Gerardo; Ogarko, Vitaliy
2014-04-01
A recent proposal in which the equation of state of a polydisperse hard-sphere mixture is mapped onto that of the one-component fluid is extrapolated beyond the freezing point to estimate the jamming packing fraction ϕJ of the polydisperse system as a simple function of M1M3/M22, where Mk is the kth moment of the size distribution. An analysis of experimental and simulation data of ϕJ for a large number of different mixtures shows a remarkable general agreement with the theoretical estimate. To give extra support to the procedure, simulation data for seventeen mixtures in the high-density region are used to infer the equation of state of the pure hard-sphere system in the metastable region. An excellent collapse of the inferred curves up to the glass transition and a significant narrowing of the different out-of-equilibrium glass branches all the way to jamming are observed. Thus, the present approach provides an extremely simple criterion to unify in a common framework and to give coherence to data coming from very different polydisperse hard-sphere mixtures.
Simple effective rule to estimate the jamming packing fraction of polydisperse hard spheres
NASA Astrophysics Data System (ADS)
Santos, Andrés; Yuste, Santos B.; López de Haro, Mariano; Odriozola, Gerardo; Ogarko, Vitaliy
2014-04-01
A recent proposal in which the equation of state of a polydisperse hard-sphere mixture is mapped onto that of the one-component fluid is extrapolated beyond the freezing point to estimate the jamming packing fraction ϕJ of the polydisperse system as a simple function of M1M3/M22, where Mk is the kth moment of the size distribution. An analysis of experimental and simulation data of ϕJ for a large number of different mixtures shows a remarkable general agreement with the theoretical estimate. To give extra support to the procedure, simulation data for seventeen mixtures in the high-density region are used to infer the equation of state of the pure hard-sphere system in the metastable region. An excellent collapse of the inferred curves up to the glass transition and a significant narrowing of the different out-of-equilibrium glass branches all the way to jamming are observed. Thus, the present approach provides an extremely simple criterion to unify in a common framework and to give coherence to data coming from very different polydisperse hard-sphere mixtures.
Depletion force in the infinite-dilution limit in a solvent of nonadditive hard spheres.
Fantoni, Riccardo; Santos, Andrés
2014-06-28
The mutual entropic depletion force felt by two solute "big" hard spheres immersed in a binary mixture solvent of nonadditive "small" hard spheres is calculated as a function of the surface-to-surface distance by means of canonical Monte Carlo simulations and through a recently proposed rational-function approximation [R. Fantoni and A. Santos, Phys. Rev. E 84, 041201 (2011)]. Four representative scenarios are investigated: symmetric solute particles and the limit where one of the two solute spheres becomes a planar hard wall, in both cases with symmetric and asymmetric solvents. In all cases, the influence on the depletion force due to the nonadditivity in the solvent is determined in the mixed state. Comparison between results from the theoretical approximation and from the simulation shows a good agreement for surface-to-surface distances greater than the smallest solvent diameter.
On the radial distribution function of a hard-sphere fluid
NASA Astrophysics Data System (ADS)
López de Haro, M.; Santos, A.; Yuste, S. B.
2006-06-01
Two related approaches, one fairly recent [A. Trokhymchuk et al., J. Chem. Phys.123, 024501 (2005)] and the other one introduced 15years ago [S. B. Yuste and A. Santos, Phys. Rev. A43, 5418 (1991)], for the derivation of analytical forms of the radial distribution function of a fluid of hard spheres are compared. While they share similar starting philosophy, the first one involves the determination of 11 parameters while the second is a simple extension of the solution of the Percus-Yevick equation. It is found that the second approach has a better global accuracy and the further asset of counting already with a successful generalization to mixtures of hard spheres and other related systems.
Computational polymer physics: Hard-sphere chain in solvent systems
NASA Astrophysics Data System (ADS)
Gautam, Avinash; Gavazzi, Daniel; Taylor, Mark
2009-10-01
In this work we present results for chain conformation in two simple chain-in-solvent systems constructed from hard-sphere monomers of diameter D. The first system consists of a flexible chain of fused hard spheres (i.e., bond length L=D) in a monomeric hard-sphere solvent. The second system consists of a flexible tangent hard-sphere chain (L=D) in a dimeric hard-sphere solvent with L=D. These systems are studied using Monte Carlo simulations which employ both single-site crankshaft and multi-site pivot moves to sample the configuration space of the chain. We report chain structure, in terms of site-site probability functions, as a function of solvent density. In all cases, increasing solvent density leads to an overall compression of the chain. At high solvent density the chain conformation is closely coupled to the local solvent structure and we speculate that incommensurate structures may lead to interesting conformational transitions.
Theory and computer simulation for the equation of state of additive hard-disk fluid mixtures
NASA Astrophysics Data System (ADS)
Barrio, C.; Solana, J. R.
2001-01-01
A procedure previously developed by the authors to obtain the equation of state for a mixture of additive hard spheres on the basis of a pure fluid equation of state is applied here to a binary mixture of additive hard disks in two dimensions. The equation of state depends on two parameters which are determined from the second and third virial coefficients for the mixture, which are known exactly. Results are compared with Monte Carlo calculations which are also reported. The agreement between theory and simulation is very good. For the fourth and fifth virial coefficients of the mixture, the equation of state gives results which are also in close agreement with exact numerical values reported in the literature.
Slip and flow of hard-sphere colloidal glasses.
Ballesta, P; Besseling, R; Isa, L; Petekidis, G; Poon, W C K
2008-12-19
We study the flow of concentrated hard-sphere colloidal suspensions along smooth, nonstick walls using cone-plate rheometry and simultaneous confocal microscopy. In the glass regime, the global flow shows a transition from Herschel-Bulkley behavior at large shear rate to a characteristic Bingham slip response at small rates, absent for ergodic colloidal fluids. Imaging reveals both the "solid" microstructure during full slip and the local nature of the "slip to shear" transition. Both the local and global flow are described by a phenomenological model, and the associated Bingham slip parameters exhibit characteristic scaling with size and concentration of the hard spheres.
Free volume distribution of nearly jammed hard sphere packings
NASA Astrophysics Data System (ADS)
Maiti, Moumita; Sastry, Srikanth
2014-07-01
We calculate the free volume distributions of nearly jammed packings of monodisperse and bidisperse hard sphere configurations. These distributions differ qualitatively from those of the fluid, displaying a power law tail at large free volumes, which constitutes a distinct signature of nearly jammed configurations, persisting for moderate degrees of decompression. We reproduce and explain the observed distribution by considering the pair correlation function within the first coordination shell for jammed hard sphere configurations. We analyze features of the equation of state near jamming, and discuss the significance of observed asphericities of the free volumes to the equation of state.
Using compressibility factor as a predictor of confined hard-sphere fluid dynamics
Mittal, Jeetain
2009-01-01
We study the correlations between the diffusivity (or viscosity) and the compressibility factor of bulk hard-sphere fluid as predicted by the ultralocal limit of the barrier hopping theory. Our specific aim is to determine if these correlations observed in the bulk equilibrium hard-sphere fluid can be used to predict the self-diffusivity of fluid confined between a slit-pore or a rectangular channel. In this work, we consider a single-component and a binary mixture of hard spheres. To represent confining walls, we use purely reflecting hard walls and interacting square-well walls. Our results clearly show that the correspondence between the diffusivity and the compressibility factor can be used along with the knowledge of the confined fluid's compressibility factor to predict its diffusivity with quantitative accuracy. Our analysis also suggests that a simple measure, the average fluid density, can be an accurate predictor of confined fluid diffusivity for very tight confinements (≈ 2-3 particle diameters wide) at low to intermediate density conditions. Together, these results provide further support for the idea that one can use robust connections between thermodynamic and dynamic quantities to predict dynamics of confined fluids from their thermodynamics. PMID:19702285
NASA Astrophysics Data System (ADS)
Largo, J.; Maeso, M. J.; Solana, J. R.; Vega, C.; MacDowell, L. G.
2003-11-01
The bonded hard-sphere (BHS) theory is extended to fluids consisting of rigid, linear, homonuclear molecules, each of them formed by n fused hard spheres. The theory shows excellent agreement with the Monte Carlo NpT simulation data which are also reported for reduced bond lengths l*=0.5 and n=2, 3, 4, 6, 8, and 10. The accuracy of the BHS prediction in comparison to simulation is similar to that of generalized Flory-dimer theory and superior to that of thermodynamic perturbation theory.
Rowlinson's concept of an effective hard sphere diameter.
Henderson, Douglas
2010-01-01
Attention is drawn to John Rowlinson's idea that the repulsive portion of the intermolecular interaction may be replaced by a temperature-dependent hard sphere diameter. It is this approximation that made the development of perturbation theory possible for realistic fluids whose intermolecular interactions have a steep, but finite, repulsion at short separations.
Rowlinson’s concept of an effective hard sphere diameter
Henderson, Douglas
2010-01-01
Attention is drawn to John Rowlinson’s idea that the repulsive portion of the intermolecular interaction may be replaced by a temperature-dependent hard sphere diameter. It is this approximation that made the development of perturbation theory possible for realistic fluids whose intermolecular interactions have a steep, but finite, repulsion at short separations. PMID:20953320
The structural origin of the hard-sphere glass transition in granular packing
Xia, Chengjie; Li, Jindong; Cao, Yixin; Kou, Binquan; Xiao, Xianghui; Fezzaa, Kamel; Xiao, Tiqiao; Wang, Yujie
2015-09-28
Glass transition is accompanied by a rapid growth of the structural relaxation time and a concomitant decrease of configurational entropy. It remains unclear whether the transition has a thermodynamic origin, and whether the dynamic arrest is associated with the growth of a certain static order. Using granular packing as a model hard-sphere glass, we show the glass transition as a thermodynamic phase transition with a ‘hidden’ polytetrahedral order. This polytetrahedral order is spatially correlated with the slow dynamics. It is geometrically frustrated and has a peculiar fractal dimension. Additionally, as the packing fraction increases, its growth follows an entropy-driven nucleation process, similar to that of the random first-order transition theory. In conclusion, our study essentially identifies a long-sought-after structural glass order in hard-sphere glasses.
The structural origin of the hard-sphere glass transition in granular packing
Xia, Chengjie; Li, Jindong; Cao, Yixin; Kou, Binquan; Xiao, Xianghui; Fezzaa, Kamel; Xiao, Tiqiao; Wang, Yujie
2015-09-28
Glass transition is accompanied by a rapid growth of the structural relaxation time and a concomitant decrease of configurational entropy. It remains unclear whether the transition has a thermodynamic origin, and whether the dynamic arrest is associated with the growth of a certain static order. Using granular packing as a model hard-sphere glass, we show the glass transition as a thermodynamic phase transition with a ‘hidden’ polytetrahedral order. This polytetrahedral order is spatially correlated with the slow dynamics. It is geometrically frustrated and has a peculiar fractal dimension. Additionally, as the packing fraction increases, its growth follows an entropy-driven nucleationmore » process, similar to that of the random first-order transition theory. In conclusion, our study essentially identifies a long-sought-after structural glass order in hard-sphere glasses.« less
The structural origin of the hard-sphere glass transition in granular packing
Xia, Chengjie; Li, Jindong; Cao, Yixin; Kou, Binquan; Xiao, Xianghui; Fezzaa, Kamel; Xiao, Tiqiao; Wang, Yujie
2015-01-01
Glass transition is accompanied by a rapid growth of the structural relaxation time and a concomitant decrease of configurational entropy. It remains unclear whether the transition has a thermodynamic origin, and whether the dynamic arrest is associated with the growth of a certain static order. Using granular packing as a model hard-sphere glass, we show the glass transition as a thermodynamic phase transition with a ‘hidden' polytetrahedral order. This polytetrahedral order is spatially correlated with the slow dynamics. It is geometrically frustrated and has a peculiar fractal dimension. Additionally, as the packing fraction increases, its growth follows an entropy-driven nucleation process, similar to that of the random first-order transition theory. Our study essentially identifies a long-sought-after structural glass order in hard-sphere glasses. PMID:26412008
Entropic forces and phase separation in binary nearly hard-sphere colloids
NASA Astrophysics Data System (ADS)
Dinsmore, Anthony Duprat
We present the results of experimental and theoretical studies of the statistical mechanics of suspensions of hard spheres of two different sizes. We have focused on the effects of entropic depletion (or excluded-volume) effects, which play an important role in many real mixtures. In the first set of experiments, we studied the phase behavior of binary hard-sphere mixtures with diameter ratios between 2 and 12. We found that even when the volume fraction of spheres was only 0.20, separation into coexisting fluid and solid phases occurred despite the absence of attractive pair interactions. We measured the structures and compositions of the equilibrium phases both in the bulk of the sample and at the wall of the container. We also propose an original, physically- transparent model that predicts fluid-solid phase separation in hard-sphere mixtures without fit parameters, in close agreement with our measurements and with previously-published results for monodisperse hard- sphere mixtures. Investigating the effects of hard (inert) surfaces, we demonstrated for the first time that inert walls of complex shape can induce entropic force fields that can trap, repel, or induce drift of the larger particles in a binary suspension. We measured the entropic force on a large sphere as a function of its position near the edge of a terrace and found that it is repelled by a 40-femto- Newton force. A similar mechanism confined large spheres in a corner and, inside rigid phospholipid vesicles, pushed the larger spheres along the wall in the direction of increasing curvature. We predict that, under some circumstances, a unilamellar vesicle will spontaneously envelop a large sphere. Aside from their fundamental interest, these results are likely to improve our understanding of the behavior of complex fluids inside porous media and of proteins inside cells. We have also developed new techniques for making arrays of submicron particles for photonic applications. Two- dimensional
Hard sphere dynamics for normal and granular fluids.
Dufty, James W; Baskaran, Aparna
2005-06-01
A fluid of N smooth, hard spheres is considered as a model for normal (elastic collision) and granular (inelastic collision) fluids. The potential energy is discontinuous for hard spheres so that the pairwise forces are singular and the usual forms of Newtonian and Hamiltonian mechanics do not apply. Nevertheless, particle trajectories in the N particle phase space are well defined and the generators for these trajectories can be identified. The first part of this presentation is a review of the generators for the dynamics of observables and probability densities. The new results presented in the second part refer to applications of these generators to the Liouville dynamics for granular fluids. A set of eigenvalues and eigenfunctions of the generator for this Liouville dynamics system is identified in a special stationary representation. This provides a class of exact solutions to the Liouville equation that are closely related to hydrodynamics for granular fluids.
Investigating hard sphere interactions through spin echo scattering angle measurement
NASA Astrophysics Data System (ADS)
Washington, Adam
Spin Echo Scattering Angle Measurement (SESAME) allows neutron scattering instruments to perform real space measurements on large micron scale samples by encoding the scattering angle into the neutron's spin state via Larmor precession. I have built a SESAME instrument at the Low Energy Neutron Source. I have also assisted in the construction of a modular SESAME instrument on the ASTERIX beamline at Los Alamos National lab. The ability to tune these instruments has been proved mathematically and optimized and automated experimentally. Practical limits of the SESAME technique with respect to polarization analyzers, neutron spectra, Larmor elements, and data analysis were investigated. The SESAME technique was used to examine the interaction of hard spheres under depletion. Poly(methyl methacrylate) spheres suspended in decalin had previously been studied as a hard sphere solution. The interparticle correlations between the spheres were found to match the Percus-Yevick closure, as had been previously seen in dynamical light scattering experiments. To expand beyond pure hard spheres, 900kDa polystyrene was added to the solution in concentrations of less than 1% by mass. The steric effects of the polystyrene were expected to produce a short-range, attractive, "sticky" potential. Experiment showed, however, that the "sticky" potential was not a stable state and that the spheres would eventually form long range aggregates.
Paricaud, P.
2015-07-28
A simple modification of the Boublík-Mansoori-Carnahan-Starling-Leland equation of state is proposed for an application to the metastable disordered region. The new model has a positive pole at the jamming limit and can accurately describe the molecular simulation data of pure hard in the stable fluid region and along the metastable branch. The new model has also been applied to binary mixtures hard spheres, and an excellent description of the fluid and metastable branches can be obtained by adjusting the jamming packing fraction. The new model for hard sphere mixtures can be used as the repulsive term of equations of state for real fluids. In this case, the modified equations of state give very similar predictions of thermodynamic properties as the original models, and one can remove the multiple liquid density roots observed for some versions of the Statistical Associating Fluid Theory (SAFT) at low temperature without any modification of the dispersion term.
Hard-sphere interactions in velocity-jump models
NASA Astrophysics Data System (ADS)
Franz, Benjamin; Taylor-King, Jake P.; Yates, Christian; Erban, Radek
2016-07-01
Group-level behavior of particles undergoing a velocity-jump process with hard-sphere interactions is investigated. We derive N -particle transport equations that include the possibility of collisions between particles and apply different approximation techniques to get expressions for the dependence of the collective diffusion coefficient on the number of particles and their diameter. The derived approximations are compared with numerical results obtained from individual-based simulations. The theoretical results compare well with Monte Carlo simulations providing the excluded-volume fraction is small.
Packing confined hard spheres denser with adaptive prism phases.
Oğuz, Erdal C; Marechal, Matthieu; Ramiro-Manzano, Fernando; Rodriguez, Isabelle; Messina, René; Meseguer, Francisco J; Löwen, Hartmut
2012-11-21
We show that hard spheres confined between two parallel hard plates pack denser with periodic adaptive prismatic structures which are composed of alternating prisms of spheres. The internal structure of the prisms adapts to the slit height which results in close packings for a range of plate separations, just above the distance where three intersecting square layers fit exactly between the plates. The adaptive prism phases are also observed in real-space experiments on confined sterically stabilized colloids and in Monte Carlo simulations at finite pressure.
Simple liquids’ quasiuniversality and the hard-sphere paradigm
NASA Astrophysics Data System (ADS)
Dyre, Jeppe C.
2016-08-01
This topical review discusses the quasiuniversality of simple liquids’ structure and dynamics and two possible justifications of it. The traditional one is based on the van der Waals picture of liquids in which the hard-sphere system reflects the basic physics. An alternative explanation argues that all quasiuniversal liquids to a good approximation conform to the same equation of motion, referring to the exponentially repulsive pair-potential system as the basic reference system. The paper, which is aimed at non-experts, ends by listing a number of open problems in the field.
Anomalous slowing down in the metastable liquid of hard spheres
NASA Astrophysics Data System (ADS)
Dzugutov, M.
2002-03-01
It is demonstrated that a straightforward extension of the Arrhenius law accurately describes diffusion in the thermodynamically stable liquid of hard spheres. A sharp negative deviation from this behavior is observed as the liquid is compressed beyond its stability limit. This dynamical anomaly can be compared with the nonlinear slowing down characteristic of the supercooled dynamics regime in liquids with continuous interaction. It is suggested that the observed dynamical transition is caused by long-time decomposition of the configuration space. This interpretation is corroborated by the observation of characteristic anomalies in the geometry of a particle trajectory in the metastable domain.
Hard-sphere interactions in velocity-jump models.
Franz, Benjamin; Taylor-King, Jake P; Yates, Christian; Erban, Radek
2016-07-01
Group-level behavior of particles undergoing a velocity-jump process with hard-sphere interactions is investigated. We derive N-particle transport equations that include the possibility of collisions between particles and apply different approximation techniques to get expressions for the dependence of the collective diffusion coefficient on the number of particles and their diameter. The derived approximations are compared with numerical results obtained from individual-based simulations. The theoretical results compare well with Monte Carlo simulations providing the excluded-volume fraction is small. PMID:27575098
Fifth to eleventh virial coefficients of hard spheres
NASA Astrophysics Data System (ADS)
Schultz, Andrew J.; Kofke, David A.
2014-08-01
Virial coefficients Bn of three-dimensional hard spheres are reported for n=5 to 11, with precision exceeding that presently available in the literature. Calculations are performed using the recursive method due to Wheatley, and a binning approach is proposed to allow more flexibility in where computational effort is directed in the calculations. We highlight the difficulty as a general measure that quantifies performance of an algorithm that computes a stochastic average and show how it can be used as the basis for optimizing such calculations.
Physics of Hard Spheres Experiment: Significant and Quantitative Findings Made
NASA Technical Reports Server (NTRS)
Doherty, Michael P.
2000-01-01
Direct examination of atomic interactions is difficult. One powerful approach to visualizing atomic interactions is to study near-index-matched colloidal dispersions of microscopic plastic spheres, which can be probed by visible light. Such spheres interact through hydrodynamic and Brownian forces, but they feel no direct force before an infinite repulsion at contact. Through the microgravity flight of the Physics of Hard Spheres Experiment (PHaSE), researchers have sought a more complete understanding of the entropically driven disorder-order transition in hard-sphere colloidal dispersions. The experiment was conceived by Professors Paul M. Chaikin and William B. Russel of Princeton University. Microgravity was required because, on Earth, index-matched colloidal dispersions often cannot be density matched, resulting in significant settling over the crystallization period. This settling makes them a poor model of the equilibrium atomic system, where the effect of gravity is truly negligible. For this purpose, a customized light-scattering instrument was designed, built, and flown by the NASA Glenn Research Center at Lewis Field on the space shuttle (shuttle missions STS 83 and STS 94). This instrument performed both static and dynamic light scattering, with sample oscillation for determining rheological properties. Scattered light from a 532- nm laser was recorded either by a 10-bit charge-coupled discharge (CCD) camera from a concentric screen covering angles of 0 to 60 or by sensitive avalanche photodiode detectors, which convert the photons into binary data from which two correlators compute autocorrelation functions. The sample cell was driven by a direct-current servomotor to allow sinusoidal oscillation for the measurement of rheological properties. Significant microgravity research findings include the observation of beautiful dendritic crystals, the crystallization of a "glassy phase" sample in microgravity that did not crystallize for over 1 year in 1g
NASA Astrophysics Data System (ADS)
Gazzillo, Domenico; Giacometti, Achille; Fantoni, Riccardo; Sollich, Peter
2006-11-01
We investigate the dependence of the stickiness parameters tij=1/(12τij) —where the τij are the conventional Baxter parameters—on the solute diameters σi and σj in multicomponent sticky hard sphere (SHS) models for fluid mixtures of mesoscopic neutral particles. A variety of simple but realistic interaction potentials, utilized in the literature to model short-ranged attractions present in real solutions of colloids or reverse micelles, is reviewed. We consider: (i) van der Waals attractions, (ii) hard-sphere-depletion forces, (iii) polymer-coated colloids, and (iv) solvation effects (in particular hydrophobic bonding and attractions between reverse micelles of water-in-oil microemulsions). We map each of these potentials onto an equivalent SHS model by requiring the equality of the second virial coefficients. The main finding is that, for most of the potentials considered, the size-dependence of tij(T,σi,σj) can be approximated by essentially the same expression, i.e., a simple polynomial in the variable σiσj/σij2 , with coefficients depending on the temperature T , or—for depletion interactions—on the packing fraction η0 of the depletant particles.
Solubilities of Solutes in Ionic Liquids from a SimplePerturbed-Hard-Sphere Theory
Qin, Yuan; Prausnitz, John M.
2005-09-20
In recent years, several publications have provided solubilities of ordinary gases and liquids in ionic liquids. This work reports an initial attempt to correlate the experimental data using a perturbed-hard-sphere theory; the perturbation is based on well-known molecular physics when the solution is considered as a dielectric continuum. For this correlation, the most important input parameters are hard-sphere diameters of the solute and of the cation and anion that constitute the ionic liquid. In addition, the correlation uses the solvent density and the solute's polarizability and dipole and quadrupole moments, if any. Dispersion-energy parameters are obtained from global correlation of solubility data. Results are given for twenty solutes in several ionic liquids at normal temperatures; in addition, some results are given for gases in two molten salts at very high temperatures. Because the theory used here is much simplified, and because experimental uncertainties (especially for gaseous solutes) are often large, the accuracy of the correlation presented here is not high; in general, predicted solubilities (Henry's constants) agree with experiment to within roughly {+-} 70%. As more reliable experimental data become available, modifications in the characterizing parameters are likely to improve accuracy. Nevertheless, even in its present form, the correlation may be useful for solvent screening in engineering design.
Compact Collision Kernels for Hard Sphere and Coulomb Cross Sections; Fokker-Planck Coefficients
Chang Yongbin; Shizgal, Bernie D.
2008-12-31
A compact collision kernel is derived for both hard sphere and Coulomb cross sections. The difference between hard sphere interaction and Coulomb interaction is characterized by a parameter {eta}. With this compact collision kernel, the calculation of Fokker-Planck coefficients can be done for both the Coulomb and hard sphere interactions. The results for arbitrary order Fokker-Planck coefficients are greatly simplified. An alternate form for the Coulomb logarithm is derived with concern to the temperature relaxation in a binary plasma.
Sticky hard spheres beyond the Percus-Yevick approximation
NASA Astrophysics Data System (ADS)
Yuste, S. Bravo; Santos, A.
1993-12-01
The radial distribution function g(r) of a sticky-hard-sphere fluid is obtained by assuming a rational-function form for a function related to the Laplace transform of rg(r), compatible with the conditions of finite y(r)==g(r)ecphi(r)/kBT at c ontact point and finite isothermal compressibility. In a recent paper [S. Bravo Yuste and A. Santos, J. Stat. Phys. 72, 703 (1993)] we have shown that the simplest rational-function approximation, namely, the Padé approximant (2,3), leads to Baxter's exact solution of the Percus-Yevick equation. Here we consider the next approximation, i.e., the Padé approximant (3,4), and determine the two new parameters by imposing the values of y(r) at contact point and of the isothermal compressibility. Comparison with Monte Carlo simulation results shows a significant improvement over the Percus-Yevick approximation.
Density Fluctuations of Hard-Sphere Fluids in Narrow Confinement
NASA Astrophysics Data System (ADS)
Nygârd, Kim; Sarman, Sten; Hyltegren, Kristin; Chodankar, Shirish; Perret, Edith; Buitenhuis, Johan; van der Veen, J. Friso; Kjellander, Roland
2016-01-01
Spatial confinement induces microscopic ordering of fluids, which in turn alters many of their dynamic and thermodynamic properties. However, the isothermal compressibility has hitherto been largely overlooked in the literature, despite its obvious connection to the underlying microscopic structure and density fluctuations in confined geometries. Here, we address this issue by probing density profiles and structure factors of hard-sphere fluids in various narrow slits, using x-ray scattering from colloid-filled nanofluidic containers and integral-equation-based statistical mechanics at the level of pair distributions for inhomogeneous fluids. Most importantly, we demonstrate that density fluctuations and isothermal compressibilities in confined fluids can be obtained experimentally from the long-wavelength limit of the structure factor, providing a formally exact and experimentally accessible connection between microscopic structure and macroscopic, thermodynamic properties. Our approach will thus, for example, allow direct experimental verification of theoretically predicted enhanced density fluctuations in liquids near solvophobic interfaces.
Intrinsic nonlinearities in the mechanics of hard sphere suspensions.
Kumar, Mansi A; Ewoldt, Randy H; Zukoski, Charles F
2016-09-28
The onset of nonlinear responses in near hard sphere suspensions is characterized as a function of oscillatory frequency and strain amplitude. At low frequencies where the viscous behavior dominates, the onset of nonlinearities is driven by increases in rate of strain. At high deformation frequency, where suspension mechanics is dominated by an elastic response, the nonlinear responses occur when deformation exceeds a characteristic strain. This strain is associated with the transient confinement of particles by nearest neighbors and its volume fraction dependence is through cage parameters derived from the high frequency elastic modulus. The onset of nonlinear responses takes on a universal behavior when deformation frequency is normalized by the characteristic time governing the shift from viscous to elastic behavior indicating that this transition is associated with transient particle localization and is expected to be observed for all volume fractions where pair interactions are important. PMID:27530863
Detecting Phase Boundaries in Hard-Sphere Suspensions
NASA Technical Reports Server (NTRS)
McDowell, Mark; Rogers, Richard B.; Gray, Elizabeth
2009-01-01
A special image-data-processing technique has been developed for use in experiments that involve observation, via optical microscopes equipped with electronic cameras, of moving boundaries between the colloidal-solid and colloidal-liquid phases of colloidal suspensions of monodisperse hard spheres. During an experiment, it is necessary to adjust the position of a microscope to keep the phase boundary within view. A boundary typically moves at a speed of the order of microns per hour. Because an experiment can last days or even weeks, it is impractical to require human intervention to keep the phase boundary in view. The present image-data-processing technique yields results within a computation time short enough to enable generation of automated-microscope-positioning commands to track the moving phase boundary
Communication: Dynamical density functional theory for dense suspensions of colloidal hard spheres.
Stopper, Daniel; Roth, Roland; Hansen-Goos, Hendrik
2015-11-14
We study structural relaxation of colloidal hard spheres undergoing Brownian motion using dynamical density functional theory. Contrary to the partial linearization route [D. Stopper et al., Phys. Rev. E 92, 022151 (2015)] which amounts to using different free energy functionals for the self and distinct part of the van Hove function G(r, t), we put forward a unified description employing a single functional for both components. To this end, interactions within the self part are removed via the zero-dimensional limit of the functional with a quenched self component. In addition, we make use of a theoretical result for the long-time mobility in hard-sphere suspensions, which we adapt to the inhomogeneous fluid. Our results for G(r, t) are in excellent agreement with numerical simulations even in the dense liquid phase. In particular, our theory accurately yields the crossover from free diffusion at short times to the slower long-time diffusion in a crowded environment.
Free Energy Calculations of Crystalline Hard Sphere Complexes Using Density Functional Theory
Gunawardana, K. G.S.H.; Song, Xueyu
2014-12-22
Recently developed fundamental measure density functional theory (FMT) is used to study binary hard sphere (HS) complexes in crystalline phases. By comparing the excess free energy, pressure and phase diagram, we show that the fundamental measure functional yields good agreements to the available simulation results of AB, AB_{2} and AB_{13} crystals. Additionally, we use this functional to study the HS models of five binary crystals, Cu_{5}Zr(C15_{b}), Cu_{51}Zr_{14}(β), Cu_{10}Zr_{7}(φ), CuZr(B2) and CuZr_{2} (C11_{b}), which are observed in the Cu-Zr system. The FMT functional gives well behaved minimum for most of the hard sphere crystal complexes in the two dimensional Gaussian space, namely a crystalline phase. However, the current version of FMT functional (white Bear) fails to give a stable minimum for the structure Cu_{10}Zr_{7}(φ). We argue that the observed solid phases for the HS models of the Cu-Zr system are true thermodynamic stable phases and can be used as a reference system in perturbation calculations.
Free Energy Calculations of Crystalline Hard Sphere Complexes Using Density Functional Theory
Gunawardana, K. G.S.H.; Song, Xueyu
2014-12-22
Recently developed fundamental measure density functional theory (FMT) is used to study binary hard sphere (HS) complexes in crystalline phases. By comparing the excess free energy, pressure and phase diagram, we show that the fundamental measure functional yields good agreements to the available simulation results of AB, AB2 and AB13 crystals. Additionally, we use this functional to study the HS models of five binary crystals, Cu5Zr(C15b), Cu51Zr14(β), Cu10Zr7(φ), CuZr(B2) and CuZr2 (C11b), which are observed in the Cu-Zr system. The FMT functional gives well behaved minimum for most of the hard sphere crystal complexes in the two dimensional Gaussian space,more » namely a crystalline phase. However, the current version of FMT functional (white Bear) fails to give a stable minimum for the structure Cu10Zr7(φ). We argue that the observed solid phases for the HS models of the Cu-Zr system are true thermodynamic stable phases and can be used as a reference system in perturbation calculations.« less
Liquid-liquid equilibrium calculations from a modified perturbed hard sphere equation of state
Min-Lon Yu; Muoi Tang; Yan-Ping Chen
1996-12-31
A modified perturbed hard sphere (MPHS) equation of state (EOS) was developed for liquid-liquid equilibrium (LLE) calculations in this work. This MPHS EOS includes a repulsive contribution of the Carnahan-Starling EOS. The attractive part of the MPHS EOS was derived from the generalized van der Waals partition function with a modified coordination number model. The MPHS EOS yielded good results on the vapor-liquid equilibrium calculations on both pure fluids and their mixtures. It also gave satisfactory results on LLE calculations. The MPHS EOS shows smaller average errors as well as less scattering of the binary interactions parameters in LLE calculations than those from other EOS models. 8 refs., 2 figs., 2 tabs.
Polydisperse hard spheres: crystallization kinetics in small systems and role of local structure
NASA Astrophysics Data System (ADS)
Campo, Matteo; Speck, Thomas
2016-08-01
We study numerically the crystallization of a hard-sphere mixture with 8% polydispersity. Although often used as a model glass former, for small system sizes we observe crystallization in molecular dynamics simulations. This opens the possibility to study the competition between crystallization and structural relaxation of the melt, which typically is out of reach due to the disparate timescales. We quantify the dependence of relaxation and crystallization times on density and system size. For one density and system size we perform a detailed committor analysis to investigate the suitability of local structures as order parameters to describe the crystallization process. We find that local structures are strongly correlated with generic bond order and add little information to the reaction coordinate.
Particle characterization using multiple scattering decorrelation methods: Hard-sphere model system
NASA Astrophysics Data System (ADS)
Heymann, Andreas; Sinn, Christian; Palberg, Thomas
2000-07-01
Applying static light scattering experiments, we characterize colloidal particles that are used as model hard-sphere systems in experiments investigating their crystallization kinetics. The particles comprise of a compact core of poly(methyl methacrylate) and short polymer hairs grafted onto the surface. We use a contrast variation procedure to determine the refractive index variation within the particles and observe that one component of the binary mixture used as a solvent penetrates the particles and masks completely the small polymer hairs. Making use of the determined refractive index variation, we obtain the average particle radius and its polydispersity from measurements of the particle form factor close to its minimae. The scattered intensity has been corrected carefully for multiple scattering contributions applying dynamic light scattering measurements with multiple scattering decorrelation. We obtain a mean particle radius of R¯=435+/-4 nm and a polydispersity of σ=2.5%, a resolution that has not been achieved with light scattering experiments before.
ADDITIVITY ASSESSMENT OF TRIHALOMETHANE MIXTURES BY PROPORTIONAL RESPONSE ADDITION
If additivity is known or assumed, the toxicity of a chemical mixture may be predicted from the dose response curves of the individual chemicals comprising the mixture. As single chemical data are abundant and mixture data sparse, mixture risk methods that utilize single chemical...
An accurate equation of state for fluids of linear homonuclear fused hard spheres
NASA Astrophysics Data System (ADS)
Maeso, M. J.; Solana, J. R.
1994-12-01
A model relating the equation of state of linear homonuclear fused hard sphere fluids to the equation of state of the hard sphere fluid is derived from the pressure equation. The equation of state reproduces simulation data practically within their accuracy for diatomic and linear triatomic hard molecular fluids.
Physics of Hard Spheres Experiment (PhaSE) or "Making Jello in Space"
NASA Technical Reports Server (NTRS)
Ling, Jerri S.; Doherty, Michael P.
1998-01-01
The Physics of Hard Spheres Experiment (PHaSE) is a highly successful experiment that flew aboard two shuttle missions to study the transitions involved in the formation of jellolike colloidal crystals in a microgravity environment. A colloidal suspension, or colloid, consists of fine particles, often having complex interactions, suspended in a liquid. Paint, ink, and milk are examples of colloids found in everyday life. In low Earth orbit, the effective force of gravity is thousands of times less than at the Earth's surface. This provides researchers a way to conduct experiments that cannot be adequately performed in an Earth-gravity environment. In microgravity, colloidal particles freely interact without the complications of settling that occur in normal gravity on Earth. If the particle interactions within these colloidal suspensions could be predicted and accurately modeled, they could provide the key to understanding fundamental problems in condensed matter physics and could help make possible the development of wonderful new "designer" materials. Industries that make semiconductors, electro-optics, ceramics, and composites are just a few that may benefit from this knowledge. Atomic interactions determine the physical properties (e.g., weight, color, and hardness) of ordinary matter. PHaSE uses colloidal suspensions of microscopic solid plastic spheres to model the behavior of atomic interactions. When uniformly sized hard spheres suspended in a fluid reach a certain concentration (volume fraction), the particle-fluid mixture changes from a disordered fluid state, in which the spheres are randomly organized, to an ordered "crystalline" state, in which they are structured periodically. The thermal energy of the spheres causes them to form ordered arrays, analogous to crystals. Seven of the eight PHaSE samples ranged in volume fraction from 0.483 to 0.624 to cover the range of interest, while one sample, having a concentration of 0.019, was included for
Local order variations in confined hard-sphere fluids
NASA Astrophysics Data System (ADS)
Nygârd, Kim; Sarman, Sten; Kjellander, Roland
2013-10-01
Pair distributions of fluids confined between two surfaces at close distance are of fundamental importance for a variety of physical, chemical, and biological phenomena, such as interactions between macromolecules in solution, surface forces, and diffusion in narrow pores. However, in contrast to bulk fluids, properties of inhomogeneous fluids are seldom studied at the pair-distribution level. Motivated by recent experimental advances in determining anisotropic structure factors of confined fluids, we analyze theoretically the underlying anisotropic pair distributions of the archetypical hard-sphere fluid confined between two parallel hard surfaces using first-principles statistical mechanics of inhomogeneous fluids. For this purpose, we introduce an experimentally accessible ensemble-averaged local density correlation function and study its behavior as a function of confining slit width. Upon increasing the distance between the confining surfaces, we observe an alternating sequence of strongly anisotropic versus more isotropic local order. The latter is due to packing frustration of the spherical particles. This observation highlights the importance of studying inhomogeneous fluids at the pair-distribution level.
Densest packings of hard spheres in a cylinder
NASA Astrophysics Data System (ADS)
Fu, Lin; Steinhardt, William; Zhao, Hao; Socolar, Joshua; Charbonneau, Patrick
Densely packing hard spheres (HS) within a cylinder is remarkably complex. Little is known about the densest achievable packings when the cylinder diameter, D, is larger than 2.85 times the sphere diameter, s. Here, we extend the identification of the densest packings up to D = 4.00s by adapting Torquato-Jiao's adaptive-shrinking-cell formulation and sequential-linear-programming technique to this geometry. We identify 17 new structures, almost all of them chiral. Beyond D, approx2.85s , most of the structures consist of an outer shell and of an inner core that compete for being close packed. In some cases the shell adopts a periodic configuration that is optimal and the stacking of core spheres within it is quasiperiodic, while in other cases a direct interplay between the two layers is observed. For some packings the very distinction between the core and shell vanishes, which results in exotic geometries, including some that are a three-dimensional extension of packing hard disks in a circle. In order to connect our results with experiments on comparable systems, we also consider the ease with which these structures assemble. Using kinetic Monte Carlo simulations, we find that some of the structures promtply assemble while others simply do not.
Velocity and energy distributions in microcanonical ensembles of hard spheres
NASA Astrophysics Data System (ADS)
Scalas, Enrico; Gabriel, Adrian T.; Martin, Edgar; Germano, Guido
2015-08-01
In a microcanonical ensemble (constant N V E , hard reflecting walls) and in a molecular dynamics ensemble (constant N V E PG , periodic boundary conditions) with a number N of smooth elastic hard spheres in a d -dimensional volume V having a total energy E , a total momentum P , and an overall center of mass position G , the individual velocity components, velocity moduli, and energies have transformed beta distributions with different arguments and shape parameters depending on d , N , E , the boundary conditions, and possible symmetries in the initial conditions. This can be shown marginalizing the joint distribution of individual energies, which is a symmetric Dirichlet distribution. In the thermodynamic limit the beta distributions converge to gamma distributions with different arguments and shape or scale parameters, corresponding respectively to the Gaussian, i.e., Maxwell-Boltzmann, Maxwell, and Boltzmann or Boltzmann-Gibbs distribution. These analytical results agree with molecular dynamics and Monte Carlo simulations with different numbers of hard disks or spheres and hard reflecting walls or periodic boundary conditions. The agreement is perfect with our Monte Carlo algorithm, which acts only on velocities independently of positions with the collision versor sampled uniformly on a unit half sphere in d dimensions, while slight deviations appear with our molecular dynamics simulations for the smallest values of N .
Avalanches mediate crystallization in a hard-sphere glass.
Sanz, Eduardo; Valeriani, Chantal; Zaccarelli, Emanuela; Poon, Wilson C K; Cates, Michael E; Pusey, Peter N
2014-01-01
By molecular-dynamics simulations, we have studied the devitrification (or crystallization) of aged hard-sphere glasses. First, we find that the dynamics of the particles are intermittent: Quiescent periods, when the particles simply "rattle" in their nearest-neighbor cages, are interrupted by abrupt "avalanches," where a subset of particles undergo large rearrangements. Second, we find that crystallization is associated with these avalanches but that the connection is not straightforward. The amount of crystal in the system increases during an avalanche, but most of the particles that become crystalline are different from those involved in the avalanche. Third, the occurrence of the avalanches is a largely stochastic process. Randomizing the velocities of the particles at any time during the simulation leads to a different subsequent series of avalanches. The spatial distribution of avalanching particles appears random, although correlations are found among avalanche initiation events. By contrast, we find that crystallization tends to take place in regions that already show incipient local order.
Classical growth of hard-sphere colloidal crystals
NASA Astrophysics Data System (ADS)
Ackerson, Bruce J.; Schätzel, Klaus
1995-12-01
The classical theory of nucleation and growth of crystals is examined for concentrated suspensions of hard-sphere colloidal particles. The work of Russel is modified, extended, and evaluated, explicitly. Specifically, the Wilson-Frenkel growth law is modified to include the Gibbs-Thomson effect and is evaluated numerically. The results demonstrate that there is a critical nucleus radius below which crystal nuclei will not grow. A kinetic coefficient determines the maximum growth velocity possible. For large values of this coefficient, quenches to densities above the melting density show interface limited growth with the crystal radius increasing linearly with time. For quenches into the coexistence region the growth is diffusion limited, with the crystal radius increasing as the square root of elapsed time. Smaller values of the kinetic coefficient produce long lived transients which evidence quasi-power-law growth behavior with exponents between one half and unity. The smaller kinetic coefficients also lead to larger crystal compression. Crystal compression and nonclassical exponents have been observed in recent experiments. The theory is compared to data from small angle scattering studies of nucleation and growth in suspensions of hard colloidal spheres. The experimental nucleation rate is much larger than the theoretically predicted value as the freezing point is approached but shows better agreement near the melting point. The crystal growth with time is described reasonably well by the theory and suggests that the experiments are observing long lived transient rather than asymptotic growth behavior. (c) 1995 The American Physical Society
Universal jamming phase diagram in the hard-sphere limit.
Haxton, Thomas K; Schmiedeberg, Michael; Liu, Andrea J
2011-03-01
We present a new formulation of the jamming phase diagram for a class of glass-forming fluids consisting of spheres interacting via finite-ranged repulsions at temperature T, packing fraction ϕ or pressure p, and applied shear stress Σ. We argue that the natural choice of axes for the phase diagram are the dimensionless quantities T/pσ³, pσ³/ε, and Σ/p, where T is the temperature, p is the pressure, Σ is the stress, σ is the sphere diameter, ε is the interaction energy scale, and m is the sphere mass. We demonstrate that the phase diagram is universal at low pσ³/ε; at low pressure, observables such as the relaxation time are insensitive to details of the interaction potential and collapse onto the values for hard spheres, provided the observables are nondimensionalized by the pressure. We determine the shape of the jamming surface in the jamming phase diagram, organize previous results in relation to the jamming phase diagram, and discuss the significance of various limits.
Apparent wall slip in non-Brownian hard-sphere suspensions.
Korhonen, Marko; Mohtaschemi, Mikael; Puisto, Antti; Illa, Xavier; Alava, Mikko J
2015-05-01
We analyze apparent wall slip, the reduction of particle concentration near the wall, in hard-sphere suspensions at concentrations well below the jamming limit utilizing a continuum level diffusion model. The approach extends a constitutive equation proposed earlier with two additional potentials describing the effects of gravitation and wall-particle repulsion. We find that although both mechanisms are shear independent by nature, due to the shear-rate-dependent counter-balancing particle migration fluxes, the resulting net effect is non-linearly shear dependent, causing larger slip at small shear rates. In effect, this shows up in the classically measured flow curves as a mild shear thickening regime at the transition from small to intermediate shear rates. PMID:25998170
A density functional model for the binary crystal of hard spheres with vacancies.
Singh, Sunil P; Das, Shankar P
2007-02-14
We study the stability of a binary mixture of hard spheres in the crystalline state in which a small fraction of lattice sites in the solid structure are vacant. The optimum vacancy concentration is obtained by minimizing the free energy of the inhomogeneous solid state. We use the modified weighted density functional approximation to compute the free energy. The necessary input for the theory is the thermodynamic properties of the homogeneous state of the mixture and is obtained from the solutions of the corresponding Percus-Yevick integral equations for the binary system. We compute the free energy for the crystal having two kinds of ordered structures in which (i) both the species lie in a disordered manner on a single face-centered-cubic lattice and (ii) each of the two species lie on a separate cubic lattice. Our theoretical model obtains equilibrium vacancy fraction of O(10(-5)) near the freezing point in both cases. The vacancy concentration decreases with the increase of density in both cases.
Avalanche mediated devitrification in a glass of pseudo hard-spheres
NASA Astrophysics Data System (ADS)
Rosales-Pelaez, P.; Montero de Hijes, P.; Sanz, E.; Valeriani, C.
2016-09-01
By means of molecular dynamics we analyse several aspects of the avalanche-mediated mechanism for glass crystallization recently reported for hard sphere glasses (Sanz et al 2014 Proc. Natl Acad. Sci. 111 75). To investigate the role of inter-particle interaction softness on the devitrification path we use a continuous version of the hard-sphere potential: the pseudo-hard sphere potential (Jover et al 2012 J. Chem. Phys. 137 144505). We observe the same crystallization mechanism as in hard spheres. However, pseudo-hard sphere glasses crystallise earlier for a given density because the development of avalanches is eased by the small degree of overlapping allowed. We analyse the impact of density on the devitrification mechanism. When increasing the density, the avalanche mechanism becomes more evident and crystallisation is retarded due to a decrease of the avalanche emergence likelihood. To conclude, the observed avalanche-mediated mechanism and its density dependence do not substantially change with the employed simulation ensemble (constant volume versus constant pressure).
Tunable long range forces mediated by self-propelled colloidal hard spheres.
Ni, Ran; Cohen Stuart, Martien A; Bolhuis, Peter G
2015-01-01
Using Brownian dynamics simulations, we systematically study the effective interaction between two parallel hard walls in a 2D suspension of self-propelled (active) colloidal hard spheres, and we find that the effective force between two hard walls can be tuned from a long range repulsion into a long range attraction by changing the density of active particles. At relatively high densities, the active hard spheres can form a dynamic crystalline bridge, which induces a strong oscillating long range dynamic wetting repulsion between the walls. With decreasing density, the dynamic bridge gradually breaks, and an intriguing long range dynamic depletion attraction arises. A similar effect occurs in a quasi-2D suspension of self-propelled colloidal hard spheres by changing the height of the confinement. Our results open up new possibilities to manipulate the motion and assembly of microscopic objects by using active matter. PMID:25615510
Tunable Long Range Forces Mediated by Self-Propelled Colloidal Hard Spheres
NASA Astrophysics Data System (ADS)
Ni, Ran; Cohen Stuart, Martien A.; Bolhuis, Peter G.
2015-01-01
Using Brownian dynamics simulations, we systematically study the effective interaction between two parallel hard walls in a 2D suspension of self-propelled (active) colloidal hard spheres, and we find that the effective force between two hard walls can be tuned from a long range repulsion into a long range attraction by changing the density of active particles. At relatively high densities, the active hard spheres can form a dynamic crystalline bridge, which induces a strong oscillating long range dynamic wetting repulsion between the walls. With decreasing density, the dynamic bridge gradually breaks, and an intriguing long range dynamic depletion attraction arises. A similar effect occurs in a quasi-2D suspension of self-propelled colloidal hard spheres by changing the height of the confinement. Our results open up new possibilities to manipulate the motion and assembly of microscopic objects by using active matter.
Stochastic Hard-Sphere Dynamics for Hydrodynamics of Non-Ideal Fluids
Donev, A; Alder, B J; Garcia, A L
2008-02-26
A novel stochastic fluid model is proposed with a nonideal structure factor consistent with compressibility, and adjustable transport coefficients. This stochastic hard-sphere dynamics (SHSD) algorithm is a modification of the direct simulation Monte Carlo algorithm and has several computational advantages over event-driven hard-sphere molecular dynamics. Surprisingly, SHSD results in an equation of state and a pair correlation function identical to that of a deterministic Hamiltonian system of penetrable spheres interacting with linear core pair potentials. The fluctuating hydrodynamic behavior of the SHSD fluid is verified for the Brownian motion of a nanoparticle suspended in a compressible solvent.
NASA Astrophysics Data System (ADS)
Henderson, D.; Plischke, M.
1987-04-01
Starting from well-known relations for the derivatives of the radial distribution functions of a mixture of fluids, and allowing the diameter of one particle to become exceedingly large, three sum rules for a fluid with density inhomogeneities are obtained. None of these sum rules are new. However, the relation between the Lovett-Mou-Buff-Wertheim and the Born-Green hierarchy of equations seems not well known. The accuracy of a recent parametrization of the pair correlation of hard spheres near a hard wall and of the solutions of the Percus-Yevick and hypernetted-chain equation for this same function are examined by determination of how well these functions satisfy these sum rules and the accuracy of their surface tension, calculated from the sum rule of Triezenberg and Zwanzig. Generally speaking, the Percus-Yevick theory gives the best results and the hypernetted-chain approximation gives the worst results with the parametrization being intermediate.
Equations of state of freely jointed hard-sphere chain fluids: Theory
Stell, G.; Lin, C.; Kalyuzhnyi, Y.V.
1999-03-01
Using the analytical solution of a multidensity integral equation solved in our previous papers [J. Chem. Phys. {bold 108}, 6513, 6525 (1998)], we derive two compressibility and two virial equations of state (EOS) for freely jointed hard-sphere chain fluids on the basis of the approximations defined by the polymer Percus{endash}Yevick (PPY) closure and of the PPY ideal-chain closure for the integral equations. We also extend a version of first-order thermodynamic perturbation theory to polymers, using a dimer fluid as the reference system, to treat mixtures of heteronuclear chain fluids and polymer solutions; the structural information of the dimer fluid is obtained from the PPY ideal-chain approximation in the complete-association limit. The attractive forces between monomers of chain molecules are treated using simple perturbation theory. We find that the compressibility EOS derived on the basis of the PPY approximation subject to the chain-connectivity condition reduces to the compressibility EOS based upon the PPY ideal-chain approximation in the complete-association limit, which is also equivalent to the EOS derived by Chiew [Mol. Phys. {bold 70}, 129 (1990)] and to the EOS derived by Kalyuzhnyi and Cummings [J. Chem. Phys. {bold 105}, 2011 (1996)]. On the other hand, the virial EOS derived on the basis of the PPY ideal-chain approximation coincides with Attard{close_quote}s virial EOS [J. Chem. Phys. {bold 102}, 5411 (1995)] only in the zero-density limit. The advantages in numerical implementation of the EOS presented in this work are also discussed, but a full quantitative assessment of our results and a detailed numerical comparison among them are made in a companion paper, as is comparison with available simulation results. {copyright} {ital 1999 American Institute of Physics.}
Stochastic interactions of two Brownian hard spheres in the presence of depletants
Karzar-Jeddi, Mehdi; Fan, Tai-Hsi; Tuinier, Remco; Taniguchi, Takashi
2014-06-07
A quantitative analysis is presented for the stochastic interactions of a pair of Brownian hard spheres in non-adsorbing polymer solutions. The hard spheres are hypothetically trapped by optical tweezers and allowed for random motion near the trapped positions. The investigation focuses on the long-time correlated Brownian motion. The mobility tensor altered by the polymer depletion effect is computed by the boundary integral method, and the corresponding random displacement is determined by the fluctuation-dissipation theorem. From our computations it follows that the presence of depletion layers around the hard spheres has a significant effect on the hydrodynamic interactions and particle dynamics as compared to pure solvent and uniform polymer solution cases. The probability distribution functions of random walks of the two interacting hard spheres that are trapped clearly shift due to the polymer depletion effect. The results show that the reduction of the viscosity in the depletion layers around the spheres and the entropic force due to the overlapping of depletion zones have a significant influence on the correlated Brownian interactions.
Stochastic interactions of two Brownian hard spheres in the presence of depletants.
Karzar-Jeddi, Mehdi; Tuinier, Remco; Taniguchi, Takashi; Fan, Tai-Hsi
2014-06-01
A quantitative analysis is presented for the stochastic interactions of a pair of Brownian hard spheres in non-adsorbing polymer solutions. The hard spheres are hypothetically trapped by optical tweezers and allowed for random motion near the trapped positions. The investigation focuses on the long-time correlated Brownian motion. The mobility tensor altered by the polymer depletion effect is computed by the boundary integral method, and the corresponding random displacement is determined by the fluctuation-dissipation theorem. From our computations it follows that the presence of depletion layers around the hard spheres has a significant effect on the hydrodynamic interactions and particle dynamics as compared to pure solvent and uniform polymer solution cases. The probability distribution functions of random walks of the two interacting hard spheres that are trapped clearly shift due to the polymer depletion effect. The results show that the reduction of the viscosity in the depletion layers around the spheres and the entropic force due to the overlapping of depletion zones have a significant influence on the correlated Brownian interactions. PMID:24908040
Density Functional Approximation for Non-Hard Sphere Fluids Subjected to External Fields
NASA Astrophysics Data System (ADS)
Zhou, Shiqi
A theoretical way is proposed, by which any hard sphere density functional approximation (DFA) can be applied to non-hard sphere fluids for the calculation of density profile in the framework of density functional theory (DFT). Used as examples, the present formalism is combined respectively with two recently proposed hard sphere DFAs to predict the density profile of Lennard-Jones (LJ) fluid, hard core square well (SW) fluid and penetrable potenial fluid subjected to diverse external fields. Extensive comparison between theoretical predictions and corresponding simulation results shows that the present theoretical way, when combined with an accurate hard sphere DFA, can perform well for calculating the density profile of the non-uniform fluids of the above mentioned potentials. Concretely speaking, for LJ and hard core SW fluid, even a less accurate FEDFA is sufficient, while for extreme potential such as the penetrable potenial, a more accurate adjustable parameter free version of LTDFA is needed to combine with the present theoretical way to predict density profile satisfactorily. The advantage of the proposed theoretical way is that the resultant DFA is applicable to both subcritical and supercritical temperature cases, thereby overcoming the disadvantages of previous two categories of DFT approach.
Note: equation of state and the freezing point in the hard-sphere model.
Robles, Miguel; López de Haro, Mariano; Santos, Andrés
2014-04-01
The merits of different analytical equations of state for the hard-sphere system with respect to the recently computed high-accuracy value of the freezing-point packing fraction are assessed. It is found that the Carnahan-Starling-Kolafa and the branch-point approximant equations of state yield the best performance.
The influence of third-order interactions on the density profile of associating hard spheres
NASA Astrophysics Data System (ADS)
Henderson, D.; Sokolowski, S.; Zagorski, R.; Trokhymchuk, A.
Canonical ensemble Monte Carlo simulations and the non-uniform Percus-Yevick (NPY) equation for the local density are used to study the influence of surface mediated thirdorder interactions on the adsorption of associating hard spheres on a hard wall. A comparison of the NPY density profiles with the computer simulations data indicates that this approximation predicts the fluid structure reasonably well.
Solano-Altamirano, J M; Goldman, Saul
2015-12-01
We determined the total system elastic Helmholtz free energy, under the constraints of constant temperature and volume, for systems comprised of one or more perfectly bonded hard spherical inclusions (i.e. "hard spheres") embedded in a finite spherical elastic solid. Dirichlet boundary conditions were applied both at the surface(s) of the hard spheres, and at the outer surface of the elastic solid. The boundary conditions at the surface of the spheres were used to describe the rigid displacements of the spheres, relative to their initial location(s) in the unstressed initial state. These displacements, together with the initial positions, provided the final shape of the strained elastic solid. The boundary conditions at the outer surface of the elastic medium were used to ensure constancy of the system volume. We determined the strain and stress tensors numerically, using a method that combines the Neuber-Papkovich spherical harmonic decomposition, the Schwartz alternating method, and Least-squares for determining the spherical harmonic expansion coefficients. The total system elastic Helmholtz free energy was determined by numerically integrating the elastic Helmholtz free energy density over the volume of the elastic solid, either by a quadrature, or a Monte Carlo method, or both. Depending on the initial position of the hard sphere(s) (or equivalently, the shape of the un-deformed stress-free elastic solid), and the displacements, either stationary or non-stationary Helmholtz free energy minima were found. The non-stationary minima, which involved the hard spheres nearly in contact with one another, corresponded to lower Helmholtz free energies, than did the stationary minima, for which the hard spheres were further away from one another. PMID:26701708
The microstructures of cold dense systems as informed by hard sphere models and optimal packings
NASA Astrophysics Data System (ADS)
Hopkins, Adam Bayne
Sphere packings, or arrangements of "billiard balls" of various sizes that never overlap, are especially informative and broadly applicable models. In particular, a hard sphere model describes the important foundational case where potential energy due to attractive and repulsive forces is not present, meaning that entropy dominates the system's free energy. Sphere packings have been widely employed in chemistry, materials science, physics and biology to model a vast range of materials including concrete, rocket fuel, proteins, liquids and solid metals, to name but a few. Despite their richness and broad applicability, many questions about fundamental sphere packings remain unanswered. For example, what are the densest packings of identical three-dimensional spheres within certain defined containers? What are the densest packings of binary spheres (spheres of two different sizes) in three-dimensional Euclidean space R3 ? The answers to these two questions are important in condensed matter physics and solid-state chemistry. The former is important to the theory of nucleation in supercooled liquids and the latter in terms of studying the structure and stability of atomic and molecular alloys. The answers to both questions are useful when studying the targeted self-assembly of colloidal nanostructures. In this dissertation, putatively optimal answers to both of these questions are provided, and the applications of these findings are discussed. The methods developed to provide these answers, novel algorithms combining sequential linear and nonlinear programming techniques with targeted stochastic searches of conguration space, are also discussed. In addition, connections between the realizability of pair correlation functions and optimal sphere packings are studied, and mathematical proofs are presented concerning the characteristics of both locally and globally maximally dense structures in arbitrary dimension d. Finally, surprising and unexpected findings are
The Dynamics of Disorder-Order Transition in Hard Sphere Colloidal Dispersions
NASA Technical Reports Server (NTRS)
Chaikin, Paul M.; Zhu, Jixiang; Cheng, Zhengdong; Phan, See-Eng; Russel, William B.; Lant, Christian T.; Doherty, Michael P.; Meyer, William V.; Rogers, Richard; Cannell, D. S.; Ottewill, R. H.
1998-01-01
The Physics of Hard Spheres Experiment (PHaSE) seeks a complete understanding of the entropically driven disorder-order transition in hard sphere colloidal dispersions. The light scattering instrument designed for flight collects Bragg and low angle light scattering in the forward direction via a CCD camera and performs conventional static and dynamic light scattering at 10-160 deg. through fiber optic cables. Here we report on the kinetics of nucleation and growth extracted from time-resolved Bragg images and measurements of the elastic modulus of crystalline phases obtained by monitoring resonant responses to sinusoidal forcing through dynamic light scattering. Preliminary analysis of the former indicates a significant difference from measurements on the ground, while the latter confirms nicely laboratory experiments with the same instrument and predictions from computer simulations.
Chemical-potential route: a hidden Percus-Yevick equation of state for hard spheres.
Santos, Andrés
2012-09-21
The chemical potential of a hard-sphere fluid can be expressed in terms of the contact value of the radial distribution function of a solute particle with a diameter varying from zero to that of the solvent particles. Exploiting the explicit knowledge of such a contact value within the Percus-Yevick theory, and using standard thermodynamic relations, a hitherto unknown Percus-Yevick equation of state, p/ρk(B)T = -(9/η) ln(1-η)-(16-31η)/2(1-η)(2), is unveiled. This equation of state turns out to be better than the one obtained from the conventional virial route. Interpolations between the chemical-potential and compressibility routes are shown to be more accurate than the widely used Carnahan-Starling equation of state. The extension to polydisperse hard-sphere systems is also presented.
Model energy landscapes of low-temperature fluids: Dipolar hard spheres.
Matyushov, Dmitry V
2007-07-01
An analytical model of non-Gaussian energy landscape of low-temperature fluids is developed based on the thermodynamics of the fluid of dipolar hard spheres. The entire excitation profile of the liquid, from the high-temperature liquid to the point of ideal-glass transition, has been obtained from Monte Carlo simulations. The fluid of dipolar hard spheres loses stability close to the point of ideal-glass transition transforming via a first-order transition into a columnar liquid phase of dipolar chains locally arranged in a body-centered-tetragonal order. Significant non-Gaussianity of the energy landscape is responsible for narrowing of the distribution of potential energies and energies of inherent structures with decreasing temperature. We suggest that the proposed functionality of the enumeration function is widely applicable to both polar and nonpolar low-temperature liquids.
Newman, Hugh D.; Yethiraj, Anand
2015-01-01
In this work, we use structure and dynamics in sedimentation equilibrium, in the presence of gravity, to examine, via confocal microscopy, a Brownian colloidal system in the presence of an external electric field. The zero field equation of state (EOS) is hard sphere without any re-scaling of particle size, and the hydrodynamic corrections to the long-time self-diffusion coefficient are quantitatively consistent with the expected value for hard spheres. Care is taken to ensure that both the dimensionless gravitational energy, which is equivalent to a Peclet number Peg, and dipolar strength Λ are of order unity. In the presence of an external electric field, anisotropic chain-chain clusters form; this cluster formation manifests itself with the appearance of a plateau in the diffusion coefficient when the dimensionless dipolar strength Λ ~ 1. The structure and dynamics of this chain-chain cluster state is examined for a monodisperse system for two particle sizes. PMID:26323363
Pizio; Trokhymchuk; Henderson; Labik
1997-07-01
A model of hard spheres adsorbed in disordered porous media is studied using the associative replica Ornstein-Zernike (ROZ) equations. Extending previous studies of adsorption in a hard sphere matrices, we investigate a polymerized matrix. We consider an associating fluid of hard spheres with two intracore attractive sites per particle; consequently chains consisting of overlapping hard spheres can be formed due to the chemical association. This is the generalization of the model with sites on the surface of Wertheim that has been studied in the bulk by Chang and Sandler. The matrix structure is obtained in the polymer Percus-Yevick approximation. We solve the ROZ equations in the associative hypernetted chain approximation. The pair distribution functions, the fluid compressibility, the equation of state and chemical potential of the adsorbed fluid are obtained and discussed. It is shown that the adsorption of a hard sphere fluid in a matrix at given density, but consisting of longer chains of overlapping hard spheres, is higher than the adsorption of this fluid in a hard sphere matrix.
New closed virial equation of state for hard-sphere fluids.
Tian, Jianxiang; Gui, Yuanxing; Mulero, Angel
2010-10-28
A new closed virial equation of state of hard-sphere fluids is proposed which reproduces the calculated or estimated values of the first 16 virial coefficients and at the same time gives very good accuracy when compared with computer simulation data for the compressibility factor over the entire fluid range, as well as having a pole at the correct closest packing density. PMID:20883000
NASA Astrophysics Data System (ADS)
van Megen, W.
2006-01-01
Mean-squared displacements (MSDs) of colloidal fluids of hard spheres are analyzed in terms of a random walk, an analysis which assumes that the process of structural relaxation among the particles can be described in terms of thermally driven memoryless encounters. For the colloidal fluid in thermodynamic equilibrium the magnitude of the stretching of the MSD is able to be reconciled by a bias in the walk. This description fails for the under-cooled colloidal fluid.
Diffusion and structure of a quasi-one-dimensional hard-sphere fluid
NASA Astrophysics Data System (ADS)
Lin, Binhua; Lee, Ji Hwan; Cui, Bianxiao
2001-03-01
We report the results of an experimental study of a quasi-one-dimensional hard-sphere fluid. The system consists of uncharged Si colloidal spheres confined in long, uncorrelated 1D-channels whose narrow width forbids mutual passage of spheres along the channel. By tracking the trajectories of the spheres using digital video microscopy, we studied the diffusion and structure of the system as a function of the density of the fluid. Our results show that the behavior of the spheres in self-diffusion is changed gradually from Fickian to non-Fickian near the onset of the collision between the spheres, indicating the correlation between the collision of the hard-spheres and the change in diffusion mechanism. At high density, the self-part of the van Hove function of the system is no longer a Gaussian distribution but a Poisson distribution which can be interpreted using a hydrodynamic analysis for effective wall-drag effect. The pair distribution function of the system can be explained by an analytical expression for a 1D hard-sphere fluid [1]. [1] Y. Rosenfeld, M. Schmidt, H. Lowen and P. Tarazona, Phys. Rev. E 55, 4245 (1997).
Tunable long range forces mediated by self-propelled colloidal hard spheres
NASA Astrophysics Data System (ADS)
Ni, Ran; Cohen Stuart, Martien; Bolhuis, Peter
2015-03-01
Most colloidal interactions can be tuned by changing properties of the medium. Here we show that activating colloidal particles with random self-propulsion can induce giant effective interactions between large objects immersed in such a suspension. Using Brownian dynamics simulations we find that the effective force between two hard walls in a 2D suspension of self-propelled (active) colloidal hard spheres can be tuned from a long range repulsion into a long range attraction by changing the active particle density. At relatively high densities, the active hard spheres can form a dynamic crystalline bridge, which induces a strong oscillating long range dynamic wetting repulsion between the walls. With decreasing density, the dynamic bridge gradually breaks, and an intriguing long range dynamic depletion attraction arises. A similar effect occurs in a quasi-2D suspension of self-propelled colloidal hard spheres by changing the height of the confinement. Our results open up new possibilities to manipulate the motion and assembly of microscopic objects by using active matter.
Thermodynamics of dipolar hard spheres with low-to-intermediate coupling constants.
Elfimova, Ekaterina A; Ivanov, Alexey O; Camp, Philip J
2012-08-01
The thermodynamic properties of the dipolar hard-sphere fluid are studied using theory and simulation. A new theory is derived using a convenient mathematical approximation for the Helmholtz free energy relative to that for the hard-sphere fluid. The approximation is designed to give the correct low-density virial expansion. New theoretical and numerical results for the fourth virial coefficient are given. Predictions of thermodynamic functions for dipolar coupling constants λ=1 and 2 show excellent agreement with simulation results, even at the highest value of the particle volume fraction φ. For higher values of λ, there are deviations at high volume fractions, but the correct low-density behavior is retained. The theory is compared critically against the established thermodynamic perturbation theory; it gives significant improvements at low densities and is more convenient in terms of the required numerics. Dipolar hard spheres provide a basic model for ferrofluids, and the theory is accurate for typical experimental parameters λ
NASA Astrophysics Data System (ADS)
Qiao, Yu; Liu, Xuejiao; Chen, Minxin; Lu, Benzhuo
2016-04-01
The hard sphere repulsion among ions can be considered in the Poisson-Nernst-Planck (PNP) equations by combining the fundamental measure theory (FMT). To reduce the nonlocal computational complexity in 3D simulation of biological systems, a local approximation of FMT is derived, which forms a local hard sphere PNP (LHSPNP) model. In the derivation, the excess chemical potential from hard sphere repulsion is obtained with the FMT and has six integration components. For the integrands and weighted densities in each component, Taylor expansions are performed and the lowest order approximations are taken, which result in the final local hard sphere (LHS) excess chemical potential with four components. By plugging the LHS excess chemical potential into the ionic flux expression in the Nernst-Planck equation, the three dimensional LHSPNP is obtained. It is interestingly found that the essential part of free energy term of the previous size modified model (Borukhov et al. in Phys Rev Lett 79:435-438, 1997; Kilic et al. in Phys Rev E 75:021502, 2007; Lu and Zhou in Biophys J 100:2475-2485, 2011; Liu and Eisenberg in J Chem Phys 141:22D532, 2014) has a very similar form to one term of the LHS model, but LHSPNP has more additional terms accounting for size effects. Equation of state for one component homogeneous fluid is studied for the local hard sphere approximation of FMT and is proved to be exact for the first two virial coefficients, while the previous size modified model only presents the first virial coefficient accurately. To investigate the effects of LHS model and the competitions among different counterion species, numerical experiments are performed for the traditional PNP model, the LHSPNP model, the previous size modified PNP (SMPNP) model and the Monte Carlo simulation. It's observed that in steady state the LHSPNP results are quite different from the PNP results, but are close to the SMPNP results under a wide range of boundary conditions. Besides, in both
Kalyuzhnyi, Y.V. |; Lin, C.; Stell, G.
1998-04-01
We continue here our series of studies in which integral-equation theory is developed and used for the monomer-monomer correlation functions in a fluid of multicomponent freely jointed hard-sphere polymers. In this study our approach is based on Wertheim{close_quote}s polymer Percus{endash}Yevick (PPY) theory supplemented by the ideal-chain approximation; it can be regarded as a simplified version of Wertheim{close_quote}s four-density PPY approximation for associating fluids considered in the complete-association limit. The numerical procedure of this simplified theory is much easier than that of the original Wertheim{close_quote}s four-density PPY approximation, but the degree of accuracy is reduced. The theory can also be regarded as an extension of the PPY theory for the homonuclear polymer system proposed by Chang and Sandler [J. Chem. Phys. {bold 102}, 437 (1995)]. Their work is based upon a description of a system of hard-sphere monomers that associate into a polydisperse system of chains of prescribed mean length. Our theory instead directly describes a multicomponent system of associating monomers that form monodisperse chains of prescribed length upon complete association. An analytical solution of the PPY ideal-chain approximation for the general case of a multicomponent mixture of heteronuclear hard-sphere linear chain molecules is given. Its use is illustrated by numerical results for two models of copolymer fluids, a symmetrical diblock copolymer system, and an alternating copolymer system. The comparison with Monte Carlo simulations is given to gauge the accuracy of the theory. We find for the molecules we study here that predictions of our theory for heteronuclear chain systems have the same degree of accuracy as Chang and Sandler{close_quote}s theory for homonuclear chain systems. {copyright} {ital 1998 American Institute of Physics.}
NASA Astrophysics Data System (ADS)
Perera-Burgos, Jorge Adrián; Méndez-Alcaraz, José Miguel; Pérez-Ángel, Gabriel; Castañeda-Priego, Ramón
2016-09-01
Depletion forces are a particular class of effective interactions that have been mainly investigated in binary mixtures of hard-spheres in bulk. Although there are a few contributions that point toward the effects of confinement on the depletion potential, little is known about such entropic potentials in two-dimensional colloidal systems. From theoretical point of view, the problem resides in the fact that there is no general formulation of depletion forces in arbitrary dimensions and, typically, any approach that works well in three dimensions has to be reformulated for lower dimensionality. However, we have proposed a theoretical framework, based on the formalism of contraction of the description within the integral equations theory of simple liquids, to account for effective interactions in colloidal liquids, whose main feature is that it does not need to be readapted to the problem under consideration. We have also shown that such an approach allows one to determine the depletion pair potential in three-dimensional colloidal mixtures even near to the demixing transition, provided the bridge functions are sufficiently accurate to correctly describe the spatial correlation between colloids [E. López-Sánchez et al., J. Chem. Phys. 139, 104908 (2013)]. We here report an extensive analysis of the structure and the entropic potentials in binary mixtures of additive hard-disks. In particular, we show that the same functional form of the modified-Verlet closure relation used in three dimensions can be straightforwardly employed to obtain an accurate solution for two-dimensional colloidal mixtures in a wide range of packing fractions, molar fractions, and size asymmetries. Our theoretical results are explicitly compared with the ones obtained by means of event-driven molecular dynamics simulations and recent experimental results. Furthermore, to assess the accuracy of our predictions, the depletion potentials are used in an effective one-component model to reproduce
Perera-Burgos, Jorge Adrián; Méndez-Alcaraz, José Miguel; Pérez-Ángel, Gabriel; Castañeda-Priego, Ramón
2016-09-14
Depletion forces are a particular class of effective interactions that have been mainly investigated in binary mixtures of hard-spheres in bulk. Although there are a few contributions that point toward the effects of confinement on the depletion potential, little is known about such entropic potentials in two-dimensional colloidal systems. From theoretical point of view, the problem resides in the fact that there is no general formulation of depletion forces in arbitrary dimensions and, typically, any approach that works well in three dimensions has to be reformulated for lower dimensionality. However, we have proposed a theoretical framework, based on the formalism of contraction of the description within the integral equations theory of simple liquids, to account for effective interactions in colloidal liquids, whose main feature is that it does not need to be readapted to the problem under consideration. We have also shown that such an approach allows one to determine the depletion pair potential in three-dimensional colloidal mixtures even near to the demixing transition, provided the bridge functions are sufficiently accurate to correctly describe the spatial correlation between colloids [E. López-Sánchez et al., J. Chem. Phys. 139, 104908 (2013)]. We here report an extensive analysis of the structure and the entropic potentials in binary mixtures of additive hard-disks. In particular, we show that the same functional form of the modified-Verlet closure relation used in three dimensions can be straightforwardly employed to obtain an accurate solution for two-dimensional colloidal mixtures in a wide range of packing fractions, molar fractions, and size asymmetries. Our theoretical results are explicitly compared with the ones obtained by means of event-driven molecular dynamics simulations and recent experimental results. Furthermore, to assess the accuracy of our predictions, the depletion potentials are used in an effective one-component model to reproduce
Radial distribution function for hard spheres in fractal dimensions: A heuristic approximation
NASA Astrophysics Data System (ADS)
Santos, Andrés; de Haro, Mariano López
2016-06-01
Analytic approximations for the radial distribution function, the structure factor, and the equation of state of hard-core fluids in fractal dimension d (1 ≤d ≤3 ) are developed as heuristic interpolations from the knowledge of the exact and Percus-Yevick results for the hard-rod and hard-sphere fluids, respectively. In order to assess their value, such approximate results are compared with those of recent Monte Carlo simulations and numerical solutions of the Percus-Yevick equation for a fractal dimension [M. Heinen et al., Phys. Rev. Lett. 115, 097801 (2015), 10.1103/PhysRevLett.115.097801], a good agreement being observed.
Temperature Dependence of the Pairwise Association of Hard Spheres in Water
NASA Astrophysics Data System (ADS)
Graziano, Giuseppe
2016-02-01
It is shown that the Gibbs energy change associated with the formation of the contact-minimum configuration of two hard spheres in water becomes more negative on increasing the temperature, at 1 atm, by extending the geometric approach previously developed [G. Graziano, Chem. Phys. Lett. 499, 79 (2010)].. This is because the decrease in water accessible surface area accompanying the association leads to a gain in translational entropy of water molecules. The process is exothermic, due to the release of some water molecules from the hydration shell to the bulk. This water reorganization is characterized by a complete enthalpy-entropy compensation and does not affect the Gibbs energy change.
No evidence of gas-liquid coexistence in dipolar hard spheres.
Rovigatti, Lorenzo; Russo, John; Sciortino, Francesco
2011-12-01
We report accurate calculations of the particle density of states in the dipolar hard-sphere fluid. Implementing efficient and tailored Monte Carlo algorithms, we are able to explore, in equilibrium, the low temperature region where a phase separation between a dilute gas of chain ends and a high-density liquid of chain junctions has been predicted to occur. Our data clearly show that the density of states remains always single peaked, definitively excluding the possibility of critical phenomena in the investigated temperature and density region. The analysis of the low temperature configurations shows that at low densities particles preferentially self-assemble into closed rings, strongly suppressing the chain ends concentration.
Equilibrium Sampling of Hard Spheres up to the Jamming Density and Beyond
NASA Astrophysics Data System (ADS)
Berthier, Ludovic; Coslovich, Daniele; Ninarello, Andrea; Ozawa, Misaki
2016-06-01
We implement and optimize a particle-swap Monte Carlo algorithm that allows us to thermalize a polydisperse system of hard spheres up to unprecedentedly large volume fractions, where previous algorithms and experiments fail to equilibrate. We show that no glass singularity intervenes before the jamming density, which we independently determine through two distinct nonequilibrium protocols. We demonstrate that equilibrium fluid and nonequilibrium jammed states can have the same density, showing that the jamming transition cannot be the end point of the fluid branch.
Equilibrium Sampling of Hard Spheres up to the Jamming Density and Beyond.
Berthier, Ludovic; Coslovich, Daniele; Ninarello, Andrea; Ozawa, Misaki
2016-06-10
We implement and optimize a particle-swap Monte Carlo algorithm that allows us to thermalize a polydisperse system of hard spheres up to unprecedentedly large volume fractions, where previous algorithms and experiments fail to equilibrate. We show that no glass singularity intervenes before the jamming density, which we independently determine through two distinct nonequilibrium protocols. We demonstrate that equilibrium fluid and nonequilibrium jammed states can have the same density, showing that the jamming transition cannot be the end point of the fluid branch. PMID:27341260
Chemical Mixture Risk Assessment Additivity-Based Approaches
Powerpoint presentation includes additivity-based chemical mixture risk assessment methods. Basic concepts, theory and example calculations are included. Several slides discuss the use of "common adverse outcomes" in analyzing phthalate mixtures.
Fundamental measure density functional theory study of hard spheres solid-liquid interface
NASA Astrophysics Data System (ADS)
Warshavsky, Vadim
2005-03-01
Interfacial free energy is an important characteristic of solid-liquid interface as it is one of the crucial parameters in many formula of interface thermodynamics such the nucleation theory. Previously different aspects of crystal-melt interfaces were intensively studied with simulations [1,2,3], but theoretical studies with Density Functional Theories (DFT) are inconclusive [4,5]. In this report the structure of hard spheres fcc crystal-melt interfaces and the anisotropy of the interfacial free energies are studied using the Rosenfeld's Fundamental Measure DFT as such a functional leads to reliable coexistence results not only for the hard sphere system but also for the Lennard-Jones systems [6]. The parameters of interfacial density profile were calculated by a proper minimization procedure. For the equilibrium density profile the interfacial free energies were compared with simulation results. 1. R.L.Davidchak and B.B.Laird, Phys.Rev.Lett., 85, 4751(2000). 2. J.J. Hoyt, M. Asta and A. Karma, Phys.Rev.Lett., 86, 5530 (2001). 3. J.R.Morris and X.Song, J.Chem.Phys., 119, 3920 (2003). 4. W.A.Curtin, Phys.Rev.B, 39, 6775(1989). 5. R.Ohnesorge, H.Lowen, and H.Wagner, Phys.Rev.E, 50, 4801 (1994). 6. V.Warshavsky and X.Song, Phys.Rev.E, 69, 061113 (2004).
NASA Astrophysics Data System (ADS)
Hanifpour, M.; Francois, N.; Robins, V.; Kingston, A.; Vaez Allaei, S. M.; Saadatfar, M.
2015-06-01
Here we present an experimental and numerical investigation on the grain-scale geometrical and mechanical properties of partially crystallized structures made of macroscopic frictional grains. Crystallization is inevitable in arrangements of monosized hard spheres with packing densities exceeding Bernal's limiting density ϕBernal≈0.64 . We study packings of monosized hard spheres whose density spans over a wide range (0.59 <ϕ <0.72 ) . These experiments harness x-ray computed tomography, three-dimensional image analysis, and numerical simulations to access precisely the geometry and the 3D structure of internal forces within the sphere packings. We show that clear geometrical transitions coincide with modifications of the mechanical backbone of the packing both at the grain and global scale. Notably, two transitions are identified at ϕBernal≈0.64 and ϕc≈0.68 . These results provide insights on how geometrical and mechanical features at the grain scale conspire to yield partially crystallized structures that are mechanically stable.
The Physics of Hard Spheres Experiment on MSL-1: Required Measurements and Instrument Performance
NASA Technical Reports Server (NTRS)
Doherty, Michael P.; Lant, Christian T.; Ling, Jerri S.
1998-01-01
The Physics of HArd Spheres Experiment (PHaSE), one of NASA Lewis Research Center's first major light scattering experiments for microgravity research on complex fluids, flew on board the Space Shuttle's Microgravity Science Laboratory (MSL-1) in 1997. Using colloidal systems of various concentrations of micron-sized plastic spheres in a refractive index-matching fluid as test samples, illuminated by laser light during and after crystallization, investigations were conducted to measure the nucleation and growth rate of colloidal crystals as well as the structure, rheology, and dynamics of the equilibrium crystal. Together, these measurements support an enhanced understanding of the nature of the liquid-to-solid transition. Achievement of the science objectives required an accurate experimental determination of eight fundamental properties for the hard sphere colloidal samples. The instrument design met almost all of the original measurement requirements, but with compromise on the number of samples on which data were taken. The instrument performs 2-D Bragg and low angle scattering from 0.4 deg. to 60 deg., dynamic and single-channel static scattering from 10 deg. to 170 deg., rheology using fiber optics, and white light imaging of the sample. As a result, PHaSE provided a timely microgravity demonstration of critical light scattering measurement techniques and hardware concepts, while generating data already showing promise of interesting new scientific findings in the field of condensed matter physics.
NASA Astrophysics Data System (ADS)
Phan, See-Eng; Li, Min; Russel, William B.; Zhu, Jixiang; Chaikin, Paul M.; Lant, Chris T.
1999-08-01
We present measurements of the high-frequency shear modulus and dynamic viscosity for nonaqueous hard sphere colloidal crystals both in normal and microgravity environments. All experiments were performed on a multipurpose PHaSE instrument. For the rheological measurements, we detect the resonant response to oscillatory forcing with a dynamic light scattering scheme. The resonant response for colloidal crystals formed in normal and microgravity environments was similar, indicating that the bulk rheological properties are unaffected by differing crystal structure and crystallite size within the experimental error. Our high-frequency shear modulus seems reasonable, lying close to Frenkel and Ladd's predictions [Phys. Rev. Lett. 59, 1169 (1987)] for the static modulus of hard sphere crystals. Our high-frequency dynamic viscosity, on the other hand, seems high, exceeding Shikata and Pearson [J. Rheol. 38, 601 (1994)] and van der Werff et al.'s measurements [Phys. Rev. A 39, 795 (1989)] on the high-frequency dynamic viscosity for metastable fluids. The measurements are in the linear regime for the shear modulus but may not be for the dynamic viscosity as Frith et al. [Powder Technol. 51, 27 (1987)] report that the dynamic viscosity passes through a maximum with strain amplitude.
NASA Astrophysics Data System (ADS)
Wagner, Norman; Cwalina, Colin
2015-03-01
Reversible shear thickening is common in concentrated dispersions of Brownian hard-spheres at high shear rates. We confirm the existence of a well-defined colloidal shear-thickened state through experimental measurements of the shear stress and the first and second normal stress differences in the shear-thickened state as a function of the particle volume fraction for a model dispersion of near hard-spheres. The shear stress and normal stress differences are observed to grow linearly with the shear rate in the shear-thickened state and both normal stress differences are observed to be negative. Our experimental results show the shear-thickened state of colloidal dispersions can be described by three material properties--the shear viscosity and first and second normal stress difference coefficients--that are a function of the volume fraction. All three material properties are found to diverge with a power law scaling with the approach to maximum packing,which is found to be 0.54 +/- 0.01. We find the magnitude of the relative shear viscosity is greater than the magnitude of the dimensionless second normal stress difference, which is greater than the magnitude of the dimensionless first normal stress difference. These results are consistent with theoretical predictions for shear thickening by hydrocluster formation and quantitatively comparable to Stokesian Dynamics simulations. We further postulate and show that these material properties are consistent with those measured for non-Brownian suspensions.
Melting and crystallization of colloidal hard-sphere suspensions under shear.
Wu, Yu Ling; Derks, Didi; van Blaaderen, Alfons; Imhof, Arnout
2009-06-30
Shear-induced melting and crystallization were investigated by confocal microscopy in concentrated colloidal suspensions of hard-sphere-like particles. Both silica and polymethylmethacrylate suspensions were sheared with a constant rate in either a countertranslating parallel plate shear cell or a counterrotating cone-plate shear cell. These instruments make it possible to track particles undergoing shear for extended periods of time in a plane of zero velocity. Although on large scales, the flow profile deviated from linearity, the crystal flowed in an aligned sliding layer structure at low shear rates. Higher shear rates caused the crystal to shear melt, but, contrary to expectations, the transition was not sudden. Instead, although the overall order decreased with shear rate, this was due to an increase in the nucleation of localized domains that temporarily lost and regained their ordered structure. Even at shear rates that were considered to have melted the crystal as a whole, ordered regions kept showing up at times, giving rise to very large fluctuations in 2D bond-orientational order parameters. Low shear rates induced initially disordered suspensions to crystallize. This time, the order parameter increased gradually in time without large fluctuations, indicating that shear-induced crystallization of hard spheres does not proceed via a nucleation and growth mechanism. We conclude that the dynamics of melting and crystallization under shear differ dramatically from their counterparts in quiescent suspensions.
Physics of Hard Sphere Experiment: Scattering, Rheology and Microscopy Study of Colloidal Particles
NASA Technical Reports Server (NTRS)
Cheng, Z.-D.; Zhu, J.; Phan, S.-E.; Russel, W. B.; Chaikin, P. M.; Meyer, W. V.
2002-01-01
The Physics of Hard Sphere Experiment has two incarnations: the first as a scattering and rheology experiment on STS-83 and STS-94 and the second as a microscopy experiment to be performed in the future on LMM on the space station. Here we describe some of the quantitative and qualitative results from previous flights on the dynamics of crystallization in microgravity and especially the observed interaction of growing crystallites in the coexistance regime. To clarify rheological measurements we also present ground based experiments on the low shear rate viscosity and diffusion coefficient of several hard sphere experiments at high volume fraction. We also show how these experiments will be performed with confocal microscopy and laser tweezers in our lab and as preparation for the phAse II experiments on LMM. One of the main aims of the microscopy study will be the control of colloidal samples using an array of applied fields with an eye toward colloidal architectures. Temperature gradients, electric field gradients, laser tweezers and a variety of switchable imposed surface patterns are used toward this control.
Hanifpour, M; Francois, N; Robins, V; Kingston, A; Allaei, S M Vaez; Saadatfar, M
2015-06-01
Here we present an experimental and numerical investigation on the grain-scale geometrical and mechanical properties of partially crystallized structures made of macroscopic frictional grains. Crystallization is inevitable in arrangements of monosized hard spheres with packing densities exceeding Bernal's limiting density ϕ(Bernal)≈0.64. We study packings of monosized hard spheres whose density spans over a wide range (0.59<ϕ<0.72). These experiments harness x-ray computed tomography, three-dimensional image analysis, and numerical simulations to access precisely the geometry and the 3D structure of internal forces within the sphere packings. We show that clear geometrical transitions coincide with modifications of the mechanical backbone of the packing both at the grain and global scale. Notably, two transitions are identified at ϕ(Bernal)≈0.64 and ϕ(c)≈0.68. These results provide insights on how geometrical and mechanical features at the grain scale conspire to yield partially crystallized structures that are mechanically stable. PMID:26172700
Direct measurement of the free energy of aging hard sphere colloidal glasses.
Zargar, Rojman; Nienhuis, Bernard; Schall, Peter; Bonn, Daniel
2013-06-21
The nature of the glass transition is one of the most important unsolved problems in condensed matter physics. The difference between glasses and liquids is believed to be caused by very large free energy barriers for particle rearrangements; however, so far it has not been possible to confirm this experimentally. We provide the first quantitative determination of the free energy for an aging hard sphere colloidal glass. The determination of the free energy allows for a number of new insights in the glass transition, notably the quantification of the strong spatial and temporal heterogeneity in the free energy. A study of the local minima of the free energy reveals that the observed variations are directly related to the rearrangements of the particles. Our main finding is that the probability of particle rearrangements shows a power law dependence on the free energy changes associated with the rearrangements similar to the Gutenberg-Richter law in seismology. PMID:23829762
Helical Defect Packings in a Quasi-One-Dimensional System of Cylindrically Confined Hard Spheres
NASA Astrophysics Data System (ADS)
Yamchi, Mahdi Zaeifi; Bowles, Richard K.
2015-07-01
We use a combination of analytical theory and molecular dynamics simulation to study the inherent structure landscape of a system of hard spheres confined to narrow cylindrical channels of diameter 1 +√{3 }/2
Single-particle fluctuations and directional correlations in driven hard-sphere glasses.
Mandal, Suvendu; Chikkadi, Vijaykumar; Nienhuis, Bernard; Raabe, Dierk; Schall, Peter; Varnik, Fathollah
2013-08-01
Via event-driven molecular dynamics simulations and experiments, we study the packing-fraction and shear-rate dependence of single-particle fluctuations and dynamic correlations in hard-sphere glasses under shear. At packing fractions above the glass transition, correlations increase as shear rate decreases: the exponential tail in the distribution of single-particle jumps broadens and dynamic four-point correlations increase. Interestingly, however, upon decreasing the packing fraction, a broadening of the exponential tail is also observed, while dynamic heterogeneity is shown to decrease. An explanation for this behavior is proposed in terms of a competition between shear and thermal fluctuations. Building upon our previous studies [Chikkadi et al., Europhys. Lett. 100, 56001 (2012)], we further address the issue of anisotropy of the dynamic correlations.
Radial distribution function for hard spheres in fractal dimensions: A heuristic approximation.
Santos, Andrés; de Haro, Mariano López
2016-06-01
Analytic approximations for the radial distribution function, the structure factor, and the equation of state of hard-core fluids in fractal dimension d (1≤d≤3) are developed as heuristic interpolations from the knowledge of the exact and Percus-Yevick results for the hard-rod and hard-sphere fluids, respectively. In order to assess their value, such approximate results are compared with those of recent Monte Carlo simulations and numerical solutions of the Percus-Yevick equation for a fractal dimension [M. Heinen et al., Phys. Rev. Lett. 115, 097801 (2015)PRLTAO0031-900710.1103/PhysRevLett.115.097801], a good agreement being observed.
Equation of state of sticky-hard-sphere fluids in the chemical-potential route.
Rohrmann, René D; Santos, Andrés
2014-04-01
The coupling-parameter method, whereby an extra particle is progressively coupled to the rest of the particles, is applied to the sticky-hard-sphere fluid to obtain its equation of state in the so-called chemical-potential route (μ route). As a consistency test, the results for one-dimensional sticky particles are shown to be exact. Results corresponding to the three-dimensional case (Baxter's model) are derived within the Percus-Yevick approximation by using different prescriptions for the dependence of the interaction potential of the extra particle on the coupling parameter. The critical point and the coexistence curve of the gas-liquid phase transition are obtained in the μ route and compared with predictions from other thermodynamics routes and from computer simulations. The results show that the μ route yields a general better description than the virial, energy, compressibility, and zero-separation routes.
Correlation between dynamical and structural heterogeneities in colloidal hard-sphere suspensions
NASA Astrophysics Data System (ADS)
Golde, Sebastian; Palberg, Thomas; Schöpe, Hans Joachim
2016-07-01
Dynamical and structural heterogeneities have long been thought to play a key role in a unified picture of solidification in view of the two competitive processes of crystallization and vitrification. Here, we study these heterogeneities by means of a combination of dynamic and static light-scattering techniques applied to the simplest model system exhibiting crystallization and vitrification: the colloidal hard-sphere system. Our method enables us to quantify and correlate the temporal evolution of the amount of ordered clusters (precursors) and the amount of slow particles. Our analysis shows that their temporal evolutions are closely related and that there is an intimate link between structural and dynamic heterogeneities, crystal nucleation and the non-crystallization transition.
Creep and aging of hard-sphere glasses under constant stress.
Ballesta, P; Petekidis, G
2016-04-01
We investigate the aging behavior of glassy suspensions of nearly hard-sphere colloids submitted to a constant shear stress. For low stresses, below the yield stress, the system is subject to creep motion. As the sample ages, the shear rate exhibits a power-law decrease with time with exponents that depend on the sample age. We use a combination of rheological experiments with time-resolved photon correlation spectroscopy to investigate the time evolution of the sample dynamics under shear on various time and length scales. Long-time light-scattering experiments reveal the occurrence of microscopic rearrangement events that are linked with the macroscopic strain deformation of the sample. Dynamic time sweep experiments indicate that while the internal microscopic dynamics slow down continuously with waiting time, the storage and loss moduli are almost constant after a fast, weak decrease, resembling the behavior of quenched systems with partially frozen-in stresses. PMID:27176358
Thermodynamic properties of non-conformal soft-sphere fluids with effective hard-sphere diameters.
Rodríguez-López, Tonalli; del Río, Fernando
2012-01-28
In this work we study a set of soft-sphere systems characterised by a well-defined variation of their softness. These systems represent an extension of the repulsive Lennard-Jones potential widely used in statistical mechanics of fluids. This type of soft spheres is of interest because they represent quite accurately the effective intermolecular repulsion in fluid substances and also because they exhibit interesting properties. The thermodynamics of the soft-sphere fluids is obtained via an effective hard-sphere diameter approach that leads to a compact and accurate equation of state. The virial coefficients of soft spheres are shown to follow quite simple relationships that are incorporated into the equation of state. The approach followed exhibits the rescaling of the density that produces a unique equation for all systems and temperatures. The scaling is carried through to the level of the structure of the fluids. PMID:22158949
Radial distribution function for hard spheres in fractal dimensions: A heuristic approximation.
Santos, Andrés; de Haro, Mariano López
2016-06-01
Analytic approximations for the radial distribution function, the structure factor, and the equation of state of hard-core fluids in fractal dimension d (1≤d≤3) are developed as heuristic interpolations from the knowledge of the exact and Percus-Yevick results for the hard-rod and hard-sphere fluids, respectively. In order to assess their value, such approximate results are compared with those of recent Monte Carlo simulations and numerical solutions of the Percus-Yevick equation for a fractal dimension [M. Heinen et al., Phys. Rev. Lett. 115, 097801 (2015)PRLTAO0031-900710.1103/PhysRevLett.115.097801], a good agreement being observed. PMID:27415227
Thermodynamic properties of non-conformal soft-sphere fluids with effective hard-sphere diameters.
Rodríguez-López, Tonalli; del Río, Fernando
2012-01-28
In this work we study a set of soft-sphere systems characterised by a well-defined variation of their softness. These systems represent an extension of the repulsive Lennard-Jones potential widely used in statistical mechanics of fluids. This type of soft spheres is of interest because they represent quite accurately the effective intermolecular repulsion in fluid substances and also because they exhibit interesting properties. The thermodynamics of the soft-sphere fluids is obtained via an effective hard-sphere diameter approach that leads to a compact and accurate equation of state. The virial coefficients of soft spheres are shown to follow quite simple relationships that are incorporated into the equation of state. The approach followed exhibits the rescaling of the density that produces a unique equation for all systems and temperatures. The scaling is carried through to the level of the structure of the fluids.
Parallelized event chain algorithm for dense hard sphere and polymer systems
Kampmann, Tobias A. Boltz, Horst-Holger; Kierfeld, Jan
2015-01-15
We combine parallelization and cluster Monte Carlo for hard sphere systems and present a parallelized event chain algorithm for the hard disk system in two dimensions. For parallelization we use a spatial partitioning approach into simulation cells. We find that it is crucial for correctness to ensure detailed balance on the level of Monte Carlo sweeps by drawing the starting sphere of event chains within each simulation cell with replacement. We analyze the performance gains for the parallelized event chain and find a criterion for an optimal degree of parallelization. Because of the cluster nature of event chain moves massive parallelization will not be optimal. Finally, we discuss first applications of the event chain algorithm to dense polymer systems, i.e., bundle-forming solutions of attractive semiflexible polymers.
Structure of hard particle fluids near a hard wall. II. yw(z) for hard spheres
NASA Astrophysics Data System (ADS)
Labik, S.; Smith, William R.; Speedy, Robin J.
1988-02-01
Predictions of the wall-cavity correlation function yw(z) for hard spheres against a hard wall are tested using the treatment that Smith and Speedy developed and examined for the case of hard disks in part I of this series, as well as an extension of this approach using an alternative procedure. yw(z) in the range 0≤z≤1 may be accurately predicted using only the thermodynamic properties of the bulk fluid, for which precise expressions are available. These predictions are tested by determining yw(z) and the cavity concentration profile nwo(z) in a computer simulation study. We also derive a new integral equation relating yw(z) near the wall to its values just outside the wall and illustrate this in examining the consistency of our computer simulation results.
An Automatic Phase-Change Detection Technique for Colloidal Hard Sphere Suspensions
NASA Technical Reports Server (NTRS)
McDowell, Mark; Gray, Elizabeth; Rogers, Richard B.
2005-01-01
Colloidal suspensions of monodisperse spheres are used as physical models of thermodynamic phase transitions and as precursors to photonic band gap materials. However, current image analysis techniques are not able to distinguish between densely packed phases within conventional microscope images, which are mainly characterized by degrees of randomness or order with similar grayscale value properties. Current techniques for identifying the phase boundaries involve manually identifying the phase transitions, which is very tedious and time consuming. We have developed an intelligent machine vision technique that automatically identifies colloidal phase boundaries. The algorithm utilizes intelligent image processing techniques that accurately identify and track phase changes vertically or horizontally for a sequence of colloidal hard sphere suspension images. This technique is readily adaptable to any imaging application where regions of interest are distinguished from the background by differing patterns of motion over time.
Thorneywork, Alice L; Roth, Roland; Aarts, Dirk G A L; Dullens, Roel P A
2014-04-28
Two-dimensional hard disks are a fundamentally important many-body model system in classical statistical mechanics. Despite their significance, a comprehensive experimental data set for two-dimensional single component and binary hard disks is lacking. Here, we present a direct comparison between the full set of radial distribution functions and the contact values of a two-dimensional binary colloidal hard sphere model system and those calculated using fundamental measure theory. We find excellent quantitative agreement between our experimental data and theoretical predictions for both single component and binary hard disk systems. Our results provide a unique and fully quantitative mapping between experiments and theory, which is crucial in establishing the fundamental link between structure and dynamics in simple liquids and glass forming systems. PMID:24784245
NASA Astrophysics Data System (ADS)
Maeso, M. J.; Solana, J. R.
1995-11-01
A theoretically based corresponding-states principle previously developed for the equation of state of hard-convex-body fluids is extended to rigid linear homonuclear fused-hard-sphere fluids. Effective volumes and shapes are introduced in order to account for the nonconvexity of the molecules. The excess compressibility factor, reduced by means of a parameter which can be determined analytically, is a common function of the effective packing fraction. The analytical expression for the function can be obtained from the equation of state of the hard-sphere fluid. Existing simulation data for diatomics, triatomics and tetraatomics show excellent agreement with the corresponding-states principle.
Yan, Zhenyu; Buldyrev, Sergey V; Giovambattista, Nicolas; Debenedetti, Pablo G; Stanley, H Eugene
2006-05-01
We investigate the equation of state, diffusion coefficient, and structural order of a family of spherically symmetric potentials consisting of a hard core and a linear repulsive ramp. This generic potential has two characteristic length scales: the hard and soft core diameters. The family of potentials is generated by varying their ratio, lambda. We find negative thermal expansion (thermodynamic anomaly) and an increase of the diffusion coefficient upon isothermal compression (dynamic anomaly) for 0< or =lambda<6/7. As in water, the regions where these anomalies occur are nested domes in the (T, p) or (T, P) planes , with the thermodynamic anomaly dome contained entirely within the dynamic anomaly dome. We calculate translational and orientational order parameters (t and Q6), and project equilibrium state points onto the (t, Q6) plane, or order map. The order map evolves from waterlike behavior to hard-sphere-like behavior upon varying lambda between 4/7 and 6/7. Thus, we traverse the range of liquid behavior encompassed by hard spheres (lanbda=1) and waterlike (lambda approximately 4/7) with a family of tunable spherically symmetric potentials by simply varying the ratio of hard to soft-core diameters. Although dynamic and thermodynamic anomalies occur almost across the entire range 0< or=lambda< or=1, waterlike structural anomalies (i.e., decrease in both t and Q6 upon compression and strictly correlated T and Q6 in the anomalous region) occur only around lambda=4/7. Waterlike anomalies in structure, dynamics and thermodynamics arise solely due to the existence of two length scales, with their ratio lambda being the single control parameter, orientation-dependent interactions being absent by design. PMID:16802925
NASA Astrophysics Data System (ADS)
Löwe, H.; Picard, G.
2015-11-01
The description of snow microstructure in microwave models is often simplified to facilitate electromagnetic calculations. Within dense media radiative transfer (DMRT), the microstructure is commonly described by sticky hard spheres (SHS). An objective mapping of real snow onto SHS is however missing which prevents measured input parameters from being used for DMRT. In contrast, the microwave emission model of layered snowpacks (MEMLS) employs a conceptually different approach, based on the two-point correlation function which is accessible by tomography. Here we show the equivalence of both electromagnetic approaches by reformulating their microstructural models in a common framework. Using analytical results for the two-point correlation function of hard spheres, we show that the scattering coefficient in both models only differs by a factor which is close to unity, weakly dependent on ice volume fraction and independent of other microstructural details. Additionally, our analysis provides an objective retrieval method for the SHS parameters (diameter and stickiness) from tomography images. For a comprehensive data set we demonstrate the variability of stickiness and compare the SHS diameter to the optical equivalent diameter. Our results confirm the necessity of a large grain-size scaling when relating both diameters in the non-sticky case, as previously suggested by several authors.
NASA Astrophysics Data System (ADS)
Löwe, H.; Picard, G.
2015-04-01
The description of snow microstructure in microwave models is often simplified to facilitate electromagnetic calculations. Within dense media radiative transfer (DMRT), the microstructure is commonly described by sticky hard spheres (SHS). An objective mapping of real snow onto SHS is however missing which prevents to use measured input parameters for DMRT. In contrast, the microwave emission model of layered snowpacks (MEMLS) employs a conceptually different approach, based on the two-point correlation function which is accessible by tomography. Here we show the equivalence of both electromagnetic approaches by reformulating their microstructural models in a common framework. Using analytical results for the two-point correlation function of hard spheres we show that the scattering coefficient in both models only differs by a factor which is close to unity, weakly dependent on ice volume fraction and independent of other microstructural details. Additionally, our analysis provides an objective retrieval method for the SHS parameters (diameter and stickiness) from tomography images. For a comprehensive data set we demonstrate the variability of stickiness and compare the SHS diameter to the optical equivalent diameter. Our results confirm the necessity of a large grain-size scaling when relating both diameters in the non-sticky case, as previously suggested by several authors.
NASA Astrophysics Data System (ADS)
Virrueta, Alejandro; O'Hern, Corey; Regan, Lynne
Methionine (Met) is a versatile amino acid found frequently both in protein cores and at protein-protein interfaces. Thus, a complete description of the structure of Met is tantamount to a fundamental understanding of protein structure and design. In previous work, we showed that our hard-sphere dipeptide model is able to recapitulate the side chain dihedral angle distributions observed in high-resolution protein crystal structures for the 8 amino acids we have studied to date: Val, Thr, Ser, Leu, Ile, Cys, Tyr, and Phe. Using the same approach, we can predict the observed Met side chain dihedral angle distributions P (χ1) and P (χ2) , but not P (χ3) . In this manuscript, we investigate the possible origins of the discrepancy and identify the minimal additions to the hard-sphere dipeptide model necessary to quantitatively predict P (χ3) of Met. We find that applying a Lennard-Jones potential with weak attraction between hydrogen atoms is sufficient to achieve predictions that match the observed χ3 side chain dihedral angle probability distributions for Met, Nle, and Mse without negatively affecting our results for the 8 previously studied amino acids. A. V. is supported by an NSF Graduate Research Fellowship and a Ford Foundation Fellowship.
Schaefer, B.; Lambert, S.M.; Song, Y.; Prausnitz, J.M.
1994-10-01
Goal of this work is the extension of a Perturbed-Hard-Sphere-Chain equation of state (PHSC EOS) to systems containing strong polar components. Three different types of association models (ten Brinke/Karasz, SAFI, modified Veytsman) were used to calculate the contribution of specific interactions like hydrogen bonding to thermodynamic quantities. Pure component parameters obtained from regression of temperature dependent density and vapor pressure data allow the prediction of VLE and LLE data. The results of simple fluids and polymer solutions were compared with experimental data. The SAFT and the modified Veytsman extension give similar results for pure fluids and mixtures with components of similar segment size. Differences increase with increasing difference of segment size.
Antiandrogenic activity of phthalate mixtures: Validity of concentration addition
Christen, Verena; Crettaz, Pierre; Oberli-Schrämmli, Aurelia; Fent, Karl
2012-03-01
Phthalates and bisphenol A have very widespread use leading to significant exposure of humans. They are suspected to interfere with the endocrine system, including the androgen, estrogen and the thyroid hormone system. Here we analyzed the antiandrogenic activity of six binary, and one ternary mixture of phthalates exhibiting complete antiandrogenic dose–response curves, and binary mixtures of phthalates and bisphenol A at equi-effective concentrations of EC{sub 10}, EC{sub 25} and EC{sub 50} in MDA-kb2 cells. Mixture activity followed the concentration addition (CA) model with a tendency to synergism at high and antagonism at low concentrations. Isoboles and the toxic unit approach (TUA) confirmed the additive to synergistic activity of the binary mixtures BBP + DBP, DBP + DEP and DEP + BPA at high concentrations. Both methods indicate a tendency to antagonism for the EC{sub 10} mixtures BBP + DBP, BBP + DEP and DBP + DEP, and the EC{sub 25} mixture of DBP + BPA. A ternary mixture revealed synergism at the EC{sub 50}, and weak antagonistic activity at the EC{sub 25} level by the TUA. A mixture of five phthalates representing a human urine composition and reflecting exposure to corresponding parent compounds showed no antiandrogenic activity. Our study demonstrates that CA is an appropriate concept to account for mixture effects of antiandrogenic phthalates and bisphenol A. The interaction indicates a departure from additivity to antagonism at low concentrations, probably due to interaction with the androgen receptor and/or cofactors. This study emphasizes that a risk assessment of phthalates should account for mixture effects by applying the CA concept. -- Highlights: ► Antiandrogenic activity of mixtures of 2 and 3 phthalates are assessed in MDA-kb2 cells. ► Mixture activities followed the concentration addition model. ► A tendency to synergism at high and antagonism at low levels occurred.
A Novel Approach for Evaluating Carbamate Mixtures for Dose Additivity
Two mathematical approaches were used to test the hypothesis ofdose-addition for a binary and a seven-chemical mixture ofN-methyl carbamates, toxicologically similar chemicals that inhibit cholinesterase (ChE). In the more novel approach, mixture data were not included in the ana...
Antiandrogenic activity of phthalate mixtures: validity of concentration addition.
Christen, Verena; Crettaz, Pierre; Oberli-Schrämmli, Aurelia; Fent, Karl
2012-03-01
Phthalates and bisphenol A have very widespread use leading to significant exposure of humans. They are suspected to interfere with the endocrine system, including the androgen, estrogen and the thyroid hormone system. Here we analyzed the antiandrogenic activity of six binary, and one ternary mixture of phthalates exhibiting complete antiandrogenic dose-response curves, and binary mixtures of phthalates and bisphenol A at equi-effective concentrations of EC(10), EC(25) and EC(50) in MDA-kb2 cells. Mixture activity followed the concentration addition (CA) model with a tendency to synergism at high and antagonism at low concentrations. Isoboles and the toxic unit approach (TUA) confirmed the additive to synergistic activity of the binary mixtures BBP+DBP, DBP+DEP and DEP+BPA at high concentrations. Both methods indicate a tendency to antagonism for the EC(10) mixtures BBP+DBP, BBP+DEP and DBP+DEP, and the EC(25) mixture of DBP+BPA. A ternary mixture revealed synergism at the EC(50), and weak antagonistic activity at the EC(25) level by the TUA. A mixture of five phthalates representing a human urine composition and reflecting exposure to corresponding parent compounds showed no antiandrogenic activity. Our study demonstrates that CA is an appropriate concept to account for mixture effects of antiandrogenic phthalates and bisphenol A. The interaction indicates a departure from additivity to antagonism at low concentrations, probably due to interaction with the androgen receptor and/or cofactors. This study emphasizes that a risk assessment of phthalates should account for mixture effects by applying the CA concept.
Variational Monte Carlo study of soliton excitations in hard-sphere Bose gases
NASA Astrophysics Data System (ADS)
Rota, R.; Giorgini, S.
2015-10-01
By using a full many-body approach, we calculate the excitation energy, the effective mass, and the density profile of soliton states in a three-dimensional Bose gas of hard spheres at zero temperature. The many-body wave function used to describe the soliton contains a one-body term, derived from the solution of the Gross-Pitaevskii equation, and a two-body Jastrow term, which accounts for the repulsive correlations between atoms. We optimize the parameters in the many-body wave function via a variational Monte Carlo procedure, calculating the grand-canonical energy and the canonical momentum of the system in a moving reference frame where the soliton is stationary. As the density of the gas is increased, significant deviations from the mean-field predictions are found for the excitation energy and the density profile of both dark and gray solitons. In particular, the soliton effective mass m* and the mass m Δ N of missing particles in the region of the density depression are smaller than the result from the Gross-Pitaevskii equation, their ratio, however, being well reproduced by this theory up to large values of the gas parameter. We also calculate the profile of the condensate density around the soliton notch, finding good agreement with the prediction of the local-density approximation.
Rovibrationally Inelastic Atom-Molecule Collision Cross Sections from a Hard Sphere Model
NASA Astrophysics Data System (ADS)
Lashner, Jacob; Stewart, Brian
2016-05-01
Hard-shell models have long been used to elucidate the principal features of molecular energy transfer and exchange reaction in the A + BC system. Nevertheless, no three-dimensional hard-shell calculation of inelastic collision cross sections has been reported. This work aims to fill that void. A particular motivation comes from our experimental results, which show the importance of equatorial impacts in the vibrational excitation process. Working with the simple hard-sphere model, we incorporated secondary impacts, defined as those in which A strikes C after striking B. Such collisions are important in systems such as Li2 - X, in which vibrational energy transfer occurs principally through side impacts. We discuss the complexity this adds to the model and present fully three-dimensional cross sections for rovibrational excitation of an initially stationary molecule in the homonuclear A + B2 system, examining the cross section as a function of the masses and radii of the atoms. We show how the features in the cross section evolve as these parameters are varied and calculate the contribution of secondary (near-equatorial) impacts to the dynamics. We compare with recent measurements in our laboratory and with the results of quasiclassical trajectories.
Thorneywork, Alice L; Rozas, Roberto E; Dullens, Roel P A; Horbach, Jürgen
2015-12-31
We compare experimental results from a quasi-two-dimensional colloidal hard sphere fluid to a Monte Carlo simulation of hard disks with small particle displacements. The experimental short-time self-diffusion coefficient D(S) scaled by the diffusion coefficient at infinite dilution, D(0), strongly depends on the area fraction, pointing to significant hydrodynamic interactions at short times in the experiment, which are absent in the simulation. In contrast, the area fraction dependence of the experimental long-time self-diffusion coefficient D(L)/D(0) is in quantitative agreement with D(L)/D(0) obtained from the simulation. This indicates that the reduction in the particle mobility at short times due to hydrodynamic interactions does not lead to a proportional reduction in the long-time self-diffusion coefficient. Furthermore, the quantitative agreement between experiment and simulation at long times indicates that hydrodynamic interactions effectively do not affect the dependence of D(L)/D(0) on the area fraction. In light of this, we discuss the link between structure and long-time self-diffusion in terms of a configurational excess entropy and do not find a simple exponential relation between these quantities for all fluid area fractions. PMID:26765032
Transport coefficients of a granular gas of inelastic rough hard spheres.
Kremer, Gilberto M; Santos, Andrés; Garzó, Vicente
2014-08-01
The Boltzmann equation for inelastic and rough hard spheres is considered as a model of a dilute granular gas. In this model, the collisions are characterized by constant coefficients of normal and tangential restitution, and hence the translational and rotational degrees of freedom are coupled. A normal solution to the Boltzmann equation is obtained by means of the Chapman-Enskog method for states near the homogeneous cooling state. The analysis is carried out to first order in the spatial gradients of the number density, the flow velocity, and the granular temperature. The constitutive equations for the momentum and heat fluxes and for the cooling rate are derived, and the associated transport coefficients are expressed in terms of the solutions of linear integral equations. For practical purposes, a first Sonine approximation is used to obtain explicit expressions of the transport coefficients as nonlinear functions of both coefficients of restitution and the moment of inertia. Known results for purely smooth inelastic spheres and perfectly elastic and rough spheres are recovered in the appropriate limits.
NASA Astrophysics Data System (ADS)
Lechman, Jeremy; Pierce, Flint
2012-02-01
Diffusive transport is a ubiquitous process that is typically understood in terms of a classical random walk of non-interacting particles. Here we present the results for a model of hard-sphere colloids in a Newtonian incompressible solvent at various volume fractions below the ordering transition (˜50%). We numerically simulate the colloidal systems via Fast Lubrication Dynamics -- a Brownian Dynamics approach with corrected mean-field hydrodynamic interactions. Colloid-colloid interactions are also included so that we effectively solve a system of interacting Langevin equations. The results of the simulations are analyzed in terms of the diffusion coefficient as a function of time with the early and late time diffusion coefficients comparing well with experimental results. An interpretation of the full time dependent behavior of the diffusion coefficient and mean-squared displacement is given in terms of a continuous time random walk. Therefore, the deterministic, continuum diffusion equation which arises from the discrete, interacting random walkers is presented. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.
A Thermodynamically-Consistent Non-Ideal Stochastic Hard-Sphere Fluid
Donev, A; Alder, B J; Garcia, A L
2009-08-03
A grid-free variant of the Direct Simulation Monte Carlo (DSMC) method is proposed, named the Isotropic DSMC (I-DSMC) method, that is suitable for simulating collision-dominated dense fluid flows. The I-DSMC algorithm eliminates all grid artifacts from the traditional DSMC algorithm and is Galilean invariant and microscopically isotropic. The stochastic collision rules in I-DSMC are modified to introduce a non-ideal structure factor that gives consistent compressibility, as first proposed in [Phys. Rev. Lett. 101:075902 (2008)]. The resulting Stochastic Hard Sphere Dynamics (SHSD) fluid is empirically shown to be thermodynamically identical to a deterministic Hamiltonian system of penetrable spheres interacting with a linear core pair potential, well-described by the hypernetted chain (HNC) approximation. We develop a kinetic theory for the SHSD fluid to obtain estimates for the transport coefficients that are in excellent agreement with particle simulations over a wide range of densities and collision rates. The fluctuating hydrodynamic behavior of the SHSD fluid is verified by comparing its dynamic structure factor against theory based on the Landau-Lifshitz Navier-Stokes equations. We also study the Brownian motion of a nano-particle suspended in an SHSD fluid and find a long-time power-law tail in its velocity autocorrelation function consistent with hydrodynamic theory and molecular dynamics calculations.
Shells of charge: a density functional theory for charged hard spheres
NASA Astrophysics Data System (ADS)
Roth, Roland; Gillespie, Dirk
2016-06-01
A functional for the electrostatic excess free-energy for charged, hard sphere fluids is proposed. The functional is derived from two complementary, but equivalent, interpretations of the mean spherical approximation (MSA). The first combines fundamental measure theory (FMT) from hard-core interactions with the idea that MSA can be interpreted in terms of the interaction spherical shells of charge. This formulation gives the free-energy density as a function of weighted densities. When all the ions have the same size, the functional adopts an FMT-like form. The second in effect ‘functionalizes’ the derivation of MSA; that is, it generalizes the MSA as a functional-based version of MSA (fMSA). This formulation defines the free-energy density as a function of a position-dependent MSA screening parameter and the weighted densities of the FMT approach. This FMT/fMSA functional is shown to give accurate density profiles, as compared to Monte Carlo simulations, under a wide range of ion concentrations, size asymmetries, and valences.
Hard-sphere-chain Equations of State for Lyotropic Polymer LiquidCrystals
Hino, T.; Prausnitz, John M.
1998-06-01
Using Parsons-type scaling, the Onsager theory for theisotropic-nematic (I-N) transition of rigid-rod lyotropic polymer liquidcrystals is combined with the equation of state for hard-sphere-chainfluids of Chapman et al. and that of Hu et al. The equation of Hu et al.gives the I-N transition pressure and density in good agreement withcomputer simulation by Wilson and Allen for a semi-flexible hard-spherechain consisting of seven segments. For real semi-flexible polymers, wefollow the Khokhlov-Semenov theory of persistent chains that introduceschain flexibility into the Onsager theory. Using a consistent procedureto regress the equation-of-state parameters, the equations of Chapman etal. and Hu et al. are also compared with the theory of DuPre and Yangthat uses the equation of Lee for hard spherocylinders. These models arecompared with experiment for two binary polymer solutions containingpoly(hexyl isocyanate) and another solution containing polysaccharideschizophyllan. The concentration of polymer at the I-N transition ispredicted as a function of the molecular weight of polymer. All modelsperform similarly and show semi-quantitative agreement withexperiment.
Gelation and state diagram for a model nanoparticle system with adhesive hard sphere interactions
NASA Astrophysics Data System (ADS)
Wagner, Norman; Aaron, Eberle
2012-02-01
We provide the first comprehensive state diagram of thermoreversible gelation in a model nanoparticle system from dilute concentrations to the attractive driven glass. We show the temperature dependence of the interparticle potential is related to a surface molecular phase transition of the brush layer using neutron reflectivity (NR) and small-angle neutron scattering (SANS) [1]. We establish the temperature dependence of the interparticle potential using SANS, dynamic light scattering (DLS), and rheology. The potential parameters extracted from SANS suggest that, for this system, gelation is an extension of the Mode Coupling Theory (MCT) attractive driven glass line (ADG) to lower volume fractions and follows the percolation transition. Below the critical concentration, gelation proceeds without competition for phase separation [2]. These results are used to develop a complete state diagram for the sticky hard sphere reference system. [4pt] [1] A.P.R. Eberle, N.J. Wagner, B. Akgun, S.K. Satija, Langmuir 26 3003 (2010).[0pt] [2] A.P.R. Eberle, N.J. Wagner, R. Castaneda-Priego, Phys. Rev. Let. 105704 (2011).
Assembly of vorticity-aligned hard-sphere colloidal strings in a simple shear flow
Cheng, Xiang; Xu, Xinliang; Rice, Stuart A.; Dinner, Aaron R.; Cohen, Itai
2012-01-01
Colloidal suspensions self-assemble into equilibrium structures ranging from face- and body-centered cubic crystals to binary ionic crystals, and even kagome lattices. When driven out of equilibrium by hydrodynamic interactions, even more diverse structures can be accessed. However, mechanisms underlying out-of-equilibrium assembly are much less understood, though such processes are clearly relevant in many natural and industrial systems. Even in the simple case of hard-sphere colloidal particles under shear, there are conflicting predictions about whether particles link up into string-like structures along the shear flow direction. Here, using confocal microscopy, we measure the shear-induced suspension structure. Surprisingly, rather than flow-aligned strings, we observe log-rolling strings of particles normal to the plane of shear. By employing Stokesian dynamics simulations, we address the mechanism leading to this out-of-equilibrium structure and show that it emerges from a delicate balance between hydrodynamic and interparticle interactions. These results demonstrate a method for assembling large-scale particle structures using shear flows. PMID:22198839
NASA Astrophysics Data System (ADS)
Virrueta, A.; Gaines, J.; O'Hern, C. S.; Regan, L.
2015-03-01
Current research in the O'Hern and Regan laboratories focuses on the development of hard-sphere models with stereochemical constraints for protein structure prediction as an alternative to molecular dynamics methods that utilize knowledge-based corrections in their force-fields. Beginning with simple hydrophobic dipeptides like valine, leucine, and isoleucine, we have shown that our model is able to reproduce the side-chain dihedral angle distributions derived from sets of high-resolution protein crystal structures. However, methionine remains an exception - our model yields a chi-3 side-chain dihedral angle distribution that is relatively uniform from 60 to 300 degrees, while the observed distribution displays peaks at 60, 180, and 300 degrees. Our goal is to resolve this discrepancy by considering clashes with neighboring residues, and averaging the reduced distribution of allowable methionine structures taken from a set of crystallized proteins. We will also re-evaluate the electron density maps from which these protein structures are derived to ensure that the methionines and their local environments are correctly modeled. This work will ultimately serve as a tool for computing side-chain entropy and protein stability. A. V. is supported by an NSF Graduate Research Fellowship and a Ford Foundation Fellowship. J. G. is supported by NIH training Grant NIH-5T15LM007056-28.
Cavity averages for hard spheres in the presence of polydispersity and incomplete data.
Schindler, Michael; Maggs, A C
2015-09-01
We develop a cavity-based method which allows to extract thermodynamic properties from position information in hard-sphere/disk systems. So far, there are available-volume and free-volume methods. We add a third one, which we call available volume after take-out, and which is shown to be mathematically equivalent to the others. In applications, where data sets are finite, all three methods show limitations, and they do this in different parameter ranges. We illustrate the principal equivalence and the limitations on data from molecular dynamics: In particular, we test robustness against missing data. We have in mind experimental limitations where there is a small polydispersity, say 4% in the particle radii, but individual radii cannot be determined. We observe that, depending on the used method, the errors in such a situation are easily 100% for the pressure and 10kT for the chemical potentials. Our work is meant as guideline to the experimentalists for choosing the right one of the three methods, in order to keep the outcome of experimental data analysis meaningful. PMID:26359237
Perera-Burgos, Jorge Adrián; Méndez-Alcaraz, José Miguel; Pérez-Ángel, Gabriel; Castañeda-Priego, Ramón
2016-09-14
Depletion forces are a particular class of effective interactions that have been mainly investigated in binary mixtures of hard-spheres in bulk. Although there are a few contributions that point toward the effects of confinement on the depletion potential, little is known about such entropic potentials in two-dimensional colloidal systems. From theoretical point of view, the problem resides in the fact that there is no general formulation of depletion forces in arbitrary dimensions and, typically, any approach that works well in three dimensions has to be reformulated for lower dimensionality. However, we have proposed a theoretical framework, based on the formalism of contraction of the description within the integral equations theory of simple liquids, to account for effective interactions in colloidal liquids, whose main feature is that it does not need to be readapted to the problem under consideration. We have also shown that such an approach allows one to determine the depletion pair potential in three-dimensional colloidal mixtures even near to the demixing transition, provided the bridge functions are sufficiently accurate to correctly describe the spatial correlation between colloids [E. López-Sánchez et al., J. Chem. Phys. 139, 104908 (2013)]. We here report an extensive analysis of the structure and the entropic potentials in binary mixtures of additive hard-disks. In particular, we show that the same functional form of the modified-Verlet closure relation used in three dimensions can be straightforwardly employed to obtain an accurate solution for two-dimensional colloidal mixtures in a wide range of packing fractions, molar fractions, and size asymmetries. Our theoretical results are explicitly compared with the ones obtained by means of event-driven molecular dynamics simulations and recent experimental results. Furthermore, to assess the accuracy of our predictions, the depletion potentials are used in an effective one-component model to reproduce
Fu, Dong; Li, Xiao-Sen
2006-08-28
The excess Helmholtz free energy functional for associating hard sphere fluid is formulated by using a modified fundamental measure theory [Y. X. Yu and J. Z. Wu, J. Chem. Phys. 117, 10156 (2002)]. Within the framework of density functional theory, the thermodynamic properties including phase equilibria for both molecules and monomers, equilibrium plate-fluid interfacial tensions and isotherms of excess adsorption, average molecule density, average monomer density, and plate-fluid interfacial tension for four-site associating hard sphere fluids confined in slit pores are investigated. The phase equilibria inside the hard slit pores and attractive slit pores are determined according to the requirement that temperature, chemical potential, and grand potential in coexistence phases should be equal and the plate-fluid interfacial tensions at equilibrium states are predicted consequently. The influences of association energy, fluid-solid interaction, and pore width on phase equilibria and equilibrium plate-fluid interfacial tensions are discussed.
NASA Astrophysics Data System (ADS)
Maeso, M. J.; Solana, J. R.
1993-07-01
Equations of state for hard-disk and hard-sphere fluids are obtained from a generalization of the Carnahan-Starling method of direct summation of the virial series. The equations of state thus obtained, besides reproducing all known virial coefficients, agree very accurately with simulation data for stable fluids. If appropriate values for the sixth and seventh virial coefficients are chosen within their uncertainty, the equations of state predict that the fluids become unstable at Kauzmann's density.
Equation of state for hard convex body fluids from the equation of state of the hard sphere fluid
NASA Astrophysics Data System (ADS)
Maeso, M. J.; Solana, J. R.
1994-02-01
A simple and accurate equation of state for fluids of hard convex molecules is derived from the pressure equation and the equation of state of the hard sphere fluid. The equation of state provides theoretical support to some equations of state used in perturbation theories for real molecular liquids. The equation of state reproduces the simulation data with an accuracy comparable to that derived from density functional theory.
Zhang, Kai; Smith, W Wendell; Wang, Minglei; Liu, Yanhui; Schroers, Jan; Shattuck, Mark D; O'Hern, Corey S
2014-09-01
We perform molecular dynamics simulations to compress binary hard spheres into jammed packings as a function of the compression rate R, size ratio α, and number fraction x(S) of small particles to determine the connection between the glass-forming ability (GFA) and packing efficiency in bulk metallic glasses (BMGs). We define the GFA by measuring the critical compression rate R(c), below which jammed hard-sphere packings begin to form "random crystal" structures with defects. We find that for systems with α≳0.8 that do not demix, R(c) decreases strongly with Δϕ(J), as R(c)∼exp(-1/Δϕ(J)(2)), where Δϕ(J) is the difference between the average packing fraction of the amorphous packings and random crystal structures at R(c). Systems with α≲0.8 partially demix, which promotes crystallization, but we still find a strong correlation between R(c) and Δϕ(J). We show that known metal-metal BMGs occur in the regions of the α and x(S) parameter space with the lowest values of R(c) for binary hard spheres. Our results emphasize that maximizing GFA in binary systems involves two competing effects: minimizing α to increase packing efficiency, while maximizing α to prevent demixing.
Description of concentration fluctuations in liquid binary mixtures with nonadditive potentials
Osman, S.M.; Singh, R.N. )
1995-01-01
The segregation or phase separation in a binary mixture is investigated within a quasilattice model and the hard-sphere-like model. The hard-sphere results are improved by incorporating a nonadditive attractive tail interaction. An analytic expression for the concentration fluctuation [ital S][sub [ital c][ital c
Additive for otto cycle engines and fuel mixture so obtained
Scifoni, M.
1985-02-12
The additive for Otto cycle engines according to the present invention consists of a mixture of water, ethanol, methanol and butanol to which is added a determined quantity of a liquid obtained by pressing prickly pear leaves. Added in a small percentage to the fuel, gasoline, LP or methane, this additive prevents the oxidation associated with the use of water and/or alcohols in Otto cycle engines, lowers fuel consumption and allows the use of low octane fuel.
Dry building mixture with complex dispersed mineral additives
NASA Astrophysics Data System (ADS)
Il'ina, Liliia; Mukhina, Irina; Teplov, Alexandr
2016-01-01
The effectiveness of the complex dispersed mineral additive consisting of diopside and limestone was provided by the following factors. Diopside, due to the high hardness, reinforces formed hardened cement paste and prevents the spread of micro-cracks in it under the action of loads. Furthermore, diopside due to the greater elastic modulus than cement paste causes redistribution of stress between the additive particles and the cement. Limestone, since it has chemical affinity with the clinker minerals and products of their hydration hardening, effects on the hydration process and the formation of the contact area between the additive particles and the cement. The optimum quantity of complex dispersed mineral additive is 7%. At the same time the strength of the solution, made of dry building mixture "rough leveler for floor", increased by 22.1%, and the strength of the solution, made of dry mortar "masonry mixture" increased by 32.7%. With the mineral additive introduction the offset of the endoeffect temperatures to higher temperatures on derivatograms is fixed. If there is a mineral additive in the hardened cement paste, which may act as substrate for the tumors crystallization, the hardened cement paste structure strengthening while the complex thermal analysis is seen.
NASA Astrophysics Data System (ADS)
van Westen, Thijs; Vlugt, Thijs J. H.; Gross, Joachim
2012-07-01
Onsager-like theories are commonly used to describe the phase behavior of nematic (only orientationally ordered) liquid crystals. A key ingredient in such theories is the orientation-dependent excluded volume of two molecules. Although for hard convex molecular models this is generally known in analytical form, for more realistic molecular models that incorporate intramolecular flexibility, one has to rely on approximations or on computationally expensive Monte Carlo techniques. In this work, we provide a general correlation for the excluded volume of tangent hard-sphere chains of arbitrary chain length and flexibility. The flexibility is introduced by means of the rod-coil model. The resulting correlation is of simple analytical form and accurately covers a wide range of pure component excluded volume data obtained from Monte Carlo simulations of two-chain molecules. The extension to mixtures follows naturally by applying simple combining rules for the parameters involved. The results for mixtures are also in good agreement with data from Monte Carlo simulations. We have expressed the excluded volume as a second order power series in sin (γ), where γ is the angle between the molecular axes. Such a representation is appealing since the solution of the Onsager Helmholtz energy functional usually involves an expansion of the excluded volume in Legendre coefficients. Both for pure components and mixtures, the correlation reduces to an exact expression in the limit of completely linear chains. The expression for mixtures, as derived in this work, is thereby an exact extension of the pure component result of Williamson and Jackson [Mol. Phys. 86, 819-836 (1995)], 10.1080/00268979500102391.
ERIC Educational Resources Information Center
Mota, A. R.; Lopes dos Santos, J. M. B.
2014-01-01
Students' misconceptions concerning colour phenomena and the apparent complexity of the underlying concepts--due to the different domains of knowledge involved--make its teaching very difficult. We have developed and tested a teaching device, the addition table of colours (ATC), that encompasses additive and subtractive mixtures in a single…
NASA Astrophysics Data System (ADS)
Atkinson, Steven; Stillinger, Frank H.; Torquato, Salvatore
2016-09-01
The nonequilibrium process by which hard-particle systems may be compressed into disordered, jammed states has received much attention because of its wide utility in describing a broad class of amorphous materials. While dynamical signatures are known to precede jamming, the task of identifying static structural signatures indicating the onset of jamming have proven more elusive. The observation that compressing hard-particle packings towards jamming is accompanied by an anomalous suppression of density fluctuations (termed "hyperuniformity") has paved the way for the analysis of jamming as an "inverted critical point" in which the direct correlation function c (r ) , rather than the total correlation function h (r ) , diverges. We expand on the notion that c (r ) provides both universal and protocol-specific information as packings approach jamming. By considering the degree and position of singularities (discontinuities in the n th derivative) as well as how they are changed by the convolutions found in the Ornstein-Zernike equation, we establish quantitative statements about the structure of c (r ) with regards to singularities it inherits from h (r ) . These relations provide a concrete means of identifying features that must be expressed in c (r ) if one hopes to reproduce various details in the pair correlation function accurately and provide stringent tests on the associated numerics. We also analyze the evolution of systems of three-dimensional monodisperse hard spheres of diameter D as they approach ordered and disordered jammed configurations. For the latter, we use the Lubachevsky-Stillinger (LS) molecular dynamics and Torquato-Jiao (TJ) sequential linear programming algorithms, which both generate disordered packings, but can show perceptible structural differences. We identify a short-ranged scaling c (r )∝-1 /r as r →0 that accompanies the formation of the delta function at c (D ) that indicates the formation of contacts in all cases, and show
Hard-sphere dispersions: Small-wave-vector structure-factor measurements in a linear shear flow
NASA Astrophysics Data System (ADS)
Ackerson, Bruce J.; van der Werff, Jos; de Kruif, C. G.
1988-06-01
Small-scattering-wave-vector structure-factor measurements have been made for model hard-sphere suspensions undergoing a steady linear shear flow. The samples are comprised of sterically stabilized silica particles in cyclohexane and have been well characterized previously by rheological, light scattering, and neutron scattering measurements. These combined measurements provide a strict test of recent theories of microscopic order in suspensions undergoing shear and suggest a picture which unifies several intuitive notions about suspensions undergoing shear flow: distortion of the pair correlation function, clustering, layering, and nonequilibrium phase transitions.
Long-range weight functions in fundamental measure theory of the non-uniform hard-sphere fluid
NASA Astrophysics Data System (ADS)
Hansen-Goos, Hendrik
2016-06-01
We introduce long-range weight functions to the framework of fundamental measure theory (FMT) of the non-uniform, single-component hard-sphere fluid. While the range of the usual weight functions is equal to the hard-sphere radius R, the modified weight functions have range 3R. Based on the augmented FMT, we calculate the radial distribution function g(r) up to second order in the density within Percus’ test particle theory. Consistency of the compressibility and virial routes on this level allows us to determine the free parameter γ of the theory. As a side result, we obtain a value for the fourth virial coefficient B 4 which deviates by only 0.01% from the exact result. The augmented FMT is tested for the dense fluid by comparing results for g(r) calculated via the test particle route to existing results from molecular dynamics simulations. The agreement at large distances (r > 6R) is significantly improved when the FMT with long-range weight functions is used. In order to improve agreement close to contact (r = 2R) we construct a free energy which is based on the accurate Carnahan-Starling equation of state, rather than the Percus-Yevick compressibility equation underlying standard FMT.
Jiang, Hao; Adidharma, Hertanto
2014-11-07
The thermodynamic modeling of flexible charged hard-sphere chains representing polyampholyte or polyelectrolyte molecules in solution is considered. The excess Helmholtz energy and osmotic coefficients of solutions containing short polyampholyte and the osmotic coefficients of solutions containing short polyelectrolytes are determined by performing canonical and isobaric-isothermal Monte Carlo simulations. A new equation of state based on the thermodynamic perturbation theory is also proposed for flexible charged hard-sphere chains. For the modeling of such chains, the use of solely the structure information of monomer fluid for calculating the chain contribution is found to be insufficient and more detailed structure information must therefore be considered. Two approaches, i.e., the dimer and dimer-monomer approaches, are explored to obtain the contribution of the chain formation to the Helmholtz energy. By comparing with the simulation results, the equation of state with either the dimer or dimer-monomer approach accurately predicts the excess Helmholtz energy and osmotic coefficients of polyampholyte and polyelectrolyte solutions except at very low density. It also well captures the effect of temperature on the thermodynamic properties of these solutions.
NASA Astrophysics Data System (ADS)
Urrutia, Ignacio
2014-12-01
This work is devoted to analyze the relation between the thermodynamic properties of a confined fluid and the shape of its confining vessel. Recently, new insights in this topic were found through the study of cluster integrals for inhomogeneous fluids that revealed the dependence on the vessel shape of the low density behavior of the system. Here, the statistical mechanics and thermodynamics of fluids confined in wedges or by edges is revisited, focusing on their cluster integrals. In particular, the well known hard sphere fluid, which was not studied in this framework so far, is analyzed under confinement and its thermodynamic properties are analytically studied up to order two in the density. Furthermore, the analysis is extended to the confinement produced by a corrugated wall. These results rely on the obtained analytic expression for the second cluster integral of the confined hard sphere system as a function of the opening dihedral angle 0 < β < 2π. It enables a unified approach to both wedges and edges.
Mirigian, Stephen; Schweizer, Kenneth
2014-01-01
We generalize the force-level nonlinear Langevin equation theory of single particle hopping to include collective effects associated with long range elastic distortion of the liquid. The activated alpha relaxation event is of a mixed spatial character, involving two distinct, but inter-related, local and collective barriers. There are no divergences at volume fractions below jamming or temperatures above zero Kelvin. The ideas are first developed and implemented analytically and numerically in the context of hard sphere fluids. In an intermediate volume fraction crossover regime, the local cage process is dominant in a manner consistent with an apparent Arrhenius behavior. The super-Arrhenius collective barrier is more strongly dependent on volume fraction, dominates the highly viscous regime, and is well described by a nonsingular law below jamming. The increase of the collective barrier is determined by the amplitude of thermal density fluctuations, dynamic shear modulus or transient localization length, and a growing microscopic jump length. Alpha relaxation time calculations are in good agreement with recent experiments and simulations on dense fluids and suspensions of hard spheres. Comparisons of the theory with elastic models and entropy crisis ideas are explored. The present work provides a foundation for constructing a quasi-universal, fit-parameter-free theory for relaxation in thermal molecular liquids over 14 orders of magnitude in time.
Urrutia, Ignacio
2014-12-28
This work is devoted to analyze the relation between the thermodynamic properties of a confined fluid and the shape of its confining vessel. Recently, new insights in this topic were found through the study of cluster integrals for inhomogeneous fluids that revealed the dependence on the vessel shape of the low density behavior of the system. Here, the statistical mechanics and thermodynamics of fluids confined in wedges or by edges is revisited, focusing on their cluster integrals. In particular, the well known hard sphere fluid, which was not studied in this framework so far, is analyzed under confinement and its thermodynamic properties are analytically studied up to order two in the density. Furthermore, the analysis is extended to the confinement produced by a corrugated wall. These results rely on the obtained analytic expression for the second cluster integral of the confined hard sphere system as a function of the opening dihedral angle 0 < β < 2π. It enables a unified approach to both wedges and edges.
NASA Astrophysics Data System (ADS)
Mirigian, Stephen; Schweizer, Kenneth S.
2014-05-01
We generalize the force-level nonlinear Langevin equation theory of single particle hopping to include collective effects associated with long range elastic distortion of the liquid. The activated alpha relaxation event is of a mixed spatial character, involving two distinct, but inter-related, local and collective barriers. There are no divergences at volume fractions below jamming or temperatures above zero Kelvin. The ideas are first developed and implemented analytically and numerically in the context of hard sphere fluids. In an intermediate volume fraction crossover regime, the local cage process is dominant in a manner consistent with an apparent Arrhenius behavior. The super-Arrhenius collective barrier is more strongly dependent on volume fraction, dominates the highly viscous regime, and is well described by a nonsingular law below jamming. The increase of the collective barrier is determined by the amplitude of thermal density fluctuations, dynamic shear modulus or transient localization length, and a growing microscopic jump length. Alpha relaxation time calculations are in good agreement with recent experiments and simulations on dense fluids and suspensions of hard spheres. Comparisons of the theory with elastic models and entropy crisis ideas are explored. The present work provides a foundation for constructing a quasi-universal, fit-parameter-free theory for relaxation in thermal molecular liquids over 14 orders of magnitude in time.
Mirigian, Stephen; Schweizer, Kenneth S
2014-05-21
We generalize the force-level nonlinear Langevin equation theory of single particle hopping to include collective effects associated with long range elastic distortion of the liquid. The activated alpha relaxation event is of a mixed spatial character, involving two distinct, but inter-related, local and collective barriers. There are no divergences at volume fractions below jamming or temperatures above zero Kelvin. The ideas are first developed and implemented analytically and numerically in the context of hard sphere fluids. In an intermediate volume fraction crossover regime, the local cage process is dominant in a manner consistent with an apparent Arrhenius behavior. The super-Arrhenius collective barrier is more strongly dependent on volume fraction, dominates the highly viscous regime, and is well described by a nonsingular law below jamming. The increase of the collective barrier is determined by the amplitude of thermal density fluctuations, dynamic shear modulus or transient localization length, and a growing microscopic jump length. Alpha relaxation time calculations are in good agreement with recent experiments and simulations on dense fluids and suspensions of hard spheres. Comparisons of the theory with elastic models and entropy crisis ideas are explored. The present work provides a foundation for constructing a quasi-universal, fit-parameter-free theory for relaxation in thermal molecular liquids over 14 orders of magnitude in time. PMID:24852549
21 CFR 80.35 - Color additive mixtures; certification and exemption from certification.
Code of Federal Regulations, 2014 CFR
2014-04-01
... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Color additive mixtures; certification and... additive mixtures; certification and exemption from certification. (a) Color additive mixtures to be certified. Any color additive mixture that contains one or more straight colors listed in part 74 of...
21 CFR 80.35 - Color additive mixtures; certification and exemption from certification.
Code of Federal Regulations, 2011 CFR
2011-04-01
... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Color additive mixtures; certification and... additive mixtures; certification and exemption from certification. (a) Color additive mixtures to be certified. Any color additive mixture that contains one or more straight colors listed in part 74 of...
21 CFR 80.35 - Color additive mixtures; certification and exemption from certification.
Code of Federal Regulations, 2010 CFR
2010-04-01
... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Color additive mixtures; certification and... additive mixtures; certification and exemption from certification. (a) Color additive mixtures to be certified. Any color additive mixture that contains one or more straight colors listed in part 74 of...
21 CFR 80.35 - Color additive mixtures; certification and exemption from certification.
Code of Federal Regulations, 2013 CFR
2013-04-01
... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Color additive mixtures; certification and... additive mixtures; certification and exemption from certification. (a) Color additive mixtures to be certified. Any color additive mixture that contains one or more straight colors listed in part 74 of...
21 CFR 80.35 - Color additive mixtures; certification and exemption from certification.
Code of Federal Regulations, 2012 CFR
2012-04-01
... 21 Food and Drugs 1 2012-04-01 2012-04-01 false Color additive mixtures; certification and... additive mixtures; certification and exemption from certification. (a) Color additive mixtures to be certified. Any color additive mixture that contains one or more straight colors listed in part 74 of...
NASA Astrophysics Data System (ADS)
Hansen-Goos, Hendrik
2016-04-01
We derive an analytical equation of state for the hard-sphere fluid that is within 0.01% of computer simulations for the whole range of the stable fluid phase. In contrast, the commonly used Carnahan-Starling equation of state deviates by up to 0.3% from simulations. The derivation uses the functional form of the isothermal compressibility from the Percus-Yevick closure of the Ornstein-Zernike relation as a starting point. Two additional degrees of freedom are introduced, which are constrained by requiring the equation of state to (i) recover the exact fourth virial coefficient B4 and (ii) involve only integer coefficients on the level of the ideal gas, while providing best possible agreement with the numerical result for B5. Virial coefficients B6 to B10 obtained from the equation of state are within 0.5% of numerical computations, and coefficients B11 and B12 are within the error of numerical results. We conjecture that even higher virial coefficients are reliably predicted.
Lurio, L. B.; Lumma, D.; Sandy, A. R.; Borthwick, M. A.; Falus, P.; Mochrie, S. G. J.; Pelletier, J. F.; Sutton, M.; Regan, Lynne; Malik, A.
2000-01-24
X-ray photon correlation spectroscopy and small-angle scattering measurements are presented of the dynamics and structure of concentrated suspensions of charge-stabilized polystyrene latex spheres dispersed in glycerol, for volume fractions from 3% to 52% . The static structures of the suspensions show essentially hard-sphere behavior, and the short-time dynamics shows good agreement with predictions for the wave-vector-dependent collective diffusion coefficient. However, the intermediate scattering function is found to violate a scaling behavior found previously for a sterically stabilized hard-sphere suspension [P. N. Segre and P. N. Pusey, Phys. Rev. Lett. 77, 771 (1996)]. (c) 2000 The American Physical Society.
NASA Astrophysics Data System (ADS)
Reiss, Howard; Manzanares, José A.
2016-09-01
Using several theoretical toolsldots (i) the nucleation theorem, (ii) an equivalent cavity, (iii) the reversible work of adding a cavity to an open hard sphere system, and (iv) the theory of "stability"... the authors estimated the density at which the hard sphere freezing transition occurs. No direct involvement of the equilibrium solid phase is involved. The reduced density \\uppi a^3ρ _f/6 (where a is the hard sphere diameter and ρ _f is the actual density at which freezing occurs) is found to be 0.4937 while the value obtained by computer simulation is 0.494. The agreement is good, but the new method still contains some approximation. However, the approximation is based on the idea that at a density just below ρ _f the fluid adopts a distorted structure resembling the solid, but different enough so that long-range order vanishes. Initial loss of stability may not be involved in every fluid-solid transition, but it may be an early step in the hard sphere and related systems.
40 CFR 716.105 - Additions of substances and mixtures to which this subpart applies.
Code of Federal Regulations, 2012 CFR
2012-07-01
... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Additions of substances and mixtures... Listings § 716.105 Additions of substances and mixtures to which this subpart applies. The requirements of this subpart will be extended periodically to cover additional substances and mixtures. Two...
40 CFR 716.105 - Additions of substances and mixtures to which this subpart applies.
Code of Federal Regulations, 2013 CFR
2013-07-01
... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Additions of substances and mixtures... Listings § 716.105 Additions of substances and mixtures to which this subpart applies. The requirements of this subpart will be extended periodically to cover additional substances and mixtures. Two...
40 CFR 716.105 - Additions of substances and mixtures to which this subpart applies.
Code of Federal Regulations, 2010 CFR
2010-07-01
... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Additions of substances and mixtures... Listings § 716.105 Additions of substances and mixtures to which this subpart applies. The requirements of this subpart will be extended periodically to cover additional substances and mixtures. Two...
40 CFR 716.105 - Additions of substances and mixtures to which this subpart applies.
Code of Federal Regulations, 2011 CFR
2011-07-01
... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Additions of substances and mixtures... Listings § 716.105 Additions of substances and mixtures to which this subpart applies. The requirements of this subpart will be extended periodically to cover additional substances and mixtures. Two...
A colloidal model system with an interaction tunable from hard sphere to soft and dipolar.
Yethiraj, Anand; van Blaaderen, Alfons
2003-01-30
Monodisperse colloidal suspensions of micrometre-sized spheres are playing an increasingly important role as model systems to study, in real space, a variety of phenomena in condensed matter physics--such as glass transitions and crystal nucleation. But to date, no quantitative real-space studies have been performed on crystal melting, or have investigated systems with long-range repulsive potentials. Here we demonstrate a charge- and sterically stabilized colloidal suspension--poly(methyl methacrylate) spheres in a mixture of cycloheptyl (or cyclohexyl) bromide and decalin--where both the repulsive range and the anisotropy of the interparticle interaction potential can be controlled. This combination of two independent tuning parameters gives rise to a rich phase behaviour, with several unusual colloidal (liquid) crystalline phases, which we explore in real space by confocal microscopy. The softness of the interaction is tuned in this colloidal suspension by varying the solvent salt concentration; the anisotropic (dipolar) contribution to the interaction potential can be independently controlled with an external electric field ranging from a small perturbation to the point where it completely determines the phase behaviour. We also demonstrate that the electric field can be used as a pseudo-thermodynamic temperature switch to enable real-space studies of melting transitions. We expect studies of this colloidal model system to contribute to our understanding of, for example, electro- and magneto-rheological fluids.
Dynamics of Disorder-Order Transitions in Hard Sphere Colloidal Dispersions in micro-g
NASA Technical Reports Server (NTRS)
Zhu, J. X.; Li, M.; Phan, S. E.; Russel, W. B.; Chaikin, Paul M.; Rogers, Rick; Meyers, W.
1996-01-01
We performed a series of experiments on 0.518 millimeter PMMA spheres suspended in an index matching mixture of decalin and tetralin the microgravity environment provided by the Shuttle Columbia on mission STS-73. The samples ranged in concentration from 0.49 to 0.62. volume fraction (phi) of spheres, which covers the range in which liquid, coexistence, solid and glass phases are expected from Earth bound experiments. Light scattering was used to probe the static structure, and the particle dynamics. Digital and 35 mm photos provided information on the morphology of the crystals. In general, the crystallites grew considerably larger (roughly an order of magnitude larger) than the same samples with identical treatment in 1 g. The dynamic light scattering shows the typical short time diffusion and long time caging effects found in 1 g. The surprises that were encountered in microgravity include the preponderance of random hexagonal close packed (RHCP) structures and the complete absence of the expected face centered cubic (FCC) structure, existence of large dendritic crystals floating in the coexistence samples (where liquid and solid phases coexist) and the rapid crystallization of samples which exist only in glass phase under the influence of one g. These results suggest that colloidal crystal growth is profoundly effected by gravity in yet unrecognized ways. We suspect that the RCHP structure is related to the nonequilibrium growth that is evident from the presence of dendrites. An analysis of the dendritic growth instabilities is presented within the framework of the Ackerson-Schatzel equation.
Gelation in a model 1-component system with adhesive hard-sphere interactions
NASA Astrophysics Data System (ADS)
Kim, Jung Min; Eberle, Aaron; Fang, Jun; Wagner, Norman
2012-02-01
Colloidal dispersions can undergo a dynamical arrest of the disperse phase leading to a system with solid-like properties when either the volume fraction or the interparticle potential is varied. Systems that contain low to moderate particulate concentrations form gels whereas higher concentrations lead to glassy states in which caging by nearest neighbors can be a significant contributor to the arrested long-time dynamics. Colloid polymer mixtures have been the prevalent model system for studying the effect of attraction, where attractions are entropically driven by depletion effects, in which gelation has been shown to be a result of phase separation [1]. Using the model 1-component octadecyl coated silica nanoparticle system, Eberle et al. [2] found the gel-line to intersect the spinodal to the left of the critical point, and at higher concentrations extended toward the mode coupling theory attractive driven glass line. . We continue this study by varying the particle diameter and find quantitative differences which we explain by gravity. 1. Lu, P.J., et al., Nature, 2008. 453(7194): p. 499-504.2. Eberle, A.P.R., N.J. Wagner, and R. Castaneda-Priego, Physical Review Letters, 2011. 106(10).
NASA Astrophysics Data System (ADS)
Siderius, Daniel William
Despite the lack of attractive interaction potentials in hard-sphere (HS) colloidal dispersions, a colloid immersed in a solvent of smaller hard-spheres may still experience a net force toward a surface due to imbalanced collisions. Consequently, depletion forces may be utilized to control self-assembly of colloidal structures on various surfaces or control aggregation of colloidal dispersions. To begin to better understand the ability of depletion forces to generate colloidal structures, guide colloidal motion, and control aggregation, accurate theoretical descriptions of depletion forces are necessary. Here, we discuss models of HS colloidal dispersions based on the ideas of Scaled Particle Theory (SPT) to provide methods of computing both HS thermophysical properties and depletion forces in HS fluids. We begin by introducing a new SPT interpolation that accurately provides many HS fluid properties, including the surface tension. We then further develop the inhomogeneous SPT (I-SPT) that describes cavities grown near a planar surface that confines a HS fluid, thereby providing a complete description of cavities near a planar surface, i.e., cavities that are centered at any position relative to the wall. The surface thermodynamics of HS cavities are then reexamined using a Gibbs dividing surface analysis, which produces thermodynamic expressions related to, among other things, the line tension of a HS cavity. Subsequently, we utilize I-SPT to compute the HS line tension and explore its behavior for different cavity locations. Using the accurate description of HS surface thermodynamics from SPT and I-SPT, we then construct a geometric model of depletion forces that is generalizable to many different surface structures and is based on different thermodynamic approximations. Versions of the geometric model based on HS surface thermodynamics (including the line tension) are demonstrated to be highly accurate, though simpler versions based on ideal gas arguments are
Schifferstein, H N
1996-02-01
The Equiratio Mixture Model predicts the psychophysical function for an equiratio mixture type on the basis of the psychophysical functions for the unmixed components. The model reliably estimates the sweetness of mixtures of sugars and sugar-alcohols, but is unable to predict intensity for aspartame/sucrose mixtures. In this paper, the sweetness of aspartame/acesulfame-K mixtures in aqueous and acidic solutions is investigated. These two intensive sweeteners probably do not comply with the model's original assumption of sensory dependency among components. However, they reveal how the Equiratio Mixture Model could be modified to describe and predict mixture functions for non-additive substances. To predict equiratio functions for all similar tasting substances, a new Equiratio Mixture Model should yield accurate predictions for components eliciting similar intensities at widely differing concentration levels, and for substances exhibiting hypo- or hyperadditivity. In addition, it should be able to correct violations of Stevens's power law. These three problems are resolved in a model that uses equi-intense units as the measure of physical concentration. An interaction index in the formula for the constant accounts for the degree of interaction between mixture components. Deviations from the power law are corrected by a nonlinear response output transformation, assuming a two-stage model of psychophysical judgment.
Sesé, Luis M
2012-06-28
A systematic study of the direct computation of the isothermal compressibility of normal quantum fluids is presented by analyzing the solving of the Ornstein-Zernike integral (OZ2) equation for the pair correlations between the path-integral necklace centroids. A number of issues related to the accuracy that can be achieved via this sort of procedure have been addressed, paying particular attention to the finite-N effects and to the definition of significant error bars for the estimates of isothermal compressibilities. Extensive path-integral Monte Carlo computations for the quantum hard-sphere fluid (QHS) have been performed in the (N, V, T) ensemble under temperature and density conditions for which dispersion effects dominate the quantum behavior. These computations have served to obtain the centroid correlations, which have been processed further via the numerical solving of the OZ2 equation. To do so, Baxter-Dixon-Hutchinson's variational procedure, complemented with Baumketner-Hiwatari's grand-canonical corrections, has been used. The virial equation of state has also been obtained and several comparisons between different versions of the QHS equation of state have been made. The results show the reliability of the procedure based on isothermal compressibilities discussed herein, which can then be regarded as a useful and quick means of obtaining the equation of state for fluids under quantum conditions involving strong repulsive interactions.
NASA Astrophysics Data System (ADS)
Zhou, Alice; O'Hern, Corey; Regan, Lynne
2013-03-01
We seek to dramatically improve computational protein design using minimal models that include only the dominant physical interactions. By modeling proteins with hard-sphere interactions and stereochemical constraints, we are able to explain the side-chain dihedral angle distributions for Leu, Ile, and other hydrophobic residues that are observed in protein crystal structures. We also consider inter-residue interactions on the distribution of side-chain dihedral angles for residues in the hydrophobic core of T4 lysozyme. We calculate the energetic and entropic contributions to the free energy differences between wildtype T4 lysozyme and several mutants involving Leu to Ala substitutions. We find a strong correlation between the entropy difference and the decrease in the melting temperature of the mutatants. These results emphasize that considering both entropy and enthalpy is crucial for obtaining a quantitative understanding of protein stability. NSF DMR-1006537 and PHY-1019147, the Raymond and Beverly Sackler Institute for Biological, Physical and Engineering Sciences, and Howard Hughes Medical Institute International Research Fellowship
NASA Astrophysics Data System (ADS)
Icardi, Matteo; Asinari, Pietro; Marchisio, Daniele; Izquierdo, Salvador; Fox, Rodney
2011-11-01
Recently the Quadrature Method of Moments (QMOM) has been extended to solve several kinetic equations, in particular for gas-particle flows and rarefied gases. This method is usually coupled with simplified linear models for particle collisions. In this work QMOM is tested as a closure for the dynamics of high-order moments with a more realistic collision model namely the hard-spheres model in the Homogeneous Isotropic Boltzmann Equation. The behavior of QMOM far away and approaching the equilibrium is studied. Results are compared to other techniques such as the Lattice-Boltzmann (LBM) and the Grad's expansion (GM) methods. Comparison with a more accurate and computationally expensive model, based on the Discrete Velocity Method (DVM), is also carried out. Our results show that QMOM describes very well the evolution when it is far away from equilibrium, without the drawbacks of the GM and LBM or the computational costs of DVM but it is not able to accurately reproduce the equilibrium and the dynamics close to it. Corrections to cure this behavior are proposed and tested.
NASA Astrophysics Data System (ADS)
Icardi, M.; Asinari, P.; Marchisio, D. L.; Izquierdo, S.; Fox, R. O.
2012-08-01
Recently the Quadrature Method of Moments (QMOM) has been extended to solve several kinetic equations, in particular for gas-particle flows and rarefied gases in which the non-equilibrium effects can be important. In this work QMOM is tested as a closure for the dynamics of the Homogeneous Isotropic Boltzmann Equation (HIBE) with a realistic description for particle collisions, namely the hard-sphere model. The behaviour of QMOM far away and approaching the equilibrium is studied. Results are compared to other techniques such as the Grad's moment method (GM) and the off-Lattice Boltzmann Method (oLBM). Comparison with a more accurate and computationally expensive approach, based on the Discrete Velocity Method (DVM), is also carried out. Our results show that QMOM describes very well the evolution when it is far away from equilibrium, without the drawbacks of the GM and oLBM or the computational costs of DVM, but it is not able to accurately reproduce equilibrium and the dynamics close to it. Static and dynamic corrections to cure this behaviour are here proposed and tested.
NASA Astrophysics Data System (ADS)
Elfimova, Ekaterina A.; Karavaeva, Tatyana E.; Ivanov, Alexey O.
2014-12-01
A method for calculation of the free energy of dipolar hard spheres under the presence of an applied magnetic field is presented. The method is based on the virial expansion in terms of density as well as the dipolar coupling constant λ, and it uses diagram technique. The formulas and the diagrams, needed to calculate the second B2 and third B3 virial coefficients, are derived up to the order of ˜λ3, and compared to the zero-field case. The formula for B2 is the same as in the zero-field case; the formula for B3, however, is different in an applied field, and a derivation is presented. This is a surprising result which is not emphasized in standard texts, but which has been noticed before in the virial expansion for flexible molecules (Caracciolo et al., 2006; Caracciolo et al., 2008). To verify the correctness of the obtained formulas, B2 and B3 were calculated within the accuracy of λ2, which were applied to initial magnetic susceptibility. The obtained expression fully coincides with the well-known theories (Morozov and Lebedev, 1990; Huke and Lücke, 2000; Ivanov and Kuznetsova, 2001), which used different methods to calculate the initial magnetic susceptibility.
Boda, Dezső; Henderson, Douglas; Eisenberg, Bob; Gillespie, Dirk
2011-01-01
In the implicit solvent models of electrolytes (such as the primitive model (PM)), the ions are modeled as point charges in the centers of spheres (hard spheres in the case of the PM). The surfaces of the spheres are not polarizable which makes these models appropriate to use in computer simulations of electrolyte systems where these ions do not leave their host dielectrics. The same assumption makes them inappropriate in simulations where these ions cross dielectric boundaries because the interaction energy of the point charge with the polarization charge induced on the dielectric boundary diverges. In this paper, we propose a procedure to treat the passage of such ions through dielectric interfaces with an interpolation method. Inspired by the “bubble ion” model (in which the ion's surface is polarizable), we define a space-dependent effective dielectric coefficient, ε eff (r), for the ion that overlaps with the dielectric boundary. Then, we replace the “bubble ion” with a point charge that has an effective charge q∕ε eff (r) and remove the portion of the dielectric boundary where the ion overlaps with it. We implement the interpolation procedure using the induced charge computation method [D. Boda, D. Gillespie, W. Nonner, D. Henderson, and B. Eisenberg, Phys. Rev. E 69, 046702 (2004)]. We analyze the various energy terms using a spherical ion passing through an infinite flat dielectric boundary as an example. PMID:21842924
Equation of state for hard convex body fluid mixtures
NASA Astrophysics Data System (ADS)
Barrio, C.; Solana, J. R.
A model previously developed for the equation of state of pure fluids consisting of hard convex body molecules is extended to mixtures. The parameters of the model can be determined from the geometrical characteristics of the molecules which form the mixture. The equation of state is in excellent agreement with simulation data for mixtures of hard spheres with hard spherocylinders.
Entropy and enthalpy convergence of hydrophobic solvation beyond the hard-sphere limit.
Sedlmeier, Felix; Horinek, Dominik; Netz, Roland R
2011-02-01
The experimentally well-known convergence of solvation entropies and enthalpies of different small hydrophobic solutes at universal temperatures seems to indicate that hydrophobic solvation is dominated by universal water features and not so much by solute specifics. The reported convergence of the denaturing entropy of a group of different proteins at roughly the same temperature as hydrophobic solutes was consequently argued to indicate that the denaturing entropy of proteins is dominated by the hydrophobic effect and used to estimate the hydrophobic contribution to protein stability. However, this appealing picture was subsequently questioned since the initially claimed universal convergence of denaturing entropies holds only for a small subset of proteins; for a larger data collection no convergence is seen. We report extensive simulation results for the solvation of small spherical solutes in explicit water with varying solute-water potentials. We show that convergence of solvation properties for solutes of different radii exists but that the convergence temperatures depend sensitively on solute-water potential features such as stiffness of the repulsive part and attraction strength, not so much on the attraction range. Accordingly, convergence of solvation properties is only expected for solutes of a homologous series that differ in the number of one species of subunits (which attests to the additivity of solvation properties) or solutes that are characterized by similar solute-water interaction potentials. In contrast, for peptides that arguably consist of multiple groups with widely disperse interactions with water, it means that thermodynamic convergence at a universal temperature cannot be expected, in general, in agreement with experimental results.
Bulk fluid phase behaviour of colloidal platelet-sphere and platelet-polymer mixtures.
de las Heras, Daniel; Schmidt, Matthias
2013-04-13
Using a geometry-based fundamental measure density functional theory, we calculate bulk fluid phase diagrams of colloidal mixtures of vanishingly thin hard circular platelets and hard spheres. We find isotropic-nematic phase separation, with strong broadening of the biphasic region, upon increasing the pressure. In mixtures with large size ratio of platelet and sphere diameters, there is also demixing between two nematic phases with differing platelet concentrations. We formulate a fundamental measure density functional for mixtures of colloidal platelets and freely overlapping spheres, which represent ideal polymers, and use it to obtain phase diagrams. We find that, for low platelet-polymer size ratio, in addition to isotropic-nematic and nematic-nematic phase coexistence, platelet-polymer mixtures also display isotropic-isotropic demixing. By contrast, we do not find isotropic-isotropic demixing in hard-core platelet-sphere mixtures for the size ratios considered.
A Four Step Approach to Evaluate Mixtures for Consistency with Dose Addition
We developed a four step approach for evaluating chemical mixture data for consistency with dose addition for use in environmental health risk assessment. Following the concepts in the U.S. EPA mixture risk guidance (EPA 2000a,b), toxicological interaction for a defined mixture (...
NASA Astrophysics Data System (ADS)
Kang, Hong Seok; Ree, Francis H.
1995-12-01
The perturbative hypernetted-chain (PHNC) equation developed recently has been applied to the one-component plasma (OCP) and the one-component charged hard-sphere (OCCHS) systems in a uniform compensating background. Computed thermodynamic properties and pair correlation functions show that the PHNC gives excellent agreement with computer simulations and that it is as accurate as (or, in some cases, superior to) the reference-hypernetted chain and the hypernetted-chain-mean spherical equations, representing the two best currently available theories. The PHNC also predicts the OCP screening function at short range in close agreement with computer simulations and is superior to other theoretical results. Reliability of the radial distribution function at the hard-sphere contact distance for the OCCHS is also discussed.
NASA Astrophysics Data System (ADS)
Hu, Jia-Wen; Yu, Yang-Xin
2009-08-01
The nth virial coefficient for a hard-sphere system is expressed as the sum of n2 and a remainder. When n >= 3, the remainders of the virials can be accurately expressed with Pade-type functions of n. The maximum deviations are only 0.039-0.053%, which are much better than the existing approaches. By using the predicted virials, the compressibility factors of the hard-sphere system can be predicted very accurately in the whole stable fluid region, and those in the metastable fluid region can also be well predicted up to a packing fraction of 0.545. The simulated B7 and B10 are found to be inconsistent with the other known virials, and thus they are refined to be 53.2467 and 105.042, respectively.
NASA Astrophysics Data System (ADS)
Parisi, Giorgio
In a hard spheres systems particles cannot overlap. Increasing the density we reach a point where most of the particles are blocked and the density cannot be increased any more: this is the jamming point. The jamming point separates the phase, where all the constraint can be satisfied, from an unsatifiable phase, where spheres do have to overlap. A scaling theory of the behavior around the jamming critical point has been formulated and a few critical exponents have been introduced. The exponents are apparently super-universal, as far as they do seem to be independent from the space dimensions. The mean field version of the model (i.e. the infinite dimensions limit) has been solved analytically using broken replica symmetry techniques and the computed critical exponents have been found in a remarkable agreement with three-dimensional and two-dimensional numerical results and experiments. The theory predicts in hard spheres (in glasses) a new transition (the Gardener transition) from the replica symmetric phase to the replica broken phase at high density (at low temperature), in agreement with simulations on hard sphere systems. I will briefly discuss the possible consequences of this new picture on the very low temperature behavior of glasses in the quantum regime.
NASA Technical Reports Server (NTRS)
Zhu, Ji-Xiang; Chaikin, P. M.; Li, Min; Russel, W. B.; Ottewill, R. H.; Rogers, R.; Meyer, W. V.
1998-01-01
Classical hard spheres have long served as a paradigm for our understanding of the structure of liquids, crystals, and glasses and the transitions between these phases. Ground-based experiments have demonstrated that suspensions of uniform polymer colloids are near-ideal physical realizations of hard spheres. However, gravity appears to play a significant and unexpected role in the formation and structure of these colloidal crystals. In the microgravity environment of the Space Shuttle, crystals grow purely via random stacking of hexagonal close-packed planes, lacking any of the face-centered cubic (FCC) component evident in crystals grown in 1 g beyond melting and allowed some time to settle. Gravity also masks 33-539 the natural growth instabilities of the hard sphere crystals which exhibit striking dendritic arms when grown in microgravity. Finally, high volume fraction "glass" samples which fail to crystallize after more than a year in 1 g begin nucleation after several days and fully crystallize in less than 2 weeks on the Space Shuttle.
40 CFR 716.105 - Additions of substances and mixtures to which this subpart applies.
Code of Federal Regulations, 2014 CFR
2014-07-01
... 40 CFR part 716, via CDX. Submission requires registration with CDX, and must be made only as set... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Additions of substances and mixtures... Listings § 716.105 Additions of substances and mixtures to which this subpart applies. The requirements...
21 CFR 73.1001 - Diluents in color additive mixtures for drug use exempt from certification.
Code of Federal Regulations, 2014 CFR
2014-04-01
... Restrictions Alcohol, specially denatured As set forth in 26 CFR, pt. 212 As set forth in 26 CFR, pt. 211... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Diluents in color additive mixtures for drug use... § 73.1001 Diluents in color additive mixtures for drug use exempt from certification. The...
21 CFR 73.1001 - Diluents in color additive mixtures for drug use exempt from certification.
Code of Federal Regulations, 2013 CFR
2013-04-01
... Restrictions Alcohol, specially denatured As set forth in 26 CFR, pt. 212 As set forth in 26 CFR, pt. 211... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Diluents in color additive mixtures for drug use... § 73.1001 Diluents in color additive mixtures for drug use exempt from certification. The...
21 CFR 73.1001 - Diluents in color additive mixtures for drug use exempt from certification.
Code of Federal Regulations, 2012 CFR
2012-04-01
... Restrictions Alcohol, specially denatured As set forth in 26 CFR, pt. 212 As set forth in 26 CFR, pt. 211... 21 Food and Drugs 1 2012-04-01 2012-04-01 false Diluents in color additive mixtures for drug use... § 73.1001 Diluents in color additive mixtures for drug use exempt from certification. The...
NASA Astrophysics Data System (ADS)
Zhou, Shiqi
2011-12-01
Thermodynamic and structural properties of liquids are of fundamental interest in physics, chemistry, and biology, and perturbation approach has been fundamental to liquid theoretical approaches since the dawn of modern statistical mechanics and remains so to this day. Although thermodynamic perturbation theory (TPT) is widely used in the chemical physics community, one of the most popular versions of the TPT, i.e. Zwanzig (Zwanzig, R. W. J. Chem. Phys. 1954, 22, 1420-1426) 1st-order high temperature series expansion (HTSE) TPT and its 2nd-order counterpart under a macroscopic compressibility approximation of Barker-Henderson (Barker, J. A.; Henderson, D. J. Chem. Phys. 1967, 47, 2856-2861), have some serious shortcomings: (i) the nth-order term of the HTSE is involved with reference fluid distribution functions of order up to 2n, and the higher-order terms hence progressively become more complicated and numerically inaccessible; (ii) the performance of the HTSE rapidly deteriorates and the calculated results become even qualitatively incorrect as the temperature of interest decreases. This account deals with the developments that we have made over the last five years or so to advance a coupling parameter series expansion (CPSE) and a non hard sphere (HS) perturbation strategy that has scored some of its greatest successes in overcoming the above-mentioned difficulties. In this account (i) we expatiate on implementation details of our schemes: how input information indispensable to high-order truncation of the CPSE in both the HS and non HS perturbation schemes is calculated by an Ornstein-Zernike integral equation theory; how high-order thermodynamic quantities, such as critical parameters and excess constant volume heat capacity, are extracted from the resulting excess Helmholtz free energy with irregular and inevitable numerical errors; how to select reference potential in the non HS perturbation scheme. (ii) We give a quantitative analysis on why convergence
NASA Astrophysics Data System (ADS)
Housiadas, Kostas D.
2015-08-01
An effective-medium fluid mechanics model based on the original idea first presented by Brinkman ["A calculation of the viscous force exerted by a flowing fluid on a dense swarm of particles," Appl. Sci. Res. 1, 27-34 (1949)] for the viscous force exerted by a flowing fluid on a dense swarm of fixed spherical particles is utilized for the prediction of the elongational viscosity of a non-colloidal, non-Brownian hard-sphere suspension in an incompressible Newtonian matrix fluid. The same model was explored by Housiadas and Tanner ["A model for the shear viscosity of non-colloidal suspensions with Newtonian matrix fluids," Rheol. Acta 53, 831-841 (2014)] for the derivation of an analytical formula for the bulk shear viscosity of the suspension as a function of the volume fraction of the solid phase, a formula which is in very good agreement with widely used semi-empirical relationships and available experimental data from the literature. In the present paper, it is assumed that a spherical particle is subject, in an average sense, to a far-field uniform uniaxial elongational flow and a suitable pressure gradient. Under steady, isothermal, creeping conditions, and imposing no-slip and no-penetration conditions at the surface of a particle in a stagnation point of the fluid and the far-field velocity and pressure profiles, the solution of the three-dimensional Brinkman equations is found analytically. The solution shows a faster decay of the velocity disturbances around a reference particle than the single-particle case. A volume average of the total stress tensor gives an analytical formula for the bulk elongational viscosity of the complex system as a function of the particle concentration. A significant increase of the elongation viscosity with increasing the particle concentration is predicted. The increase is larger than the corresponding increase of the shear viscosity, in qualitative accordance with the theoretical formula of Batchelor and Green ["The
Evaluation of Warm Mix Asphalt Additives for Use in Modified Asphalt Mixtures
NASA Astrophysics Data System (ADS)
Chamoun, Zahi
The objective of this research effort is to evaluate the use of warm-mix additives with polymer modified and terminal blend tire rubber asphalt mixtures from Nevada and California. The research completed over two stages: first stage evaluated two different WMA technologies; Sasobit and Advera, and second stage evaluated one additional WMA technology; Evotherm. The experimental program covered the evaluation of resistance of the mixtures to moisture damage, the performance characteristics of the mixtures, and mechanistic analysis of mixtures in simulated pavements. In the both stages, the mixture resistance to moisture damage was evaluated using the indirect tensile test and the dynamic modulus at multiple freeze-thaw cycles, and the resistance of the various asphalt mixtures to permanent deformation using the Asphalt Mixture Performance Tester (AMPT). Resistance of the untreated mixes to fatigue cracking using the flexural beam fatigue was only completed for the first stage. One source of aggregates was sampled in, two different batches, three warm mix asphalt technologies (Advera, Sasobit and Evotherm) and three asphalt binder types (neat, polymer-modified, and terminal blend tire rubber modified asphalt binders) typically used in Nevada and California were evaluated in this study. This thesis presents the resistance of the first stage mixtures to permanent deformation and fatigue cracking using two warm-mix additives; Advera and Sasobit, and the resistance to moisture damage and permanent deformation of the second stage mixtures with only one warm-mix additive; Evotherm.
Additive and synergistic antiandrogenic activities of mixtures of azol fungicides and vinclozolin
Christen, Verena; Crettaz, Pierre; Fent, Karl
2014-09-15
Objective: Many pesticides including pyrethroids and azole fungicides are suspected to have an endocrine disrupting property. At present, the joint activity of compound mixtures is only marginally known. Here we tested the hypothesis that the antiandrogenic activity of mixtures of azole fungicides can be predicted by the concentration addition (CA) model. Methods: The antiandrogenic activity was assessed in MDA-kb2 cells. Following assessing single compounds activities mixtures of azole fungicides and vinclozolin were investigated. Interactions were analyzed by direct comparison between experimental and estimated dose–response curves assuming CA, followed by an analysis by the isobole method and the toxic unit approach. Results: The antiandrogenic activity of pyrethroids deltamethrin, cypermethrin, fenvalerate and permethrin was weak, while the azole fungicides tebuconazole, propiconazole, epoxiconazole, econazole and vinclozolin exhibited strong antiandrogenic activity. Ten binary and one ternary mixture combinations of five antiandrogenic fungicides were assessed at equi-effective concentrations of EC{sub 25} and EC{sub 50}. Isoboles indicated that about 50% of the binary mixtures were additive and 50% synergistic. Synergism was even more frequently indicated by the toxic unit approach. Conclusion: Our data lead to the conclusion that interactions in mixtures follow the CA model. However, a surprisingly high percentage of synergistic interactions occurred. Therefore, the mixture activity of antiandrogenic azole fungicides is at least additive. Practice: Mixtures should also be considered for additive antiandrogenic activity in hazard and risk assessment. Implications: Our evaluation provides an appropriate “proof of concept”, but whether it equally translates to in vivo effects should further be investigated. - Highlights: • Humans are exposed to pesticide mixtures such as pyrethroids and azole fungicides. • We assessed the antiandrogenicity of
A four-step approach to evaluate mixtures for consistency with dose addition.
Hertzberg, Richard C; Pan, Yi; Li, Ruosha; Haber, Lynne T; Lyles, Robert H; Herr, David W; Moser, Virginia C; Simmons, Jane Ellen
2013-11-16
Mixture risk assessment is often hampered by the lack of dose-response information on the mixture being assessed, forcing reliance on component formulas such as dose addition. We present a four-step approach for evaluating chemical mixture data for consistency with dose addition for use in supporting a component based mixture risk assessment. Following the concepts in the U.S. EPA mixture risk guidance (U.S. EPA, 2000a,b), toxicological interaction for a defined mixture (all components known) is departure from a clearly articulated definition of component additivity. For the common approach of dose additivity, the EPA guidance identifies three desirable characteristics, foremost of which is that the component chemicals are toxicologically similar. The other two characteristics are empirical: the mixture components have toxic potencies that are fixed proportions of each other (throughout the dose range of interest), and the mixture dose term in the dose additive prediction formula, which we call the combined prediction model (CPM), can be represented by a linear combination of the component doses. A consequent property of the proportional toxic potencies is that the component chemicals must share a common dose-response model, where only the dose coefficients depend on the chemical components. A further consequence is that the mixture data must be described by the same mathematical function ("mixture model") as the components, but with a distinct coefficient for the total mixture dose. The mixture response is predicted from the component dose-response curves by using the dose additive CPM and the prediction is then compared with the observed mixture results. The four steps are to evaluate: (1) toxic proportionality by determining how well the CPM matches the single chemical models regarding mean and variance; (2) fit of the mixture model to the mixture data; (3) agreement between the mixture data and the CPM prediction; and (4) consistency between the CPM and the
A four-step approach to evaluate mixtures for consistency with dose addition.
Hertzberg, Richard C; Pan, Yi; Li, Ruosha; Haber, Lynne T; Lyles, Robert H; Herr, David W; Moser, Virginia C; Simmons, Jane Ellen
2013-11-16
Mixture risk assessment is often hampered by the lack of dose-response information on the mixture being assessed, forcing reliance on component formulas such as dose addition. We present a four-step approach for evaluating chemical mixture data for consistency with dose addition for use in supporting a component based mixture risk assessment. Following the concepts in the U.S. EPA mixture risk guidance (U.S. EPA, 2000a,b), toxicological interaction for a defined mixture (all components known) is departure from a clearly articulated definition of component additivity. For the common approach of dose additivity, the EPA guidance identifies three desirable characteristics, foremost of which is that the component chemicals are toxicologically similar. The other two characteristics are empirical: the mixture components have toxic potencies that are fixed proportions of each other (throughout the dose range of interest), and the mixture dose term in the dose additive prediction formula, which we call the combined prediction model (CPM), can be represented by a linear combination of the component doses. A consequent property of the proportional toxic potencies is that the component chemicals must share a common dose-response model, where only the dose coefficients depend on the chemical components. A further consequence is that the mixture data must be described by the same mathematical function ("mixture model") as the components, but with a distinct coefficient for the total mixture dose. The mixture response is predicted from the component dose-response curves by using the dose additive CPM and the prediction is then compared with the observed mixture results. The four steps are to evaluate: (1) toxic proportionality by determining how well the CPM matches the single chemical models regarding mean and variance; (2) fit of the mixture model to the mixture data; (3) agreement between the mixture data and the CPM prediction; and (4) consistency between the CPM and the
NASA Astrophysics Data System (ADS)
Hayashi, Tomohiko; Oshima, Hiraku; Harano, Yuichi; Kinoshita, Masahiro
2016-09-01
For neutral hard-sphere solutes, we compare the reduced density profile of water around a solute g(r), solvation free energy μ, energy U, and entropy S under the isochoric condition predicted by the two theories: dielectrically consistent reference interaction site model (DRISM) and angle-dependent integral equation (ADIE) theories. A molecular model for water pertinent to each theory is adopted. The hypernetted-chain (HNC) closure is employed in the ADIE theory, and the HNC and Kovalenko-Hirata (K-H) closures are tested in the DRISM theory. We also calculate g(r), U, S, and μ of the same solute in a hard-sphere solvent whose molecular diameter and number density are set at those of water, in which case the radial-symmetric integral equation (RSIE) theory is employed. The dependences of μ, U, and S on the excluded volume and solvent-accessible surface area are analyzed using the morphometric approach (MA). The results from the ADIE theory are in by far better agreement with those from computer simulations available for g(r), U, and μ. For the DRISM theory, g(r) in the vicinity of the solute is quite high and becomes progressively higher as the solute diameter d U increases. By contrast, for the ADIE theory, it is much lower and becomes further lower as d U increases. Due to unphysically positive U and significantly larger |S|, μ from the DRISM theory becomes too high. It is interesting that μ, U, and S from the K-H closure are worse than those from the HNC closure. Overall, the results from the DRISM theory with a molecular model for water are quite similar to those from the RSIE theory with the hard-sphere solvent. Based on the results of the MA analysis, we comparatively discuss the different theoretical methods for cases where they are applied to studies on the solvation of a protein.
NASA Astrophysics Data System (ADS)
Hayashi, Tomohiko; Oshima, Hiraku; Harano, Yuichi; Kinoshita, Masahiro
2016-09-01
For neutral hard-sphere solutes, we compare the reduced density profile of water around a solute g(r), solvation free energy μ, energy U, and entropy S under the isochoric condition predicted by the two theories: dielectrically consistent reference interaction site model (DRISM) and angle-dependent integral equation (ADIE) theories. A molecular model for water pertinent to each theory is adopted. The hypernetted-chain (HNC) closure is employed in the ADIE theory, and the HNC and Kovalenko–Hirata (K–H) closures are tested in the DRISM theory. We also calculate g(r), U, S, and μ of the same solute in a hard-sphere solvent whose molecular diameter and number density are set at those of water, in which case the radial-symmetric integral equation (RSIE) theory is employed. The dependences of μ, U, and S on the excluded volume and solvent-accessible surface area are analyzed using the morphometric approach (MA). The results from the ADIE theory are in by far better agreement with those from computer simulations available for g(r), U, and μ. For the DRISM theory, g(r) in the vicinity of the solute is quite high and becomes progressively higher as the solute diameter d U increases. By contrast, for the ADIE theory, it is much lower and becomes further lower as d U increases. Due to unphysically positive U and significantly larger |S|, μ from the DRISM theory becomes too high. It is interesting that μ, U, and S from the K–H closure are worse than those from the HNC closure. Overall, the results from the DRISM theory with a molecular model for water are quite similar to those from the RSIE theory with the hard-sphere solvent. Based on the results of the MA analysis, we comparatively discuss the different theoretical methods for cases where they are applied to studies on the solvation of a protein.
Hayashi, Tomohiko; Oshima, Hiraku; Harano, Yuichi; Kinoshita, Masahiro
2016-09-01
For neutral hard-sphere solutes, we compare the reduced density profile of water around a solute g(r), solvation free energy μ, energy U, and entropy S under the isochoric condition predicted by the two theories: dielectrically consistent reference interaction site model (DRISM) and angle-dependent integral equation (ADIE) theories. A molecular model for water pertinent to each theory is adopted. The hypernetted-chain (HNC) closure is employed in the ADIE theory, and the HNC and Kovalenko-Hirata (K-H) closures are tested in the DRISM theory. We also calculate g(r), U, S, and μ of the same solute in a hard-sphere solvent whose molecular diameter and number density are set at those of water, in which case the radial-symmetric integral equation (RSIE) theory is employed. The dependences of μ, U, and S on the excluded volume and solvent-accessible surface area are analyzed using the morphometric approach (MA). The results from the ADIE theory are in by far better agreement with those from computer simulations available for g(r), U, and μ. For the DRISM theory, g(r) in the vicinity of the solute is quite high and becomes progressively higher as the solute diameter d U increases. By contrast, for the ADIE theory, it is much lower and becomes further lower as d U increases. Due to unphysically positive U and significantly larger |S|, μ from the DRISM theory becomes too high. It is interesting that μ, U, and S from the K-H closure are worse than those from the HNC closure. Overall, the results from the DRISM theory with a molecular model for water are quite similar to those from the RSIE theory with the hard-sphere solvent. Based on the results of the MA analysis, we comparatively discuss the different theoretical methods for cases where they are applied to studies on the solvation of a protein.
Oshima, Hiraku; Kinoshita, Masahiro
2015-04-14
In earlier works, we showed that the entropic effect originating from the translational displacement of water molecules plays the pivotal role in protein folding and denaturation. The two different solvent models, hard-sphere solvent and model water, were employed in theoretical methods wherein the entropic effect was treated as an essential factor. However, there were similarities and differences in the results obtained from the two solvent models. In the present work, to unveil the physical origins of the similarities and differences, we simultaneously consider structural transition, cold denaturation, and pressure denaturation for the same protein by employing the two solvent models and considering three different thermodynamic states for each solvent model. The solvent-entropy change upon protein folding/unfolding is decomposed into the protein-solvent pair (PA) and many-body (MB) correlation components using the integral equation theories. Each component is further decomposed into the excluded-volume (EV) and solvent-accessible surface (SAS) terms by applying the morphometric approach. The four physically insightful constituents, (PA, EV), (PA, SAS), (MB, EV), and (MB, SAS), are thus obtained. Moreover, (MB, SAS) is discussed by dividing it into two factors. This all-inclusive investigation leads to the following results: (1) the protein-water many-body correlation always plays critical roles in a variety of folding/unfolding processes; (2) the hard-sphere solvent model fails when it does not correctly reproduce the protein-water many-body correlation; (3) the hard-sphere solvent model becomes problematic when the dependence of the many-body correlation on the solvent number density and temperature is essential: it is not quite suited to studies on cold and pressure denaturating of a protein; (4) when the temperature and solvent number density are limited to the ambient values, the hard-sphere solvent model is usually successful; and (5) even at the ambient
NASA Astrophysics Data System (ADS)
Oshima, Hiraku; Kinoshita, Masahiro
2015-04-01
In earlier works, we showed that the entropic effect originating from the translational displacement of water molecules plays the pivotal role in protein folding and denaturation. The two different solvent models, hard-sphere solvent and model water, were employed in theoretical methods wherein the entropic effect was treated as an essential factor. However, there were similarities and differences in the results obtained from the two solvent models. In the present work, to unveil the physical origins of the similarities and differences, we simultaneously consider structural transition, cold denaturation, and pressure denaturation for the same protein by employing the two solvent models and considering three different thermodynamic states for each solvent model. The solvent-entropy change upon protein folding/unfolding is decomposed into the protein-solvent pair (PA) and many-body (MB) correlation components using the integral equation theories. Each component is further decomposed into the excluded-volume (EV) and solvent-accessible surface (SAS) terms by applying the morphometric approach. The four physically insightful constituents, (PA, EV), (PA, SAS), (MB, EV), and (MB, SAS), are thus obtained. Moreover, (MB, SAS) is discussed by dividing it into two factors. This all-inclusive investigation leads to the following results: (1) the protein-water many-body correlation always plays critical roles in a variety of folding/unfolding processes; (2) the hard-sphere solvent model fails when it does not correctly reproduce the protein-water many-body correlation; (3) the hard-sphere solvent model becomes problematic when the dependence of the many-body correlation on the solvent number density and temperature is essential: it is not quite suited to studies on cold and pressure denaturating of a protein; (4) when the temperature and solvent number density are limited to the ambient values, the hard-sphere solvent model is usually successful; and (5) even at the ambient
Oshima, Hiraku; Kinoshita, Masahiro
2015-04-14
In earlier works, we showed that the entropic effect originating from the translational displacement of water molecules plays the pivotal role in protein folding and denaturation. The two different solvent models, hard-sphere solvent and model water, were employed in theoretical methods wherein the entropic effect was treated as an essential factor. However, there were similarities and differences in the results obtained from the two solvent models. In the present work, to unveil the physical origins of the similarities and differences, we simultaneously consider structural transition, cold denaturation, and pressure denaturation for the same protein by employing the two solvent models and considering three different thermodynamic states for each solvent model. The solvent-entropy change upon protein folding/unfolding is decomposed into the protein-solvent pair (PA) and many-body (MB) correlation components using the integral equation theories. Each component is further decomposed into the excluded-volume (EV) and solvent-accessible surface (SAS) terms by applying the morphometric approach. The four physically insightful constituents, (PA, EV), (PA, SAS), (MB, EV), and (MB, SAS), are thus obtained. Moreover, (MB, SAS) is discussed by dividing it into two factors. This all-inclusive investigation leads to the following results: (1) the protein-water many-body correlation always plays critical roles in a variety of folding/unfolding processes; (2) the hard-sphere solvent model fails when it does not correctly reproduce the protein-water many-body correlation; (3) the hard-sphere solvent model becomes problematic when the dependence of the many-body correlation on the solvent number density and temperature is essential: it is not quite suited to studies on cold and pressure denaturating of a protein; (4) when the temperature and solvent number density are limited to the ambient values, the hard-sphere solvent model is usually successful; and (5) even at the ambient
Humans are exposed to chemical mixtures via diet, occupation, and the environment. Previous data demonstrated that low doses of polycyclic halogenated aromatic hydrocarbons (PHAHs) acting through similar mechanisms result in an additive reduction of thyroxine (T4). If xenobioti...
Stork, LeAnna M.; Gennings, Chris; Carchman, Richard; Carter, Jr., Walter H.; Pounds, Joel G.; Mumtaz, Moiz
2006-12-01
Several assumptions, defined and undefined, are used in the toxicity assessment of chemical mixtures. In scientific practice mixture components in the low-dose region, particularly subthreshold doses, are often assumed to behave additively (i.e., zero interaction) based on heuristic arguments. This assumption has important implications in the practice of risk assessment, but has not been experimentally tested. We have developed methodology to test for additivity in the sense of Berenbaum (Advances in Cancer Research, 1981), based on the statistical equivalence testing literature where the null hypothesis of interaction is rejected for the alternative hypothesis of additivity when data support the claim. The implication of this approach is that conclusions of additivity are made with a false positive rate controlled by the experimenter. The claim of additivity is based on prespecified additivity margins, which are chosen using expert biological judgment such that small deviations from additivity, which are not considered to be biologically important, are not statistically significant. This approach is in contrast to the usual hypothesis-testing framework that assumes additivity in the null hypothesis and rejects when there is significant evidence of interaction. In this scenario, failure to reject may be due to lack of statistical power making the claim of additivity problematic. The proposed method is illustrated in a mixture of five organophosphorus pesticides that were experimentally evaluated alone and at relevant mixing ratios. Motor activity was assessed in adult male rats following acute exposure. Four low-dose mixture groups were evaluated. Evidence of additivity is found in three of the four low-dose mixture groups.The proposed method tests for additivity of the whole mixture and does not take into account subset interactions (e.g., synergistic, antagonistic) that may have occurred and cancelled each other out.
Watt, James; Webster, Thomas F; Schlezinger, Jennifer J
2016-09-01
The vast array of potential environmental toxicant combinations necessitates the development of efficient strategies for predicting toxic effects of mixtures. Current practices emphasize the use of concentration addition to predict joint effects of endocrine disrupting chemicals in coexposures. Generalized concentration addition (GCA) is one such method for predicting joint effects of coexposures to chemicals and has the advantage of allowing for mixture components to have differences in efficacy (ie, dose-response curve maxima). Peroxisome proliferator-activated receptor gamma (PPARγ) is a nuclear receptor that plays a central role in regulating lipid homeostasis, insulin sensitivity, and bone quality and is the target of an increasing number of environmental toxicants. Here, we tested the applicability of GCA in predicting mixture effects of therapeutic (rosiglitazone and nonthiazolidinedione partial agonist) and environmental PPARγ ligands (phthalate compounds identified using EPA's ToxCast database). Transcriptional activation of human PPARγ1 by individual compounds and mixtures was assessed using a peroxisome proliferator response element-driven luciferase reporter. Using individual dose-response parameters and GCA, we generated predictions of PPARγ activation by the mixtures, and we compared these predictions with the empirical data. At high concentrations, GCA provided a better estimation of the experimental response compared with 3 alternative models: toxic equivalency factor, effect summation and independent action. These alternatives provided reasonable fits to the data at low concentrations in this system. These experiments support the implementation of GCA in mixtures analysis with endocrine disrupting compounds and establish PPARγ as an important target for further studies of chemical mixtures.
Defining an additivity framework for mixture research in inducible whole-cell biosensors
Martin-Betancor, K.; Ritz, C.; Fernández-Piñas, F.; Leganés, F.; Rodea-Palomares, I.
2015-01-01
A novel additivity framework for mixture effect modelling in the context of whole cell inducible biosensors has been mathematically developed and implemented in R. The proposed method is a multivariate extension of the effective dose (EDp) concept. Specifically, the extension accounts for differential maximal effects among analytes and response inhibition beyond the maximum permissive concentrations. This allows a multivariate extension of Loewe additivity, enabling direct application in a biphasic dose-response framework. The proposed additivity definition was validated, and its applicability illustrated by studying the response of the cyanobacterial biosensor Synechococcus elongatus PCC 7942 pBG2120 to binary mixtures of Zn, Cu, Cd, Ag, Co and Hg. The novel method allowed by the first time to model complete dose-response profiles of an inducible whole cell biosensor to mixtures. In addition, the approach also allowed identification and quantification of departures from additivity (interactions) among analytes. The biosensor was found to respond in a near additive way to heavy metal mixtures except when Hg, Co and Ag were present, in which case strong interactions occurred. The method is a useful contribution for the whole cell biosensors discipline and related areas allowing to perform appropriate assessment of mixture effects in non-monotonic dose-response frameworks PMID:26606975
Defining an additivity framework for mixture research in inducible whole-cell biosensors
NASA Astrophysics Data System (ADS)
Martin-Betancor, K.; Ritz, C.; Fernández-Piñas, F.; Leganés, F.; Rodea-Palomares, I.
2015-11-01
A novel additivity framework for mixture effect modelling in the context of whole cell inducible biosensors has been mathematically developed and implemented in R. The proposed method is a multivariate extension of the effective dose (EDp) concept. Specifically, the extension accounts for differential maximal effects among analytes and response inhibition beyond the maximum permissive concentrations. This allows a multivariate extension of Loewe additivity, enabling direct application in a biphasic dose-response framework. The proposed additivity definition was validated, and its applicability illustrated by studying the response of the cyanobacterial biosensor Synechococcus elongatus PCC 7942 pBG2120 to binary mixtures of Zn, Cu, Cd, Ag, Co and Hg. The novel method allowed by the first time to model complete dose-response profiles of an inducible whole cell biosensor to mixtures. In addition, the approach also allowed identification and quantification of departures from additivity (interactions) among analytes. The biosensor was found to respond in a near additive way to heavy metal mixtures except when Hg, Co and Ag were present, in which case strong interactions occurred. The method is a useful contribution for the whole cell biosensors discipline and related areas allowing to perform appropriate assessment of mixture effects in non-monotonic dose-response frameworks
Defining an additivity framework for mixture research in inducible whole-cell biosensors.
Martin-Betancor, K; Ritz, C; Fernández-Piñas, F; Leganés, F; Rodea-Palomares, I
2015-01-01
A novel additivity framework for mixture effect modelling in the context of whole cell inducible biosensors has been mathematically developed and implemented in R. The proposed method is a multivariate extension of the effective dose (EDp) concept. Specifically, the extension accounts for differential maximal effects among analytes and response inhibition beyond the maximum permissive concentrations. This allows a multivariate extension of Loewe additivity, enabling direct application in a biphasic dose-response framework. The proposed additivity definition was validated, and its applicability illustrated by studying the response of the cyanobacterial biosensor Synechococcus elongatus PCC 7942 pBG2120 to binary mixtures of Zn, Cu, Cd, Ag, Co and Hg. The novel method allowed by the first time to model complete dose-response profiles of an inducible whole cell biosensor to mixtures. In addition, the approach also allowed identification and quantification of departures from additivity (interactions) among analytes. The biosensor was found to respond in a near additive way to heavy metal mixtures except when Hg, Co and Ag were present, in which case strong interactions occurred. The method is a useful contribution for the whole cell biosensors discipline and related areas allowing to perform appropriate assessment of mixture effects in non-monotonic dose-response frameworks. PMID:26606975
Gordon, Christopher J; Herr, David W; Gennings, Chris; Graff, Jaimie E; McMurray, Matthew; Stork, LeAnna; Coffey, Todd; Hamm, Adam; Mack, Cina M
2006-01-01
Most toxicity data are based on studies using single compounds. This study assessed if there is an interaction between mixtures of the anticholinesterase insecticides chlorpyrifos (CHP) and carbaryl (CAR) using hypothermia and cholinesterase (ChE) inhibition as toxicological endpoints. Core temperature (T(c)) was continuously monitored by radiotelemetry in adult Long-Evans rats administered CHP at doses ranging from 0 to 50mg/kg and CAR doses of 0-150 mg/kg. The temperature index (TI), an integration of the change in T(c) over a 12h period, was quantified. Effects of mixtures of CHP and CAR in 2:1 and 1:1 ratios on the TI were examined and the data analyzed using a statistical model designed to assess significant departures from additivity for chemical mixtures. CHP and CAR elicited a marked hypothermia and dose-related decrease in the TI. The TI response to a 2:1 ratio of CHP:CAR was significantly less than that predicted by additivity. The TI response to a 1:1 ratio of CHP and CAR was not significantly different from the predicted additivity. Plasma and brain ChE activity were measured 4h after dosing with CHP, CAR, and mixtures in separate groups of rats. There was a dose-additive interaction for the inhibition of brain ChE for the 2:1 ratio, but an antagonistic effect for the 1:1 ratio. The 2:1 and 1:1 mixtures had an antagonistic interaction on plasma ChE. Overall, the departures from additivity for the physiological (i.e., temperature) and biochemical (i.e., ChE inhibition) endpoints for the 2:1 and 1:1 mixtures studies did not coincide as expected. An interaction between CHP and CAR appears to depend on the ratio of compounds in the mixture as well as the biological endpoint. PMID:16182429
Theoretical study of miscibility and glass-forming trends in mixtures of polystyrene spheres
NASA Technical Reports Server (NTRS)
Shih, W.-H.; Stroud, D.
1984-01-01
A theoretical study of glass-forming trends and miscibility in mixtures of polystyrene spheres (polyballs) of different diameters, suspended in an aqueous solution, is presented. The polyballs are assumed to be charged and to interact via a Debye-Hueckel screened Coulomb potential. The Helmholtz free energy is calculated from a variational principle based on the Gibbs-Bogoliubov inequality, in which a mixture of hard spheres of different diameters is chosen as the reference system. It is found that when the charges of the two types of polyballs are sufficiently different, the variationally determined ratio of hard-sphere diameters differs substantially, leading to packing difficulties characteristic of glass formation. The experimentally observed range of glass formation corresponds to a ratio of hard-sphere diameters of 0.8 or less. Calculations of the free energy as a function of concentration indicate that the liquid polyball mixture is stable against the phase separation, even for widely different polyball charges.
Mixture additives inhibit the dermal permeation of the fatty acid, ricinoleic acid.
Baynes, R E; Riviere, J E
2004-02-28
Ricinoleic acid (RA) like many of the ingredients in machine cutting fluids and other industrial formulations are potential dermal irritants, yet very little is known about its permeability in skin. 3H-ricinoleic acid mixtures were formulated with three commonly used cutting fluid additives; namely, triazine (TRI), linear alkylbenzene sulfonate (LAS), and triethanolamine (TEA) and topically applied to inert silastic membranes and porcine skin in vitro as aqueous mineral oil (MO) or polyethylene glycol (PEG) mixtures. These additives significantly decreased ricinoleic acid partitioning from the formulation into the stratum corneum (SC) in PEG-based mixtures. Except for LAS, all other additives produced a more basic formulation (pH = 9.3-10.3). In silastic membranes and porcine skin, individual additives or combination of additives significantly reduced ricinoleic permeability. This trend in ricinoleic acid disposition in both membranes suggests that the mixture interaction is more physicochemical in nature and probably not related to the chemical-induced changes in the biological membrane as may be assumed with topical exposures to potentially irritant formulations.
Watt, James; Webster, Thomas F; Schlezinger, Jennifer J
2016-09-01
The vast array of potential environmental toxicant combinations necessitates the development of efficient strategies for predicting toxic effects of mixtures. Current practices emphasize the use of concentration addition to predict joint effects of endocrine disrupting chemicals in coexposures. Generalized concentration addition (GCA) is one such method for predicting joint effects of coexposures to chemicals and has the advantage of allowing for mixture components to have differences in efficacy (ie, dose-response curve maxima). Peroxisome proliferator-activated receptor gamma (PPARγ) is a nuclear receptor that plays a central role in regulating lipid homeostasis, insulin sensitivity, and bone quality and is the target of an increasing number of environmental toxicants. Here, we tested the applicability of GCA in predicting mixture effects of therapeutic (rosiglitazone and nonthiazolidinedione partial agonist) and environmental PPARγ ligands (phthalate compounds identified using EPA's ToxCast database). Transcriptional activation of human PPARγ1 by individual compounds and mixtures was assessed using a peroxisome proliferator response element-driven luciferase reporter. Using individual dose-response parameters and GCA, we generated predictions of PPARγ activation by the mixtures, and we compared these predictions with the empirical data. At high concentrations, GCA provided a better estimation of the experimental response compared with 3 alternative models: toxic equivalency factor, effect summation and independent action. These alternatives provided reasonable fits to the data at low concentrations in this system. These experiments support the implementation of GCA in mixtures analysis with endocrine disrupting compounds and establish PPARγ as an important target for further studies of chemical mixtures. PMID:27255385
Testing for departures from additivity in mixtures of perfluoroalkyl acids (PFAAs)
This study is a follow-up to a paper by Carr, et al. that determined a design structure to optimally test for departures from additivity in a fixed ratio mixture of four perfluoroalkyl acids (PFAAs) using an in vitro transiently-transfected COS- 1 PPARa reporter model with an NHA...
Jing, Zhicheng; Karato, Shun-ichiro
2012-04-20
Density of ultramafic silicate melts was determined using the sink/float technique at high pressures. Seven melt compositions were studied, among which three were dry compositions with different Mg's (molar MgO/(MgO + FeO) x 100) and the other four were hydrous compositions synthesized by adding 2-7 wt.% H{sub 2}O to the anhydrous ones. Experimental conditions range from 9 to 15 GPa and from 2173 to 2473 K. The sinking and floatation of density markers were observed for all melt compositions. Melt density data were analyzed by applying the Birch-Murnaghan equation of state and a newly developed equation of state for silicate melts based on the model of hard sphere mixtures. The presence of water can significantly reduce the density of melts due to its small molecular mass. On the other hand, water makes hydrous silicate melts more compressible than anhydrous melts and therefore the effect of H{sub 2}O on melt density is less significant at high pressures. The density of hydrous melts was then calculated as a function of H{sub 2}O content at the conditions of the bottom of the upper mantle, and was compared with the density of the dominant upper mantle minerals. Results show that the conditions for a negatively buoyant melt that coexists with a pyrolite mantle atop the 410 km discontinuity are marginally satisfied if H{sub 2}O is the only volatile component to facilitate melting, but such conditions will be satisfied by a broader range of conditions when other heavier volatile elements (C, K, etc.) are also present.
Evaluating mixtures of 14 hygroscopic additives to improve antibody microarray performance.
Bergeron, Sébastien; Laforte, Veronique; Lo, Pik-Shan; Li, Huiyan; Juncker, David
2015-11-01
Microarrays allow the miniaturization and multiplexing of biological assays while only requiring minute amounts of samples. As a consequence of the small volumes used for spotting and the assays, evaporation often deteriorates the quality, reproducibility of spots, and the overall assay performance. Glycerol is commonly added to antibody microarray printing buffers to decrease evaporation; however, it often decreases the binding of antibodies to the surface, thereby negatively affecting assay sensitivity. Here, combinations of 14 hygroscopic chemicals were used as additives to printing buffers for contact-printed antibody microarrays on four different surface chemistries. The ability of the additives to suppress evaporation was quantified by measuring the residual buffer volume in open quill pins over time. The seven best additives were then printed either individually or as a 1:1 mixture of two additives, and the homogeneity, intensity, and reproducibility of both the spotted protein and of a fluorescently labeled analyte in an assay were quantified. Among the 28 combinations on the four slides, many were found to outperform glycerol, and the best additive mixtures were further evaluated by changing the ratio of the two additives. We observed that the optimal additive mixture was dependent on the slide chemistry, and that it was possible to increase the binding of antibodies to the surface threefold compared to 50 % glycerol, while decreasing whole-slide coefficient of variation to 5.9 %. For the two best slides, improvements were made for both the limit of detection (1.6× and 5.9×, respectively) and the quantification range (1.2× and 2.1×, respectively). The additive mixtures identified here thus help improve assay reproducibility and performance, and might be beneficial to all types of microarrays that suffer from evaporation of the printing buffers.
Evidence for dose-additive effects of a type II pyrethroid mixture. In vitro assessment.
Romero, A; Ares, I; Ramos, E; Castellano, V; Martínez, M; Martínez-Larrañaga, M R; Anadón, A; Martínez, M A
2015-04-01
Despite the widespread use of pyrethroid insecticides that led to common exposure in the population, few studies have been conducted to quantitatively assess dose-additive effects of pyrethroids using a funcional measure involved in the common toxic mode of action. The aim of this study was to evaluate the potency and efficacy of 6 Type II pyretroids (α-cypermethrin, cyfluthrin, λ-cyhalothrin, deltamethrin, cyphenothrin and esfenvalerate) to evoke induction of both nitric oxide and lipid peroxides levels measured as malondialdehyde in three in vitro models (SH-SY5Y, HepG2 and Caco-2 human cells) as well as to test the hypothesis of dose additivity for mixtures of these same 6 pyrethroids. Concentration-responses for 6 pyrethroids were determined as well as the response to mixtures of all 6 pyrethroids. Additivity was tested assuming a dose-additive model. The human neuroblastoma SH-SY5Y cell line was the most sensitive in vitro model. The rank order of potency for cell SH-SY5Y viability MTT assay was deltamethrin>cyphenothrin>λ-cyhalothrin>cyfluthrin>esfenvalerate>α-cypermethrin. When 6 pyrethroids were present in the mixture at an equitoxic mixing ratio, the action on nitric oxide (NO) and lipid peroxides measured as malondialdehyde (MDA) production was consistent with a dose-additive model. The results of the present study are consistent with previous reports of additivity of pyrethroids in vivo e in vitro.
The Combined Carcinogenic Risk for Exposure to Mixtures of Drinking Water Disinfection By-Products May be Less Than Additive
Risk assessment methods for chemical mixtures in drinking water are not well defined. Current default risk assessments for chemical mixtures assume...
Influence of propane additives on the detonation characteristics of H2-air mixtures
NASA Astrophysics Data System (ADS)
Cheng, Guanbing; Bauer, Pascal; Zitoun, Ratiba
2014-03-01
Hydrogen is more and more considered as a potential fuel for propulsion applications. However, due to its low ignition energy and wide flammability limits, H2-air mixtures raise a concern in terms of safety. This aspect can be partly solved by adding an alkane to these mixtures, which plays the role of an inhibitor. The present paper provides data on such binary fuel-air mixtures where various amounts of propane are added to hydrogen. The behavior of the corresponding mixtures, in terms of detonation characteristics and other fundamental properties, such as the cell size of the detonation front and induction delay, are presented and discussed for a series of equivalence ratios and propane addition. The experimental detonation velocity is in good agreement with calculated theoretical Chapman-Jouguet values. Based on soot tracks records, the cell size λ is measured, whereas the induction length L i is derived from data using a GRI-Mech kinetic mechanism. These data allow providing a value of the coefficient K = λ/L i .
Zhou, Shiqi; Solana, J R
2013-08-01
The first three coefficients of the high temperature series expansion (HTSE) of the Helmholtz free energy for a number of simple potential models with hard-sphere cores plus continuous tails are obtained for the first time from Monte Carlo simulations. The potential models considered include Square-well, Sutherland, attractive Yukawa, and triangle-well with different potential ranges, as well as a model potential qualitatively resembling the depletion potential in colloidal dispersions. The simulation data are used to evaluate performance of a recent coupling parameter series expansion (CPSE) in calculating for these coefficients, and a traditional macroscopic compressibility approximation (MCA) for the second-order coefficient only. A comprehensive comparison based on these coefficients from the two theoretical approaches and simulations enables one to conclude that (i) unlike one common experience that the widely used MCA usually underestimates the second-order coefficient, the MCA can both overestimate and underestimate the second-order coefficient, and worsens as the range of the potential decreases; and (ii) in contrast, the CPSE not only reproduce the trends in the density dependence of the perturbation coefficients, even the third one, observed in the simulations, but also the agreement is quantitative in most cases, and this clearly highlights the potential of the CPSE in providing accurate estimations for the higher-order coefficients, thus giving rise to an accurate higher-order HTSE.
NASA Technical Reports Server (NTRS)
Woo, Myeung-Jouh; Greber, Isaac
1995-01-01
Molecular dynamics simulation is used to study the piston driven shock wave at Mach 1.5, 3, and 10. A shock tube, whose shape is a circular cylinder, is filled with hard sphere molecules having a Maxwellian thermal velocity distribution and zero mean velocity. The piston moves and a shock wave is generated. All collisions are specular, including those between the molecules and the computational boundaries, so that the shock development is entirely causal, with no imposed statistics. The structure of the generated shock is examined in detail, and the wave speed; profiles of density, velocity, and temperature; and shock thickness are determined. The results are compared with published results of other methods, especially the direct simulation Monte-Carlo method. Property profiles are similar to those generated by direct simulation Monte-Carlo method. The shock wave thicknesses are smaller than the direct simulation Monte-Carlo results, but larger than those of the other methods. Simulation of a shock wave, which is one-dimensional, is a severe test of the molecular dynamics method, which is always three-dimensional. A major challenge of the thesis is to examine the capability of the molecular dynamics methods by choosing a difficult task.
Dose addition is the most frequently-used component-based approach for predicting dose response for a mixture of toxicologically-similar chemicals and for statistical evaluation of whether the mixture response is consistent with dose additivity and therefore predictable from the ...
A common default assumption in risk assessment of chemical mixtures is that the chemicals combine additively in the low dose region. Under additivity, with information from single chemical dose-response data, the risk associated with the mixture can be estimated. The objective ...
THE CARCINOGENIC RESPONSE TO A MIXTURE OF DRINKING WATER DISINFECTION BY -PRODUCTS (DBP) W AS LESS THAN ADDITIVE.
Current default risk assessments for chemical mixtures assume additivity of carcinogenic effects but this may under or over represent the actual biological res...
Additive toxicity of herbicide mixtures and comparative sensitivity of tropical benthic microalgae.
Magnusson, Marie; Heimann, Kirsten; Quayle, Pamela; Negri, Andrew P
2010-11-01
Natural waters often contain complex mixtures of unknown contaminants potentially posing a threat to marine communities through chemical interactions. Here, acute effects of the photosystem II-inhibiting herbicides diuron, tebuthiuron, atrazine, simazine, and hexazinone, herbicide breakdown products (desethyl-atrazine (DEA) and 3,4-dichloroaniline (3,4-DCA)) and binary mixtures, were investigated using three tropical benthic microalgae; Navicula sp. and Cylindrotheca closterium (Ochrophyta) and Nephroselmis pyriformis (Chlorophyta), and one standard test species, Phaeodactylum tricornutum (Ochrophyta), in a high-throughput Maxi-Imaging-PAM bioassay (Maxi-IPAM). The order of toxicity was; diuron > hexazinone > tebuthiuron > atrazine > simazine > DEA > 3,4-DCA for all species. The tropical green alga N. pyriformis was up to 10-fold more sensitive than the diatoms tested here and reported for coral symbionts, and is recommended as a standard tropical test species for future research. All binary mixtures exhibited additive toxicity, and the use of herbicide equivalents (HEq) is therefore recommended in order to incorporate total-maximum-load measures for environmental regulatory purposes.
NASA Technical Reports Server (NTRS)
Shahshahani, Behzad M.; Landgrebe, David A.
1992-01-01
The effect of additional unlabeled samples in improving the supervised learning process is studied in this paper. Three learning processes. supervised, unsupervised, and combined supervised-unsupervised, are compared by studying the asymptotic behavior of the estimates obtained under each process. Upper and lower bounds on the asymptotic covariance matrices are derived. It is shown that under a normal mixture density assumption for the probability density function of the feature space, the combined supervised-unsupervised learning is always superior to the supervised learning in achieving better estimates. Experimental results are provided to verify the theoretical concepts.
A computer simulation study of racemic mixtures
NASA Astrophysics Data System (ADS)
Largo, J.; Vega, C.; MacDowell, L. G.; Solana, J. R.
A simple model for a chiral molecule is proposed. The model consists of a central atom bonded to four different atoms in tetrahedral coordination. Two different potentials were used to describe the pair potentials between atoms: the hard sphere potential and the Lennard-Jones potential. For both the hard sphere and the Lennard-Jones chiral models, computer simulations have been performed for the pure enantiomers and also for the racemic mixture. The racemic mixture consisted of an equimolar mixture of the two optically active enantiomers. It is found that the equations of state are the same, within statistical uncertainty, for the pure enantiomer fluid and for the racemic mixture. Only at high pressures does the racemic mixture seem to have a higher density, for a given pressure, than the pure enantiomer. Concering the structure, no difference is found in the site-site correlation functions between like and unlike molecules in the racemic mixture either at low or at high densities. However, small differences are found for the site-site correlations of the pure enantiomer and those of the racemic mixtures. In the Lennard-Jones model, similar conclusions are drawn. The extension of Wertheim's first-order perturbation theory, denoted bonded hard sphere theory (ARCHER, A. L., and JACKSON, G., 1991, Molec. Phys. , 73 , 881; AMOS, M. D., and JACKSON, G., 1992, J. chem. Phys. , 96 , 4604), successfully reproduces the simulation results for the hard chiral model. Virial coefficients of the hard chiral model up to the fourth have also been evaluated. Again, no differences are found between virial coefficients of the pure fluid and of the racemic mixture. All the results of this work illustrate the quasi-ideal behaviour of racemic mixtures in the fluid phase.
Leunissen, Mirjam E; Sullivan, Matthew T; Chaikin, Paul M; van Blaaderen, Alfons
2008-04-28
This work concerns the use of electric field gradients to manipulate the local particle concentration in a hard-sphere-like suspension. Inside a specially designed "electric bottle," we observed our colloids to collect in the regions of lowest field strength ("negative dielectrophoresis"). This allows for the use of larger field gradients and stronger dielectrophoretic forces than in the original electric bottle design, which was based on positive dielectrophoresis [M. T. Sullivan et al., Phys. Rev. Lett. 96, 015703 (2006)]. We used confocal scanning laser microscopy to quantitatively follow the time-dependent change in the particle density and the suspension structure. Within a few days, the dielectrophoretic compression was seen to initiate a heterogeneouslike growth of large single crystals, which took place far out-of-equilibrium. The crystals had a random hexagonal close-packed structure and displayed an intriguing growth mechanism, during which the entire crystal was continuously transported, while growing both on the "high-field" and the "low-field" sides, although at different rates. After switching off the electric field, the compressed crystals were found to relax to a lower packing fraction and melt, at a much slower rate than the crystal growth. Besides revealing the particular (far out-of-equilibrium) crystal growth mechanism in these electric bottles, our observations also shed light on the role of the different particle transport processes in the cell and some of the relevant tuning parameters. This is useful for different types of experiments, for instance, focusing more on melting, homogeneous crystallization, or the glass transition.
Our objective was to determine an optimal experimental design for a mixture of perfluoroalkyl acids (PFAAs) that is robust to the assumption of additivity. Of particular focus to this research project is whether an environmentally relevant mixture of four PFAAs with long half-liv...
Synthesis and Properties of a Clean and Sustainable Deicing Additive for Asphalt Mixture
Peng, Chao; Yu, Jianying; Zhao, Zhijie; Dai, Jing; Fu, Jingyi; Zhao, Meiling; Wang, Wei
2015-01-01
A clean and sustainable deicing additive was prepared via the adsorption of acetate anions (Ac-) by magnesium (Mg) and aluminum (Al) calcined layered double hydroxide (Mg/Al-CLDH). Fourier transform infrared spectroscopy spectrums proved that Ac- had intercalated into LDH structure. X-ray diffraction patterns, scanning electron microscopy and transmission electron microscopy images showed that the intercalation spacing and platelet thickness of Mg and Al layered double hydroxide containing Ac- anions (Mg/Al-Ac- LDH) had been enlarged due to substitution of divalent CO32- anions by a larger quantity of monovalent Ac– anions. Differential scanning calorimetry tests testified that the insoluble Mg2/Al-Ac- LDH evidently decreased the freeze point (FP) of water to -10.68°C. X-ray photoelectron spectroscopy analyses confirmed that the Ac- were strongly confined by the metal layers of LDHs. FP test of asphalt mixtures confirmed that Mg/Al-Ac- LDHs reduced FP to -5.5°C. Immersion test results indicated that Mg/Al-Ac- LDH had a good deicing durability and Ac- did not released from asphalt mixture. Snow melting observation was conducted further testified that Mg/Al-Ac- LDH melted snow or ice sustainably. PMID:25625279
Ciullini, Ilaria; Gullotto, Antonella; Tilli, Silvia; Sannia, Giovanni; Basosi, Riccardo; Scozzafava, Andrea; Briganti, Fabrizio
2012-10-01
The effects of different components of real dyeing bath formulations, such as the equalizing and fixing additives-acids, salts, and surfactants-on the decolorization catalyzed by Funalia trogii enzymatic extracts, were investigated to understand their influence on the recalcitrance to biodegradation of this type of wastewater. The decolorization of selected dyes and dye mixtures after tissue dyeing was performed in the presence/absence of auxiliary compounds. All spent dyeing baths were enzymatically decolorized to different extents, by the addition of extracts containing laccase only or laccase plus cellobiose dehydrogenase. Whereas surfactant auxiliaries, in some instances, inhibit the decolorization of spent dyeing baths, in several occurrences the acid/salt additives favor the enzymatic process. In general, the complete spent dyeing formulations are better degraded than those containing the dyes only. The comparison of extracellular extracts obtained from spent straws from the commercial growth of Pleurotus sp. mushrooms with those from F. trogii reveals similar decolorization extents thus allowing to further reduce the costs of bioremediation.
Silva, Emília; Cerejeira, Maria José
2015-05-01
A two-tiered outline for the predictive environmental risk assessment of chemical mixtures with effect assessments based on concentration addition (CA) approaches as first tier and consideration of independent action (IA) as the second tier was applied based on realistic pesticide mixtures measured in surface waters from 2002 to 2008 within three important Portuguese river basins ('Mondego', 'Sado' and 'Tejo'). The CA-based risk quotients, based on acute data and an assessment factor of 100, exceeded 1 in more than 39 % of the 281 samples, indicating a potential risk for the aquatic environment, namely to algae. Seven herbicide compounds and three insecticides were the most toxic compounds in the pesticide mixtures and provided at least 50 % of the mixture's toxicity in almost 100 % of the samples with risk quotients based on the sum of toxic units (RQSTU) above 1. In eight samples, the maximum cumulative ratio (MCR) and the Junghan's ratio values indicated that a chemical-by-chemical approach underestimated the toxicity of the pesticide mixtures, and CA predicted higher mixture toxicity than that of IA. From a risk management perspective, the results pointed out that, by deriving appropriate programmes of measures to a limited number of pesticides with the highest contribution to the total mixture toxicity, relevant benefits also on mixture impact could be produced. PMID:25424034
Wang, Na; Wang, Xiaochang C; Ma, Xiaoyan
2015-03-01
The concentration addition (CA) model has been widely applied to predict mixture toxicity. However, its applicability is difficult to evaluate due to the complexity of interactions among substances. Considering that the concentration-response curve (CRC) of each component of the mixture is closely related to the prediction of mixture toxicity, mathematical treatments were used to derive a characteristic index kECx (k was the slope of the tangent line of a CRC at concentration ECx). The implication is that the CA model would be applicable for predicting the mixture toxicity only when chemical components have similar kECx in the whole or part of the concentration range. For five selected chemicals whose toxicity was detected using luminescent bacteria, sodium dodecyl benzene sulfonate (SDBS) showed much higher kECx values than the others and its existence in the binary mixtures brought about overestimation of the mixture toxicity with the CA model. The higher the mass ratio of SDBS in a multi-mixture was, the more the toxicity prediction deviated from measurements. By applying the method proposed in this study to analyze some published data, it is confirmed that some components having significantly different kECx values from the other components could explain the large deviation of the mixture toxicity predicted by the CA model. PMID:25499050
NASA Astrophysics Data System (ADS)
Trinh, Thi-Kim-Hoang; Passarello, Jean-Philippe; de Hemptinne, Jean-Charles; Lugo, Rafael; Lachet, Veronique
2016-03-01
This work consists of the adaptation of a non-additive hard sphere theory inspired by Malakhov and Volkov [Polym. Sci., Ser. A 49(6), 745-756 (2007)] to a square-well chain. Using the thermodynamic perturbation theory, an additional term is proposed that describes the effect of perturbing the chain of square well spheres by a non-additive parameter. In order to validate this development, NPT Monte Carlo simulations of thermodynamic and structural properties of the non-additive square well for a pure chain and a binary mixture of chains are performed. Good agreements are observed between the compressibility factors originating from the theory and those from molecular simulations.
Hwang, Young-Jung; Hwang, Seol-A; Lee, Ju-Woon
2016-01-01
This study was conducted to improve sensory quality of Jokbal (Korean Pettitoes) made from frozen pig feet by addition of herbal mixture (glasswort, raspberry and Sansa powders). After adding herbal mixture, lipid oxidation (2-thiobarbituric acid values, TBARS), sensory property, and textural property were determined. Herbs were individually added into cooking soup at concentration of 6% (low concentration treatment, LCT) or 12% (high concentration treatment, HCT) of raw pig feet. Refrigerated pig feet were used as control. Thawed feet without any herbal mixture were used as freezing treatment (FT). TBARS in LCT or HCT were lower than that in FT, and showed the similar to that in Control. Addition of the herbal mixture was effective in improving the flavor and textural property of thawed feet by inhibiting lipid oxidation and protein denaturation in a dose-dependent manner. PMID:27499659
Lee, Ju-Woon
2016-01-01
This study was conducted to improve sensory quality of Jokbal (Korean Pettitoes) made from frozen pig feet by addition of herbal mixture (glasswort, raspberry and Sansa powders). After adding herbal mixture, lipid oxidation (2-thiobarbituric acid values, TBARS), sensory property, and textural property were determined. Herbs were individually added into cooking soup at concentration of 6% (low concentration treatment, LCT) or 12% (high concentration treatment, HCT) of raw pig feet. Refrigerated pig feet were used as control. Thawed feet without any herbal mixture were used as freezing treatment (FT). TBARS in LCT or HCT were lower than that in FT, and showed the similar to that in Control. Addition of the herbal mixture was effective in improving the flavor and textural property of thawed feet by inhibiting lipid oxidation and protein denaturation in a dose-dependent manner. PMID:27499659
Shi, Andong; Marschner, Petra
2013-11-01
Addition of clay-rich subsoils to sandy top soils is an agricultural management option to increase water and nutrient retention and may also increase organic carbon sequestration by decreasing the decomposition rates. An incubation experiment was carried out in a loamy sand top soil mixed with a clay-rich subsoil (84% clay) at 0, 10 and 30% (w/w) amended with finely ground mature shoot residues of two native perennial grasses and annual barley individually or in 1:1 mixtures of two residues. Extractable C, microbial biomass C, available N and soil pH were analysed at days 0, 3, 14 and 28. Cumulative respiration after 28 days was highest with barley residue and lowest with Wallaby grass at all clay soil addition rates; 30% clay soil addition reduced cumulative respiration, especially with barley alone. In the mixture of native grasses and barley, the measured respiration was lower than expected at a clay soil addition rate of 10%. A synergistic effect (higher than expected cumulative respiration) was only found in mixture of Kangaroo grass and barley at a clay soil addition rate of 30%. Clay soil addition also decreased extractable C, available N and soil pH. The temporal change in microbial biomass C and available N in residue mixtures differed among clay addition rates. In the mixture of Wallaby grass and Kangaroo grass, microbial biomass C (MBC) decreased from day 0 to day 28 at clay soil addition rates of 0 and 10%, whereas at 30% clay MBC increased from day 0 to day 3 and then decreased. Our study shows that addition of a clay-rich subsoil to a loamy sand soil can increase C sequestration by reducing CO2 release and extractable C which are further modulated by the type of residues present individually or as mixtures.
Chapman, Samantha K.; Newman, Gregory S.; Hart, Stephen C.; Schweitzer, Jennifer A.; Koch, George W.
2013-01-01
To what extent microbial community composition can explain variability in ecosystem processes remains an open question in ecology. Microbial decomposer communities can change during litter decomposition due to biotic interactions and shifting substrate availability. Though relative abundance of decomposers may change due to mixing leaf litter, linking these shifts to the non-additive patterns often recorded in mixed species litter decomposition rates has been elusive, and links community composition to ecosystem function. We extracted phospholipid fatty acids (PLFAs) from single species and mixed species leaf litterbags after 10 and 27 months of decomposition in a mixed conifer forest. Total PLFA concentrations were 70% higher on litter mixtures than single litter types after 10 months, but were only 20% higher after 27 months. Similarly, fungal-to-bacterial ratios differed between mixed and single litter types after 10 months of decomposition, but equalized over time. Microbial community composition, as indicated by principal components analyses, differed due to both litter mixing and stage of litter decomposition. PLFA biomarkers a15∶0 and cy17∶0, which indicate gram-positive and gram-negative bacteria respectively, in particular drove these shifts. Total PLFA correlated significantly with single litter mass loss early in decomposition but not at later stages. We conclude that litter mixing alters microbial community development, which can contribute to synergisms in litter decomposition. These findings advance our understanding of how changing forest biodiversity can alter microbial communities and the ecosystem processes they mediate. PMID:23658639
Fixed-ratio ray designs have been used for detecting and characterizing interactions of large numbers of chemicals in combination. Single chemical dose-response data are used to predict an “additivity curve” along an environmentally relevant ray. A “mixture curve” is estimated fr...
The main objectives of this study were to: (1) determine whether dissimilar antiandrogenic compounds display additive effects when present in combination and (2) to assess the ability of modelling approaches to accurately predict these mixture effects based on data from single ch...
Our objective is to determine an optimal experimental design for a mixture of perfluoroalkyl acids (PFAAs) that is robust to the assumption of additivity. PFAAs are widely used in consumer products and industrial applications. The presence and persistence of PFAAs, especially in ...
NON-ADDITIVE INTERACTIONS OF AN ORGANOPHOSPHORUS PESTICIDE MIXTURE IN ADULT AND PREWEANLING RATS.
Critical features of risk assessment include the evaluation of risk following exposure to pesticide mixtures as well as the potential for increased sensitivity of the young. The US EPA is required to regulate pesticides acting via a common mechanism of action as a group, e.g.,...
Fuel and lubricant additives from acid treated mixtures of vegetable oil derived amides and esters
Bonazza, B.R.; Devault, A.N.
1981-05-26
Vegetable oils such as corn oil, peanut oil, and soy oil are reacted with polyamines to form a mixture containing amides, imides, half esters, and glycerol with subsequent treatment with a strong acid such as sulfonic acid to produce a product mix that has good detergent properties in fuels and lubricants.
Cancer risk assessment methods for chemical mixtures in drinking water are not well defined. Current default risk assessments for chemical mixtures assume additivity of carcinogenic effects but this may not represent the actual biological response. A rodent model of hereditary ...
Depletion, melting and reentrant solidification in mixtures of soft and hard colloids.
Marzi, Daniela; Capone, Barbara; Marakis, John; Merola, Maria Consiglia; Truzzolillo, Domenico; Cipelletti, Luca; Moingeon, Firmin; Gauthier, Mario; Vlassopoulos, Dimitris; Likos, Christos N; Camargo, Manuel
2015-11-14
We present extensive experimental and theoretical investigations on the structure, phase behavior, dynamics and rheology of model soft-hard colloidal mixtures realized with large, multiarm star polymers as the soft component and smaller, compact stars as the hard one. The number and length of the arms in star polymers control their softness, whereas the size ratio, the overall density and the composition are additional parameters varied for the mixtures. A coarse-grained theoretical strategy is employed to predict the structure of the systems as well as their ergodicity properties on the basis of mode coupling theory, for comparison with rheological measurements on the samples. We discovered that dynamically arrested star-polymer solutions recover their ergodicity upon addition of colloidal additives. At the same time the system displays demixing instability, and the binodal of the latter meets the glass line in a way that leads, upon addition of a sufficient amount of colloidal particles, to an arrested phase separation and reentrant solidification. We present evidence for a subsequent solid-to-solid transition well within the region of arrested phase separation, attributed to a hard-sphere-mixture type of glass, due to osmotic shrinkage of the stars at high colloidal particle concentrations. We systematically investigated the interplay of star functionality and size ratio with glass melting and demixing, and rationalized our findings by the depletion of the big stars due to the smaller colloids. This new depletion potential in which, contrary to the classic colloid-polymer case, the hard component depletes the soft one, has unique and novel characteristics and allows the calculation of phase diagrams for such mixtures. This work covers a broad range of soft-hard colloidal mixture compositions in which the soft component exceeds the hard one in size and provides general guidelines for controlling the properties of such complex mixtures.
The influence of additives on coal-water mixtures prepared with beneficiated coal
Ekmann, J.M.; Wildman, D.J.
1986-01-01
Use of coal-water mixtures (CWM) as fuels for utility and industrial applications is currently constrained by a number of factors, including the cost of compliance with environmental quality regulations. From a utilization standpoint, limiting ash and sulfur contents to levels comparable to those for residual fuel oil produces an attractive alternate fuel provided the unit cost is equal to that for the fuel oil. Reduction in the mineral matter content of the coal has been identified as a target for continued development of CWM. Changes in coal type or in the characteristics of a single coal have been shown to affect CWM properties. It appears worthwhile to examine the impact that beneficiation might have on CWM properties.
NASA Technical Reports Server (NTRS)
Jacob, B. A.; Veltri, R. D.
1974-01-01
The chemical vapor process for preparing a large diameter carbon-base monofilament from a BCl3, Ch4 and H2 gas mixture with a carbon substrate fiber was studied. The effect of reactor geometry, total gas flows and deposition temperature on the tensile strength of the monofilament were investigated. It was noted that consistent results could only be obtained when the carbon substrate fiber was cleaned. The strength of the monofilament was found to depend on the highest temperature and the temperature profile of the monofilament in the reactor. The strength of monofilament produced in the dc and RF reactors were found to be similar and similar alloy compositions in the monofilament were attained when the same gas ratios were used. The tensile strength of the monofilament at 500 C was found to be 60 to 70% of the room temperature tensile strength. No degradation was noted after exposure to molten aluminum.
A thermodynamic self-consistent theory of asymmetric hard-core Yukawa mixtures.
Pellicane, Giuseppe; Caccamo, Carlo
2016-10-19
We perform structural and thermodynamic calculations in the framework of the modified hypernetted chain (MHNC) integral equation closure to the Ornstein-Zernike equation for binary mixtures of size-different particles interacting with hard-core Yukawa pair potentials. We use the Percus-Yevick (PY) bridge functions of a binary mixture of hard-sphere (HSM) particles. The hard-sphere diameters of the PY bridge functions of the HSM system are adjusted so to achieve thermodynamic consistency between the virial and compressibility equations of state. We show the benefit of thermodynamic consistency by comparing the MHNC results with the available computer simulation data reported in the literature, and we demonstrate that the self-consistent thermodynamic theory provides a better reproduction of the simulation data over other microscopic theories. PMID:27545096
A thermodynamic self-consistent theory of asymmetric hard-core Yukawa mixtures
NASA Astrophysics Data System (ADS)
Pellicane, Giuseppe; Caccamo, Carlo
2016-10-01
We perform structural and thermodynamic calculations in the framework of the modified hypernetted chain (MHNC) integral equation closure to the Ornstein-Zernike equation for binary mixtures of size-different particles interacting with hard-core Yukawa pair potentials. We use the Percus-Yevick (PY) bridge functions of a binary mixture of hard-sphere (HSM) particles. The hard-sphere diameters of the PY bridge functions of the HSM system are adjusted so to achieve thermodynamic consistency between the virial and compressibility equations of state. We show the benefit of thermodynamic consistency by comparing the MHNC results with the available computer simulation data reported in the literature, and we demonstrate that the self-consistent thermodynamic theory provides a better reproduction of the simulation data over other microscopic theories.
Tank mixture additives approach to improve efficiency of bentazon against broadleaf weeds in peas.
Balah, Mohamed A; Hanafi, Ahmad; Ghani, Sherif B Abdel
2012-01-01
Efficiency of different tank-mixed additives with bentazon at half rate was investigated on (Malva parviflora) and other broad leaf weeds compared with bentazon at the full recommended rate without additives in peas in open field. All the tested additives enhanced the efficiency of bentazon at the half rate. Nonyl phenol and toximol S proved to be the most effective additives in comparison with the full rate treatment. The tested treatments did not show any significant effect on chlorophyll content and soil microorganisms. Bentazon residues were determined in certain treatments to investigate the effect of the tested additives on bentazon deposition. Samples were extracted using QuEChERS method and residues were determined using LC-MS/MS. Residues after 24 hours in the half rate treatment reached 4 times lower than the Maximum Residues Limit (MRL) (0.11 mg kg(-1)), compared to the full rate treatment (0.51 mg kg(-1)), that was slightly above the MRL.
Entropic selectivity of binary mixtures in cylindrical pores
NASA Astrophysics Data System (ADS)
González, A.; White, J. A.; Román, F. L.; Velasco, S.
2011-10-01
We show that a simple model consisting of a binary hard-sphere mixture in a narrow cylindrical pore can lead to strong size selectivity by considering a situation where each species of the mixture sees a different radius of the cylinder. Two mechanisms are proposed to explain the observed results depending on the radius of the cylinder: for large radii the selectivity is driven by an enhancement of the depletion forces at the cylinder walls whereas for the narrowest cylinders excluded-volume effects lead to a shift of the effective chemical potential of the particles in the pore.
A Simple and Inexpensive Device for Slow, Controlled Addition of a Solution to a Reaction Mixture
NASA Astrophysics Data System (ADS)
Osvath, Peter
1995-07-01
A number of reactions require the slow and controlled addition of a solution containing one reagent to another. Attempting to control the flow rate over a number of hours using a conventional constant pressure addition funnel is a frustrating exercise; commercially available constant volume addition funnels are expensive and must be adjusted by trial and error each time a reaction is carried out. The use of an (expensive) peristaltic pump or syringe pump overcomes these problems but can introduce other complications. We have recently had occasion to carry out the synthesis of thioether macrocycles and cages requiring the slow and controlled addition of DMF solutions of (offensively odoriferous) thiols or (air-sensitive) thiolates to a reactant solution under nitrogen(1), Although the use of a syringe pump was called for, there are obvious difficulties associated with purging the solution and assembling such an apparatus under nitrogen, and we report a simple and inexpensive solution. A Male Luer Lock tip (recovered from a broken syringe) was sweated onto the flattened tip of a pressure-equalizing addition funnel and a syringe needle was attached. Judicious selection of needle length, bore size, and reactant volume can be used to control the addition time simply and reproducibly. With a 250-mL funnel, the flow rate changes by <25% from the beginning to the end of the addition. (In fact, a reduction in the rate of addition may even be advantageous as the reaction proceeds, the reagent in the receiving flask is consumed, its concentration drops, and the rate of reaction will decrease). A piece of fine Teflon tubing of appropriate length attached to the needle can be used to reduce the flow rate even further, but this is only necessary for very slow rates of addition. For example, the time of addition of 200 mL, of an ethanolic solution could be varied from approximately 5 minutes (150mm/17 gauge) to approximately 5 h (200mm/22 gauge), and once the addition time for a
Polettini, A; Pomi, R; Trinci, L; Muntoni, A; Lo Mastro, S
2004-09-01
An experimental work was carried out to investigate the feasibility of application of a sintering process to mixtures composed of Municipal Solid Waste Incinerator (MSWI) fly ash and low-cost additives (waste from feldspar production and cullet). The proportions of the three constituents were varied to adjust the mixture compositions to within the optimal range for sintering. The material was compacted in cylindrical specimens and treated at 1100 and 1150 degrees C for 30 and 60 min. Engineering and environmental characteristics including weight loss, dimensional changes, density, open porosity, mechanical strength, chemical stability and leaching behavior were determined for the treated material, allowing the relationship between the degree of sintering and both mixture composition and treatment conditions to be singled out. Mineralogical analyses detected the presence of neo-formation minerals from the pyroxene group. Estimation of the extent of metal loss from the samples indicated that the potential for volatilization of species of Pb, Cd and Zn is still a matter of major concern when dealing with thermal treatment of incinerator ash. PMID:15268956
Polettini, A; Pomi, R; Trinci, L; Muntoni, A; Lo Mastro, S
2004-09-01
An experimental work was carried out to investigate the feasibility of application of a sintering process to mixtures composed of Municipal Solid Waste Incinerator (MSWI) fly ash and low-cost additives (waste from feldspar production and cullet). The proportions of the three constituents were varied to adjust the mixture compositions to within the optimal range for sintering. The material was compacted in cylindrical specimens and treated at 1100 and 1150 degrees C for 30 and 60 min. Engineering and environmental characteristics including weight loss, dimensional changes, density, open porosity, mechanical strength, chemical stability and leaching behavior were determined for the treated material, allowing the relationship between the degree of sintering and both mixture composition and treatment conditions to be singled out. Mineralogical analyses detected the presence of neo-formation minerals from the pyroxene group. Estimation of the extent of metal loss from the samples indicated that the potential for volatilization of species of Pb, Cd and Zn is still a matter of major concern when dealing with thermal treatment of incinerator ash.
Belda, Petra M; Mielck, Jobst B
2005-05-01
The weighted arithmetic mean from values of a feature derived from the individual components is often used to calculate the theoretically expected compression behaviour of powder mixtures if no interparticulate interactions between the components occur. Alternatively, simulated and experimental double layer tablets are presented. The suitability of the various methods to serve as a reference for the assessment of the compression behaviour of powder mixtures shall be compared. Narrow and similar sieve fractions of maltitol and metamizol were mixed in various ratios of true volumes. Constant total true volumes of the single substances, powder mixtures, and layered powders of the same composition were compressed on an eccentric tabletting machine to a constant maximum geometric mean punch force. In addition, the compression of double layer tablets was mathematically simulated from the dynamic relative density-force data of the pure materials. At a given momentary force, the relative density of a simulated double layered powder bed is given by the harmonic mean of the relative density values of the pure materials weighted by their true volume fractions. The results show that the total, the net, and the expansion work change indeed almost linearly with the true volume fraction of the components in the double layer tablets, with the consequence that the plasticity index (=net work/total workx100) proceeds non-linearly. The slope of the Heckel plot 'at pressure' and the apparent mean yield pressure obtained from these Heckel data are non-linearly related to the true volume fraction. If the weighted arithmetic mean is used to analyse the compression behaviour of the powder mixtures, results are obtained which are incompatible or even contradictory between interrelated features. On the other hand, the double layer model provides a consistent evaluation. A good agreement between the results of the experimental and the simulated double layer tablets is found.
Equation of state of additive hard-disk fluid mixtures: A critical analysis of two recent proposals
NASA Astrophysics Data System (ADS)
López de Haro, M.; Yuste, S. B.; Santos, A.
2002-09-01
A detailed analysis of two different theoretical equations of state for a binary mixture of additive hard disks [C. Barrio and J. R. Solana, Phys. Rev. E 63, 011201 (2001); A. Santos, S. B. Yuste, and M. López de Haro, Mol. Phys. 96, 1 (1999)], including their comparison with Monte Carlo results, is carried out. It is found that both proposals, which require the equation of state of the single-component system as input, lead to comparable accuracy when the same input is used in both, but that advocated by Santos et al. is simpler and complies with the exact limit in which the small disks are point particles.
Alsop, Derek; Wood, Chris M
2013-09-15
The acute toxicities and mechanisms of action of a variety of environmental contaminants were examined using zebrafish larvae (Danio rerio; 4-8 days post fertilization). Toxic interactions were observed between metals. For example, the addition of a sublethal level of nickel (15% of the LC50, one third of the LC01) to all copper treatments decreased the copper 96 h LC50 by 58%, while sublethal copper exposure (6% of the copper LC50, 13% of the LC01) decreased the cadmium 96 h LC50 by 47%. Two predictive models were assessed, the concentration addition (CA) model, which assumes similar mechanisms of action, and the independent action (IA) model, which assumes different mechanisms of action. Quantitative comparisons indicated the CA model performed better than the IA model; the latter tended to underestimate combined toxicity to a greater extent. The effects of mixtures with nickel or ammonia were typically additive, while mixtures with copper or cadmium were typically greater than additive. Larvae exposed to cadmium, copper or nickel experienced whole body ion loss. Decreases were greatest for Na(+) followed by K(+) (as high as 19% and 9%, respectively, in 24h). Additive toxicity between copper and other pharmaceutical compounds such as fluoxetine (Prozac™), β-naphthoflavone, estrogen and 17α-ethinylestradiol were also observed. Similar to metals, acutely toxic concentrations of fluoxetine, β-naphthoflavone and ammonia all decreased whole body Na(+) and K(+). Overall, whole body Na(+) loss showed the greatest correlation with mortality across a variety of toxicants. We theorize that a disruption of ion homeostasis may be a common mechanism underlying the acute additive toxicity of many contaminants in fish.
Lynch, Natalie R; Hoang, Tham C; O'Brien, Timothy E
2016-02-01
Metal mixture toxicity has been studied for decades. However, the results are not consistent, and thus ecological risk assessment and regulation of mixtures has been difficult. The objective of the present study was to use a systematic experimental design to characterize the toxicity of binary-metal mixture of Cu, Zn, and Ni to Pimephales promelas, typically to determine whether the effect of these binary-metal mixtures on P. promelas is more-than-additive. Standard 96-h toxicity tests were conducted with larval P. promelas based on US Environmental and Protection Agency methods to determine metal mixture effects. All experiments were conducted in synthetic moderately hard water with no addition of dissolved organic matter. Three different effect analysis approaches, the MixTox model, the Finney model, and the toxic unit method, were used for comparison. The results indicate that the toxicity of Cu+Zn, Cu+Ni, and Zn+Ni mixtures to P. promelas was more-than-additive. Among the 3 mixtures, the effect of the Cu+Ni mixture was the most profound. The results of the present study are useful for applications to models such as the metal mixture biotic ligand model. More research should be conducted to determine the mechanisms of acute and chronic toxicity of metal mixtures.
Explanation of non-additive effects in mixtures of similar mode of action chemicals.
Kamo, Masashi; Yokomizo, Hiroyuki
2015-09-01
Many models have been developed to predict the combined effect of drugs and chemicals. Most models are classified into two additive models: independent action (IA) and concentration addition (CA). It is generally considered if the modes of action of chemicals are similar then the combined effect obeys CA; however, many empirical studies report nonlinear effects deviating from the predictions by CA. Such deviations are termed synergism and antagonism. Synergism, which leads to a stronger toxicity, requires more careful management, and hence it is important to understand how and which combinations of chemicals lead to synergism. In this paper, three types of chemical reactions are mathematically modeled and the cause of the nonlinear effects among chemicals with similar modes of action was investigated. Our results show that combined effects obey CA only when the modes of action are exactly the same. Contrary to existing knowledge, combined effects are generally nonlinear even if the modes of action of the chemicals are similar. Our results further show that the nonlinear effects vanish out when the chemical concentrations are low, suggesting that the current management procedure of assuming CA is rarely inappropriate because environmental concentrations of chemicals are generally low.
Marquez, J A; Murr, L E; Agüero, V
2000-08-01
The perception that mercury in dental amalgam is toxic to the human organism has prompted worldwide efforts by the scientific community to develop alternative amalgam-like materials that utilize little or no mercury. In this investigation, an attempt is made to develop a new dental alloy system by adding liquid mercury to silver-coated Ag4Sn intermetallic particles in lesser amounts than are used in conventional amalgam alloys. An effort to precipitate the important eta-prime (Cu6Sn5) phase was made by adding pure Cu and Sn powders to the alloy formulation during trituration. Tytin a popular Ag-Sn-Cu single-composition, spray-atomized conventional dental alloy was used as the control to obtain baseline data for comparisons of microstructures and mechanical properties. Amalgamation of the coated particles with mercury, with or without the addition of Cu and Sn powders, mostly produced specimens with chemically non-coherent microstructures that were relatively weak in compression. These results were due, in part, to mercury's inability to chemically wet the Ag-coated particles and Cu and Sn powders because of naturally occurring surface oxide films. The strongest specimens tested had silver dendritic coatings, resulting in compression strength values up to 40% of the control's. Their higher strength is attributed to mechanical interlocking at the particle/matrix interfaces.
NASA Technical Reports Server (NTRS)
Dass, Amala; Oh, Woon Su; Gao, Xue-Rong; Rawashdeh, Abdel M.; Leventis, Nicholas
2004-01-01
We have published recently the effect of dissimilar diffusion coefficients on the size of the voltammetric waves from a mixture of two redox-active compounds. Similarly, at the potential range where three redox-active species, decamethylferrocene (dMeFc), ferrocene (Fc) and N-methylphenothiazine (MePTZ), are oxidized simultaneously with rates controlled by linear diffusion, electrogenerated radicals diffusing outwards from the electrode react with the original species diffusing towards the electrode from the bulk; thus, Fc(+) reacts with dMeFc producing Fc and dMeFc(+), while MePTZ(+) reacts both with dMeFc producing MePTZ and dMeFc(+), and with Fc producing MePTZ and Fc(+). These reactions replace dMeFc with Fc at the second plateau, and both dMeFc and Fc with MePTZ at the third plateau. Since the diffusion coefficients of the three species are not equal, the mass-transfer limited currents of the second and the third oxidation wave plateaus change by approx. 10%. Numerical simulations of the experimental voltamograms support this mechanism. Similar results were also obtained for a mixture of four redoxactive compounds. The implications of this non-additive nature of currents on: (a) the use of internal voltammetric standards for quantitative analysis of a mixture of redox-active compounds; and, (b) the half wave potentials (E1/2) of the 2nd, 3rd and 4th waves for qualitative analysis, will be discussed.
D-OPTIMAL EXPERIMENTAL DESIGNS TO TEST FOR DEPARTURE FROM ADDITIVITY IN A FIXED-RATIO RAY MIXTURE.
Risk assessors are becoming increasingly aware of the importance of assessing interactions between chemicals in a mixture. Most traditional designs for evaluating interactions are prohibitive when the number of chemicals in the mixture is large. However, evaluation of interacti...
Zhang, Ling; Zhang, Yaojun; Zou, Jianwen; Siemann, Evan
2014-01-01
Solidago canadensis is an aggressive invader in China. Solidago invasion success is partially attributed to allelopathic compounds release and more benefits from AM fungi, which potentially makes the properties of Solidago litter different from co-occurring natives. These properties may comprehensively affect litter decomposition of co-occurring natives. We conducted a field experiment to examine litter mixing effects in a Phragmites australis dominated community invaded by Solidago in southeast China. Solidago had more rapid mass and N loss rate than Phragmites when they decomposed separately. Litter mixing decreased N loss rate in Phragmites litter and increased that of Solidago. Large decreases in Phragmites mass loss and smaller increases in Solidago mass loss caused negative non-additive effect. Solidago litter extracts reduced soil C decomposition and N processes, suggested an inhibitory effect of Solidago secondary compounds. These results are consistent with the idea that nutrient transfer and secondary compounds both affected litter mixtures decomposition. PMID:24976274
NASA Astrophysics Data System (ADS)
Zhang, Ling; Zhang, Yaojun; Zou, Jianwen; Siemann, Evan
2014-06-01
Solidago canadensis is an aggressive invader in China. Solidago invasion success is partially attributed to allelopathic compounds release and more benefits from AM fungi, which potentially makes the properties of Solidago litter different from co-occurring natives. These properties may comprehensively affect litter decomposition of co-occurring natives. We conducted a field experiment to examine litter mixing effects in a Phragmites australis dominated community invaded by Solidago in southeast China. Solidago had more rapid mass and N loss rate than Phragmites when they decomposed separately. Litter mixing decreased N loss rate in Phragmites litter and increased that of Solidago. Large decreases in Phragmites mass loss and smaller increases in Solidago mass loss caused negative non-additive effect. Solidago litter extracts reduced soil C decomposition and N processes, suggested an inhibitory effect of Solidago secondary compounds. These results are consistent with the idea that nutrient transfer and secondary compounds both affected litter mixtures decomposition.
Zhang, Ling; Zhang, Yaojun; Zou, Jianwen; Siemann, Evan
2014-06-30
Solidago canadensis is an aggressive invader in China. Solidago invasion success is partially attributed to allelopathic compounds release and more benefits from AM fungi, which potentially makes the properties of Solidago litter different from co-occurring natives. These properties may comprehensively affect litter decomposition of co-occurring natives. We conducted a field experiment to examine litter mixing effects in a Phragmites australis dominated community invaded by Solidago in southeast China. Solidago had more rapid mass and N loss rate than Phragmites when they decomposed separately. Litter mixing decreased N loss rate in Phragmites litter and increased that of Solidago. Large decreases in Phragmites mass loss and smaller increases in Solidago mass loss caused negative non-additive effect. Solidago litter extracts reduced soil C decomposition and N processes, suggested an inhibitory effect of Solidago secondary compounds. These results are consistent with the idea that nutrient transfer and secondary compounds both affected litter mixtures decomposition.
Zhang, Ling; Zhang, Yaojun; Zou, Jianwen; Siemann, Evan
2014-01-01
Solidago canadensis is an aggressive invader in China. Solidago invasion success is partially attributed to allelopathic compounds release and more benefits from AM fungi, which potentially makes the properties of Solidago litter different from co-occurring natives. These properties may comprehensively affect litter decomposition of co-occurring natives. We conducted a field experiment to examine litter mixing effects in a Phragmites australis dominated community invaded by Solidago in southeast China. Solidago had more rapid mass and N loss rate than Phragmites when they decomposed separately. Litter mixing decreased N loss rate in Phragmites litter and increased that of Solidago. Large decreases in Phragmites mass loss and smaller increases in Solidago mass loss caused negative non-additive effect. Solidago litter extracts reduced soil C decomposition and N processes, suggested an inhibitory effect of Solidago secondary compounds. These results are consistent with the idea that nutrient transfer and secondary compounds both affected litter mixtures decomposition. PMID:24976274
Ujaczki, Éva; Feigl, Viktória; Molnár, Mónika; Vaszita, Emese; Uzinger, Nikolett; Erdélyi, Attila; Gruiz, Katalin
2016-06-01
Red mud, the by-product of aluminum production, has been regarded as a problematic residue all over the world. Its storage involves risks as evidenced by the Ajka red mud spill, an accident in Hungary where the slurry broke free, flooding the surrounding areas. As an immediate remediation measure more than 5cm thick red mud layer was removed from the flooded soil surface. The removed red mud and soil mixture (RMSM) was transferred into the reservoirs for storage. In this paper the application of RMSM is evaluated in a field study aiming at re-utilizing waste, decreasing cost of waste disposal and providing a value-added product. The purpose was to investigate the applicability of RMSM as surface layer component of landfill cover systems. The field study was carried out in two steps: in lysimeters and in field plots. The RMSM was mixed at ratios ranging between 0 and 50% w/w with low quality subsoil (LQS) originally used as surface layer of an interim landfill cover. The characteristics of the LQS+RMSM mixtures compared to the subsoil (LQS) and the RMSM were determined by physical-chemical, biological and ecotoxicological methods. The addition of RMSM to the subsoil (LQS) at up to 20% did not result any ecotoxic effect, but it increased the water holding capacity. In addition, the microbial substrate utilization became about triple of subsoil (LQS) after 10months. According to our results the RMSM mixed into subsoil (LQS) at 20% w/w dose may be applied as surface layer of landfill cover systems. PMID:27266315
Tang, C. L.; Huang, Z. H.; Law, C. K.
2010-08-30
The stretch-affected propagation speeds of expanding spherical flames of n-butane–air mixtures with hydrogen addition were measured at atmospheric pressure and subsequently processed through a nonlinear regression analysis to yield the stretch-free laminar flame speeds. Based on a hydrogen addition parameter (R_{H}) and an effective fuel equivalence ratio (Φ_{F}), these laminar flame speeds were found to increase almost linearly with R_{H}, for Φ_{F} between 0.6 and 1.4 and RHRH from 0 to 0.5, with the slope of the variation assuming a minimum around stoichiometry. These experimental results also agree well with computed values using a detailed reaction mechanism. Furthermore, a mechanistic investigation aided by sensitivity analysis identified that kinetic effects through the global activation energy, followed by thermal effects through the adiabatic flame temperature, have the most influence on the increase in the flame speeds and the associated linear variation with R_{H} due to hydrogen addition. Nonequidiffusion effects due to the high mobility of hydrogen, through the global Lewis number, have the least influence. Further calculations for methane, ethene, and propane as the fuel showed similar behavior, leading to possible generalization of the phenomena and correlation.
Pizio, O.; Sokołowski, S.; Sokołowska, Z.
2014-05-07
We investigate microscopic structure, adsorption, and electric properties of a mixture that consists of amphiphilic molecules and charged hard spheres in contact with uncharged or charged solid surfaces. The amphiphilic molecules are modeled as spheres composed of attractive and repulsive parts. The electrolyte component of the mixture is considered in the framework of the restricted primitive model (RPM). The system is studied using a density functional theory that combines fundamental measure theory for hard sphere mixtures, weighted density approach for inhomogeneous charged hard spheres, and a mean-field approximation to describe anisotropic interactions. Our principal focus is in exploring the effects brought by the presence of ions on the distribution of amphiphilic particles at the wall, as well as the effects of amphiphilic molecules on the electric double layer formed at solid surface. In particular, we have found that under certain thermodynamic conditions a long-range translational and orientational order can develop. The presence of amphiphiles produces changes of the shape of the differential capacitance from symmetric or non-symmetric bell-like to camel-like. Moreover, for some systems the value of the potential of the zero charge is non-zero, in contrast to the RPM at a charged surface.
Pizio, O; Sokołowski, S; Sokołowska, Z
2014-05-01
We investigate microscopic structure, adsorption, and electric properties of a mixture that consists of amphiphilic molecules and charged hard spheres in contact with uncharged or charged solid surfaces. The amphiphilic molecules are modeled as spheres composed of attractive and repulsive parts. The electrolyte component of the mixture is considered in the framework of the restricted primitive model (RPM). The system is studied using a density functional theory that combines fundamental measure theory for hard sphere mixtures, weighted density approach for inhomogeneous charged hard spheres, and a mean-field approximation to describe anisotropic interactions. Our principal focus is in exploring the effects brought by the presence of ions on the distribution of amphiphilic particles at the wall, as well as the effects of amphiphilic molecules on the electric double layer formed at solid surface. In particular, we have found that under certain thermodynamic conditions a long-range translational and orientational order can develop. The presence of amphiphiles produces changes of the shape of the differential capacitance from symmetric or non-symmetric bell-like to camel-like. Moreover, for some systems the value of the potential of the zero charge is non-zero, in contrast to the RPM at a charged surface.
NASA Technical Reports Server (NTRS)
Smalheer, C. V.
1973-01-01
The chemistry of lubricant additives is discussed to show what the additives are chemically and what functions they perform in the lubrication of various kinds of equipment. Current theories regarding the mode of action of lubricant additives are presented. The additive groups discussed include the following: (1) detergents and dispersants, (2) corrosion inhibitors, (3) antioxidants, (4) viscosity index improvers, (5) pour point depressants, and (6) antifouling agents.
Belda, Petra M; Mielck, Jobst B
2006-11-01
The theoretically expected breaking strength of tablets from powder mixtures is often calculated by the weighted arithmetic mean from the breaking strength of the single components, which corresponds to a linear interpolation. The validity of this additivity of fracture strength shall be evaluated by the underlying model of parallel couplings. It assumes the components linked in parallel with respect to the direction of loading during diametrical strength testing. Parallel couplings were experimentally realised by the preparation of double layer tablets from crystalline and spray-dried lactose on the one hand and from maltitol and metamizol-sodium on the other. Constant total true volumes of the single substances and of layered powders in varying ratios of true volume were compressed on an eccentric tabletting machine to constant geometric mean punch force. Simulated crushing profiles of parallel couplings were derived from force-displacement profiles measured during diametrical compression of the one-component tablets. At given finely graded deformation levels, the forces exerted by the components during loading were added in the proportion of the true volume fractions of the components in the coupling. The results from the experiments and from the simulations are in good accordance. They demonstrate that a linear change of the crushing strength in dependence on the true volume fraction of the components can only be assumed if the single components deform to the same extent up to the point of fracture. This behaviour was approximately found with the parallel lactose system. In all other cases it must be expected that the crushing strength of parallel systems will be lowered beneath the weighted arithmetic mean values or even below the crushing strength of the single components. The latter was observed with the maltitol-metamizol combinations. Thus, if tablets from binary powder mixtures exhibit a crushing strength depression, this is not necessarily an indication
Nazareth, Marilyn; Ghoshal, Pabitra; Namshikar, Viraj; Gaude, Yogesh
2013-01-01
Context: This study was undertaken in 100 patients scheduled for lower limb orthopaedic surgeries. Aim: The objective of this study was to study the effect of addition of intrathecal fentanyl to bupivacaine clonidine mixture on the quality of subarachnoid block and compare it with intrathecal bupivacaine clonidine mixture without fentanyl. Settings and Design: In this prospective and double blind randomized controlled study, one hundred patients, between 20-40 years of age, of either sex, weighing between 40-65 Kg, measuring more than 150 cm in height, of ASA Grade I and II who were undergoing orthopaedic lower limb surgeries were selected in order to study the quality of subarachnoid block and post-operative analgesia produced by a combination of bupivacaine clonidine and fentanyl in comparison with bupivacaine clonidine. Materials and Methods: The patients were randomly divided in two groups of 50 each: Group BC: 2.4 ml of 0.5% hyperbaric bupivacaine (12 mg) + 0.2 ml (30 μg) clonidine + 0.4 ml of 0.9% NaCl. Group BCF: 2.4 ml of 0.5% hyperbaric bupivacaine (12 mg) + 0.2 ml (30 μg) clonidine + 0.4 ml (20 μg) of fentanyl. The total volume of solution in both the groups was 3.0 ml. The quality of subarachnoid block and post-operative analgesia were studied. Statistical Analysis Used: The data thus obtained was statistically analysed using the following tests: Unpaired student's t-test. Average % change in data over baseline values to detect trends. A ‘P’ value of <0.05 was considered to be statistically significant. Results: There was no significant difference in duration of sensory and motor blockade in group BCF compared to BC. The duration of analgesia as assessed by, either VAS score of >5 or demand of additional analgesia was > 524.6 ± 32.21 mins in group BC and > 774.4 ± 59.59 mins in group BCF. This prolongation of duration of analgesia in group BCF compared to group BC has statistical significance. Blood pressure and heart rate changes were not
Internal structure of shock waves in disparate mass mixtures
NASA Technical Reports Server (NTRS)
Chung, Chan-Hong; De Witt, Kenneth J.; Jeng, Duen-Ren; Penko, Paul F.
1992-01-01
The detailed flow structure of a normal shock wave for a gas mixture is investigated using the direct-simulation Monte Carlo method. A variable diameter hard-sphere (VDHS) model is employed to investigate the effect of different viscosity temperature exponents (VTE) for each species in a gas mixture. Special attention is paid to the irregular behavior in the density profiles which was previously observed in a helium-xenon experiment. It is shown that the VTE can have substantial effects in the prediction of the structure of shock waves. The variable hard-sphere model of Bird shows good agreement, but with some limitations, with the experimental data if a common VTE is chosen properly for each case. The VDHS model shows better agreement with the experimental data without adjusting the VTE. The irregular behavior of the light-gas component in shock waves of disparate mass mixtures is observed not only in the density profile, but also in the parallel temperature profile. The strength of the shock wave, the type of molecular interactions, and the mole fraction of heavy species have substantial effects on the existence and structure of the irregularities.
Internal structure of shock waves in disparate mass mixtures
Chung, Chan-Hong; De witt, K.J.; Jeng, Duen-Ren; Penko, P.F. Toledo, University, OH )
1992-01-01
The detailed flow structure of a normal shock wave for a gas mixture is investigated using the direct-simulation Monte Carlo method. A variable diameter hard-sphere (VDHS) model is employed to investigate the effect of different viscosity temperature exponents (VTE) for each species in a gas mixture. Special attention is paid to the irregular behavior in the density profiles which was previously observed in a helium-xenon experiment. It is shown that the VTE can have substantial effects in the prediction of the structure of shock waves. The variable hard-sphere model of Bird shows good agreement, but with some limitations, with the experimental data if a common VTE is chosen properly for each case. The VDHS model shows better agreement with the experimental data without adjusting the VTE. The irregular behavior of the light-gas component in shock waves of disparate mass mixtures is observed not only in the density profile, but also in the parallel temperature profile. The strength of the shock wave, the type of molecular interactions, and the mole fraction of heavy species have substantial effects on the existence and structure of the irregularities. 14 refs.
Pereira, Ana Carolina da Silva; Wurlitzer, Nedio Jair; Dionisio, Ana Paula; Lacerda Soares, Marcia Valéria; Rocha Bastos, Maria do Socorro; Elesbão Alves, Ricardo; Montenegro Brasil, Isabella
2015-06-01
The objective of this work was investigate the synergistic, additive and antagonistic effects of fruit mixtures on total antioxidant capacities and bioactive compounds in tropical fruit juices, and optimize its formulation by the response surface methodology based on the responses: total polyphenols (TP), total antioxidant capacity (TAC), ascorbic acid content and sensorial acceptance. Camu-camu, acerola and acai were the major factors that influenced the antioxidant potential of the juice; and the yellow mombin showed a positive effect on the acceptance of the tropical juice. It was observed an/antagonistic effect between acerola and camu-camu for the TAC response. The optimum formulation obtained was 20% acerola, 10% camu-camu, 10% yellow mombin, 10% cashew apple and 10% acai, which was responsible for a response of 155.46 mg.100 g(-1) of ascorbic acid, 103.01 mg of GAE.100 g-1 of TP, 10.27 µM Trolox g(-1) of TAC and approximately 6.1 of acceptance. PMID:26817384
Free Volume of the Hard Spheres Gas
ERIC Educational Resources Information Center
Shutler, P. M. E.; Martinez, J. C.; Springham, S. V.
2007-01-01
The Enskog factor [chi] plays a central role in the theory of dense gases, quantifying how the finite size of molecules causes many physical quantities, such as the equation of state, the mean free path, and the diffusion coefficient, to deviate from those of an ideal gas. We suggest an intuitive but rigorous derivation of this fact by showing how…
Hard quasispherical particle models for the viscosity of solutions of protein mixtures.
Minton, Allen P
2012-08-01
Recently reported measurements of the viscosity of three monoclonal antibodies, their binary mixtures, and a binary mixture of an antibody and albumin over a broad range of compositions (Galush et al., J. Pharm. Sci. 2011,101, 1012) were quantitatively accounted for to within experimental uncertainty by an extension of the hard quasispherical particle model suggested by Ross and Minton (Biochem. Biophys. Res. Commun. 1977, 76, 971) and by a generalization of the hard sphere equation of Krieger and Dougherty (Trans. Soc. Rheol. 1959, 3, 137) . Further generalization of these equations to treat the concentration-dependent viscosity of self-associating proteins is suggested.
D-OPTIMAL EXPERIMENTAL DESIGNS TO TEST FOR DEPARTURE FROM ADDITIVITY IN A FIXED-RATIO MIXTURE RAY.
Traditional factorial designs for evaluating interactions among chemicals in a mixture are prohibitive when the number of chemicals is large. However, recent advances in statistically-based experimental design have made it easier to evaluate interactions involving many chemicals...
Howdeshell, Kembra L; Rider, Cynthia V; Wilson, Vickie S; Furr, Johnathan R; Lambright, Christy R; Gray, L Earl
2015-12-01
Challenges in cumulative risk assessment of anti-androgenic phthalate mixtures include a lack of data on all the individual phthalates and difficulty determining the biological relevance of reduction in fetal testosterone (T) on postnatal development. The objectives of the current study were 2-fold: (1) to test whether a mixture model of dose addition based on the fetal T production data of individual phthalates would predict the effects of a 5 phthalate mixture on androgen-sensitive postnatal male reproductive tract development, and (2) to determine the biological relevance of the reductions in fetal T to induce abnormal postnatal reproductive tract development using data from the mixture study. We administered a dose range of the mixture (60, 40, 20, 10, and 5% of the top dose used in the previous fetal T production study consisting of 300 mg/kg per chemical of benzyl butyl (BBP), di(n)butyl (DBP), diethyl hexyl phthalate (DEHP), di-isobutyl phthalate (DiBP), and 100 mg dipentyl (DPP) phthalate/kg; the individual phthalates were present in equipotent doses based on their ability to reduce fetal T production) via gavage to Sprague Dawley rat dams on GD8-postnatal day 3. We compared observed mixture responses to predictions of dose addition based on the previously published potencies of the individual phthalates to reduce fetal T production relative to a reference chemical and published postnatal data for the reference chemical (called DAref). In addition, we predicted DA (called DAall) and response addition (RA) based on logistic regression analysis of all 5 individual phthalates when complete data were available. DA ref and DA all accurately predicted the observed mixture effect for 11 of 14 endpoints. Furthermore, reproductive tract malformations were seen in 17-100% of F1 males when fetal T production was reduced by about 25-72%, respectively. PMID:26350170
Auffret, Marc; Labbé, Diane; Thouand, Gérald; Greer, Charles W.; Fayolle-Guichard, Françoise
2009-01-01
Two strains, identified as Rhodococcus wratislaviensis IFP 2016 and Rhodococcus aetherivorans IFP 2017, were isolated from a microbial consortium that degraded 15 petroleum compounds or additives when provided in a mixture containing 16 compounds (benzene, toluene, ethylbenzene, m-xylene, p-xylene, o-xylene, octane, hexadecane, 2,2,4-trimethylpentane [isooctane], cyclohexane, cyclohexanol, naphthalene, methyl tert-butyl ether [MTBE], ethyl tert-butyl ether [ETBE], tert-butyl alcohol [TBA], and 2-ethylhexyl nitrate [2-EHN]). The strains had broad degradation capacities toward the compounds, including the more recalcitrant ones, MTBE, ETBE, isooctane, cyclohexane, and 2-EHN. R. wratislaviensis IFP 2016 degraded and mineralized to different extents 11 of the compounds when provided individually, sometimes requiring 2,2,4,4,6,8,8-heptamethylnonane (HMN) as a cosolvent. R. aetherivorans IFP 2017 degraded a reduced spectrum of substrates. The coculture of the two strains degraded completely 13 compounds, isooctane and 2-EHN were partially degraded (30% and 73%, respectively), and only TBA was not degraded. Significant MTBE and ETBE degradation rates, 14.3 and 116.1 μmol of ether degraded h−1 g−1 (dry weight), respectively, were measured for R. aetherivorans IFP 2017. The presence of benzene, toluene, ethylbenzene, and xylenes (BTEXs) had a detrimental effect on ETBE and MTBE biodegradation, whereas octane had a positive effect on the MTBE biodegradation by R. wratislaviensis IFP 2016. BTEXs had either beneficial or detrimental effects on their own degradation by R. wratislaviensis IFP 2016. Potential genes involved in hydrocarbon degradation in the two strains were identified and partially sequenced. PMID:19837842
Malijevský, Alexandr; Jackson, George; Varga, Szabolcs
2008-10-14
The extension of Onsager's second-virial theory [L. Onsager, Ann. N.Y. Acad. Sci. 51, 627 (1949)] for the orientational ordering of hard rods to mixtures of nonspherical hard bodies with finite length-to-breadth ratios is examined using the decoupling approximations of Parsons [Phys. Rev. A 19, 1225 (1979)] and Lee [J. Chem. Phys. 86, 6567 (1987); 89, 7036 (1988)]. Invariably the extension of the Parsons-Lee (PL) theory to mixtures has in the past involved a van der Waals one-fluid treatment in which the properties of the mixture are approximated by those of a reference one-component hard-sphere fluid with an effective diameter which depends on the composition of the mixture and the molecular parameters of the various components; commonly this is achieved by equating the molecular volumes of the effective hard sphere and of the components in the mixture and is referred to as the PL theory of mixtures. It is well known that a one-fluid treatment is not the most appropriate for the description of the thermodynamic properties of isotropic fluids, and inadequacies are often rectified with a many-fluid (MF) theory. Here, we examine MF theories which are developed from the virial theorem and the virial expansion of the Helmholtz free energy of anisotropic fluid mixtures. The use of the decoupling approximation of the pair distribution function at the level of a multicomponent hard-sphere reference system leads to our MF Parsons (MFP) theory of anisotropic mixtures. Alternatively the mapping of the virial coefficients of the hard-body mixtures onto those of equivalent hard-sphere systems leads to our MF Lee (MFL) theory. The description of the isotropic-nematic phase behavior of binary mixtures of hard Gaussian overlap particles is used to assess the adequacy of the four different theories, namely, the original second-virial theory of Onsager, the usual PL one-fluid theory, and the MF theories based on the Lee (MFL) and Parsons (MFP) approaches. A comparison with the
Malijevský, Alexandr; Jackson, George; Varga, Szabolcs
2008-10-14
The extension of Onsager's second-virial theory [L. Onsager, Ann. N.Y. Acad. Sci. 51, 627 (1949)] for the orientational ordering of hard rods to mixtures of nonspherical hard bodies with finite length-to-breadth ratios is examined using the decoupling approximations of Parsons [Phys. Rev. A 19, 1225 (1979)] and Lee [J. Chem. Phys. 86, 6567 (1987); 89, 7036 (1988)]. Invariably the extension of the Parsons-Lee (PL) theory to mixtures has in the past involved a van der Waals one-fluid treatment in which the properties of the mixture are approximated by those of a reference one-component hard-sphere fluid with an effective diameter which depends on the composition of the mixture and the molecular parameters of the various components; commonly this is achieved by equating the molecular volumes of the effective hard sphere and of the components in the mixture and is referred to as the PL theory of mixtures. It is well known that a one-fluid treatment is not the most appropriate for the description of the thermodynamic properties of isotropic fluids, and inadequacies are often rectified with a many-fluid (MF) theory. Here, we examine MF theories which are developed from the virial theorem and the virial expansion of the Helmholtz free energy of anisotropic fluid mixtures. The use of the decoupling approximation of the pair distribution function at the level of a multicomponent hard-sphere reference system leads to our MF Parsons (MFP) theory of anisotropic mixtures. Alternatively the mapping of the virial coefficients of the hard-body mixtures onto those of equivalent hard-sphere systems leads to our MF Lee (MFL) theory. The description of the isotropic-nematic phase behavior of binary mixtures of hard Gaussian overlap particles is used to assess the adequacy of the four different theories, namely, the original second-virial theory of Onsager, the usual PL one-fluid theory, and the MF theories based on the Lee (MFL) and Parsons (MFP) approaches. A comparison with the
An Additive Effect of a Mixture of Ammonium Perchlorate
and Sodium Chlorate on Pitutary-Thyroid Axis in Male F-344 Rats
Moazzam A. Khan 1,2,, 3Suzanne E. Fenton. 2Adam E. Swank, ZGeremy W. Knapp, 2Susan D.
Hester, and 2Douglas C. Wolf. 1NRC, 2Environmental Carcinog...
In 1996 the USEPA was charged under the FQPA to consider the cumulative effects of chemicals in their risk assessments. Our studies were conducted to provide a framework for assessing the cumulative effects of antiandrogens. Toxicants were administered individually or as mixtures...
Disinfection of water decreases waterborne disease. Disinfection byproducts (DBPs) are formed by the reaction of oxidizing disinfectants with inorganic and organic materials in the source water. The U.S. EPA regulates five haloacetic acid (HAA) DBPs as a mixture. The objective ...
A corresponding states principle for the equation of state of hard body fluid mixtures
NASA Astrophysics Data System (ADS)
Barrio, C.; Largo, J.; Solana, J. R.
2001-01-01
A theoretically based corresponding-states principle is developed for athermal mixtures consisting of hard molecules. The principle states that when scaled appropriately, the excess compressibility factor for such mixtures reduces to a universal function of the effective packing fraction of the mixture. The latter represents the number density reduced by means of the effective molecular volume, which is defined as the volume a molecule excludes to any point of another molecule and depends on the geometry of both molecules. The scaling factor is related to a sort of effective nonsphericity parameter for the mixture that depends on composition as well as the nonsphericity parameters of the molecules which form the mixture and their effective molecular volumes. The universal function represents the excess compressibility factor of a pure hard-sphere fluid. Results are in good agreement with available simulation data.
Auffret, Marc D; Yergeau, Etienne; Labbé, Diane; Fayolle-Guichard, Françoise; Greer, Charles W
2015-03-01
A bacterial consortium (Mix3) composed of microorganisms originating from different environments (soils and wastewater) was obtained after enrichment in the presence of a mixture of 16 hydrocarbons, gasoline, and diesel oil additives. After addition of the mixture, the development of the microbial composition of Mix3 was monitored at three different times (35, 113, and 222 days) using fingerprinting method and dominant bacterial species were identified. In parallel, 14 bacteria were isolated after 113 days and identified. Degradation capacities for Mix3 and the isolated bacterial strains were characterized and compared. At day 113, we induced the expression of catabolic genes in Mix3 by adding the substrate mixture to resting cells and the metatranscriptome was analyzed. After addition of the substrate mixture, the relative abundance of Actinobacteria increased at day 222 while a shift between Rhodococcus and Mycobacterium was observed after 113 days. Mix3 was able to degrade 13 compounds completely, with partial degradation of isooctane and 2-ethylhexyl nitrate, but tert-butyl alcohol was not degraded. Rhodococcus wratislaviensis strain IFP 2016 isolated from Mix3 showed almost the same degradation capacities as Mix3: these results were not observed with the other isolated strains. Transcriptomic results revealed that Actinobacteria and in particular, Rhodococcus species, were major contributors in terms of total and catabolic gene transcripts while other species were involved in cyclohexane degradation. Not all the microorganisms identified at day 113 were active except R. wratislaviensis IFP 2016 that appeared to be a major player in the degradation activity observed in Mix3.
Heneweer, Marjoke . E-mail: M.Heneweer@iras.uu.nl; Muusse, Martine; Berg, Martin van den; Sanderson, J. Thomas
2005-10-15
In order to protect consumers from ultraviolet (UV) radiation and enhance light stability of the product, three to eight UV filters are usually added to consumer sunscreen products. High lipophilicity of the UV filters has been shown to cause bioaccumulation in fish and humans, leading to environmental levels of UV filters that are similar to those of PCBs and DDT. In this paper, estrogen-regulated pS2 gene transcription in the human mammary tumor cell line MCF-7 was used as a measure of estrogenicity of four individual UV filters. Since humans are exposed to more than one UV filter at a time, an equipotent binary mixture of 2-hydroxy-4-methoxy-benzophenone (BP-3) and its metabolite 2,4-dihydroxy benzophenone (BP-1), as well as an equipotent multi-component mixture of BP-1, BP-3, octyl methoxy cinnamate (OMC) and 3-(4-methylbenzylidene) camphor (4-MBC), were also evaluated for their ability to induce pS2 gene transcription in order to examine additivity. An estrogen receptor-mediated mechanism of action was expected for all UV filters. Therefore, our null-hypothesis was that combined estrogenic responses, measured as increased pS2 gene transcription in MCF-7 cells after exposure to mixtures of UV filters, are additive, according to a concentration-addition model. Not all UV filters produced a full concentration-response curve within the concentration range tested (100 nM-1 {mu}M). Therefore, instead of using EC{sub 50} values for comparison, the concentration at which each compound caused a 50% increase of basal pS2 gene transcription was defined as the C50 value for that compound and used to calculate relative potencies. For comparison, the EC{sub 50} value of a compound is the concentration at which the compound elicits an effect that is 50% of its maximal effect. Individual UV filters increased pS2 gene transcription concentration-dependently with C50 values of 0.12 {mu}M, 0.5 {mu}M, 1.9 {mu}M, and 1.0 {mu}M for BP-1, BP-3, 4-MBC and OMC, respectively. Estradiol
Blackburn, J.C.; Kilpatrick, P.K. )
1993-04-01
The effects of added salt (CsOH, CsCl), long-chain carboxylic acid, and long-chain alcohol on the lyotropic liquid crystalline phase behavior in the cesium n-tetradecanoate (CsTD)-water system is reported. The transitional region between the hexagonal (H) and lamellar (L) phases was the compositional range of focus. Three transitional phases were observed: (i) the ribbon (R) phase, a biaxial phase consisting of cylinders of ellipsoidal cross section; (ii) the viscous isotropic (VI) phase, an isotropic phase thought to consist of interconnected rods on an Ia3d lattice; and (iii) the intermediate (Int) phase, a uniaxial anisotropic phase thought to consist of interconnected rods on a planar lattice. The effect of the additives was to decrease the interfacial curvature of the surfactant head group layer by varying head group repulsion and by varying the surfactant tail volume relative to the surfactant head group area. These changes resulted in formation of transitional phases seeming to possess curvature between that of the cylindrical H phase and the planar L phase. The ionic repulsion between carboxylate head groups was reduced by the addition of CsOH or CsCl, and resulted in destabilization of the VI phase and the formation of the anisotropic Int phase. With the addition of cosurfactants, n-tetradecanoic acid (TDA) and 1-tetradecanol (TDOH), no Int phase was observed. With 7 wt% added TDA the R phase was stabilized up to temperatures of 336 K, above the 330 K temperature limit in the binary CsTD-D[sub 2]O system. In all four systems, sufficient additive (5-10 wt%) resulted in a transition to the L phase, which was stable over a large portion of the compositional range. In order of apparently decreasing mean curvature, the phase sequence is: hexagonal, ribbon, viscous isotropic, intermediate, and lamellar.
NASA Technical Reports Server (NTRS)
Morales, Wilfredo; Koch, Victor R.; Street, Kenneth W., Jr.; Richard, Ryan M.
2008-01-01
Ionic liquids are salts, many of which are typically viscous fluids at room temperature. The fluids are characterized by negligible vapor pressures under ambient conditions. These properties have led us to study the effectiveness of ionic liquids containing both organic cations and anions for use as space lubricants. In the previous paper we have measured the vapor pressure and some tribological properties of two distinct ionic liquids under simulated space conditions. In this paper we will present vapor pressure measurements for two new ionic liquids and friction coefficient data for boundary lubrication conditions in a spiral orbit tribometer using stainless steel tribocouples. In addition we present the first tribological data on mixed ionic liquids and an ionic liquid additive. Post mortem infrared and Raman analysis of the balls and races indicates the major degradation pathway for these two organic ionic liquids is similar to those of other carbon based lubricants, i.e. deterioration of the organic structure into amorphous graphitic carbon. The coefficients of friction and lifetimes of these lubricants are comparable to or exceed these properties for several commonly used space oils.
Muhlisin; Kang, Sun Moon; Choi, Won Hee; Lee, Keun Taik; Cheong, Sung Hee; Lee, Sung Ki
2013-01-01
The effect of modified atmosphere packaging (MAP; 30% CO2+70% N2 or 100% N2) and an additive mixture (500 ppm rosemary extract, 3,000 ppm sodium acetate and 1,500 ppm calcium lactate) on the quality of pre-cooked hamburger patties during storage at 5°C for 14 d was evaluated. The addition of the additive mixture reduced aerobic and anaerobic bacteria counts in both 30% CO2-MAP (30% CO2+70% N2) and 100% N2-MAP (p<0.05). The 30% CO2-MAP was more effective to suppress the microbial growth than 100% N2-MAP, moreover the 30% CO2-MAP combined with additive mixture resulted in the lowest bacterial counts. The hamburger patties with additive mixture showed lower CIE L* and CIE a*, and higher CIE b* than those with no additive mixture. The 30% CO2-MAP tended to decrease the TBARS during storage regardless of the addition of additives. The use of 30% CO2-MAP in combination with additives mixture was effective for maintaining the quality and extending the shelf-life of pre-cooked hamburger patties. PMID:25049716
The glass transition in binary mixtures of hard colloidal spheres
NASA Astrophysics Data System (ADS)
Williams, S. R.; van Megen, W.
2000-06-01
Particle dynamics have been measured by dynamic light scattering for mixtures of colloidal particles with hard sphere interactions. The diameter ratio (small:large) is 0.6. The optical properties of the suspended particles are such that the relative contrast of the two species is very sensitive to temperature, a feature we exploit to obtain the three partial intermediate scattering functions. The glass transition is identified by the onset of structural arrest, or the arrest of the alpha process, on the time scale of the experiment. This is observed in the one-component suspension at the packing fraction 0.57. Introduction of the smaller particles, at fixed packing fraction, releases the alpha process, ie, the glass melts. Increasing the fraction of smaller particles speeds up the alpha process but interestingly, increases its amplitude. .
Krewski, D; Thomas, R D
1992-03-01
Human populations are generally exposed simultaneously to a number of toxicants present in the environment, including complex mixtures of unknown and variable origin. While scientific methods for evaluating the potential carcinogenic risks of pure compounds are relatively well established, methods for assessing the risks of complex mixtures are somewhat less developed. This article provides a report of a recent workshop on carcinogenic mixtures sponsored by the Committee on Toxicology of the U.S. National Research Council, in which toxicological, epidemiological, and statistical approaches to carcinogenic risk assessment for mixtures were discussed. Complex mixtures, such as diesel emissions and tobacco smoke, have been shown to have carcinogenic potential. Bioassay-directed fractionation based on short-term screening test for genotoxicity has also been used in identifying carcinogenic components of mixtures. Both toxicological and epidemiological studies have identified clear interactions between chemical carcinogens, including synergistic effects at moderate to high doses. To date, laboratory studies have demonstrated over 900 interactions involving nearly 200 chemical carcinogens. At lower doses, theoretical arguments suggest that risks may be near additive. Thus, additivity at low doses has been invoked as as a working hypothesis by regulatory authorities in the absence of evidence to the contrary. Future studies of the joint effects of carcinogenic agents may serve to elucidate the mechanisms by which interactions occur at higher doses.
A computational investigation of the thermodynamics and structure in colloid and polymer mixtures
NASA Astrophysics Data System (ADS)
Mahynski, Nathan Alexander
In this dissertation I use computational tools to study the structure and thermodynamics of colloid-polymer mixtures. I show that fluid-fluid phase separation in mixtures of colloids and linear polymers cannot be universally reduced using polymer-based scaling principles since these assume the binodals exist in a single scaling regime, whereas accurate simulations clearly demonstrate otherwise. I show that rethinking these solutions in terms of multiple length scales is necessary to properly explain the thermodynamic stability and structure of these fluid phases, and produce phase diagrams in nearly quantitative agreement with experimental results. I then extend this work to encompass more geometrically complex "star" polymers revealing how the phase behavior for many of these binary mixtures may be mapped onto that of mixtures containing only linear polymers. I further consider the depletion-driven crystallization of athermal colloidal hard spheres induced by polymers. I demonstrate how the partitioning of a finite amount of polymer into the colloidal crystal phase implies that the polymer's architecture can be tailored to interact with the internal void structure of different crystal polymorphs uniquely, thus providing a direct route to thermodynamically stabilizing one arbitrarily chosen structure over another, e.g., the hexagonal close-packed crystal over the face-centered cubic. I then begin to generalize this result by considering the consequences of thermal interactions and complex polymer architectures. These principles lay the groundwork for intelligently engineering co-solute additives in crystallizing colloidal suspensions that can be used to thermodynamically isolate single crystal morphologies. Finally, I examine the competition between self-assembly and phase separation in polymer-grafted nanoparticle systems by comparing and contrasting the validity of two different models for grafted nanoparticles: "nanoparticle amphiphiles" versus "patchy particles
Šišková, Karolína M.; Machala, Libor; Tuček, Jiři; Kašlík, Josef; Mojzeš, Peter; Zbořil, Radek
2013-01-01
Owing to Mössbauer spectroscopy, an advanced characterization technique for iron-containing materials, the present study reveals previously unknown possibilities using l-amino acids for the generation of magnetic particles. Based on our results, a simple choice of the order of l-amino acids addition into a reaction mixture containing ferrous ions leads to either superparamagnetic ferric oxide/oxyhydroxide particles, or magnetically strong Fe0-Fe2O3/FeOOH core-shell particles after chemical reduction. Conversely, when ferric salts are employed with the addition of selected l-amino acids, only Fe0-Fe2O3/FeOOH core-shell particles are observed, regardless of the addition order. We explain this phenomenon by a specific transient/intermediate complex formation between Fe2+ and l-glutamic acid. This type of complexation prevents ferrous ions from spontaneous oxidation in solutions with full air access. Moreover, due to surface-enhanced Raman scattering spectroscopy we show that the functional groups of l-amino acids are not destroyed during the borohydride-induced reduction. These functionalities can be further exploited for (i) attachment of l-amino acids to the as-prepared magnetic particles, and (ii) for targeted bio- and/or environmental applications where the surface chemistry needs to be tailored and directed toward biocompatible species. PMID:24071943
NASA Astrophysics Data System (ADS)
Lalia, Boor Singh; Yoshimoto, Nobuko; Egashira, Minato; Morita, Masayuki
A binary mixture of triethylphosphate (TEP) and ethylene carbonate (EC) has been examined as a new non-flammable additive for ionic liquid-based electrolytes for lithium-ion batteries. The optimized electrolyte composition consists of 0.6 mol dm -3 (=M) LiTFSI in PP13TFSI mixed with TEP and EC in volume ratio of 80:10:10, where TFSI and PP13 denote bis(trifluoromethanesulfonyl)imide and N-methyl- N-propylpiperidinium, respectively. The ionic conductivity of PP13TFSI dissolving 0.4 M LiTFSI was improved from 8.2 × 10 -4 S cm -1 to 3.5 × 10 -3 S cm -1 (at 20 °C) with the addition of TEP and EC. The electrochemical behavior of 0.4 M LiTFSI/PP13TFSI with and without TEP and EC was studied by cyclic voltammetry, which showed no deteriorating effect by the addition of TEP and EC on the electrochemical window of PP13TFSI. The flammability of the electrolyte was tested by a direct flame test. The proposed ionic liquid-based electrolyte revealed significant improvements in the electrochemical charge-discharge characteristics for both graphite negative and LiMn 2O 4 positive electrodes.
Maguire, David R; France, Charles P
2016-02-01
Pain is a significant clinical problem, and there is a need for pharmacotherapies that are more effective with fewer adverse effects than currently available medications. Cannabinoid receptor agonists enhance the antinociceptive effects of μ-opioid receptor agonists; it is unclear whether they impact the effects of agonists acting at other opioid receptors. κ-Opioid receptor agonists have antinociceptive effects, but their clinical use is precluded by adverse effects; however, their therapeutic potential might be realized if antinociceptive effects could be selectively enhanced. In this study, the antinociceptive effects of the cannabinoid receptor agonist CP55940 and the κ-opioid receptor agonist spiradoline, alone and in combination, were studied in rats (n=7) using a warm water tail-withdrawal procedure. When administered alone, CP55940 (0.032-1.0 mg/kg) and spiradoline (1.0-32.0 mg/kg) increased tail-withdrawal latency, and mixtures of CP55940 and spiradoline (ratios of 1 : 3, 1 : 1, and 3 : 1) produced additive effects. It remains to be determined whether this additive interaction between a κ-opioid receptor agonist and a cannabinoid receptor agonist is selective for antinociception and whether it can be generalized to other drugs. PMID:26292184
NASA Astrophysics Data System (ADS)
Sun, Haoyu; Ge, Hongming; Zheng, Min; Lin, Zhifen; Liu, Ying
2016-09-01
Previous studies have identified a phenomenon in which the concentration-response curves (CRCs) for mixtures cross the curves for concentration addition model when predicting or judging joint toxic actions. However, mechanistic investigations of this phenomenon are extremely limited. In this study, a similar phenomenon was observed when we determined the joint toxic actions of sulfonamides (SAs) and erythromycin (ERY) on Escherichia coli (E. coli), which we named the “cross-phenomenon”, and it was characterized by antagonism in the low-concentration range, addition in the medium-concentration range, and synergism in the high-concentration range. The mechanistic investigation of the cross-phenomenon was as follows: SAs and ERY could form a double block to inhibit the bacterial growth by exhibiting a synergistic effect; however, the hormetic effect of SAs on E. coli led to antagonism in the low-concentration range, resulting from the stimulation of sdiA mRNA expression by SAs, which increased the expression of the efflux pump (AcrAB-TolC) to discharge ERY. Furthermore, this cross-phenomenon was observed to be a time-dependent process induced by the increase of both the concentration and extent of stimulation of sdiA mRNA with exposure time. This work explains the dose-dependent and time-dependent cross-phenomenon and provides evidence regarding the interaction between hormesis and cross-phenomenon.
Sun, Haoyu; Ge, Hongming; Zheng, Min; Lin, Zhifen; Liu, Ying
2016-01-01
Previous studies have identified a phenomenon in which the concentration-response curves (CRCs) for mixtures cross the curves for concentration addition model when predicting or judging joint toxic actions. However, mechanistic investigations of this phenomenon are extremely limited. In this study, a similar phenomenon was observed when we determined the joint toxic actions of sulfonamides (SAs) and erythromycin (ERY) on Escherichia coli (E. coli), which we named the "cross-phenomenon", and it was characterized by antagonism in the low-concentration range, addition in the medium-concentration range, and synergism in the high-concentration range. The mechanistic investigation of the cross-phenomenon was as follows: SAs and ERY could form a double block to inhibit the bacterial growth by exhibiting a synergistic effect; however, the hormetic effect of SAs on E. coli led to antagonism in the low-concentration range, resulting from the stimulation of sdiA mRNA expression by SAs, which increased the expression of the efflux pump (AcrAB-TolC) to discharge ERY. Furthermore, this cross-phenomenon was observed to be a time-dependent process induced by the increase of both the concentration and extent of stimulation of sdiA mRNA with exposure time. This work explains the dose-dependent and time-dependent cross-phenomenon and provides evidence regarding the interaction between hormesis and cross-phenomenon. PMID:27644411
Sun, Haoyu; Ge, Hongming; Zheng, Min; Lin, Zhifen; Liu, Ying
2016-01-01
Previous studies have identified a phenomenon in which the concentration-response curves (CRCs) for mixtures cross the curves for concentration addition model when predicting or judging joint toxic actions. However, mechanistic investigations of this phenomenon are extremely limited. In this study, a similar phenomenon was observed when we determined the joint toxic actions of sulfonamides (SAs) and erythromycin (ERY) on Escherichia coli (E. coli), which we named the “cross-phenomenon”, and it was characterized by antagonism in the low-concentration range, addition in the medium-concentration range, and synergism in the high-concentration range. The mechanistic investigation of the cross-phenomenon was as follows: SAs and ERY could form a double block to inhibit the bacterial growth by exhibiting a synergistic effect; however, the hormetic effect of SAs on E. coli led to antagonism in the low-concentration range, resulting from the stimulation of sdiA mRNA expression by SAs, which increased the expression of the efflux pump (AcrAB-TolC) to discharge ERY. Furthermore, this cross-phenomenon was observed to be a time-dependent process induced by the increase of both the concentration and extent of stimulation of sdiA mRNA with exposure time. This work explains the dose-dependent and time-dependent cross-phenomenon and provides evidence regarding the interaction between hormesis and cross-phenomenon. PMID:27644411
Electronic structure and enthalpy of hydrogen and helium mixtures
NASA Astrophysics Data System (ADS)
Ross, M.; Klepeis, J. E.; Schafer, K. J.; Barbee, T. W., III
1992-11-01
The first local density approximation (LDA) calculations of the electronic structure, equation of state, and enthalpy of mixing were carried out for a number of different compositions of hydrogen and helium in bcc and fcc lattices. These are fully quantum mechanical, self-consistent calculations utilizing state-of-the-art methods of electron band theory, which make no assumptions regarding pressure ionization. The major approximation in the LDA method is that the exchange and correlation energy is given by a free electron functional in terms of the local electron density. The majority of previous mixture calculations start with the assumption that both hydrogen and helium are pressure-ionized so that the electronic structure is approximately that of free or weakly screened electrons in the presence of positive ions. Stevenson used a hard-sphere mixture model for the ions with an ion-ion pseudopotential to account for electron screening and predicted that a mixture containing 7% helium by number, the composition believed to be present in Jupiter and Saturn, would phase separate at a temperature of about 7000 K at 8 Mbar. Subsequent calculations carried out for the fully ionized mixture and for a mixture of screened ions (linear response theory) have all arrived at predictions similar to those of Stevenson. MacFarlane and Hubbard performed Thomas-Fermi-Dirac calculations for mixing enthalpies of hydrogen and helium in bcc and fcc lattices and predicted that phase separation would not occur at any temperature.
Thermodynamic properties of model CdTe/CdSe mixtures
van Swol, Frank; Zhou, Xiaowang W.; Challa, Sivakumar R.; Martin, James E.
2015-02-20
We report on the thermodynamic properties of binary compound mixtures of model groups II–VI semiconductors. We use the recently introduced Stillinger–Weber Hamiltonian to model binary mixtures of CdTe and CdSe. We use molecular dynamics simulations to calculate the volume and enthalpy of mixing as a function of mole fraction. The lattice parameter of the mixture closely follows Vegard's law: a linear relation. This implies that the excess volume is a cubic function of mole fraction. A connection is made with hard sphere models of mixed fcc and zincblende structures. We found that the potential energy exhibits a positive deviation frommore » ideal soluton behaviour; the excess enthalpy is nearly independent of temperatures studied (300 and 533 K) and is well described by a simple cubic function of the mole fraction. Using a regular solution approach (combining non-ideal behaviour for the enthalpy with ideal solution behaviour for the entropy of mixing), we arrive at the Gibbs free energy of the mixture. The Gibbs free energy results indicate that the CdTe and CdSe mixtures exhibit phase separation. The upper consolute temperature is found to be 335 K. Finally, we provide the surface energy as a function of composition. Moreover, it roughly follows ideal solution theory, but with a negative deviation (negative excess surface energy). This indicates that alloying increases the stability, even for nano-particles.« less
Thermodynamic properties of model CdTe/CdSe mixtures
van Swol, Frank; Zhou, Xiaowang W.; Challa, Sivakumar R.; Martin, James E.
2015-02-20
We report on the thermodynamic properties of binary compound mixtures of model groups II–VI semiconductors. We use the recently introduced Stillinger–Weber Hamiltonian to model binary mixtures of CdTe and CdSe. We use molecular dynamics simulations to calculate the volume and enthalpy of mixing as a function of mole fraction. The lattice parameter of the mixture closely follows Vegard's law: a linear relation. This implies that the excess volume is a cubic function of mole fraction. A connection is made with hard sphere models of mixed fcc and zincblende structures. We found that the potential energy exhibits a positive deviation from ideal soluton behaviour; the excess enthalpy is nearly independent of temperatures studied (300 and 533 K) and is well described by a simple cubic function of the mole fraction. Using a regular solution approach (combining non-ideal behaviour for the enthalpy with ideal solution behaviour for the entropy of mixing), we arrive at the Gibbs free energy of the mixture. The Gibbs free energy results indicate that the CdTe and CdSe mixtures exhibit phase separation. The upper consolute temperature is found to be 335 K. Finally, we provide the surface energy as a function of composition. Moreover, it roughly follows ideal solution theory, but with a negative deviation (negative excess surface energy). This indicates that alloying increases the stability, even for nano-particles.
Pehrsson, L; Ingman, F; Johansson, S
A general method for evaluating titration data for mixtures of acids and for acids in mixture with weak bases is presented. Procedures are given that do not require absolute [H]-data, i.e., relative [H]-data may be used. In most cases a very rough calibration of the electrode system is enough. Further, for simple systems, very approximate values of the stability constants are sufficient. As examples, the titration of the following are treated in some detail: a mixture of two acids, a diprotic acid, an acid in presence of its conjugate base, and an ampholyte.
Direct solution of the Boltzmann equation for a binary mixture on GPUs
NASA Astrophysics Data System (ADS)
Frezzotti, Aldo; Pietro Ghiroldi, Gian; Gibelli, Livio
2011-05-01
We show how to accelerate the numerical solution of the Boltzmann equation for a binary gas mixture by using Graphics Processing Units (GPUs). In order to fully exploit the computational power of the GPU, we adopt a semi-regular method of solution which combines a finite difference discretization of the free-streaming term with a Monte Carlo evaluation of the collision integral. The efficiency of the code is demonstrated by studying the propagation of plane harmonic waves of small amplitude in a binary gas mixture of hard spheres for a wide range of Knudsen numbers and wave frequencies. The GPU-based code is about two order of magnitudes faster than the CPU version thus proving that GPUs can substantially speedup the numerical solution of kinetic equations.
NASA Astrophysics Data System (ADS)
Zhao, Yan; Gao, Wei; Xu, Bo; Li, Ying-Ai; Li, Hong-Dong; Gu, Guang-Rui; Yin, Hong
2016-10-01
The excellent physical and chemical properties of cubic boron nitride (c-BN) film make it a promising candidate for various industry applications. However, the c-BN film thickness restricts its practical applications in many cases. Thus, it is indispensable to develop an economic, simple and environment-friend way to synthesize high-quality thick, stable c-BN films. High-cubic-content BN films are prepared on silicon (100) substrates by radio frequency (RF) magnetron sputtering from an h-BN target at low substrate temperature. Adhesions of the c-BN films are greatly improved by adding hydrogen to the argon/nitrogen gas mixture, allowing the deposition of a film up to 5-μm thick. The compositions and the microstructure morphologies of the c-BN films grown at different substrate temperatures are systematically investigated with respect to the ratio of H2 gas content to total working gas. In addition, a primary mechanism for the deposition of thick c-BN film is proposed. Project supported by the National Natural Science Foundation of China (Grant Nos. 51572105, 61504046, and 51272224), the Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry, China, the Development and Reform Commission of Jilin Province, China (Grant No. 2015Y050), and the Scientific Research Foundation for the Returned Overseas of Jilin Province, China.
Tuning structure and mobility of solvation shells surrounding tracer additives
Carmer, James; Jain, Avni; Bollinger, Jonathan A.; Truskett, Thomas M.; Swol, Frank van
2015-03-28
Molecular dynamics simulations and a stochastic Fokker-Planck equation based approach are used to illuminate how position-dependent solvent mobility near one or more tracer particle(s) is affected when tracer-solvent interactions are rationally modified to affect corresponding solvation structure. For tracers in a dense hard-sphere fluid, we compare two types of tracer-solvent interactions: (1) a hard-sphere-like interaction, and (2) a soft repulsion extending beyond the hard core designed via statistical mechanical theory to enhance tracer mobility at infinite dilution by suppressing coordination-shell structure [Carmer et al., Soft Matter 8, 4083–4089 (2012)]. For the latter case, we show that the mobility of surrounding solvent particles is also increased by addition of the soft repulsive interaction, which helps to rationalize the mechanism underlying the tracer’s enhanced diffusivity. However, if multiple tracer surfaces are in closer proximity (as at higher tracer concentrations), similar interactions that disrupt local solvation structure instead suppress the position-dependent solvent dynamics.
Tuning structure and mobility of solvation shells surrounding tracer additives
NASA Astrophysics Data System (ADS)
Carmer, James; Jain, Avni; Bollinger, Jonathan A.; van Swol, Frank; Truskett, Thomas M.
2015-03-01
Molecular dynamics simulations and a stochastic Fokker-Planck equation based approach are used to illuminate how position-dependent solvent mobility near one or more tracer particle(s) is affected when tracer-solvent interactions are rationally modified to affect corresponding solvation structure. For tracers in a dense hard-sphere fluid, we compare two types of tracer-solvent interactions: (1) a hard-sphere-like interaction, and (2) a soft repulsion extending beyond the hard core designed via statistical mechanical theory to enhance tracer mobility at infinite dilution by suppressing coordination-shell structure [Carmer et al., Soft Matter 8, 4083-4089 (2012)]. For the latter case, we show that the mobility of surrounding solvent particles is also increased by addition of the soft repulsive interaction, which helps to rationalize the mechanism underlying the tracer's enhanced diffusivity. However, if multiple tracer surfaces are in closer proximity (as at higher tracer concentrations), similar interactions that disrupt local solvation structure instead suppress the position-dependent solvent dynamics.
Ermler, Sibylle; Scholze, Martin; Kortenkamp, Andreas
2011-12-15
The risks associated with human exposures to chemicals capable of antagonising the effects of endogenous androgens have attracted considerable recent interest. Exposure is typically to large numbers of chemicals with androgen receptor (AR) antagonist activity, yet there is limited evidence of the combined effects of multi-component mixtures of these chemicals. A few in vitro studies with mixtures of up to six AR antagonists suggest that the concept of concentration addition (CA) provides good approximations of experimentally observed mixture effects, but studies with larger numbers of anti-androgens, and with more varied structural features, are missing. Here we show that the mixture effects of up to 17 AR antagonists, comprising compounds as diverse as UV-filter substances, parabens, perfluorinated compounds, bisphenol-A, benzo({alpha})pyrene, synthetic musks, antioxidants and polybrominated biphenyls, can be predicted well on the basis of the anti-androgenicity of the single components using the concept of CA. We tested these mixtures in an in vitro AR-dependent luciferase reporter gene assay, based on MDA-kb2 cells. The effects of further mixtures, composed of four and six anti-androgens, could be predicted accurately by CA. However, there was a shortfall from expected additivity with a ten-component mixture at two different mixture ratios, but attempts to attribute these deviations to differential expression of hormone-metabolising CYP isoforms did not produce conclusive results. CA provides good approximations of in vitro mixture effects of anti-androgens with varying structural features. -- Highlights: Black-Right-Pointing-Pointer Humans are exposed to a large number of androgen receptor antagonists. Black-Right-Pointing-Pointer There is limited evidence of the combined effects of anti-androgenic chemicals. Black-Right-Pointing-Pointer We modelled the predictability of combined effects of up to 17 anti-androgens. Black-Right-Pointing-Pointer We tested the
Detecting and characterizing interactions among chemicals is an important environmental issue. This study was conducted to test for the existence of a significant departure from additivity for a mixture of two cholinesterase (ChE)-inhibiting pesticides: chlorpyrifos (CPF), an org...
Perfluoroalkyl acids (PFAAs) are found globally in the environment and in animal tissues, and are present as mixtures of PFAA congeners. Mechanistic studies have found that in vivo effects of PFAAs are mediated by PPARL. Our previous studies showed that individual PFAAs activate ...
Challenges in cumulative risk assessment of anti-androgenic phthalate mixtures include a lack of data on all the individual phthalates and difficulty determining the biological relevance of reduction in fetal testosterone (T) on postnatal development. The objectives of the curren...
Efner, H. F.; Schiff, S.
1985-03-12
Vegetable oils, particularly soybean oil, tall oil acid, or aralkyl acids, particularly phenylstearic acid, are reacted with multiamines, particularly tetraethylenepentamine, to form a product mixture for subsequent reaction with SO/sub 2/ to produce a product mix that has good detergent properties in fuels.
Bansal, Artee; Asthagiri, D; Cox, Kenneth R; Chapman, Walter G
2016-08-21
A mixture of solvent particles with short-range, directional interactions and solute particles with short-range, isotropic interactions that can bond multiple times is of fundamental interest in understanding liquids and colloidal mixtures. Because of multi-body correlations, predicting the structure and thermodynamics of such systems remains a challenge. Earlier Marshall and Chapman [J. Chem. Phys. 139, 104904 (2013)] developed a theory wherein association effects due to interactions multiply the partition function for clustering of particles in a reference hard-sphere system. The multi-body effects are incorporated in the clustering process, which in their work was obtained in the absence of the bulk medium. The bulk solvent effects were then modeled approximately within a second order perturbation approach. However, their approach is inadequate at high densities and for large association strengths. Based on the idea that the clustering of solvent in a defined coordination volume around the solute is related to occupancy statistics in that defined coordination volume, we develop an approach to incorporate the complete information about hard-sphere clustering in a bulk solvent at the density of interest. The occupancy probabilities are obtained from enhanced sampling simulations but we also develop a concise parametric form to model these probabilities using the quasichemical theory of solutions. We show that incorporating the complete reference information results in an approach that can predict the bonding state and thermodynamics of the colloidal solute for a wide range of system conditions.
NASA Astrophysics Data System (ADS)
Bansal, Artee; Asthagiri, D.; Cox, Kenneth R.; Chapman, Walter G.
2016-08-01
A mixture of solvent particles with short-range, directional interactions and solute particles with short-range, isotropic interactions that can bond multiple times is of fundamental interest in understanding liquids and colloidal mixtures. Because of multi-body correlations, predicting the structure and thermodynamics of such systems remains a challenge. Earlier Marshall and Chapman [J. Chem. Phys. 139, 104904 (2013)] developed a theory wherein association effects due to interactions multiply the partition function for clustering of particles in a reference hard-sphere system. The multi-body effects are incorporated in the clustering process, which in their work was obtained in the absence of the bulk medium. The bulk solvent effects were then modeled approximately within a second order perturbation approach. However, their approach is inadequate at high densities and for large association strengths. Based on the idea that the clustering of solvent in a defined coordination volume around the solute is related to occupancy statistics in that defined coordination volume, we develop an approach to incorporate the complete information about hard-sphere clustering in a bulk solvent at the density of interest. The occupancy probabilities are obtained from enhanced sampling simulations but we also develop a concise parametric form to model these probabilities using the quasichemical theory of solutions. We show that incorporating the complete reference information results in an approach that can predict the bonding state and thermodynamics of the colloidal solute for a wide range of system conditions.
Bansal, Artee; Asthagiri, D; Cox, Kenneth R; Chapman, Walter G
2016-08-21
A mixture of solvent particles with short-range, directional interactions and solute particles with short-range, isotropic interactions that can bond multiple times is of fundamental interest in understanding liquids and colloidal mixtures. Because of multi-body correlations, predicting the structure and thermodynamics of such systems remains a challenge. Earlier Marshall and Chapman [J. Chem. Phys. 139, 104904 (2013)] developed a theory wherein association effects due to interactions multiply the partition function for clustering of particles in a reference hard-sphere system. The multi-body effects are incorporated in the clustering process, which in their work was obtained in the absence of the bulk medium. The bulk solvent effects were then modeled approximately within a second order perturbation approach. However, their approach is inadequate at high densities and for large association strengths. Based on the idea that the clustering of solvent in a defined coordination volume around the solute is related to occupancy statistics in that defined coordination volume, we develop an approach to incorporate the complete information about hard-sphere clustering in a bulk solvent at the density of interest. The occupancy probabilities are obtained from enhanced sampling simulations but we also develop a concise parametric form to model these probabilities using the quasichemical theory of solutions. We show that incorporating the complete reference information results in an approach that can predict the bonding state and thermodynamics of the colloidal solute for a wide range of system conditions. PMID:27544123
Exact solution of the Percus-Yevick integral equation for fluid mixtures of hard hyperspheres
NASA Astrophysics Data System (ADS)
Rohrmann, René D.; Santos, Andrés
2011-10-01
Structural and thermodynamic properties of multicomponent hard-sphere fluids at odd dimensions have recently been derived in the framework of the rational function approximation (RFA) [Rohrmann and Santos, Phys. Rev. EPLEEE81539-375510.1103/PhysRevE.83.011201 83, 011201 (2011)]. It is demonstrated here that the RFA technique yields the exact solution of the Percus-Yevick (PY) closure to the Ornstein-Zernike (OZ) equation for binary mixtures at arbitrary odd dimensions. The proof relies mainly on the Fourier transforms ĉij(k) of the direct correlation functions defined by the OZ relation. From the analysis of the poles of ĉij(k) we show that the direct correlation functions evaluated by the RFA method vanish outside the hard core, as required by the PY theory.
Mixtures of ions and amphiphilic molecules in slit-like pores: A density functional approach
Pizio, O.; Rżysko, W. Sokołowski, S.; Sokołowska, Z.
2015-04-28
We investigate microscopic structure and thermodynamic properties of a mixture that contains amphiphilic molecules and charged hard spheres confined in slit-like pores with uncharged hard walls. The model and the density functional approach are the same as described in details in our previous work [Pizio et al., J. Chem. Phys. 140, 174706 (2014)]. Our principal focus is in exploring the effects brought by the presence of ions on the structure of confined amphiphilic particles. We have found that for some cases of anisotropic interactions, the change of the structure of confined fluids occurs via the first-order transitions. Moreover, if anions and cations are attracted by different hemispheres of amphiphiles, a charge at the walls appears at the zero value of the wall electrostatic potential. For a given thermodynamic state, this charge is an oscillating function of the pore width.
Exact solution of the Percus-Yevick integral equation for fluid mixtures of hard hyperspheres.
Rohrmann, René D; Santos, Andrés
2011-10-01
Structural and thermodynamic properties of multicomponent hard-sphere fluids at odd dimensions have recently been derived in the framework of the rational function approximation (RFA) [Rohrmann and Santos, Phys. Rev. E 83, 011201 (2011)]. It is demonstrated here that the RFA technique yields the exact solution of the Percus-Yevick (PY) closure to the Ornstein-Zernike (OZ) equation for binary mixtures at arbitrary odd dimensions. The proof relies mainly on the Fourier transforms c(ij)(k) of the direct correlation functions defined by the OZ relation. From the analysis of the poles of c(ij)(k) we show that the direct correlation functions evaluated by the RFA method vanish outside the hard core, as required by the PY theory.
Thiam, Abdoulaye; Sirés, Ignasi; Brillas, Enric
2015-09-15
The degradation of 130 mL of mixtures of food azo dyes E122, E124 and E129 has been studied by electro-Fenton (EF) and UVA photoelectro-Fenton (PEF) using a stirred tank reactor with either a boron-doped diamond (BDD) or Pt anode and an air-diffusion cathode. The main oxidant was hydroxyl radical formed at the anode from water oxidation and in the bulk from Fenton's reaction between added Fe(2+) and H2O2 generated at the cathode. In sulfate medium, fast decolorization was found for all systems, but the almost total mineralization was more rapidly achieved by PEF with BDD. The performance with a real water matrix was slightly worse, although the removal of total organic load was still as high as 95%. The solar PEF (i.e., SPEF) treatment of dye mixtures using a 2.5 L flow plant with a BDD/air-diffusion cell coupled to a planar solar photoreactor is also reported. Fast decolorization and almost total mineralization was found in the presence of either sulfate, perchlorate, nitrate or a mixture of sulfate + chloride ions. In chloride medium, however, the formation of recalcitrant chloroderivatives decelerated the degradation process. Greater current efficiency and lower specific energy consumption were attained in sulfate medium at lower current density and higher azo dye content. A plausible reaction sequence based on 18 aromatic intermediates identified by GC-MS and 6 short-linear carboxylic acids detected by ion-exclusion HPLC has been proposed. The SPEF process promoted the photodegradation of Fe(III)-oxalate complexes and other undetected products. Sulfate and nitrate ions were always released to the medium.
Thiam, Abdoulaye; Sirés, Ignasi; Brillas, Enric
2015-09-15
The degradation of 130 mL of mixtures of food azo dyes E122, E124 and E129 has been studied by electro-Fenton (EF) and UVA photoelectro-Fenton (PEF) using a stirred tank reactor with either a boron-doped diamond (BDD) or Pt anode and an air-diffusion cathode. The main oxidant was hydroxyl radical formed at the anode from water oxidation and in the bulk from Fenton's reaction between added Fe(2+) and H2O2 generated at the cathode. In sulfate medium, fast decolorization was found for all systems, but the almost total mineralization was more rapidly achieved by PEF with BDD. The performance with a real water matrix was slightly worse, although the removal of total organic load was still as high as 95%. The solar PEF (i.e., SPEF) treatment of dye mixtures using a 2.5 L flow plant with a BDD/air-diffusion cell coupled to a planar solar photoreactor is also reported. Fast decolorization and almost total mineralization was found in the presence of either sulfate, perchlorate, nitrate or a mixture of sulfate + chloride ions. In chloride medium, however, the formation of recalcitrant chloroderivatives decelerated the degradation process. Greater current efficiency and lower specific energy consumption were attained in sulfate medium at lower current density and higher azo dye content. A plausible reaction sequence based on 18 aromatic intermediates identified by GC-MS and 6 short-linear carboxylic acids detected by ion-exclusion HPLC has been proposed. The SPEF process promoted the photodegradation of Fe(III)-oxalate complexes and other undetected products. Sulfate and nitrate ions were always released to the medium. PMID:26057717
Thermodynamic perturbation theory for self-assembling mixtures of divalent single patch colloids.
Marshall, Bennett D; Chapman, Walter G
2014-07-28
In this work we extend Wertheim's thermodynamic perturbation theory (TPT) to binary mixtures (species A and species B) of patchy colloids were each species has a single patch which can bond a maximum of twice (divalent). Colloids are treated as hard spheres with a directional conical association site. We restrict the system such that only patches between unlike species share attractions; meaning there are AB attractions but no AA or BB attractions. The theory is derived in Wertheim's two density formalism for one site associating fluids. Since the patches are doubly bondable, associated chains, of all chain lengths, as well as 4-mer rings consisting of two species A and two species B colloids are accounted for. With the restriction of only AB attractions, triatomic rings of doubly bonded colloids, which dominate in the corresponding pure component case, cannot form. The theory is shown to be in good agreement with Monte Carlo simulation data for the structure and thermodynamics of these patchy colloid mixtures as a function of temperature, density, patch size and composition. It is shown that 4-mer rings dominate at low temperature, inhibiting the polymerization of the mixture into long chains. Mixtures of this type have been recently synthesized by researchers. This work provides the first theory capable of accurately modeling these mixtures.
Piepel, Gregory F.
2007-12-01
A mixture experiment involves combining two or more components in various proportions or amounts and then measuring one or more responses for the resulting end products. Other factors that affect the response(s), such as process variables and/or the total amount of the mixture, may also be studied in the experiment. A mixture experiment design specifies the combinations of mixture components and other experimental factors (if any) to be studied and the response variable(s) to be measured. Mixture experiment data analyses are then used to achieve the desired goals, which may include (i) understanding the effects of components and other factors on the response(s), (ii) identifying components and other factors with significant and nonsignificant effects on the response(s), (iii) developing models for predicting the response(s) as functions of the mixture components and any other factors, and (iv) developing end-products with desired values and uncertainties of the response(s). Given a mixture experiment problem, a practitioner must consider the possible approaches for designing the experiment and analyzing the data, and then select the approach best suited to the problem. Eight possible approaches include 1) component proportions, 2) mathematically independent variables, 3) slack variable, 4) mixture amount, 5) component amounts, 6) mixture process variable, 7) mixture of mixtures, and 8) multi-factor mixture. The article provides an overview of the mixture experiment designs, models, and data analyses for these approaches.
Ashton, Douglas J; Liu, Jiwen; Luijten, Erik; Wilding, Nigel B
2010-11-21
Highly size-asymmetrical fluid mixtures arise in a variety of physical contexts, notably in suspensions of colloidal particles to which much smaller particles have been added in the form of polymers or nanoparticles. Conventional schemes for simulating models of such systems are hamstrung by the difficulty of relaxing the large species in the presence of the small one. Here we describe how the rejection-free geometrical cluster algorithm of Liu and Luijten [J. Liu and E. Luijten, Phys. Rev. Lett. 92, 035504 (2004)] can be embedded within a restricted Gibbs ensemble to facilitate efficient and accurate studies of fluid phase behavior of highly size-asymmetrical mixtures. After providing a detailed description of the algorithm, we summarize the bespoke analysis techniques of [Ashton et al., J. Chem. Phys. 132, 074111 (2010)] that permit accurate estimates of coexisting densities and critical-point parameters. We apply our methods to study the liquid-vapor phase diagram of a particular mixture of Lennard-Jones particles having a 10:1 size ratio. As the reservoir volume fraction of small particles is increased in the range of 0%-5%, the critical temperature decreases by approximately 50%, while the critical density drops by some 30%. These trends imply that in our system, adding small particles decreases the net attraction between large particles, a situation that contrasts with hard-sphere mixtures where an attractive depletion force occurs.
NASA Astrophysics Data System (ADS)
Shen, Gulou; Ji, Xiaoyan; Öberg, Sven; Lu, Xiaohua
2013-11-01
The perturbed-chain statistical associating fluid theory (PC-SAFT) density functional theory developed in our previous work was extended to the description of inhomogeneous confined behavior in nanopores for mixtures. In the developed model, the modified fundamental measure theory and the weighted density approximation were used to represent the hard-sphere and dispersion free energy functionals, respectively, and the chain free energy functional from interfacial statistical associating fluid theory was used to account for the chain connectivity. The developed model was verified by comparing the model prediction with molecular simulation results, and the agreement reveals the reliability of the proposed model in representing the confined behaviors of chain mixtures in nanopores. The developed model was further used to predict the adsorption of methane-carbon dioxide mixtures on activated carbons, in which the parameters of methane and carbon dioxide were taken from the bulk PC-SAFT and those for solid surface were determined from the fitting to the pure-gas adsorption isotherms measured experimentally. The comparison of the model prediction with the available experimental data of mixed-gas adsorption isotherms shows that the model can reliably reproduce the confined behaviors of physically existing mixtures in nanopores.
da Silva, Diana Dias; Silva, Elisabete; Carvalho, Félix; Carmo, Helena
2014-06-01
Hepatic injury after 3,4-methylenedioxymethamphetamine (MDMA; ecstasy) intoxications is highly unpredictable and does not seem to correlate with either dosage or frequency of use. The mechanisms involved include the drug metabolic bioactivation and the hyperthermic state of the liver triggered by its thermogenic action and exacerbated by the environmental circumstances of abuse at hot and crowded venues. We became interested in understanding the interaction between ecstasy and its metabolites generated in vivo as users are always exposed to mixtures of parent drug and metabolites. With this purpose, Hep G2 cells were incubated with MDMA and its main human metabolites methylenedioxyamphetamine (MDA), α-methyldopamine (α-MeDA) and N-methyl-α-methyldopamine (N-Me-α-MeDA), individually and in mixture (drugs combined in proportion to their individual EC01 ), at normal (37 °C) and hyperthermic (40.5 °C) conditions. After 48 h, viability was assessed by the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) assay. Extensive concentration-response analysis was performed with single drugs and the parameters of the individual non-linear logit fits were used to predict joint effects using the well-founded models of concentration addition (CA) and independent action (IA). Experimental testing revealed that mixture effects on cell viability conformed to CA, for both temperature settings. Additionally, substantial combination effects were attained even when each substance was present at concentrations that individually produced unnoticeable effects. Hyperthermic incubations dramatically increased the toxicity of the tested drug and metabolites, both individually and combined. These outcomes suggest that MDMA metabolism has hazard implications to liver cells even when metabolites are found in low concentrations, as they contribute additively to the overall toxic effect of MDMA.
Hass, B.S.; Brooks, E.E.; Schumann, K.E.; Dornfeld, S.S.
1981-01-01
Binary mixtures of benzo(a)pyrene (B(a)P) and benzo(e)pyrene (B(e)P) produce synergistic mutagenic (comutagenic) responses in Salmonella typhimurium strain TA98 (a frameshift detector). The optimum enhancement (25 X) was found at B(a)P concentration of 0.3 ..mu..g/plate and B(e)P concentration of 1.5 ..mu..g/plate. The response of strain TA100 (mostly a base-substitution detector) is opposite that of TA98, showing antagonism and additivity in similiar concentration ranges.
NASA Astrophysics Data System (ADS)
Iida, K.; Notani, M.; Uesugi, Y.; Tanaka, Y.; Ishijima, T.
2015-08-01
Control of tritium retention and its removal from the first wall of future fusion devices are one of the most crucial issues for safety and effective use for fuel. Nitrogen addition into remote edge plasmas has been considered and tested as an effective method for suppression of carbon film deposition and reduction of hydrogen isotope absorption in the deposited films. In this paper we have investigated the scavenger effects of nitrogen injected into low temperature D2/CH4 plasmas on hydrogenated carbon film growth using a small helical device. The result of the deposition shows that the key reactive particles with CN and ND(H) bonds to suppression of hydrogenated carbon film growth and hydrogen isotope absorption are much slowly generated compared with hydrocarbon particles such as CD(H)x and C2D(H)x. This may be due to the slow atomic nitrogen diffusion into hydrogenated carbon layer and the chemical equilibrium between nitrogen absorption.
Erdy, C.; Anton, D.; Gray, J.
2010-12-08
The destabilized complex hydride system composed of LiNH{sub 2}:MgH{sub 2} (1:1 molar ratio) is one of the leading candidates of hydrogen storage with a reversible hydrogen storage capacity of 8.1 wt%. A low sorption enthalpy of {approx}32 kJ/mole H{sub 2} was first predicted by Alapati et al. utilizing first principle density function theory (DFT) calculations and has been subsequently confirmed empirically by Lu et al. through differential thermal analysis (DTA). This enthalpy suggests that favorable sorption kinetics should be obtainable at temperatures in the range of 160 C to 200 C. Preliminary experiments reported in the literature indicate that sorption kinetics are substantially lower than expected in this temperature range despite favorable thermodynamics. Systematic isothermal and isobaric sorption experiments were performed using a Sievert's apparatus to form a baseline data set by which to compare kinetic results over the pressure and temperature range anticipated for use of this material as a hydrogen storage media. Various material preparation methods and compositional modifications were performed in attempts to increase the kinetics while lowering the sorption temperatures. This paper outlines the results of these systematic tests and describes a number of beneficial additions which influence kinetics as well as NH{sub 3} formation.
Issa, Mahmoud Mohamed; Nejem, R'afat Mahmoud; Abu Shanab, Alaa Mohamed; Shaat, Nahed Talab
2013-10-01
Simple, reliable, and sensitive kinetic spectrophotometric method has been developed for the simultaneous determination of diloxanide furoate and metronidazole using H-point standard addition method (HPSAM). The method is based on the oxidation rate difference of diloxanide and metronidazole by potassium permanganate in basic medium. A green color has been developed and measured at 610 nm. Different experimental parameters were carefully optimized. The limiting logarithmic and the initial-rate methods were adopted for the construction of the calibration curve of each individual reaction with potassium permanganate. Under the optimum conditions, Beer's law was obeyed in the range of 1.0-20.0 and 5.0-25.0 μg ml(-1) for diloxanide furoate and metronidazole, respectively. The detection limits were 0.22 μg ml(-1) for diloxanide furoate and 0.83 μg ml(-1) for metronidazole. Correlation coefficients of the regression equations were greater than 0.9970 in all cases. The precision of the method was satisfactory; the maximum value of relative standard deviation did not exceed 1.06% (n=5). The accuracy, expressed as recovery was between 99.4% and 101.4% with relative error of 0.12 and 0.14 for diloxanide furoate and metronidazole, respectively. The proposed method was successfully applied for the simultaneous determination of both drugs in pharmaceutical dosage forms and human urine samples and compared with alternative HPLC method.
Non-equilibrium dynamics of glass-forming liquid mixtures
NASA Astrophysics Data System (ADS)
Sánchez-Díaz, Luis Enrique; Lázaro-Lázaro, Edilio; Olais-Govea, José Manuel; Medina-Noyola, Magdaleno
2014-06-01
The non-equilibrium self-consistent generalized Langevin equation theory of irreversible processes in glass-forming liquids [P. Ramírez-González and M. Medina-Noyola, Phys. Rev. E 82, 061503 (2010)] is extended here to multi-component systems. The resulting theory describes the statistical properties of the instantaneous local particle concentration profiles nα(r, t) of species α in terms of the coupled time-evolution equations for the mean value overline{n}_α ({r},t) and for the covariance σ _{α β }({r},{r}^' };t)equiv overline{δ n_α ({r},t)δ n_β ({r}^' },t)} of the fluctuations δ n_α ({r},t) = n_α ({r},t)- overline{n}_α ({r},t). As in the monocomponent case, these two coarse-grained equations involve a local mobility function bα(r, t) for each species, written in terms of the memory function of the two-time correlation function C_{α β }({r},{r}^' };t,t^' }) equiv overline{δ n_α ({r},t)δ n_β ({r}^' },t^' })}. If the system is constrained to remain spatially uniform and subjected to a non-equilibrium preparation protocol described by a given temperature and composition change program T(t) and overline{n}_α (t), these equations predict the irreversible structural relaxation of the partial static structure factors Sαβ(k; t) and of the (collective and self) intermediate scattering functions Fαβ(k, τ; t) and F^S_{α β }(k,τ ;t). We illustrate the applicability of the resulting theory with two examples involving simple model mixtures subjected to an instantaneous temperature quench: an electroneutral binary mixture of equally sized and oppositely charged hard-spheres, and a binary mixture of soft-spheres of moderate size-asymmetry.
CO2-helium and CO2-neon mixtures at high pressures.
Mallick, B; Ninet, S; Le Marchand, G; Munsch, P; Datchi, F
2013-01-28
The properties of mixtures of carbon dioxide with helium or neon have been investigated as a function of CO(2) concentration and pressure up to 30 GPa at room temperature. The binary phase diagrams of these mixtures are determined over the full range of CO(2) concentrations using visual observations and Raman scattering measurements. Both diagrams are of eutectic type, with a fluid-fluid miscibility gap for CO(2) concentrations in the range [5, 75] mol. % for He and [8, 55] mol. % for Ne, and a complete separation between the two components in the solid phase. The absence of alloys or stoichiometric compounds for these two binary systems is consistent with the Hume-Rothery rules of hard sphere mixtures. The Raman spectra and x-ray diffraction patterns of solid CO(2) embedded in He or Ne for various initial concentrations have been measured up to 30 GPa and 12 GPa, respectively. The frequencies of the Raman modes and the volume of solid phase I are identical, within error bars, to those reported for 100% CO(2) samples, thus confirming the total immiscibility of CO(2) with He and Ne in the solid phase. These results demonstrate the possibility to perform high-pressure experiments on solid CO(2) under (quasi-)hydrostatic conditions using He or Ne as pressure transmitting medium.
Kelly, Michele P; Logue, Sheree F; Dwyer, Jason M; Beyer, Chad E; Majchrowski, Heather; Cai, Zhang; Liu, Zhi; Adedoyin, Adedayo; Rosenzweig-Lipson, Sharon; Comery, Thomas A
2009-06-01
One of the few preclinical models used to identify mood stabilizers is an assay in which amphetamine-induced hyperactivity (AMPH) is potentiated by the benzodiazepine chlordiazepoxide (CDP), an effect purportedly blocked by mood stabilizers. Our data here challenge this standard interpretation of the AMPH-CDP model. We show that the potentiating effects of AMPH-CDP are not explained by a pharmacokinetic interaction as both drugs have similar brain and plasma exposures whether administered alone or in combination. Of concern, however, we find that combining CDP (1-12 mg/kg) with AMPH (3 mg/kg) results in an inverted-U dose response in outbred CD-1 as well as inbred C57Bl/6N and 129S6 mice (peak hyperactivity at 3 mg/kg CDP+3 mg/kg AMPH). Such an inverted-U dose response complicates interpreting whether a reduction in hyperactivity produced by a mood stabilizer reflects a "blockade" or a "potentiation" of the mixture. In fact, we show that the prototypical mood stabilizer valproic acid augments the effects of CDP on hypolocomotion and anxiolytic-like behavior (increases punished crossings by Swiss-Webster mice in the four-plate test). We argue that these data, in addition to other practical and theoretical concerns surrounding the model, limit the utility of the AMPH-CDP mixture model in drug discovery. PMID:19303035
Generalized transport coefficients for inelastic Maxwell mixtures under shear flow.
Garzó, Vicente; Trizac, Emmanuel
2015-11-01
The Boltzmann equation framework for inelastic Maxwell models is considered to determine the transport coefficients associated with the mass, momentum, and heat fluxes of a granular binary mixture in spatially inhomogeneous states close to the simple shear flow. The Boltzmann equation is solved by means of a Chapman-Enskog-type expansion around the (local) shear flow distributions f(r)(0) for each species that retain all the hydrodynamic orders in the shear rate. Due to the anisotropy induced by the shear flow, tensorial quantities are required to describe the transport processes instead of the conventional scalar coefficients. These tensors are given in terms of the solutions of a set of coupled equations, which can be analytically solved as functions of the shear rate a, the coefficients of restitution α(rs), and the parameters of the mixture (masses, diameters, and composition). Since the reference distribution functions f(r)(0) apply for arbitrary values of the shear rate and are not restricted to weak dissipation, the corresponding generalized coefficients turn out to be nonlinear functions of both a and α(rs). The dependence of the relevant elements of the three diffusion tensors on both the shear rate and dissipation is illustrated in the tracer limit case, the results showing that the deviation of the generalized transport coefficients from their forms for vanishing shear rates is in general significant. A comparison with the previous results obtained analytically for inelastic hard spheres by using Grad's moment method is carried out, showing a good agreement over a wide range of values for the coefficients of restitution. Finally, as an application of the theoretical expressions derived here for the transport coefficients, thermal diffusion segregation of an intruder immersed in a granular gas is also studied.
Generalized transport coefficients for inelastic Maxwell mixtures under shear flow.
Garzó, Vicente; Trizac, Emmanuel
2015-11-01
The Boltzmann equation framework for inelastic Maxwell models is considered to determine the transport coefficients associated with the mass, momentum, and heat fluxes of a granular binary mixture in spatially inhomogeneous states close to the simple shear flow. The Boltzmann equation is solved by means of a Chapman-Enskog-type expansion around the (local) shear flow distributions f(r)(0) for each species that retain all the hydrodynamic orders in the shear rate. Due to the anisotropy induced by the shear flow, tensorial quantities are required to describe the transport processes instead of the conventional scalar coefficients. These tensors are given in terms of the solutions of a set of coupled equations, which can be analytically solved as functions of the shear rate a, the coefficients of restitution α(rs), and the parameters of the mixture (masses, diameters, and composition). Since the reference distribution functions f(r)(0) apply for arbitrary values of the shear rate and are not restricted to weak dissipation, the corresponding generalized coefficients turn out to be nonlinear functions of both a and α(rs). The dependence of the relevant elements of the three diffusion tensors on both the shear rate and dissipation is illustrated in the tracer limit case, the results showing that the deviation of the generalized transport coefficients from their forms for vanishing shear rates is in general significant. A comparison with the previous results obtained analytically for inelastic hard spheres by using Grad's moment method is carried out, showing a good agreement over a wide range of values for the coefficients of restitution. Finally, as an application of the theoretical expressions derived here for the transport coefficients, thermal diffusion segregation of an intruder immersed in a granular gas is also studied. PMID:26651684
Thermodynamics and phase separation of dense fully-ionized hydrogen-helium fluid mixtures
NASA Technical Reports Server (NTRS)
Stevenson, D. J.
1975-01-01
The free energy of a hydrogen-helium fluid mixture is evaluated for the temperatures and densities appropriate to the deep interior of a giant planet such as Jupiter. The electrons are assumed to be fully pressure-ionized and degenerate. In this regime, an appropriate first approximation to the ionic distribution functions can be found by assuming hard sphere interactions. Corrections to this approximation are incorporated by means of the perturbation theory of Anderson and Chandler. Approximations for the three-body interactions and the nonlinear response of the electron gas to the ions are included. It is predicted that a hydrogen-helium mixture, containing 10% by number of helium ions, separates into hydrogen-rich and helium-rich phases below about 8000 K, at the pressures relevant to Jupiter (4-40 Megabars). It is also predicted that the alloy occupies less volume per ion than the separated phases. The equations of state and other thermodynamic derivatives are tabulated. Implications of these results are discussed.
PVT measurements of carbon dioxide + methane mixtures and an equation of state development
Hwang, C.A.
1988-01-01
A mixture apparatus has been constructed for preparing mixtures of accurately known composition using a gravimetric method and has been used to prepare mixtures needed in this study. Two experimental techniques have been used to measure accurately the densities of carbon dioxide + methane mixtures over wide ranges of temperature and pressure. A continuously weighed pycnometer which can provide one density measurement about every twenty minutes in an isothermal run has been used to measure densities of four carbon dioxide + methane mixtures from 225 to 350 K up to 35 MPa. The Burnett apparatus can provide the bets low density measurements and the best determinations of the virial coefficients; it has been used to obtain the densities and virial coefficients for four carbon dioxide + methane and pure methane at 300 and 320 K up to 10 MPa. The ac.curacy of the density measurements using the pycnometer is 0.1 kg/m{sup 3} or 01%, whichever is greater, and that of the Burnett apparatus is 0.023%. An innovative approach to the reference system of an EOS has been developed. It consists of three parts: (1) the choice of a proper pair potential and its division into reference and perturbation potentials; (2) the method used to calculate the effective hard-sphere diameter; and (3) different forms for the hard-body equations. The authors have investigated step-ramp and Born (exponential) pair potentials, and Carnahan-Starling and random closest packing basis hard-body equations. The random closet packing basis hard-body equation plus Born pair potential provides the best representation of the experimental saturated liquid densities and vapor pressures of argon.
NASA Technical Reports Server (NTRS)
Tong, Penger
1996-01-01
In this paper we focus on the polymer-induced depletion attraction and its effect on colloidal sedimentation in colloid-polymer mixtures. We first report a small angle neutron scattering (SANS) study of the depletion effect in a mixture of hard-sphere-like colloid and non-adsorbing polymer. Then we present results of our recent sedimentation measurements in the same colloid-polymer mixture. A key parameter in controlling the sedimentation of heavy colloidal particles is the interparticle potential U(tau), which is the work required to bring two colloidal particles from infinity to a distance tau under a give solvent condition. This potential is known to affect the average settling velocity of the particles and experimentally one needs to have a way to continuously vary U(tau) in order to test the theory. The interaction potential U(tau) can be altered by adding polymer molecules into the colloidal suspension. In a mixture of colloid and non-adsorbing polymer, the potential U(tau) can develop an attractive well because of the depletion effect, in that the polymer chains are expelled from the region between two colloidal particles when their surface separation becomes smaller than the size of the polymer chains. The exclusion of polymer molecules from the space between the colloidal particles leads to an unbalanced osmotic pressure difference pushing the colloidal particles together, which results in an effective attraction between the two colloidal particles. The polymer-induced depletion attraction controls the phase stability of many colloid-polymer mixtures, which are directly of interest to industry.
NASA Astrophysics Data System (ADS)
Nourazar, S. S.; Jahangiri, P.; Aboutalebi, A.; Ganjaei, A. A.; Nourazar, M.; Khadem, J.
2011-06-01
The effect of new terms in the improved algorithm, the modified direct simulation Monte-Carlo (MDSMC) method, is investigated by simulating a rarefied binary gas mixture flow inside a rotating cylinder. Dalton law for the partial pressures contributed by each species of the binary gas mixture is incorporated into our simulation using the MDSMC method and the direct simulation Monte-Carlo (DSMC) method. Moreover, the effect of the exponent of the cosine of deflection angle (α) in the inter-molecular collision models, the variable soft sphere (VSS) and the variable hard sphere (VHS), is investigated in our simulation. The improvement of the results of simulation is pronounced using the MDSMC method when compared with the results of the DSMC method. The results of simulation using the VSS model show some improvements on the result of simulation for the mixture temperature at radial distances close to the cylinder wall where the temperature reaches the maximum value when compared with the results using the VHS model.
Martínez, Luis; Cilla, Irene; Beltrán, José Antonio; Roncalés, Pedro
2006-06-28
The effects of rosemary, in combination with ascorbic acid, red beet root, and sodium lactate, as well as their mixtures, on the inhibition of both lipid and pigment oxidation of fresh pork sausages packaged in a modified atmosphere were studied. Sausages (240) were packaged in a 80% O2 + 20% CO2 gas mixture and analyzed for CIE a, metmyoglobin, TBARS, psychrotrophic aerobes, and sensory discoloration and off-odor throughout 20 days of storage at 2 +/- 1 degrees C. The mixture of rosemary + ascorbic acid + sodium lactate + red beet root extract extended the shelf life of fresh pork sausages from 8 to 16 days. Results demonstrated that all of the components of the mixture contributed to obtaining the maximum delay in color and/or odor decay, due to a combined inhibitory action on both pigment and lipid oxidation, as well as on microbial growth. PMID:16787014
Martínez, Luis; Cilla, Irene; Beltrán, José Antonio; Roncalés, Pedro
2006-06-28
The effects of rosemary, in combination with ascorbic acid, red beet root, and sodium lactate, as well as their mixtures, on the inhibition of both lipid and pigment oxidation of fresh pork sausages packaged in a modified atmosphere were studied. Sausages (240) were packaged in a 80% O2 + 20% CO2 gas mixture and analyzed for CIE a, metmyoglobin, TBARS, psychrotrophic aerobes, and sensory discoloration and off-odor throughout 20 days of storage at 2 +/- 1 degrees C. The mixture of rosemary + ascorbic acid + sodium lactate + red beet root extract extended the shelf life of fresh pork sausages from 8 to 16 days. Results demonstrated that all of the components of the mixture contributed to obtaining the maximum delay in color and/or odor decay, due to a combined inhibitory action on both pigment and lipid oxidation, as well as on microbial growth.
Mixture design and multivariate analysis in mixture research.
Eide, I; Johnsen, H G
1998-01-01
Mixture design has been used to identify possible interactions between mutagens in a mixture. In this paper the use of mixture design in multidimensional isobolographic studies is introduced. Mutagenicity of individual nitro-polycyclic aromatic hydrocarbons (PAH) was evaluated is an organic extract of diesel exhaust particles (DEPs). The particles were extracted with dichloromethane (DCM). After replacing DCM with dimethyl sulfoxide, the extract was spiked with three individual nitro-PAH: 1-nitropyrene, 2-nitrofluorene, and 1,8-dinitropyrene. The nitro-PAH were added separately and in various combinations to the extract to determine the effects of each variable and to identify possible interactions between the individual nitro-PAH and between the nitro-PAH and the extract. The composition of the mixtures was determined by mixture design (linear axial normal) with four variables (the DEP extract and the three nitro-PAH, giving 8 different mixtures plus a triplicate centerpoint, i.e., a total of 11. The design supports a model with linear and interaction (product) terms. Two different approaches were used: traditional mixture design within a well-defined range on the linear part of the dose-response curves and an isobolographic mixture design with equipotent doses of each variable. The mixtures were tested for mutagenicity in the Ames assay using the TA98 strain of Salmonella typhimurium. The data were analyzed with projections to latent structures (PLS). The three individual nitro-PAH and the DEP extract acted additively in the Ames test. The use of mixture design either within a well-defined range of the linear part on the dose-response curve or with equipotent doses saves experiments and reduces the possibility of false interaction terms in situations with dose additivity or response additivity. Images Figure 1 Figure 2 PMID:9860895
Mixture design and multivariate analysis in mixture research.
Eide, I; Johnsen, H G
1998-12-01
Mixture design has been used to identify possible interactions between mutagens in a mixture. In this paper the use of mixture design in multidimensional isobolographic studies is introduced. Mutagenicity of individual nitro-polycyclic aromatic hydrocarbons (PAH) was evaluated is an organic extract of diesel exhaust particles (DEPs). The particles were extracted with dichloromethane (DCM). After replacing DCM with dimethyl sulfoxide, the extract was spiked with three individual nitro-PAH: 1-nitropyrene, 2-nitrofluorene, and 1,8-dinitropyrene. The nitro-PAH were added separately and in various combinations to the extract to determine the effects of each variable and to identify possible interactions between the individual nitro-PAH and between the nitro-PAH and the extract. The composition of the mixtures was determined by mixture design (linear axial normal) with four variables (the DEP extract and the three nitro-PAH, giving 8 different mixtures plus a triplicate centerpoint, i.e., a total of 11. The design supports a model with linear and interaction (product) terms. Two different approaches were used: traditional mixture design within a well-defined range on the linear part of the dose-response curves and an isobolographic mixture design with equipotent doses of each variable. The mixtures were tested for mutagenicity in the Ames assay using the TA98 strain of Salmonella typhimurium. The data were analyzed with projections to latent structures (PLS). The three individual nitro-PAH and the DEP extract acted additively in the Ames test. The use of mixture design either within a well-defined range of the linear part on the dose-response curve or with equipotent doses saves experiments and reduces the possibility of false interaction terms in situations with dose additivity or response additivity. PMID:9860895
Polyimide processing additives
NASA Technical Reports Server (NTRS)
Fletcher, James C. (Inventor); Pratt, J. Richard (Inventor); St.clair, Terry L. (Inventor); Stoakley, Diane M. (Inventor); Burks, Harold D. (Inventor)
1992-01-01
A process for preparing polyimides having enhanced melt flow properties is described. The process consists of heating a mixture of a high molecular weight poly-(amic acid) or polyimide with a low molecular weight amic acid or imide additive in the range of 0.05 to 15 percent by weight of additive. The polyimide powders so obtained show improved processability, as evidenced by lower melt viscosity by capillary rheometry. Likewise, films prepared from mixtures of polymers with additives show improved processability with earlier onset of stretching by TMA.
Polyimide processing additives
NASA Technical Reports Server (NTRS)
Pratt, J. Richard (Inventor); St.clair, Terry L. (Inventor); Stoakley, Diane M. (Inventor); Burks, Harold D. (Inventor)
1993-01-01
A process for preparing polyimides having enhanced melt flow properties is described. The process consists of heating a mixture of a high molecular weight poly-(amic acid) or polyimide with a low molecular weight amic acid or imide additive in the range of 0.05 to 15 percent by weight of the additive. The polyimide powders so obtained show improved processability, as evidenced by lower melt viscosity by capillary rheometry. Likewise, films prepared from mixtures of polymers with additives show improved processability with earlier onset of stretching by TMA.
The Boltzmann Equation for a Multi-species Mixture Close to Global Equilibrium
NASA Astrophysics Data System (ADS)
Briant, Marc; Daus, Esther S.
2016-07-01
We study the Cauchy theory for a multi-species mixture, where the different species can have different masses, in a perturbative setting on the three dimensional torus. The ultimate aim of this work is to obtain the existence, uniqueness and exponential trend to equilibrium of solutions to the multi-species Boltzmann equation in {L^1_vL^∞_x(m)} , where {m˜ (1+ |v|^k)} is a polynomial weight. We prove the existence of a spectral gap for the linear multi-species Boltzmann operator allowing different masses, and then we establish a semigroup property thanks to a new explicit coercive estimate for the Boltzmann operator. Then we develop an {L^2-L^E&infty}; theory à la Guo for the linear perturbed equation. Finally, we combine the latter results with a decomposition of the multi-species Boltzmann equation in order to deal with the full equation. We emphasize that dealing with different masses induces a loss of symmetry in the Boltzmann operator which prevents the direct adaptation of standard mono-species methods (for example Carleman representation, Povzner inequality). Of important note is the fact that all methods used and developed in this work are constructive. Moreover, they do not require any Sobolev regularity and the {L^1_vL^∞_x} framework is dealt with for any {k > k_0} , recovering the optimal physical threshold of finite energy {k_0=2} in the particular case of a multi-species hard spheres mixture with the same masses.
Deciding which chemical mixtures risk assessment methods work best for what mixtures
Teuschler, Linda K.
2007-09-01
The most commonly used chemical mixtures risk assessment methods involve simple notions of additivity and toxicological similarity. Newer methods are emerging in response to the complexities of chemical mixture exposures and effects. Factors based on both science and policy drive decisions regarding whether to conduct a chemical mixtures risk assessment and, if so, which methods to employ. Scientific considerations are based on positive evidence of joint toxic action, elevated human exposure conditions or the potential for significant impacts on human health. Policy issues include legislative drivers that may mandate action even though adequate toxicity data on a specific mixture may not be available and risk assessment goals that impact the choice of risk assessment method to obtain the amount of health protection desired. This paper discusses three important concepts used to choose among available approaches for conducting a chemical mixtures risk assessment: (1) additive joint toxic action of mixture components; (2) toxicological interactions of mixture components; and (3) chemical composition of complex mixtures. It is proposed that scientific support for basic assumptions used in chemical mixtures risk assessment should be developed by expert panels, risk assessment methods experts, and laboratory toxicologists. This is imperative to further develop and refine quantitative methods and provide guidance on their appropriate applications. Risk assessors need scientific support for chemical mixtures risk assessment methods in the form of toxicological data on joint toxic action for high priority mixtures, statistical methods for analyzing dose-response for mixtures, and toxicological and statistical criteria for determining sufficient similarity of complex mixtures.
Mixture distributions in human genetics research.
Schork, N J; Allison, D B; Thiel, B
1996-06-01
The use of mixture distributions in genetics research dates back to at least the late 1800s when Karl Pearson applied them in an analysis of crab morphometry. Pearson's use of normal mixture distributions to model the mixing of different species of crab (or 'families' of crab as he referred to them) within a defined geographic area motivated further use of mixture distributions in genetics research settings, and ultimately led to their development and recognition as intuitive modelling devices for the effects of underlying genes on quantitative phenotypic (i.e. trait) expression. In addition, mixture distributions are now used routinely to model or accommodate the genetic heterogeneity thought to underlie many human diseases. Specific applications of mixture distribution models in contemporary human genetics research are, in fact, too numerous to count. Despite this long, consistent and arguably illustrious history of use, little mention of mixture distributions in genetics research is made in many recent reviews on mixture models. This review attempts to rectify this by providing insight into the role that mixture distributions play in contemporary human genetics research. Tables providing examples from the literature that describe applications of mixture models in human genetics research are offered as a way of acquainting the interested reader with relevant studies. In addition, some of the more problematic aspects of the use of mixture models in genetics research are outlined and addressed. PMID:8817796
Metal mixtures modeling evaluation project: 1. Background.
Meyer, Joseph S; Farley, Kevin J; Garman, Emily R
2015-04-01
Despite more than 5 decades of aquatic toxicity tests conducted with metal mixtures, there is still a need to understand how metals interact in mixtures and to predict their toxicity more accurately than what is currently done. The present study provides a background for understanding the terminology, regulatory framework, qualitative and quantitative concepts, experimental approaches, and visualization and data-analysis methods for chemical mixtures, with an emphasis on bioavailability and metal-metal interactions in mixtures of waterborne metals. In addition, a Monte Carlo-type randomization statistical approach to test for nonadditive toxicity is presented, and an example with a binary-metal toxicity data set demonstrates the challenge involved in inferring statistically significant nonadditive toxicity. This background sets the stage for the toxicity results, data analyses, and bioavailability models related to metal mixtures that are described in the remaining articles in this special section from the Metal Mixture Modeling Evaluation project and workshop. It is concluded that although qualitative terminology such as additive and nonadditive toxicity can be useful to convey general concepts, failure to expand beyond that limited perspective could impede progress in understanding and predicting metal mixture toxicity. Instead of focusing on whether a given metal mixture causes additive or nonadditive toxicity, effort should be directed to develop models that can accurately predict the toxicity of metal mixtures.
Interpreting Y chromosome STR haplotype mixture.
Ge, Jianye; Budowle, Bruce; Chakraborty, Ranajit
2010-05-01
Mixture interpretation is a challenging problem in forensic DNA analyses. The interpretation of Y short tandem repeat (STR) haplotype mixtures, due to a lack of recombination, differs somewhat from that of the autosomal DNA markers and is more complex. We describe approaches for calculating the probability of exclusion (PE) and likelihood ratio (LR) methods to interpret Y-STR mixture evidence with population substructure incorporated. For a mixture sample, first, all possible contributor haplotypes in a reference database are listed as a candidate list. The PE is the complement of the summation of the frequencies of haplotypes in the candidate list. The LR method compares the probabilities of the evidence given alternative hypotheses. The hypotheses are possible explanations for the mixture. Population substructure may be further incorporated in likelihood calculation. The maximum number of contributors is based on the candidate list and the computing complexity is polynomial. Additionally, mixtures were simulated by combining two or three 16 Y-STR marker haplotypes derived from the US forensic Y-STR database. The average PE was related to the size of database. With a database comprised of 500 haplotypes an average PE value of at least 0.995 can be obtained for two-person mixtures. The PE decreases with an increasing number of contributors to the mixture. Using the total sample population, the average number of candidate haplotypes of two-person mixtures is 3.73 and 95% mixtures have less than or equal to 10 candidate haplotypes. More than 98.7% of two-person mixtures can only be explained by the haplotype combinations that mixtures are composed. These values are generally higher for three-person mixtures. A small proportion of three-person mixture can also be explained by only two haplotypes.
Inquiry into thermodynamic behavior of hard sphere plus repulsive barrier of finite height
NASA Astrophysics Data System (ADS)
Zhou, Shiqi; Solana, J. R.
2009-11-01
A bridge function approximation is proposed to close the Ornstein-Zernike (OZ) integral equation for fluids with purely repulsive potentials. The performance of the bridge function approximation is then tested by applying the approximation to two kinds of repulsive potentials, namely, the square shoulder potential and the triangle shoulder potential. An extensive comparison between simulation and the OZ approach is performed over a wide density range for the fluid phase and several temperatures. It is found that the agreement between the two routes is excellent for not too low temperatures and satisfactory for extremely low temperatures. Then, this globally trustworthy OZ approach is used to investigate the possible existence or not of a liquid anomaly, i.e., a liquid-liquid phase transition at low temperatures and negative values of the thermal expansion coefficient in certain region of the phase diagram. While the existence of the liquid anomaly in the square shoulder potential has been previously predicted by a traditional first-order thermodynamic perturbation theory (TPT), the present investigation indicates that the liquid-liquid phase transition disappears in the OZ approach, so that its prediction by the first-order TPT is only an artifact originating from the low temperature inadequacy of the first-order TPT. However, the OZ approach indeed predicts negative thermal expansion coefficients. The present bridge function approximation, free of adjustable parameters, is suitable to be used within the context of a recently proposed nonhard sphere perturbation scheme.
Periodic and Aperiodic Close Packing: A Spontaneous Hard-Sphere Model.
ERIC Educational Resources Information Center
van de Waal, B. W.
1985-01-01
Shows how to make close-packed models from balloons and table tennis balls to illustrate structural features of clusters and organometallic cluster-compounds (which are of great interest in the study of chemical reactions). These models provide a very inexpensive and tactile illustration of the organization of matter for concrete operational…
Hypersonic acoustic excitations in binary colloidal crystals: big versus small hard sphere control.
Tommaseo, G; Petekidis, G; Steffen, W; Fytas, G; Schofield, A B; Stefanou, N
2007-01-01
The phononic band structure of two binary colloidal crystals, at hypersonic frequencies, is studied by means of Brillouin light scattering and analyzed in conjunction with corresponding dispersion diagrams of the single colloidal crystals of the constituent particles. Besides the acoustic band of the average medium, the authors' results show the existence of narrow bands originating from resonant multipole modes of the individual particles as well as Bragg-type modes due to the (short-range) periodicity. Strong interaction, leading to the occurrence of hybridization gaps, is observed between the acoustic band and the band of quadrupole modes of the particles that occupy the largest fractional volume of the mixed crystal; the effective radius is either that of the large (in the symmetric NaCl-type crystalline phase) or the small (in the asymmetric NaZn(13)-type crystalline phase) particles. The possibility to reveal a universal behavior of the phononic band structure for different single and binary colloidal crystalline suspensions, by representing in the dispersion diagrams reduced quantities using an appropriate length scale, is discussed.
NASA Astrophysics Data System (ADS)
Stradner, Anna; Bucciarelli, Saskia; Casal, Lucia; Foffi, Giuseppe; Thurston, George; Farago, Bela; Schurtenberger, Peter
2014-03-01
The occurrence of an arrest transition in concentrated colloid suspensions and its dependence on the interaction potential is a hot topic in soft matter. Such arrest transitions can also occur in concentrated protein solutions, as they exist e.g. in biological cells or are increasingly used in pharmaceutical formulations. Here we demonstrate the applicability of concepts from colloid science to understand the dynamics of concentrated protein solutions. In this presentation we report a combination of 3D light scattering, small-angle X-ray scattering and neutron spin echo measurements to study the structural properties as well as the collective and self diffusion of proteins in highly concentrated solutions on the relevant length and time scales. We demonstrate that various arrest scenarios indeed exist for different globular proteins. The proteins chosen are different bovine lens crystallins. We report examples of hard and attractive glass transitions and arrested spinodal decomposition directly linked to the effective pair potentials determined in static scattering experiments for the different proteins. We discuss these different arrest scenarios in view of possible applications of dense protein solutions as well as in view of their possible relevance for living systems.
NASA Astrophysics Data System (ADS)
Rubinstein, Robert
2015-11-01
It is well known that collision models based on an assumed intermolecular potential (IPL, LJ, ...) can be successfully replaced by simplified surrogates (VHS, VSS, VS, ...) in DSMC calculations. But these surrogates only reproduce certain gross properties of the molecular model, for example, the temperature dependence of the viscosity; they do not approximate, and even mis-state, the details of the particle interactions. The success of the simplified models in problems at finite Knudsen number, where the Navier-Stokes approximation is not valid, may therefore seem surprising. To understand this success in a very special case, we showed that the first seven relaxation rates of the linearized Boltzmann equation for Maxwellian molecules are well approximated by the corresponding relaxation rates of its VHS surrogate. We will show that this analysis can be extended in somewhat less generality to IPL interactions, and to some extent to more realistic models including LJ. We believe that this analysis can help address the more general problem of identifying the properties of the collision model that dominate the predictions of the Boltzmann equation.
Chu, Fong Lam; Sleno, Lekha; Yaylayan, Varoujan A
2011-11-01
Pyrolysis was used as a microscale sample preparation tool to generate glucose/alanine reaction products to minimize the use of expensive labeled precursors in isotope labeling studies. The residue remaining after the pyrolysis at 250 °C was analyzed by electrospray time-of-flight mass spectrometry (ESI-TOF-MS). It was observed that a peak at m/z 199.1445 in the ESI-TOF-MS spectrum appeared only when the model system contained at least 2-fold excess alanine. The accurate mass determination indeed indicated the presence of two nitrogen atoms in the molecular formula (C(10)H(18)N(2)O(2)). To verify the origin of the carbon atoms in this unknown compound, model studies with [(13)U(6)]glucose, [(13)C-1]alanine, [(13)C-2]alanine, [(13)C-3]alanine, and [(15)N]alanine were also performed. Glucose furnished six carbon atoms, and alanine provides four carbon (2 × C-2 and 2 × C-3) and two nitrogen atoms. When commercially available fructosylalanine (N-attached to C-1) was reacted with only 1 mol of alanine, a peak at m/z 199.1445 was once again observed. In addition, when 3-deoxyglucosone (3-DG) was reacted with a 2-fold excess of alanine, a peak at m/z 199.1433 was also generated, confirming the points of attachment of the two amino acids at C-1 and C-2 atoms of 3-DG. These studies have indicated that amino acids can undergo multiple addition reactions with 1,2-dicarbonyl compounds such as 3-deoxyglucosone and eventually form a tetrahydropyrazine moiety.
Carburetor mixture control apparatus
Dalke, A.E.
1983-11-29
A mixture control device is disclosed for automatically controlling the air to fuel mixture of a conventional carburetor involving a plurality of sloped radial vanes circumferentially located within the annulus formed by the booster venturi and the venturi tube. By inducing significant centrifugal motion in the air passing outside the booster venturi the problems associated with fuel to air mixture changes associated with changes in elevation and changes in seasonal temperatures are alleviated.
Spencer, Michael
1974-01-01
Food additives are discussed from the food technology point of view. The reasons for their use are summarized: (1) to protect food from chemical and microbiological attack; (2) to even out seasonal supplies; (3) to improve their eating quality; (4) to improve their nutritional value. The various types of food additives are considered, e.g. colours, flavours, emulsifiers, bread and flour additives, preservatives, and nutritional additives. The paper concludes with consideration of those circumstances in which the use of additives is (a) justified and (b) unjustified. PMID:4467857
NASA Technical Reports Server (NTRS)
Turmon, Michael
2004-01-01
We consider mixture density estimation under the symmetry constraint x = Az for an orthogonal matrix A. This distributional constraint implies a corresponding constraint on the mixture parameters. Focusing on the gaussian case, we derive an expectation-maximization (EM) algorithm to enforce the constraint and show results for modeling of image feature vectors.
Gaskill, Stacey J; Bruce, Erica D
2016-05-01
Polycyclic aromatic hydrocarbons (PAHs) have been labeled contaminants of concern due to their carcinogenic potential, insufficient toxicological data, environmental ubiquity, and inconsistencies in the composition of environmental mixtures. The Environmental Protection Agency is reevaluating current methods for assessing the toxicity of PAHs, including the assumption of toxic additivity in mixtures. This study was aimed at testing mixture interactions through in vitro cell culture experimentation, and modeling the toxicity using quantitative structure-activity relationships (QSAR). Clone-9 rat liver cells were used to analyze cellular proliferation, viability, and genotoxicity of 15 PAHs in single doses and binary mixtures. Tests revealed that many mixtures have nonadditive toxicity, but display varying mixture effects depending on the mixture composition. Many mixtures displayed antagonism, similar to other published studies. QSARs were then developed using the genetic function approximation algorithm to predict toxic activity both in single PAH congeners and in binary mixtures. Effective concentrations inhibiting 50% of the cell populations were modeled, with R(2) = 0.90, 0.99, and 0.84, respectively. The QSAR mixture algorithms were then adjusted to account for the observed mixture interactions as well as the mixture composition (ratios) to assess the feasibility of QSARs for mixtures. Based on these results, toxic addition is improbable and therefore environmental PAH mixtures are likely to see nonadditive responses when complex interactions occur between components. Furthermore, QSAR may be a useful tool to help bridge these data gaps surrounding the assessment of human health risks that are associated with PAH exposures.
Analysis of interaction in binary odorant mixtures.
Smith, B H
1998-12-01
An understanding of the olfactory system of any animal must account for how odor mixtures are perceived and processed. The present experiments apply associationist models to the study of how elements are processed in binary odorant mixtures. Using experimental designs for Proboscis Extension Conditioning of honey bees, I show that learning about a pure odorant element is frequently affected by its occurrence in a mixture with a second odorant. Presence of a background odor when an odorant is associated with sucrose reinforcement decreases the rate and/or asymptotic level of associative strength that accumulates to that odorant. This interaction is in part due to synthetic qualities that arise in sensory transduction and initial processing. In addition, it involves an attention-like processing system like that involved in overshadowing. Therefore, a model that includes representations of the component and configural qualities of odorants in mixtures is needed to provide a more complete account of learning about odor mixtures. PMID:9877404
Depletion potential in the infinite dilution limit
NASA Astrophysics Data System (ADS)
Yuste, Santos Bravo; Santos, Andrés; López de Haro, Mariano
2008-04-01
The depletion force and depletion potential between two in principle unequal "big" hard spheres embedded in a multicomponent mixture of "small" hard spheres are computed using the rational function approximation method for the structural properties of hard-sphere mixtures [S. B. Yuste, A. Santos, and M. López de Haro, J. Chem. Phys. 108, 3683 (1998)]. The cases of equal solute particles and of one big particle and a hard planar wall in a background monodisperse hard-sphere fluid are explicitly analyzed. An improvement over the performance of the Percus-Yevick theory and good agreement with available simulation results are found.
Time-dependence in mixture toxicity prediction
Dawson, Douglas A.; Allen, Erin M.G.; Allen, Joshua L.; Baumann, Hannah J.; Bensinger, Heather M.; Genco, Nicole; Guinn, Daphne; Hull, Michael W.; Il'Giovine, Zachary J.; Kaminski, Chelsea M.; Peyton, Jennifer R.; Schultz, T. Wayne; Pöch, Gerald
2014-01-01
The value of time-dependent toxicity (TDT) data in predicting mixture toxicity was examined. Single chemical (A and B) and mixture (A + B) toxicity tests using Microtox® were conducted with inhibition of bioluminescence (Vibrio fischeri) being quantified after 15, 30 and 45-min of exposure. Single chemical and mixture tests for 25 sham (A1:A2) and 125 true (A:B) combinations had a minimum of seven duplicated concentrations with a duplicated control treatment for each test. Concentration/response (x/y) data were fitted to sigmoid curves using the five-parameter logistic minus one parameter (5PL-1P) function, from which slope, EC25, EC50, EC75, asymmetry, maximum effect, and r2 values were obtained for each chemical and mixture at each exposure duration. Toxicity data were used to calculate percentage-based TDT values for each individual chemical and mixture of each combination. Predicted TDT values for each mixture were calculated by averaging the TDT values of the individual components and regressed against the observed TDT values obtained in testing, resulting in strong correlations for both sham (r2 = 0.989, n = 25) and true mixtures (r2 = 0.944, n = 125). Additionally, regression analyses confirmed that observed mixture TDT values calculated for the 50% effect level were somewhat better correlated with predicted mixture TDT values than at the 25 and 75% effect levels. Single chemical and mixture TDT values were classified into five levels in order to discern trends. The results suggested that the ability to predict mixture TDT by averaging the TDT of the single agents was modestly reduced when one agent of the combination had a positive TDT value and the other had a minimal or negative TDT value. PMID:25446331
75 FR 53867 - Additions to Listing of Exempt Chemical Mixtures
Federal Register 2010, 2011, 2012, 2013, 2014
2010-09-02
... Product name \\1\\ Form Date Cerilliant Corporation 1R,2S(-)-Ephedrine hydrochloride 1.0 Liquid 8/2/2007 mg...(+)-Ephedrine-D3 hydrochloride Liquid 8/2/2007 0.1 mg/ml as free base in one of: 1,2- dimethoxyethane... tetrahydrofuran. ] Cerilliant Corporation 1S,2R(+)-Ephedrine-D3 hydrochloride Liquid 8/2/2007 1.0 mg/ml as...
Perception of trigeminal mixtures.
Filiou, Renée-Pier; Lepore, Franco; Bryant, Bruce; Lundström, Johan N; Frasnelli, Johannes
2015-01-01
The trigeminal system is a chemical sense allowing for the perception of chemosensory information in our environment. However, contrary to smell and taste, we lack a thorough understanding of the trigeminal processing of mixtures. We, therefore, investigated trigeminal perception using mixtures of 3 relatively receptor-specific agonists together with one control odor in different proportions to determine basic perceptual dimensions of trigeminal perception. We found that 4 main dimensions were linked to trigeminal perception: sensations of intensity, warmth, coldness, and pain. We subsequently investigated perception of binary mixtures of trigeminal stimuli by means of these 4 perceptual dimensions using different concentrations of a cooling stimulus (eucalyptol) mixed with a stimulus that evokes warmth perception (cinnamaldehyde). To determine if sensory interactions are mainly of central or peripheral origin, we presented stimuli in a physical "mixture" or as a "combination" presented separately to individual nostrils. Results showed that mixtures generally yielded higher ratings than combinations on the trigeminal dimensions "intensity," "warm," and "painful," whereas combinations yielded higher ratings than mixtures on the trigeminal dimension "cold." These results suggest dimension-specific interactions in the perception of trigeminal mixtures, which may be explained by particular interactions that may take place on peripheral or central levels. PMID:25500807
Perception of trigeminal mixtures.
Filiou, Renée-Pier; Lepore, Franco; Bryant, Bruce; Lundström, Johan N; Frasnelli, Johannes
2015-01-01
The trigeminal system is a chemical sense allowing for the perception of chemosensory information in our environment. However, contrary to smell and taste, we lack a thorough understanding of the trigeminal processing of mixtures. We, therefore, investigated trigeminal perception using mixtures of 3 relatively receptor-specific agonists together with one control odor in different proportions to determine basic perceptual dimensions of trigeminal perception. We found that 4 main dimensions were linked to trigeminal perception: sensations of intensity, warmth, coldness, and pain. We subsequently investigated perception of binary mixtures of trigeminal stimuli by means of these 4 perceptual dimensions using different concentrations of a cooling stimulus (eucalyptol) mixed with a stimulus that evokes warmth perception (cinnamaldehyde). To determine if sensory interactions are mainly of central or peripheral origin, we presented stimuli in a physical "mixture" or as a "combination" presented separately to individual nostrils. Results showed that mixtures generally yielded higher ratings than combinations on the trigeminal dimensions "intensity," "warm," and "painful," whereas combinations yielded higher ratings than mixtures on the trigeminal dimension "cold." These results suggest dimension-specific interactions in the perception of trigeminal mixtures, which may be explained by particular interactions that may take place on peripheral or central levels.
Lipscomb, R.; Craig, A.; Labrow, S.; Dunn, J.F.
1958-10-28
An apparatus is presented for separating gaseous mixtures by selectively freezing a constituent of the mixture and subsequently separating the frozen gas. The gas mixture is passed through a cylinder fltted with a cooling jacket, causing one gas to freeze on the walls of the cylinder. A set of scraper blades are provided in the interior of the cyllnder, and as the blades oscillate, the frozen gas is scraped to the bottom of the cylinder. Means are provided for the frozen material to pass into a heating chamber where it is vaporized and the product gas collected.
D’Adamo, Giuseppe; Pelissetto, Andrea; Pierleoni, Carlo
2014-12-28
A coarse-graining strategy, previously developed for polymer solutions, is extended here to mixtures of linear polymers and hard-sphere colloids. In this approach, groups of monomers are mapped onto a single pseudoatom (a blob) and the effective blob-blob interactions are obtained by requiring the model to reproduce some large-scale structural properties in the zero-density limit. We show that an accurate parametrization of the polymer-colloid interactions is obtained by simply introducing pair potentials between blobs and colloids. For the coarse-grained (CG) model in which polymers are modelled as four-blob chains (tetramers), the pair potentials are determined by means of the iterative Boltzmann inversion scheme, taking full-monomer (FM) pair correlation functions at zero-density as targets. For a larger number n of blobs, pair potentials are determined by using a simple transferability assumption based on the polymer self-similarity. We validate the model by comparing its predictions with full-monomer results for the interfacial properties of polymer solutions in the presence of a single colloid and for thermodynamic and structural properties in the homogeneous phase at finite polymer and colloid density. The tetramer model is quite accurate for q ≲ 1 (q=R{sup ^}{sub g}/R{sub c}, where R{sup ^}{sub g} is the zero-density polymer radius of gyration and R{sub c} is the colloid radius) and reasonably good also for q = 2. For q = 2, an accurate coarse-grained description is obtained by using the n = 10 blob model. We also compare our results with those obtained by using single-blob models with state-dependent potentials.
Mixture risk assessment: a case study of Monsanto experiences.
Nair, R S; Dudek, B R; Grothe, D R; Johannsen, F R; Lamb, I C; Martens, M A; Sherman, J H; Stevens, M W
1996-01-01
Monsanto employs several pragmatic approaches for evaluating the toxicity of mixtures. These approaches are similar to those recommended by many national and international agencies. When conducting hazard and risk assessments, priority is always given to using data collected directly on the mixture of concern. To provide an example of the first tier of evaluation, actual data on acute respiratory irritation studies on mixtures were evaluated to determine whether the principle of additivity was applicable to the mixture evaluated. If actual data on the mixture are unavailable, extrapolation across similar mixtures is considered. Because many formulations are quite similar in composition, the toxicity data from one mixture can be extended to a closely related mixture in a scientifically justifiable manner. An example of a family of products where such extrapolations have been made is presented to exemplify this second approach. Lastly, if data on similar mixtures are unavailable, data on component fractions are used to predict the toxicity of the mixture. In this third approach, process knowledge and scientific judgement are used to determine how the known toxicological properties of the individual fractions affect toxicity of the mixture. Three examples of plant effluents where toxicological data on fractions were used to predict the toxicity of the mixture are discussed. The results of the analysis are used to discuss the predictive value of each of the above mentioned toxicological approaches for evaluating chemical mixtures.
Harrup, Mason K; Rollins, Harry W
2013-11-26
An additive comprising a phosphazene compound that has at least two reactive functional groups and at least one capping functional group bonded to phosphorus atoms of the phosphazene compound. One of the at least two reactive functional groups is configured to react with cellulose and the other of the at least two reactive functional groups is configured to react with a resin, such as an amine resin of a polycarboxylic acid resin. The at least one capping functional group is selected from the group consisting of a short chain ether group, an alkoxy group, or an aryloxy group. Also disclosed are an additive-resin admixture, a method of treating a wood product, and a wood product.
Rudolf Keller
2004-08-10
In this project, a concept to improve the performance of aluminum production cells by introducing potlining additives was examined and tested. Boron oxide was added to cathode blocks, and titanium was dissolved in the metal pool; this resulted in the formation of titanium diboride and caused the molten aluminum to wet the carbonaceous cathode surface. Such wetting reportedly leads to operational improvements and extended cell life. In addition, boron oxide suppresses cyanide formation. This final report presents and discusses the results of this project. Substantial economic benefits for the practical implementation of the technology are projected, especially for modern cells with graphitized blocks. For example, with an energy savings of about 5% and an increase in pot life from 1500 to 2500 days, a cost savings of $ 0.023 per pound of aluminum produced is projected for a 200 kA pot.
Estrogenic activity of UV filter mixtures
Kunz, Petra Y. . E-mail: petra.kunz@fhnw.ch; Fent, Karl . E-mail: karl.fent@bluewin.ch
2006-11-15
UV-absorbing chemicals (UV filters) are widely used for protection against UV radiation in sunscreens and in a variety of cosmetic products and materials. Depending on the breadth and factor of UV protection, they are added as single compounds or as a combination thereof. Some UV filters have estrogenic activity, but their activity and interactions in mixtures are largely unknown. In this work, we analyzed 8 commonly used UV filters, which are pure or partial hER{alpha} agonists, for their estrogenic activity in equieffective mixtures in a recombinant yeast assay carrying the human estrogen receptor alpha (hER{alpha}). Mixtures of two, four and eight UV filters alone, or in combination with 17 {beta} estradiol (E2), were assessed at different effect levels and no-observed-effect-concentrations (NOEC). Predictions of the joint effects of these mixtures were calculated by employing the concentration addition (Canada) and independent action (IA) model. Most binary mixtures comprising of pure hER{alpha} agonists showed a synergistic activity at all mixture combinations. Only in combination with benzophenone-1, antagonistic activity was observed at some effect levels. All mixtures of four or eight, pure or pure and partial hER{alpha} agonists, alone or including E2, showed synergistic activity at concentrations giving an increase of 10% of basal activity (BC10). This occurred even at concentrations that were at the NOEC level of each single compound. Hence, there were substantial mixture effects even though each UV filter was present at its NOEC level. These results show that significant interactions occur in UV filter mixtures, which is important for the hazard and risk assessments of these personal care products.
Structure of multi-component/multi-Yukawa mixtures
NASA Astrophysics Data System (ADS)
Blum, L.; Arias, M.
2006-09-01
\\begin{equation} \\fl 2 \\pi \\tilde{g}_{ij}(s)=-\\frac{\\rme^{-s \\sigma_{ij}}}{D_{\\tau}(s)} \\left\\{{1\\over s^2}+{1\\over s}Q^{\\prime}_{ij}(\\sigma_{ij})+\\sum_{m=1}^{M}{{ z_m \\tilde{\\cal{X}}}_i^{(m)}{f}_j^{(m)}\\over{s+z_m}}\\right\\}. \\label{eq2} \\end{equation} This function is also easily transformed into S(k) by replacing s\\Rightarrow \\rmi k . For low density situations (dilute colloids) D_{\\tau } (s)\\sim 1+{\\cal {O}(\\rho)} and S(k) is a sum of M Lorentzians. For hard sphere PY mixtures we get the simple (compare Lebowitz 1964 Phys. Rev. 133 A895 and Blum and Stell 1979 J. Chem. Phys. 71 42) \\[ 2 \\pi \\tilde{g}_{ij}(s)=-\\frac{\\rme^{-s \\sigma_{ij}}}{s^2 D_{\\tau}(s)} \\left\\{1+s\\left[(Q^{HS})^{\\prime}_{ij}(\\sigma_{ij})\\right]\\right\\} \\] where Dτ(s) is a scalar function. For polydisperse electrolytes in the MSA a simpler expression is also obtained (compare Blum and Hoye 1977 J. Phys. Chem. 81 1311). An explicit continued fraction solution of the one component multi-Yukawa case is also given.
Well treating fluids and additives therefor
Patel, B.
1991-07-16
This patent describes a solid, dry additive for reducing the water loss and improving other properties of well treating fluids in high temperature environments. It comprises a mixture of a water soluble copolymer of N-vinyl pyrrolidone and the sodium salt of 2- acrylamido-2-methylpropane sulfonic acid and an organic compound selected from the group consisting of lignites, tannins, asphaltic materials, derivatives thereof and mixtures of such compounds, the mixture of the water soluble copolymer and organic compound being prepared by mixing a water and oil emulsion containing the copolymer with the organic compound followed by removing the oil and water from the resultant mixture.
Synergy and other ineffective mixture risk definitions.
Hertzberg, R.; MacDonell, M.; Environmental Assessment
2002-04-08
A substantial effort has been spent over the past few decades to label toxicologic interaction outcomes as synergistic, antagonistic, or additive. Although useful in influencing the emotions of the public and the press, these labels have contributed fairly little to our understanding of joint toxic action. Part of the difficulty is that their underlying toxicological concepts are only defined for two chemical mixtures, while most environmental and occupational exposures are to mixtures of many more chemicals. Furthermore, the mathematical characterizations of synergism and antagonism are inextricably linked to the prevailing definition of 'no interaction,' instead of some intrinsic toxicological property. For example, the US EPA has selected dose addition as the no-interaction definition for mixture risk assessment, so that synergism would represent toxic effects that exceed those predicted from dose addition. For now, labels such as synergism are useful to regulatory agencies, both for qualitative indications of public health risk as well as numerical decision tools for mixture risk characterization. Efforts to quantify interaction designations for use in risk assessment formulas, however, are highly simplified and carry large uncertainties. Several research directions, such as pharmacokinetic measurements and models, and toxicogenomics, should promote significant improvements by providing multi-component data that will allow biologically based mathematical models of joint toxicity to replace these pairwise interaction labels in mixture risk assessment procedures.
Predicting skin permeability from complex chemical mixtures
Riviere, Jim E. . E-mail: Jim_Riviere@ncsu.edu; Brooks, James D.
2005-10-15
Occupational and environmental exposure to topical chemicals is usually in the form of complex chemical mixtures, yet risk assessment is based on experimentally derived data from individual chemical exposures from a single, usually aqueous vehicle, or from computed physiochemical properties. We present an approach using hybrid quantitative structure permeation relationships (QSPeR) models where absorption through porcine skin flow-through diffusion cells is well predicted using a QSPeR model describing the individual penetrants, coupled with a mixture factor (MF) that accounts for physicochemical properties of the vehicle/mixture components. The baseline equation is log k {sub p} = c + mMF + a{sigma}{alpha} {sub 2} {sup H} + b{sigma}{beta} {sub 2} {sup H} + s{pi} {sub 2} {sup H} + rR {sub 2} + vV {sub x} where {sigma}{alpha} {sub 2} {sup H} is the hydrogen-bond donor acidity, {sigma}{beta} {sub 2} {sup H} is the hydrogen-bond acceptor basicity, {pi} {sub 2} {sup H} is the dipolarity/polarizability, R {sub 2} represents the excess molar refractivity, and V {sub x} is the McGowan volume of the penetrants of interest; c, m, a, b, s, r, and v are strength coefficients coupling these descriptors to skin permeability (k {sub p}) of 12 penetrants (atrazine, chlorpyrifos, ethylparathion, fenthion, methylparathion, nonylphenol, {rho}-nitrophenol, pentachlorophenol, phenol, propazine, simazine, and triazine) in 24 mixtures. Mixtures consisted of full factorial combinations of vehicles (water, ethanol, propylene glycol) and additives (sodium lauryl sulfate, methyl nicotinate). An additional set of 4 penetrants (DEET, SDS, permethrin, ricinoleic acid) in different mixtures were included to assess applicability of this approach. This resulted in a dataset of 16 compounds administered in 344 treatment combinations. Across all exposures with no MF, R{sup 2} for absorption was 0.62. With the MF, correlations increased up to 0.78. Parameters correlated to the MF include refractive
Theoretical study of inhomogenous fluids
NASA Astrophysics Data System (ADS)
Noworyta, Jerzy Piotr
1998-07-01
Binary, additive mixtures of hard spheres near the structureless 'hard' walls are studied with the grand canonical Monte Carlo (MC) simulation method. Binary mixtures of hard spheres and hard sphere systems in the neighborhood of hard walls had been studied separately before. This research for the first time incorporates both elements. A brief survey of the alternative methods that can be applied to study inhomogenous fluid systems is presented, with special attention paid to the integral equation theory. Well-known formulas utilizing the idea of a radial distribution function and a direct correlation function to describe the thermodynamics of the uniform hard sphere fluid through the solution of the Ornstein- Zernike (OZ) integral equation within the Percus-Yevick (PY) closure are given, as well as their generalization to the mixtures. Also presented are the empirical expressions (BMCSL), based on the PY and the scaled particle theory (SPT). The main features of the model assumed for the purpose of this study are hard spheres of two sizes, the conditions of the grand canonical ensemble and the existence of two parallel flat and structureless walls. In contrast to some recently published results, chemical potential is held constant for both species. Some details of the application of the classical Monte Carlo method to the investigated model are presented, including the procedure to ensure an unbiased Markov chain of states. The results of the simulation are analyzed with special attention to the choice of the equilibration point and the extrapolation of the density to the contact separation from the wall. The standard deviation is estimated through the block average method. Results are presented for the mixtures of hard spheres with a 3:5 and 1:3 diameter ratio. The applied range of chemical potentials allowed the simulation of moderately high densities, below the packing fraction of 0.4. Generally, the plots of the obtained reduced density profiles show good
MixtureTree annotator: a program for automatic colorization and visual annotation of MixtureTree.
Chen, Shu-Chuan; Ogata, Aaron
2015-01-01
The MixtureTree Annotator, written in JAVA, allows the user to automatically color any phylogenetic tree in Newick format generated from any phylogeny reconstruction program and output the Nexus file. By providing the ability to automatically color the tree by sequence name, the MixtureTree Annotator provides a unique advantage over any other programs which perform a similar function. In addition, the MixtureTree Annotator is the only package that can efficiently annotate the output produced by MixtureTree with mutation information and coalescent time information. In order to visualize the resulting output file, a modified version of FigTree is used. Certain popular methods, which lack good built-in visualization tools, for example, MEGA, Mesquite, PHY-FI, TreeView, treeGraph and Geneious, may give results with human errors due to either manually adding colors to each node or with other limitations, for example only using color based on a number, such as branch length, or by taxonomy. In addition to allowing the user to automatically color any given Newick tree by sequence name, the MixtureTree Annotator is the only method that allows the user to automatically annotate the resulting tree created by the MixtureTree program. The MixtureTree Annotator is fast and easy-to-use, while still allowing the user full control over the coloring and annotating process. PMID:25826378
MixtureTree annotator: a program for automatic colorization and visual annotation of MixtureTree.
Chen, Shu-Chuan; Ogata, Aaron
2015-01-01
The MixtureTree Annotator, written in JAVA, allows the user to automatically color any phylogenetic tree in Newick format generated from any phylogeny reconstruction program and output the Nexus file. By providing the ability to automatically color the tree by sequence name, the MixtureTree Annotator provides a unique advantage over any other programs which perform a similar function. In addition, the MixtureTree Annotator is the only package that can efficiently annotate the output produced by MixtureTree with mutation information and coalescent time information. In order to visualize the resulting output file, a modified version of FigTree is used. Certain popular methods, which lack good built-in visualization tools, for example, MEGA, Mesquite, PHY-FI, TreeView, treeGraph and Geneious, may give results with human errors due to either manually adding colors to each node or with other limitations, for example only using color based on a number, such as branch length, or by taxonomy. In addition to allowing the user to automatically color any given Newick tree by sequence name, the MixtureTree Annotator is the only method that allows the user to automatically annotate the resulting tree created by the MixtureTree program. The MixtureTree Annotator is fast and easy-to-use, while still allowing the user full control over the coloring and annotating process.
Toxicity evaluation of PAH mixtures using Microtox
Thompkins, J.; Guthrie, E.; Pfaender, F.
1995-12-31
Polycyclic aromatic hydrocarbons (PAH) are produced from both natural and anthropogenic combustion processes. PAHs are known to be toxic and carcinogenic, are prevalent at many hazardous waste sites, and pose a potential risk to both ecological and human health. To date, few researchers have assessed the toxicity of polycyclic aromatic hydrocarbon (PAH) mixtures. The toxicity of chrysene, anthracene, pyrene, phenanthrene, fluoranthrene, acenaphthene, fluorene, and naphthalene were evaluated using Microtox, and acute toxicity assay that uses bioluminescent bacteria, Photobacterium phosphoreum, to measure toxicity. In this study, the toxicities of 2, 3, and 4 ring PAHs were determined for individual compounds. Synergistic or additive effects of PAH mixtures was assessed by comparing the toxicity of mixtures with that of pure compounds. Each PAH or mixture was evaluated at their respective water solubility concentrations, For individual PAHs tested, the toxicity of PAHs is inversely related to water solubility. Mixtures of two and three PAHs with disparate water solubilities resulted in synergistic interactions. Antagonistic interactions, a decrease in toxicity, were observed for mixtures of similar water solubilities.
Laminar flame speeds of moist syngas mixtures
Das, Apurba K.; Kumar, Kamal; Sung, Chih-Jen
2011-02-15
This work experimentally investigates the effect of the presence of water vapor on the laminar flame speeds of moist syngas/air mixtures using the counterflow twin-flame configuration. The experimental results presented here are for fuel lean syngas mixtures with molar percentage of hydrogen in the hydrogen and carbon monoxide mixture varying from 5% to 100%, for an unburned mixture temperature of 323 K, and under atmospheric pressure. At a given equivalence ratio, the effect of varying amount of water vapor addition on the measured laminar flame speed is demonstrated. The experimental laminar flame speeds are also compared with computed values using chemical kinetic mechanisms reported in the literature. It is found that laminar flame speed varies non-monotonically with addition of water for the carbon monoxide rich mixtures. It first increases with increasing amount of water addition, reaches a maximum value, and then decreases. An integrated reaction path analysis is further conducted to understand the controlling mechanism responsible for the non-monotonic variation in laminar flame speed due to water addition. On the other hand, for higher values of H{sub 2}/CO ratio the laminar flame speed monotonically decreases with increasing water addition. It is shown that the competition between the chemical and thermal effects of water addition leads to the observed response. Furthermore, reaction rate sensitivity analysis as well as binary diffusion coefficient sensitivity analysis are conducted to identify the possible sources of discrepancy between the experimental and predicted values. The sensitivity results indicate that the reaction rate constant of H{sub 2}+OH = H{sub 2}O+H is worth revisiting and refinement of binary diffusion coefficient data of N{sub 2}-H{sub 2}O, N{sub 2}-H{sub 2}, and H{sub 2}-H{sub 2}O pairs can be considered. (author)
NASA Astrophysics Data System (ADS)
Shizgal, Bernie D.; Dridi, Raouf
2010-09-01
A Maple code is provided which is used to compute the matrix elements of the collision operators in the Boltzmann equation for arbitrary differential elastic collision cross section. The present paper describes an efficient method for the calculation of the matrix elements of the collision operators in the Sonine basis set. The method employs the generating functions for these polynomials. The transport properties of gaseous mixtures of atoms and/or ions are generally determined from solutions of the Boltzmann equation. The solution of the Boltzmann equation for the velocity distribution functions requires a representation of the integral collision operators defined by the differential cross sections describing collisions between pairs of particles. Many applications have considered either the simple hard sphere cross section or the cross section corresponding to the inverse fourth power of the inter-particle distance ("Maxwell molecules"). There are a few applications where realistic quantum mechanical cross sections have been used. The basis set of Sonine (or Laguerre) polynomials is the basis set of choice used to represent the distribution functions. The Maple code provided is used to express the matrix elements of the collision operators in terms of a finite sum of the omega integrals of transport theory and defined by the differential cross section. Thus the matrix representations of the collision operators are applicable to arbitrary interaction potentials. Program summaryProgram title: MCBC Catalogue identifier: AEGJ_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEGJ_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 2422 No. of bytes in distributed program, including test data, etc.: 48 653 Distribution format: tar.gz Programming language: Maple
Superconductor precursor mixtures made by precipitation method
Bunker, Bruce C.; Lamppa, Diana L.; Voigt, James A.
1989-01-01
Method and apparatus for preparing highly pure homogeneous precursor powder mixtures for metal oxide superconductive ceramics. The mixes are prepared by instantaneous precipitation from stoichiometric solutions of metal salts such as nitrates at controlled pH's within the 9 to 12 range, by addition of solutions of non-complexing pyrolyzable cations, such as alkyammonium and carbonate ions.
A Four-step Approach for Evaluation of Dose Additivity
A four step approach was developed for evaluating toxicity data on a chemical mixture for consistency with dose addition. Following the concepts in the U.S. EPA mixture guidance (EPA 2000), toxicologic interaction for a defined mixture (all components known) is departure from a c...
Accelerated Hazards Mixture Cure Model
Zhang, Jiajia; Peng, Yingwei
2010-01-01
We propose a new cure model for survival data with a surviving or cure fraction. The new model is a mixture cure model where the covariate effects on the proportion of cure and the distribution of the failure time of uncured patients are separately modeled. Unlike the existing mixture cure models, the new model allows covariate effects on the failure time distribution of uncured patients to be negligible at time zero and to increase as time goes by. Such a model is particularly useful in some cancer treatments when the treat effect increases gradually from zero, and the existing models usually cannot handle this situation properly. We develop a rank based semiparametric estimation method to obtain the maximum likelihood estimates of the parameters in the model. We compare it with existing models and methods via a simulation study, and apply the model to a breast cancer data set. The numerical studies show that the new model provides a useful addition to the cure model literature. PMID:19697127
Predicting microbial toxicity of nonuniform multicomponent mixtures of organic chemicals
Peace, J.; Daniel, D.; Nirmalakhandan, N.; Egemen, E.
1997-04-01
Three schemes proposed in the literature for analyzing joint toxic effects of multicomponent mixtures on fish, namely the additivity index (AI), the mixture toxicity index (MTI), and the similarity parameter ({lambda}) are evaluated in this study for microbial toxicity. A new approach is proposed to establish acceptance limits for the similarity parameter, {lambda}, based on experimental errors and uncertainties. Quantitative structure activity relationship (QSAR) techniques are then used to develop a model to predict the concentrations of components in mixtures that would jointly cause 50% inhibition of microbial respiration. The application of this approach is demonstrated on the experimental toxicity data of six eight-component organic chemical mixtures on microorganisms.
A constitutive theory of reacting electrolyte mixtures
NASA Astrophysics Data System (ADS)
Costa Reis, Martina; Wang, Yongqi; Bono Maurizio Sacchi Bassi, Adalberto
2013-11-01
A constitutive theory of reacting electrolyte mixtures is formulated. The intermolecular interactions among the constituents of the mixture are accounted for through additional freedom degrees to each constituent of the mixture. Balance equations for polar reacting continuum mixtures are accordingly formulated and a proper set of constitutive equations is derived with basis in the Müller-Liu formulation of the second law of thermodynamics. Moreover, the non-equilibrium and equilibrium responses of the reacting mixture are investigated in detail by emphasizing the inner and reactive structures of the medium. From the balance laws and constitutive relations, the effects of molecular structure of constituents upon the fluid flow are studied. It is also demonstrated that the local thermodynamic equilibrium state can be reached without imposing that the set of independent constitutive variables is time independent, neither spatially homogeneous nor null. The resulting constitutive relations presented throughout this work are of relevance to many practical applications, such as swelling of clays, developing of bio and polymeric membranes, and use of electrorheological fluids in industrial processes. The first author acknowledges financial support from National Counsel of Technological and Scientific Development (CNPq) and German Academic Exchange Service (DAAD).
Mixture Models for Distance Sampling Detection Functions
Miller, David L.; Thomas, Len
2015-01-01
We present a new class of models for the detection function in distance sampling surveys of wildlife populations, based on finite mixtures of simple parametric key functions such as the half-normal. The models share many of the features of the widely-used “key function plus series adjustment” (K+A) formulation: they are flexible, produce plausible shapes with a small number of parameters, allow incorporation of covariates in addition to distance and can be fitted using maximum likelihood. One important advantage over the K+A approach is that the mixtures are automatically monotonic non-increasing and non-negative, so constrained optimization is not required to ensure distance sampling assumptions are honoured. We compare the mixture formulation to the K+A approach using simulations to evaluate its applicability in a wide set of challenging situations. We also re-analyze four previously problematic real-world case studies. We find mixtures outperform K+A methods in many cases, particularly spiked line transect data (i.e., where detectability drops rapidly at small distances) and larger sample sizes. We recommend that current standard model selection methods for distance sampling detection functions are extended to include mixture models in the candidate set. PMID:25793744
ERIC Educational Resources Information Center
Henson, James M.; Reise, Steven P.; Kim, Kevin H.
2007-01-01
The accuracy of structural model parameter estimates in latent variable mixture modeling was explored with a 3 (sample size) [times] 3 (exogenous latent mean difference) [times] 3 (endogenous latent mean difference) [times] 3 (correlation between factors) [times] 3 (mixture proportions) factorial design. In addition, the efficacy of several…
[Construction of Three-Dimensional Isobologram for Ternary Pollutant Mixtures].
2015-12-01
Tongji University, Shanghai 200092, China) Isobolographic analysis was widely used in the interaction assessment of binary mixtures. However, how to construct a three-dimensional (3D) isobologram for the assessment of toxicity interaction within ternary mixtures is still not reported up to date. The main purpose of this paper is to develop a 3D isobologram where the relative concentrations of three components are acted as three coordinate axes in 3D space to examine the toxicity interaction within ternary mixtures. Taking six commonly used pesticides in China, including three herbicides (2, 4-D, desmetryne and simetryn) and three insecticides ( dimethoate, imidacloprid and propoxur) as the mixture components, the uniform design ray procedure (UD-Ray) was used to rationally design the concentration composition of various components in the ternary mixtures so that effectively and comprehensively reflected the variety of actual environmental concentrations. The luminescent inhibition toxicities of single pesticides and their ternary mixtures to Vibrio fischeri at various concentration levels were determined by the microplate toxicity analysis. Selecting concentration addition (CA) as the addition reference, 3D isobolograms were constructed to study the toxicity interactions of various ternary mixtures. The results showed that the 3D isobologram could clearly and directly exhibit the toxicity interactions of ternary mixtures, and extend the use of isobolographic analysis into the ternary mixtures.
Maximum likelihood estimation of finite mixture model for economic data
NASA Astrophysics Data System (ADS)
Phoong, Seuk-Yen; Ismail, Mohd Tahir
2014-06-01
Finite mixture model is a mixture model with finite-dimension. This models are provides a natural representation of heterogeneity in a finite number of latent classes. In addition, finite mixture models also known as latent class models or unsupervised learning models. Recently, maximum likelihood estimation fitted finite mixture models has greatly drawn statistician's attention. The main reason is because maximum likelihood estimation is a powerful statistical method which provides consistent findings as the sample sizes increases to infinity. Thus, the application of maximum likelihood estimation is used to fit finite mixture model in the present paper in order to explore the relationship between nonlinear economic data. In this paper, a two-component normal mixture model is fitted by maximum likelihood estimation in order to investigate the relationship among stock market price and rubber price for sampled countries. Results described that there is a negative effect among rubber price and stock market price for Malaysia, Thailand, Philippines and Indonesia.
Nuclear fuel alloys or mixtures and method of making thereof
Mariani, Robert Dominick; Porter, Douglas Lloyd
2016-04-05
Nuclear fuel alloys or mixtures and methods of making nuclear fuel mixtures are provided. Pseudo-binary actinide-M fuel mixtures form alloys and exhibit: body-centered cubic solid phases at low temperatures; high solidus temperatures; and/or minimal or no reaction or inter-diffusion with steel and other cladding materials. Methods described herein through metallurgical and thermodynamics advancements guide the selection of amounts of fuel mixture components by use of phase diagrams. Weight percentages for components of a metallic additive to an actinide fuel are selected in a solid phase region of an isothermal phase diagram taken at a temperature below an upper temperature limit for the resulting fuel mixture in reactor use. Fuel mixtures include uranium-molybdenum-tungsten, uranium-molybdenum-tantalum, molybdenum-titanium-zirconium, and uranium-molybdenum-titanium systems.
Evaluating Whole Chemical Mixtures and Sufficient Similarity
This powerpoint presentation supports apresentation describing dose-response assessment for complex chemical mixtures including deriving reference doses for mixtures evaluating sufficient similarity among chemical mixtures.
A mixture of seven antiandrogens induces reproductive malformations in rats.
To date, regulatory agencies have not considered conducting cumulative risk assessments for mixtures of chemicals with diverse mechanisms of toxicity because it is assumed that the chemicals will act independently and the individual chemical doses are not additive. However, this ...
Toxicological approaches to complex mixtures.
Mauderly, J L
1993-01-01
This paper reviews the role of toxicological studies in understanding the health effects of environmental exposures to mixtures. The approach taken is to review mixtures that have received the greatest emphasis from toxicology; major mixtures research programs; the toxicologist's view of mixtures and approaches to their study; and the complementary roles of toxicological, clinical, and epidemiological studies. Studies of tobacco smoke, engine exhaust, combustion products, and air pollutants comprise most of the past research on mixtures. Because of their great experimental control over subjects, exposures, and endpoints, toxicologists tend to consider a wider range of toxic interactions among mixture components and sequential exposures than is practical for human studies. The three fundamental experimental approaches used by toxicologists are integrative (studying the mixture as a whole), dissective (dissecting a mixture to determine causative constituents), and synthetic (studying interactions between agents in simple combinations). Toxicology provides information on potential hazards, mechanisms by which mixture constituents interact to cause effects, and exposure dose-effect relationships; but extrapolation from laboratory data to quantitative human health risks is problematic. Toxicological, clinical, and epidemiological approaches are complementary but are seldom coordinated. Fostering synergistic interactions among the disciplines in studying the risks from mixtures could be advantageous. PMID:7515806
Toxicological approaches to complex mixtures.
Mauderly, J L
1993-12-01
This paper reviews the role of toxicological studies in understanding the health effects of environmental exposures to mixtures. The approach taken is to review mixtures that have received the greatest emphasis from toxicology; major mixtures research programs; the toxicologist's view of mixtures and approaches to their study; and the complementary roles of toxicological, clinical, and epidemiological studies. Studies of tobacco smoke, engine exhaust, combustion products, and air pollutants comprise most of the past research on mixtures. Because of their great experimental control over subjects, exposures, and endpoints, toxicologists tend to consider a wider range of toxic interactions among mixture components and sequential exposures than is practical for human studies. The three fundamental experimental approaches used by toxicologists are integrative (studying the mixture as a whole), dissective (dissecting a mixture to determine causative constituents), and synthetic (studying interactions between agents in simple combinations). Toxicology provides information on potential hazards, mechanisms by which mixture constituents interact to cause effects, and exposure dose-effect relationships; but extrapolation from laboratory data to quantitative human health risks is problematic. Toxicological, clinical, and epidemiological approaches are complementary but are seldom coordinated. Fostering synergistic interactions among the disciplines in studying the risks from mixtures could be advantageous.
Tang, Janet Y M; Escher, Beate I
2014-06-01
Mixture toxicity studies with herbicides have focused on a few priority components that are most likely to cause environmental impacts, and experimental mixtures were often designed as equipotent mixtures; however, real-world mixtures are made up of chemicals with different modes of toxic action at arbitrary concentration ratios. The toxicological significance of environmentally realistic mixtures has only been scarcely studied. Few studies have simultaneously compared the mixture effect of water samples with designed reference mixtures comprised of the ratios of analytically detected concentrations in toxicity tests. In the present study, the authors address the effect of herbicides and other chemicals on inhibition of photosynthesis and algal growth rate. The authors tested water samples including secondary treated wastewater effluent, recycled water, drinking water, and storm water in the combined algae assay. The detected chemicals were mixed in the concentration ratios detected, and the biological effects of the water samples were compared with the designed mixtures of individual detected chemicals to quantify the fraction of effect caused by unknown chemicals. The results showed that herbicides dominated the algal toxicity in these environmentally realistic mixtures, and the contribution by the non-herbicides was negligible. A 2-stage model, which used concentration addition within the groups of herbicides and non-herbicides followed by the model of independent action to predict the mixture effect of the two groups, could predict the experimental mixture toxicity effectively, but the concentration addition model for herbicides was robust and sufficient for complex mixtures. Therefore, the authors used the bioanalytical equivalency concept to derive effect-based trigger values for algal toxicity for monitoring water quality in recycled and surface water. All water samples tested would be compliant with the proposed trigger values associated with the
Tang, Janet Y M; Escher, Beate I
2014-06-01
Mixture toxicity studies with herbicides have focused on a few priority components that are most likely to cause environmental impacts, and experimental mixtures were often designed as equipotent mixtures; however, real-world mixtures are made up of chemicals with different modes of toxic action at arbitrary concentration ratios. The toxicological significance of environmentally realistic mixtures has only been scarcely studied. Few studies have simultaneously compared the mixture effect of water samples with designed reference mixtures comprised of the ratios of analytically detected concentrations in toxicity tests. In the present study, the authors address the effect of herbicides and other chemicals on inhibition of photosynthesis and algal growth rate. The authors tested water samples including secondary treated wastewater effluent, recycled water, drinking water, and storm water in the combined algae assay. The detected chemicals were mixed in the concentration ratios detected, and the biological effects of the water samples were compared with the designed mixtures of individual detected chemicals to quantify the fraction of effect caused by unknown chemicals. The results showed that herbicides dominated the algal toxicity in these environmentally realistic mixtures, and the contribution by the non-herbicides was negligible. A 2-stage model, which used concentration addition within the groups of herbicides and non-herbicides followed by the model of independent action to predict the mixture effect of the two groups, could predict the experimental mixture toxicity effectively, but the concentration addition model for herbicides was robust and sufficient for complex mixtures. Therefore, the authors used the bioanalytical equivalency concept to derive effect-based trigger values for algal toxicity for monitoring water quality in recycled and surface water. All water samples tested would be compliant with the proposed trigger values associated with the
Abe, M.; Moriyama, N.; Yamamura, M.
1981-02-24
A stabilizer for fuel mixtures of finely divided coal and fuel oil is composed of an active ingredient, a non-ionic surface active agent consisting of a block copolymer represented by the following general formula (I): R/sub 1/O-(C/sub 2/H/sup 4/O)l-(C/sub 3/H/sup 6/O)m-(C/sub 2/H/sup 4/O)n-R/sub 2/ (I) wherein r/sub 1/ and r/sub 2/ stand for a hydrogen atom or an alklyl group having 1 to 6 carbon atoms, the mole number (L+n) of added ethylene oxide is in the range of from 30 to 300, the mole number (M) of added propylene oxide is in the range of from 15 to 80, and the content of ethylene oxide in the whole molecule is 40 to 85% by weight.
Radiation method for determining brine tolerant surfactants in complex mixtures
Schmitt, K. D.
1984-12-11
This invention provides a method for determining the concentration of a brine tolerant sulfonate surfactant in a complex mixture containing, in addition to said brine tolerant sulfonate surfactant, lignosulfonates, crude oil, salts, and water and, optionally, petroleum sulfonates and alcohols, that comprises incorporating into the brine tolerant sulfonate surfactant molecule a small amount of tritium prior to addition to the complex mixture and determining the concentration of the brine tolerant sulfonate surfactant by measuring its radioactivity.
Rutter, P.R.; Veal, C.J.
1984-11-27
Fuel composition comprises 15 to 60% be weight, preferably 40 to 55%, of a friable solid fuel, e.g. coal, a stabilizing additive composition and a fuel oil. The additive comprises the combination of a polymer containing functional groups, e.g., maleinized polybutadiene, and a surfactant. The composition is suitable for use as a liquid fuel for industrial burners.
Sear, R P
1999-06-01
At low temperature, spheres with a very short-ranged attraction exist as a near-close-packed solid coexisting with an almost infinitely dilute gas. We find that the ratio of the interfacial tension between these two phases to the thermal energy diverges as the range of the attraction tends to zero. The large tensions when the interparticle attractions are short ranged may be why globular proteins only crystallize over a narrow range of conditions. PMID:11969672
Lin, Neil Y C; Cheng, Xiang; Cohen, Itai
2014-03-28
Using a novel biaxial confocal rheoscope, we investigate the flow of the shear induced vorticity aligned string phase [X. Cheng et al., Proc. Natl. Acad. Sci. U. S. A., 2011, 109, 63], which has a highly anisotropic microstructure. Using biaxial shear protocols we show that we have excellent control of the string phase anisotropic morphology. We choose a shear protocol that drives the system into the string phase. Subsequently, a biaxial force measurement device is used to determine the suspension rheology along both the flow and vorticity directions. We find no measurable dependence of the suspension stress response along the shear and vorticity directions due to the hydrodynamically induced string morphology. In particular, we find that the suspension's high frequency stress response is nearly identical along the two orthogonal directions. While we do observe an anisotropic stress response at lower shear frequencies associated with shear thinning, we show that this anisotropy is independent of the shear induced string structure. These results suggest that for the range of flows explored, Brownian and hydrodynamic contributions to the stress arising from the anisotropic suspension microstructure are sufficiently weak that they do not significantly contribute to the rheology. Collectively, this study presents a general and powerful approach for using biaxial confocal rheometry to elucidate the relationship between microstructure and rheology in complex fluids driven far-from-equilibrium.
Mixtures of Ultracold Fermions with Unequal Masses
NASA Astrophysics Data System (ADS)
de Melo, Carlos A. R. Sa
2008-05-01
The quantum phases of ultracold fermions with unequal masses are discussed in continuum and lattice models for a wide variety of mixtures which exhibit Feshbach resonances, e.g., mixtures of ^6Li and ^40K. The evolution of superfluidity from the Bardeen-Cooper-Schrieffer (BCS) to the Bose-Einstein condensation (BEC) regime in the continuum is analyzed as a function of scattering parameter, population imbalance and mass anisotropy. In the continuum case, regions corresponding to normal, phase-separated or coexisting uniform-superfluid/excess-fermion phases are identified and the possibility of topological phase transitions is discussed [1]. For optical lattices, the phase diagrams as a function of interaction strength, population imbalance, filling fraction and tunneling parameters are presented [2]. In addition to the characteristic phases of the continuum, a series of insulating phases emerge in the phase diagrams of optical lattices, including a Bose-Mott insulator (BMI), a Fermi-Pauli insulator (FPI), a phase-separated BMI/FPI mixture, and a Bose-Fermi checkerboard (BFC) phase. Lastly, the effects of harmonic traps and the emergence of unusual shell structures are discussed for mixtures of fermions with unequal masses. [1] M. Iskin, and C. A. R. S' a de Melo, Phys. Rev. Lett 97, 100404 (2006); [2] M. Iskin, and C. A. R. S' a de Melo, Phys. Rev. Lett. 99, 080403 (2007).
Continuous Crystallization of Urea-Water Mixture
NASA Astrophysics Data System (ADS)
Hokamura, Taku; Ohkubo, Hidetoshi; Watanabe, Satoshi; Seki, Mitsuo; Murakoshi, Hiromichi
Ice slurries have been used as environmentally-friendly secondary refrigerants. In addition to such ice slurries, aqueous solutions in slurry-state have also been put to practical use at temperatures below 0 oC. Urea-water mixture is a multi-component substance that has a eutectic point. If we can form a two-phase fluid substance by the liquid-solid phases at the eutectic point, it can be used as a fluid latent heat storage material, which will maintain the secondary refrigerant in a heat exchanger at constant temperature. In the present study, we propose a urea-water mixture as a novel functional thermal fluid that can be used as a fluid latent heat material. To demonstrate its feasibility, we first measured the latent heat and density of a urea-water mixture, and then used a counter-flow double tube heat exchanger to produce a liquid-solid two-phase flow of the urea-water mixture. This work demonstrates that it is possible to make a fluid latent heat storage material continuously from an aqueous solution at the eutectic point by flowing it through a double tube heat exchanger equipped with a stirrer.
Mixtures with relatives and linked markers.
Dørum, Guro; Kling, Daniel; Tillmar, Andreas; Vigeland, Magnus Dehli; Egeland, Thore
2016-05-01
Mixture DNA profiles commonly appear in forensic genetics, and a large number of statistical methods and software are available for such cases. However, most of the literature concerns mixtures where the contributors are assumed unrelated and the genetic markers are unlinked. In this paper, we consider mixtures of linked markers and related contributors. If no relationships are involved, linkage can be ignored. While unlinked markers can be treated independently, linkage introduces dependencies. The use of linked markers presents statistical and computational challenges, but may also lead to a considerable increase in power since the number of markers available is much larger if we do not require the markers to be unlinked. In addition, some cases that cannot be solved with an unlimited number of unlinked autosomal markers can be solved with linked markers. We focus on two special cases of linked markers: pairs of linked autosomal markers and X-chromosomal markers. A framework is presented for calculation of likelihood ratios for mixtures with general relationships and with linkage between any number of markers. Finally, we explore the effect of linkage disequilibrium, also called allelic association, on the likelihood ratio.
Thermophysical Properties of Hydrocarbon Mixtures
National Institute of Standards and Technology Data Gateway
SRD 4 NIST Thermophysical Properties of Hydrocarbon Mixtures (PC database for purchase) Interactive computer program for predicting thermodynamic and transport properties of pure fluids and fluid mixtures containing up to 20 components. The components are selected from a database of 196 components, mostly hydrocarbons.
COMPLEX MIXTURES AND GROUNDWATER QUALITY
Experience has shown that many soil and ground-water contamination problems involve complex mixtures of chemicals. his manuscript identifies and discusses, in a generic sense, some of the important processes which must be considered when dealing with complex mixtures in the subsu...
Latent classiness and other mixtures.
Neale, Michael C
2014-05-01
The aim of this article is to laud Lindon Eaves' role in the development of mixture modeling in genetic studies. The specification of models for mixture distributions was very much in its infancy when Professor Eaves implemented it in his own FORTRAN programs, and extended it to data collected from relatives such as twins. It was his collaboration with the author of this article which led to the first implementation of mixture distribution modeling in a general-purpose structural equation modeling program, Mx, resulting in a 1996 article on linkage analysis in Behavior Genetics. Today, the popularity of these methods continues to grow, encompassing methods for genetic association, latent class analysis, growth curve mixture modeling, factor mixture modeling, regime switching, marginal maximum likelihood, genotype by environment interaction, variance component twin modeling in the absence of zygosity information, and many others. This primarily historical article concludes with some consideration of some possible future developments. PMID:24477932
Superfluid and Insulating Phases of Fermion Mixtures in Optical Lattices
NASA Astrophysics Data System (ADS)
Iskin, M.; de Melo, C. A. R. Sá
2007-08-01
The ground state phase diagram of fermion mixtures in optical lattices is analyzed as a function of interaction strength, fermion filling factor, and tunneling parameters. In addition to standard superfluid, phase-separated or coexisting superfluid excess-fermion phases found in homogeneous or harmonically trapped systems, fermions in optical lattices have several insulating phases, including a molecular Bose-Mott insulator (BMI), a Fermi-Pauli (band) insulator (FPI), a phase-separated BMI-FPI mixture or a Bose-Fermi checkerboard (BFC). The molecular BMI phase is the fermion mixture counterpart of the atomic BMI found in atomic Bose systems, the BFC or BMI-FPI phases exist in Bose-Fermi mixtures, and lastly the FPI phase is particular to the Fermi nature of the constituent atoms of the mixture.
Encoding of mixtures in a simple olfactory system
Shen, Kai; Tootoonian, Sina; Laurent, Gilles
2013-01-01
SUMMARY Natural odors are usually mixtures; yet humans and animals can experience them as unitary percepts. Olfaction also enables stimulus categorization and generalization. We addressed how these computations are performed with the responses of 168 locust antennal lobe projection neurons (PNs) to varying mixtures of two monomolecular odors, and 174 PNs and 209 mushroom body Kenyon cells (KCs) to mixtures of up to 8 monomolecular odors. Single PN responses showed strong hypo-additivity, and population trajectories clustered by odor concentration and mixture similarity. KC responses were much sparser on average than with PNs and often signaled the presence of single components in mixtures. Linear classifiers could read out the responses of both populations in single time bins to perform odor identification, categorization, and generalization. Our results suggest that odor representations in the mushroom body may result from competing optimization constraints to facilitate memorization (sparseness) while enabling identification, classification and generalization. PMID:24210905
Influence of hydroxypropylcyclodextrins on the toxicity of mixtures.
Lin, Zhifen; Kong, Deyang; Zhong, Ping; Yin, Kedong; Dong, Lihua
2005-03-01
We studied the influence of hydroxypropylcyclodextrins (HPCDs) on the toxicity of some mixtures. Using the Photobacterium phosphoreum toxicity test, the joint toxicological effect for Mixture I (containing p-nitrobenzaldehyde and 1-nitronaphthalene) and Mixture II (containing p-nitrobenzaldehyde and malononitrile) were determined in water and in aqueous solutions of HPCDs. The results indicate that, although the toxicological joint effect for Mixture I (simple addition) differs from that of Mixture II (synergism), alpha- and beta-HPCD can significantly reduce the toxicity of the test compounds, whereas gamma-HPCD has only a slight effect. Explanations for these observations are given that invoke the molecular structure of the individual chemicals as well as the structures of HPCDs. This provides information to assist the application of HPCDs in remediation of environmental pollution.
Schoenfuss, Heiko L.; Furlong, Edward T.; Phillips, Patrick J.; Scott, Tia-Marie; Kolpin, Dana W.; Cetkovic-Cvrlje, Marina; Lesteberg, Kelsey E.; Rearick, Daniel C.
2016-01-01
Pharmaceuticals are present in low concentrations (<100 ng/L) in most municipal wastewater effluents but may be elevated locally because of factors such as input from pharmaceutical formulation facilities. Using existing concentration data, the authors assessed pharmaceuticals in laboratory exposures of fathead minnows (Pimephales promelas) and added environmental complexity through effluent exposures. In the laboratory, larval and mature minnows were exposed to a simple opioid mixture (hydrocodone, methadone, and oxycodone), an opioid agonist (tramadol), a muscle relaxant (methocarbamol), a simple antidepressant mixture (fluoxetine, paroxetine, venlafaxine), a sleep aid (temazepam), or a complex mixture of all compounds. Larval minnow response to effluent exposure was not consistent. The 2010 exposures resulted in shorter exposed minnow larvae, whereas the larvae exposed in 2012 exhibited altered escape behavior. Mature minnows exhibited altered hepatosomatic indices, with the strongest effects in females and in mixture exposures. In addition, laboratory-exposed, mature male minnows exposed to all pharmaceuticals (except the selective serotonin reuptake inhibitor mixture) defended nest sites less rigorously than fish in the control group. Tramadol or antidepressant mixture exposure resulted in increased splenic T lymphocytes. Only male minnows exposed to whole effluent responded with increased plasma vitellogenin concentrations. Female minnows exposed to pharmaceuticals (except the opioid mixture) had larger livers, likely as a compensatory result of greater prominence of vacuoles in liver hepatocytes. The observed alteration of apical endpoints central to sustaining fish populations confirms that effluents containing waste streams from pharmaceutical formulation facilities can adversely impact fish populations but that the effects may not be temporally consistent. The present study highlights the importance of including diverse biological endpoints spanning
Schoenfuss, Heiko L; Furlong, Edward T; Phillips, Pat J; Scott, Tia-Marie; Kolpin, Dana W; Cetkovic-Cvrlje, Marina; Lesteberg, Kelsey E; Rearick, Daniel C
2016-04-01
Pharmaceuticals are present in low concentrations (<100 ng/L) in most municipal wastewater effluents but may be elevated locally because of factors such as input from pharmaceutical formulation facilities. Using existing concentration data, the authors assessed pharmaceuticals in laboratory exposures of fathead minnows (Pimephales promelas) and added environmental complexity through effluent exposures. In the laboratory, larval and mature minnows were exposed to a simple opioid mixture (hydrocodone, methadone, and oxycodone), an opioid agonist (tramadol), a muscle relaxant (methocarbamol), a simple antidepressant mixture (fluoxetine, paroxetine, venlafaxine), a sleep aid (temazepam), or a complex mixture of all compounds. Larval minnow response to effluent exposure was not consistent. The 2010 exposures resulted in shorter exposed minnow larvae, whereas the larvae exposed in 2012 exhibited altered escape behavior. Mature minnows exhibited altered hepatosomatic indices, with the strongest effects in females and in mixture exposures. In addition, laboratory-exposed, mature male minnows exposed to all pharmaceuticals (except the selective serotonin reuptake inhibitor mixture) defended nest sites less rigorously than fish in the control group. Tramadol or antidepressant mixture exposure resulted in increased splenic T lymphocytes. Only male minnows exposed to whole effluent responded with increased plasma vitellogenin concentrations. Female minnows exposed to pharmaceuticals (except the opioid mixture) had larger livers, likely as a compensatory result of greater prominence of vacuoles in liver hepatocytes. The observed alteration of apical endpoints central to sustaining fish populations confirms that effluents containing waste streams from pharmaceutical formulation facilities can adversely impact fish populations but that the effects may not be temporally consistent. The present study highlights the importance of including diverse biological endpoints spanning
Schoenfuss, Heiko L; Furlong, Edward T; Phillips, Pat J; Scott, Tia-Marie; Kolpin, Dana W; Cetkovic-Cvrlje, Marina; Lesteberg, Kelsey E; Rearick, Daniel C
2016-04-01
Pharmaceuticals are present in low concentrations (<100 ng/L) in most municipal wastewater effluents but may be elevated locally because of factors such as input from pharmaceutical formulation facilities. Using existing concentration data, the authors assessed pharmaceuticals in laboratory exposures of fathead minnows (Pimephales promelas) and added environmental complexity through effluent exposures. In the laboratory, larval and mature minnows were exposed to a simple opioid mixture (hydrocodone, methadone, and oxycodone), an opioid agonist (tramadol), a muscle relaxant (methocarbamol), a simple antidepressant mixture (fluoxetine, paroxetine, venlafaxine), a sleep aid (temazepam), or a complex mixture of all compounds. Larval minnow response to effluent exposure was not consistent. The 2010 exposures resulted in shorter exposed minnow larvae, whereas the larvae exposed in 2012 exhibited altered escape behavior. Mature minnows exhibited altered hepatosomatic indices, with the strongest effects in females and in mixture exposures. In addition, laboratory-exposed, mature male minnows exposed to all pharmaceuticals (except the selective serotonin reuptake inhibitor mixture) defended nest sites less rigorously than fish in the control group. Tramadol or antidepressant mixture exposure resulted in increased splenic T lymphocytes. Only male minnows exposed to whole effluent responded with increased plasma vitellogenin concentrations. Female minnows exposed to pharmaceuticals (except the opioid mixture) had larger livers, likely as a compensatory result of greater prominence of vacuoles in liver hepatocytes. The observed alteration of apical endpoints central to sustaining fish populations confirms that effluents containing waste streams from pharmaceutical formulation facilities can adversely impact fish populations but that the effects may not be temporally consistent. The present study highlights the importance of including diverse biological endpoints spanning
A structural investigation of ionic liquid mixtures.
Matthews, Richard P; Villar-Garcia, Ignacio J; Weber, Cameron C; Griffith, Jeraime; Cameron, Fiona; Hallett, Jason P; Hunt, Patricia A; Welton, Tom
2016-03-28
The structures of mixtures of ionic liquids (ILs) featuring a common 1-butyl-3-methylimidazolium ([C4C1im](+)) cation but different anions have been investigated both experimentally and computationally. (1)H and (13)C NMR of the ILs and their mixtures has been performed both on the undiluted liquids and those diluted by CD2Cl2. These experiments have been complemented by quantum chemical density functional theory calculations and molecular dynamics simulations. These techniques have identified the formation of preferential interactions between H(2) of the imidazolium cation and the most strongly hydrogen bond (H-bond) accepting anion. In addition, a preference for the more weakly H-bond accepting anion to interact above the imidazolium ring through anion-π(+) interactions has been identified. The modelling of these data has identified that the magnitude of these preferences are small, of the order of only a few kJ mol(-1), for all IL mixtures. No clustering of the anions around a specific cation could be observed, indicating that these interactions arise from the reorientation of the cation within a randomly assigned network of anions. π(+)-π(+) stacking of the imidazolium cations was also studied and found to be promoted by ILs with a strong H-bond accepting anion. Stacking interactions are easily disrupted by the introduction of small proportions (<50 mol%) of a weakly coordinating anion due to their propensity to form anion-π(+) interactions. These results suggest that the formation of IL mixtures with different anions leads to subtle structural changes of much lower energy than the Coulombic ordering of ions, accounting for why most IL mixtures exhibit ideal, or nearly ideal, behaviour. PMID:26947103
A structural investigation of ionic liquid mixtures.
Matthews, Richard P; Villar-Garcia, Ignacio J; Weber, Cameron C; Griffith, Jeraime; Cameron, Fiona; Hallett, Jason P; Hunt, Patricia A; Welton, Tom
2016-03-28
The structures of mixtures of ionic liquids (ILs) featuring a common 1-butyl-3-methylimidazolium ([C4C1im](+)) cation but different anions have been investigated both experimentally and computationally. (1)H and (13)C NMR of the ILs and their mixtures has been performed both on the undiluted liquids and those diluted by CD2Cl2. These experiments have been complemented by quantum chemical density functional theory calculations and molecular dynamics simulations. These techniques have identified the formation of preferential interactions between H(2) of the imidazolium cation and the most strongly hydrogen bond (H-bond) accepting anion. In addition, a preference for the more weakly H-bond accepting anion to interact above the imidazolium ring through anion-π(+) interactions has been identified. The modelling of these data has identified that the magnitude of these preferences are small, of the order of only a few kJ mol(-1), for all IL mixtures. No clustering of the anions around a specific cation could be observed, indicating that these interactions arise from the reorientation of the cation within a randomly assigned network of anions. π(+)-π(+) stacking of the imidazolium cations was also studied and found to be promoted by ILs with a strong H-bond accepting anion. Stacking interactions are easily disrupted by the introduction of small proportions (<50 mol%) of a weakly coordinating anion due to their propensity to form anion-π(+) interactions. These results suggest that the formation of IL mixtures with different anions leads to subtle structural changes of much lower energy than the Coulombic ordering of ions, accounting for why most IL mixtures exhibit ideal, or nearly ideal, behaviour.
Acute toxicity to goldfish of mixtures of chloramines, copper, and linear alkylate sulfonate
Tsai, C.F.; McKee, J.A.
1980-01-01
The toxicity to goldfish (Carassius auratus) of mixtures of chloramines, copper, and linear alkylate sulfonate (LAS) was studied by continuous-flow toxicity tests during an exposure period of 96 hours. The individual toxicities of these three chemicals are either additive or synergistic in mixtures, depending on the rate of toxic action of the individual chemical, the toxicity ratio of the chemicals in the mixtures, and the concentration of the mixtures.
Phyu, Y L; Palmer, C G; Warne, M St J; Hose, G C; Chapman, J C; Lim, R P
2011-11-01
Pesticides predominantly occur in aquatic ecosystems as mixtures of varying complexity, yet relatively few studies have examined the toxicity of pesticide mixtures. Atrazine, chlorothalonil and permethrin are widely used pesticides that have different modes of action. This study examined the chronic toxicities (7-d reproductive impairment) of these pesticides in binary and ternary mixtures to the freshwater cladoceran Ceriodaphnia cf. dubia. The toxicity of the mixtures was compared to that predicted by the independent action (IA) model for mixtures, as this is the most appropriate model for chemicals with different modes of action. Following this they were compared to the toxicity predicted by the concentration addition (CA) model for mixtures. According to the IA model, the toxicity of the chlorothalonil plus atrazine mixture conformed to antagonism, while that of chlorothalonil and permethrin conformed to synergism. The toxicity of the atrazine and permethrin mixture as well as the ternary mixture conformed to IA implying there was either no interaction between the components of these mixtures and/or in the case of the ternary mixture the interactions cancelled each other out to result in IA. The synergistic and antagonistic mixtures deviated from IA by factors greater than 3 and less than 2.5, respectively. When the toxicity of the mixtures was compared to the predictions of the CA model, the binary mixture of chlorothalonil plus atrazine, permethrin plus atrazine and the ternary mixture all conformed to antagonism, while the binary mixture of chlorothalonil plus permethrin conformed to CA. Using the CA model provided estimates of mixture toxicity that did not markedly underestimate the measured toxicity, unlike the IA model, and therefore the CA model is the most suitable to use in ecological risk assessments of these pesticides.
Hierarchical similarity transformations between Gaussian mixtures.
Rigas, George; Nikou, Christophoros; Goletsis, Yorgos; Fotiadis, Dimitrios I
2013-11-01
In this paper, we propose a method to estimate the density of a data space represented by a geometric transformation of an initial Gaussian mixture model. The geometric transformation is hierarchical, and it is decomposed into two steps. At first, the initial model is assumed to undergo a global similarity transformation modeled by translation, rotation, and scaling of the model components. Then, to increase the degrees of freedom of the model and allow it to capture fine data structures, each individual mixture component may be transformed by another, local similarity transformation, whose parameters are distinct for each component of the mixture. In addition, to constrain the order of magnitude of the local transformation (LT) with respect to the global transformation (GT), zero-mean Gaussian priors are imposed onto the local parameters. The estimation of both GT and LT parameters is obtained through the expectation maximization framework. Experiments on artificial data are conducted to evaluate the proposed model, with varying data dimensionality, number of model components, and transformation parameters. In addition, the method is evaluated using real data from a speech recognition task. The obtained results show a high model accuracy and demonstrate the potential application of the proposed method to similar classification problems. PMID:24808615
Constraint optimized weight adaptation for Gaussian mixture reduction
NASA Astrophysics Data System (ADS)
Chen, H. D.; Chang, K. C.; Smith, Chris
2010-04-01
Gaussian mixture model (GMM) has been used in many applications for dynamic state estimation such as target tracking or distributed fusion. However, the number of components in the mixture distribution tends to grow rapidly when multiple GMMs are combined. In order to keep the computational complexity bounded, it is necessary to approximate a Gaussian mixture by one with reduced number of components. Gaussian mixture reduction is traditionally conducted by recursively selecting two components that appear to be most similar to each other and merging them. Different definitions on similarity measure have been used in literature. For the case of one-dimensional Gaussian mixtures, Kmeans algorithms and some variations are recently proposed to cluster Gaussian mixture components in groups, use a center component to represent all in each group, readjust parameters in the center components, and finally perform weight optimization. In this paper, we focus on multi-dimensional Gaussian mixture models. With a variety of reduction algorithms and possible combinations, we developed a hybrid algorithm with constraint optimized weight adaptation to minimize the integrated squared error (ISE). In additions, with extensive simulations, we showed that the proposed algorithm provides an efficient and effective Gaussian mixture reduction performance in various random scenarios.
Patch testing with perfume mixture.
Veien, N K; Hattel, T; Justesen, O; Nørholm, A
1982-01-01
145 of 1116 patients patch tested with the standard series of the International Contact Dermatitis Research Group, including the recently introduced perfume mixture, had positive patch test reactions to at least one of the traditional screening agents for fragrance allergy or to the perfume mixture. In 96 of 145 patients the positive patch tests could be explained as being related to fragrance allergy. The perfume mixture was considered a useful screening agent for fragrance allergy. However, the results indicate that it is still necessary to employ several screening agents to detect this type of hypersensitivity.
Viscosity of Mixtures of α-Tocopherol Acetate + Mesitylene
NASA Astrophysics Data System (ADS)
Szwajczaka, Elżbieta; Stagraczyński, Ryszard; Herba, Henryk; Świergielb, Jolanta; Jadżyn, Jan
2009-08-01
The paper presents results of the share viscosity measurements performed as a function of temperature and concentration for mixtures of α-tocopherol acetate (vitamine E acetate) and mesitylene, two liquids of essentially different viscosity (four order of magnitude difference at 280 K). The viscosity/ temperature dependence for pure α-tocopherol acetate as well as for the mixtures studied can be well described with the Vogel-Fulcher-Tammann equation. The viscosities of the mixtures exhibit a strong negative deviation from the rule of additive dependence on concentration and for increasing temperature the maximum value of the deviation shows an exponential decreasing.
Supersonic combustion of a silane/methane mixture
NASA Technical Reports Server (NTRS)
Northam, G. B.; Mclain, A. G.
1985-01-01
A test program was conducted to evaluate the ignition and combustion characteristics of a 20 volume percent silane/methane mixture using a model scramjet combustor with Mach 2 combustor entrance conditions. The test gas total temperature was varied from 1200 to 3900 R. The mixture autoignited at a total temperature of 1650 R. This autoignition temperature can be contrasted with 2330 R for hydrogen and 1350 R for a 20 percent silane/hydrogen mixture in similar hardware. Methane without the silane additive did not autoignite in this configuration at temperatures as high as 3900 R.
Endocrine activity of mycotoxins and mycotoxin mixtures.
Demaegdt, Heidi; Daminet, Britt; Evrard, Annick; Scippo, Marie-Louise; Muller, Marc; Pussemier, Luc; Callebaut, Alfons; Vandermeiren, Karine
2016-10-01
Reporter gene assays incorporating nuclear receptors (estrogen, androgen, thyroid β and PPARγ2) have been implemented to assess the endocrine activity of 13 mycotoxins and their mixtures. As expected, zearalenone and its metabolites α-zearalenol and β- zearalenol turned out to have the strongest estrogenic potency (EC50 8,7 10-10 ± 0,8; 3,1 10-11 ± 0,5 and 1,3 10-8 ± 0,3 M respectively). The metabolite of deoxynivalenol, 3-acetyl-deoxynivalenol also had estrogenic activity (EC50 3,8 10-7 ± 1,1 M). Furthermore, most of the mycotoxins (and their mixtures) showed anti-androgenic effects (15-acetyldeoxynivalenol, 3-acetyl-deoxynivalenol and α-zearalenol with potencies within one order of magnitude of that of the reference compound flutamide). In particular, deoxynivalenol and 15-acetyl-deoxynivalenol acted as antagonists for the PPARy2 receptor. When testing mixtures of mycotoxins on the same cell systems, we showed that most of the mixtures reacted as predicted by the concentration addition (CA) theory. Generally, the CA was within the 95% confidence interval of the observed ones, only minor deviations were detected. Although these reporter gene tests cannot be directly extrapolated in vivo, they can be the basis for further research. Especially the additive effects of ZEN and its metabolites are of importance and could have repercussions in vivo. PMID:27481073
Endocrine activity of mycotoxins and mycotoxin mixtures.
Demaegdt, Heidi; Daminet, Britt; Evrard, Annick; Scippo, Marie-Louise; Muller, Marc; Pussemier, Luc; Callebaut, Alfons; Vandermeiren, Karine
2016-10-01
Reporter gene assays incorporating nuclear receptors (estrogen, androgen, thyroid β and PPARγ2) have been implemented to assess the endocrine activity of 13 mycotoxins and their mixtures. As expected, zearalenone and its metabolites α-zearalenol and β- zearalenol turned out to have the strongest estrogenic potency (EC50 8,7 10-10 ± 0,8; 3,1 10-11 ± 0,5 and 1,3 10-8 ± 0,3 M respectively). The metabolite of deoxynivalenol, 3-acetyl-deoxynivalenol also had estrogenic activity (EC50 3,8 10-7 ± 1,1 M). Furthermore, most of the mycotoxins (and their mixtures) showed anti-androgenic effects (15-acetyldeoxynivalenol, 3-acetyl-deoxynivalenol and α-zearalenol with potencies within one order of magnitude of that of the reference compound flutamide). In particular, deoxynivalenol and 15-acetyl-deoxynivalenol acted as antagonists for the PPARy2 receptor. When testing mixtures of mycotoxins on the same cell systems, we showed that most of the mixtures reacted as predicted by the concentration addition (CA) theory. Generally, the CA was within the 95% confidence interval of the observed ones, only minor deviations were detected. Although these reporter gene tests cannot be directly extrapolated in vivo, they can be the basis for further research. Especially the additive effects of ZEN and its metabolites are of importance and could have repercussions in vivo.
Evolution of weak disturbances in inert binary mixtures
NASA Technical Reports Server (NTRS)
Rasmussen, M. L.
1977-01-01
The evolution of weak disturbances in inert binary mixtures is determined for the one-dimensional piston problem. The interaction of the dissipative and nonlinear mechanisms is described by Burgers' equation. The binary mixture diffusion mechanisms enter as an additive term in an effective diffusivity. Results for the impulsive motion of a piston moving into an ambient medium and the sinusoidally oscillating piston are used to illustrate the results and elucidate the incorrect behavior pertaining to the associated linear theory.
Experimental Study of Additives on Viscosity biodiesel at Low Temperature
NASA Astrophysics Data System (ADS)
Fajar, Berkah; Sukarno
2015-09-01
An experimental investigation was performed to find out the viscosity of additive and biodiesel fuel mixture in the temperature range from 283 K to 318 K. Solutions to reduce the viscosity of biodiesel is to add the biodiesel with some additive. The viscosity was measured using a Brookfield Rheometer DV-II. The additives were the generic additive (Diethyl Ether/DDE) and the commercial additive Viscoplex 10-330 CFI. Each biodiesel blends had a concentration of the mixture: 0.0; 0.25; 0.5; 0.75; 1.0; and 1.25% vol. Temperature of biodiesel was controlled from 40°C to 0°C. The viscosity of biodiesel and additive mixture at a constant temperature can be approximated by a polynomial equation and at a constant concentration by exponential equation. The optimum mixture is at 0.75% for diethyl ether and 0.5% for viscoplex.
TEA laser gas mixture optimization
NASA Astrophysics Data System (ADS)
Lipchak, W. Michael; Luck, Clarence F.
1982-11-01
The topographical plot of an optimized parameter, such as pulse energy or peak power, on the gas mixture plane is presented as a useful aid in realizing optimum mixtures of helium, carbon dioxide, and nitrogen, for operation of CO2 TEA lasers. A method for generating such a plot is discussed and an example is shown. The potential benefits of this graphical technique are also discussed.
TEA laser gas mixture optimization
Lipchak, W.M.; Luck, C.F.
1982-11-01
The topographical plot of an optimized parameter, such as pulse energy or peak power, on the gas mixture plane is presented as a useful aid in realizing optimum mixtures of helium, carbon dioxide, and nitrogen, for operation of CO/sub 2/ TEA lasers. A method for generating such a plot is discussed and an example is shown. The potential benefits of this graphical technique are also discussed.
Ionization coefficients in gas mixtures
NASA Astrophysics Data System (ADS)
Marić, D.; Šašić, O.; Jovanović, J.; Radmilović-Rađenović, M.; Petrović, Z. Lj.
2007-03-01
We have tested the application of the common E/N ( E—electric field, N—gas number density) or Wieland approximation [Van Brunt, R.J., 1987. Common parametrizations of electron transport, collision cross section, and dielectric strength data for binary gas mixtures. J. Appl. Phys. 61 (5), 1773-1787.] and the common mean energy (CME) combination of the data for pure gases to obtain ionization coefficients for mixtures. Test calculations were made for Ar-CH4, Ar-N2, He-Xe and CH4-N2 mixtures. Standard combination procedure gives poor results in general, due to the fact that the electron energy distribution is considerably different in mixtures and in individual gases at the same values of E/N. The CME method may be used for mixtures of gases with ionization coefficients that do not differ by more than two orders of magnitude which is better than any other technique that was proposed [Marić, D., Radmilović-Rađenović, M., Petrović, Z.Lj., 2005. On parametrization and mixture laws for electron ionization coefficients. Eur. Phys. J. D 35, 313-321.].
Anthracene + Pyrene Solid Mixtures: Eutectic and Azeotropic Character
Rice, James W.; Fu, Jinxia; Suuberg, Eric M.
2010-01-01
To better characterize the thermodynamic behavior of a binary polycyclic aromatic hydrocarbon mixture, thermochemical and vapor pressure experiments were used to examine the phase behavior of the anthracene (1) + pyrene (2) system. A solid-liquid phase diagram was mapped for the mixture. A eutectic point occurs at 404 K at x1 = 0.22. A model based on eutectic formation can be used to predict the enthalpy of fusion associated with the mixture. For mixtures that contain x1 < 0.90, the enthalpy of fusion is near that of pure pyrene. This and X-ray diffraction results indicate that mixtures of anthracene and pyrene have pyrene-like crystal structures and energetics until the composition nears that of pure anthracene. Solid-vapor equilibrium studies show that mixtures of anthracene and pyrene form solid azeotropes at x1 of 0.03 and 0.14. Additionally, mixtures at x1 = 0.99 sublime at the vapor pressure of pure anthracene, suggesting that anthracene behavior is not significantly influenced by x2 = 0.01 in the crystal structure. PMID:21116474
Anthracene + Pyrene Solid Mixtures: Eutectic and Azeotropic Character.
Rice, James W; Fu, Jinxia; Suuberg, Eric M
2010-09-01
To better characterize the thermodynamic behavior of a binary polycyclic aromatic hydrocarbon mixture, thermochemical and vapor pressure experiments were used to examine the phase behavior of the anthracene (1) + pyrene (2) system. A solid-liquid phase diagram was mapped for the mixture. A eutectic point occurs at 404 K at x(1) = 0.22. A model based on eutectic formation can be used to predict the enthalpy of fusion associated with the mixture. For mixtures that contain x(1) < 0.90, the enthalpy of fusion is near that of pure pyrene. This and X-ray diffraction results indicate that mixtures of anthracene and pyrene have pyrene-like crystal structures and energetics until the composition nears that of pure anthracene. Solid-vapor equilibrium studies show that mixtures of anthracene and pyrene form solid azeotropes at x(1) of 0.03 and 0.14. Additionally, mixtures at x(1) = 0.99 sublime at the vapor pressure of pure anthracene, suggesting that anthracene behavior is not significantly influenced by x(2) = 0.01 in the crystal structure.
Reflectance properties of spinel-plagioclase mixtures
NASA Astrophysics Data System (ADS)
Cheek, L.; Jackson, C.; Dhingra, D.; Pieters, C. M.; Prissel, T. C.; Williams, K. B.
2012-12-01
Near-infrared spectra displaying the diagnostic properties of Mg-spinel have recently been reported in several lunar craters based on Moon Mineralogy Mapper (M3) data [1-5]. These spectra lack evidence for olivine or pyroxene, suggesting that they represent a spinel-plagioclase lithology [1]. Current hypotheses [6, 7] suggest that this lithology formed by interactions of a mafic or ultramafic liquid with an anorthositic country rock, but the proportions of spinel and plagioclase are unknown. The aim of this work is to constrain the modal abundances of spinel and plagioclase in the observed lithology using laboratory reflectance spectroscopy of particulate mixtures. Reflectance spectra of Mg-spinel display a strong absorption at ~2000 nm due to Fe2+ in a tetrahedral site [e.g., 8]. At higher FeO contents, > ~5 wt%, an octahedral absorption near 1000 nm is also apparent [9]. Plagioclase often displays a broad absorption centered near 1250 nm due to trace amounts (0.1 wt%) of Fe2+ in the Ca2+ site. Previous studies have noted that plagioclase must be present in extremely high abundances (~85 vol%) in order for the 1250 nm absorption to be apparent in mixtures with olivine and pyroxene [10, 11]. Recent nonlinear modeling has suggested that at least 50% plagioclase is necessary for the 1250 nm absorption to be apparent in a calculated mixture with spinel [12]. Our approach involves making mineral mixtures of spinel and plagioclase particulate samples and measuring near-infrared spectra of the bulk material. For the plagioclase endmember, we use terrestrial gem quality labradorite with ~0.3 wt% FeO. The spinel endmember was produced experimentally at Brown University (1500 C; fO2~ IW; sintered 72 hrs), and contains 5 wt% FeO. Preliminary results show that spectra of a 90% plagioclase - 10% spinel mixture only display the spectral properties of the spinel component; the 1250 nm absorption is not apparent. Importantly, the addition of 90% plagioclase does not significantly
Combined toxicity of heavy metal mixtures in liver cells.
Lin, Xialu; Gu, Yuanliang; Zhou, Qi; Mao, Guochuan; Zou, Baobo; Zhao, Jinshun
2016-09-01
With rapid industrialization, China is now facing great challenges in heavy metal contamination in the environment. Human exposure to heavy metals through air, water and food commonly involves a mixture consisting of multiple heavy metals. In this study, eight common heavy metals (Pb, Cd, Hg, Cu, Zn, Mn, Cr, Ni) that cause environmental contamination were selected to investigate the combined toxicity of different heavy metal mixtures in HL7702 cells. Toxicity (24 h LC50 ) of each individual metal on the cells ranked Hg > Cr = Cd > Cu > Zn > Ni > Mn > Pb; toxicity of the different mixtures ranked: M5 > M3PbHgCd > M5+Mn > M5+Cu > M2CdNi > M4A > M8-Mn > M8 > M5+Zn > M4B > M8-Cr > M8-Zn > M8-Cu > M8-Pb > M8-Cd > M8-Hg > M8-Ni > M3PbHgNi > M3CuZnMn. The cytotoxicity data of individual metals were successfully used to build the additive models of two- to eight-component metal mixtures. The comparison between additive model and combination model or partly additive model was useful to evaluate the combined effects in mixture. Synergistic, antagonistic or additive effects of the toxicity were observed in different mixtures. These results suggest that the combined effects should be considered in the risk assessment of heavy metal co-exposure, and more comprehensive investigations on the combined effects of different heavy metal mixtures are needed in the future. Copyright © 2016 John Wiley & Sons, Ltd.
Forced convection heat transfer to air/water vapor mixtures
NASA Technical Reports Server (NTRS)
Richards, D. R.; Florschuetz, L. W.
1986-01-01
Heat transfer coefficients were measured using both dry air and air/water vapor mixtures in the same forced convection cooling test rig (jet array impingement configurations) with mass ratios of water vapor to air up to 0.23. The primary objective was to verify by direct experiment that selected existing methods for evaluation of viscosity and thermal conductivity of air/water vapor mixtures could be used with confidence to predict heat transfer coefficients for such mixtures using as a basis heat transfer data for dry air only. The property evaluation methods deemed most appropriate require as a basis a measured property value at one mixture composition in addition to the property values for the pure components.
Bayesian Kernel Mixtures for Counts
Canale, Antonio; Dunson, David B.
2011-01-01
Although Bayesian nonparametric mixture models for continuous data are well developed, there is a limited literature on related approaches for count data. A common strategy is to use a mixture of Poissons, which unfortunately is quite restrictive in not accounting for distributions having variance less than the mean. Other approaches include mixing multinomials, which requires finite support, and using a Dirichlet process prior with a Poisson base measure, which does not allow smooth deviations from the Poisson. As a broad class of alternative models, we propose to use nonparametric mixtures of rounded continuous kernels. An efficient Gibbs sampler is developed for posterior computation, and a simulation study is performed to assess performance. Focusing on the rounded Gaussian case, we generalize the modeling framework to account for multivariate count data, joint modeling with continuous and categorical variables, and other complications. The methods are illustrated through applications to a developmental toxicity study and marketing data. This article has supplementary material online. PMID:22523437
Bayesian Kernel Mixtures for Counts.
Canale, Antonio; Dunson, David B
2011-12-01
Although Bayesian nonparametric mixture models for continuous data are well developed, there is a limited literature on related approaches for count data. A common strategy is to use a mixture of Poissons, which unfortunately is quite restrictive in not accounting for distributions having variance less than the mean. Other approaches include mixing multinomials, which requires finite support, and using a Dirichlet process prior with a Poisson base measure, which does not allow smooth deviations from the Poisson. As a broad class of alternative models, we propose to use nonparametric mixtures of rounded continuous kernels. An efficient Gibbs sampler is developed for posterior computation, and a simulation study is performed to assess performance. Focusing on the rounded Gaussian case, we generalize the modeling framework to account for multivariate count data, joint modeling with continuous and categorical variables, and other complications. The methods are illustrated through applications to a developmental toxicity study and marketing data. This article has supplementary material online. PMID:22523437
Extension of the standard addition method by blank addition.
Steliopoulos, Panagiotis
2015-01-01
Standard addition involves adding varying amounts of the analyte to sample portions of fixed mass or fixed volume and submitting those portions to the sample preparation procedure. After measuring the final extract solutions, the observed signals are linearly regressed on the spiked amounts. The original unknown amount is estimated by the opposite of the abscissa intercept of the fitted straight line [1]. A limitation of this method is that only data points with abscissa values equal to and greater than zero are available so that there is no information on whether linearity holds below the spiking level zero. An approach to overcome this limitation is introduced.•Standard addition is combined with blank addition.•Blank addition means that defined mixtures of blank matrix and sample material are subjected to sample preparation to give final extract solutions.•Equations are presented to estimate the original unknown amount and to calculate the 1-2α confidence interval about this estimate using the combined data set.
Extension of the standard addition method by blank addition
Steliopoulos, Panagiotis
2015-01-01
Standard addition involves adding varying amounts of the analyte to sample portions of fixed mass or fixed volume and submitting those portions to the sample preparation procedure. After measuring the final extract solutions, the observed signals are linearly regressed on the spiked amounts. The original unknown amount is estimated by the opposite of the abscissa intercept of the fitted straight line [1]. A limitation of this method is that only data points with abscissa values equal to and greater than zero are available so that there is no information on whether linearity holds below the spiking level zero. An approach to overcome this limitation is introduced.•Standard addition is combined with blank addition.•Blank addition means that defined mixtures of blank matrix and sample material are subjected to sample preparation to give final extract solutions.•Equations are presented to estimate the original unknown amount and to calculate the 1-2α confidence interval about this estimate using the combined data set. PMID:26844210
Understanding the human health effects of chemical mixtures.
Carpenter, David O; Arcaro, Kathleen; Spink, David C
2002-01-01
Most research on the effects of chemicals on biologic systems is conducted on one chemical at a time. However, in the real world people are exposed to mixtures, not single chemicals. Although various substances may have totally independent actions, in many cases two substances may act at the same site in ways that can be either additive or nonadditive. Many even more complex interactions may occur if two chemicals act at different but related targets. In the extreme case there may be synergistic effects, in which case the effects of two substances together are greater than the sum of either effect alone. In reality, most persons are exposed to many chemicals, not just one or two, and therefore the effects of a chemical mixture are extremely complex and may differ for each mixture depending on the chemical composition. This complexity is a major reason why mixtures have not been well studied. In this review we attempt to illustrate some of the principles and approaches that can be used to study effects of mixtures. By the nature of the state of the science, this discussion is more a presentation of what we do not know than of what we do know about mixtures. We approach the study of mixtures at three levels, using specific examples. First, we discuss several human diseases in relation to a variety of environmental agents believed to influence the development and progression of the disease. We present results of selected cellular and animal studies in which simple mixtures have been investigated. Finally, we discuss some of the effects of mixtures at a molecular level. PMID:11834461
Unrestricted Mixture Models for Class Identification in Growth Mixture Modeling
ERIC Educational Resources Information Center
Liu, Min; Hancock, Gregory R.
2014-01-01
Growth mixture modeling has gained much attention in applied and methodological social science research recently, but the selection of the number of latent classes for such models remains a challenging issue, especially when the assumption of proper model specification is violated. The current simulation study compared the performance of a linear…
Landfilling ash/sludge mixtures
Benoit, J.; Eighmy, T.T.; Crannell, B.S.
1999-10-01
The geotechnical properties of a mixture of municipal solid waste incinerator bottom ash and municipal wastewater treatment plant sludge was investigated for a proposed ash/sludge secure landfill. The components as well as mixtures ranging from 10:1 to 5:1 (ash:sludge, by volume) were evaluated, where appropriate, for a number of geotechnical index and mechanical properties including particle size, water content, specific gravity, density-moisture relationships, shear strength, and compressibility. The results from a compactibility study and stability analysis of the proposed landfill were used to help approve a landfill codisposal concept; a full-scale facility was constructed and is currently operating successfully.
Phylogenetic mixture models for proteins.
Le, Si Quang; Lartillot, Nicolas; Gascuel, Olivier
2008-12-27
Standard protein substitution models use a single amino acid replacement rate matrix that summarizes the biological, chemical and physical properties of amino acids. However, site evolution is highly heterogeneous and depends on many factors: genetic code; solvent exposure; secondary and tertiary structure; protein function; etc. These impact the substitution pattern and, in most cases, a single replacement matrix is not enough to represent all the complexity of the evolutionary processes. This paper explores in maximum-likelihood framework phylogenetic mixture models that combine several amino acid replacement matrices to better fit protein evolution.We learn these mixture models from a large alignment database extracted from HSSP, and test the performance using independent alignments from TREEBASE.We compare unsupervised learning approaches, where the site categories are unknown, to supervised ones, where in estimations we use the known category of each site, based on its exposure or its secondary structure. All our models are combined with gamma-distributed rates across sites. Results show that highly significant likelihood gains are obtained when using mixture models compared with the best available single replacement matrices. Mixtures of matrices also improve over mixtures of profiles in the manner of the CAT model. The unsupervised approach tends to be better than the supervised one, but it appears difficult to implement and highly sensitive to the starting values of the parameters, meaning that the supervised approach is still of interest for initialization and model comparison. Using an unsupervised model involving three matrices, the average AIC gain per site with TREEBASE test alignments is 0.31, 0.49 and 0.61 compared with LG (named after Le & Gascuel 2008 Mol. Biol. Evol. 25, 1307-1320), WAG and JTT, respectively. This three-matrix model is significantly better than LG for 34 alignments (among 57), and significantly worse for 1 alignment only. Moreover
16 CFR 1500.5 - Hazardous mixtures.
Code of Federal Regulations, 2014 CFR
2014-01-01
... 16 Commercial Practices 2 2014-01-01 2014-01-01 false Hazardous mixtures. 1500.5 Section 1500.5... HAZARDOUS SUBSTANCES AND ARTICLES; ADMINISTRATION AND ENFORCEMENT REGULATIONS § 1500.5 Hazardous mixtures. For a mixture of substances, the determination of whether the mixture is a “hazardous substance”...
14 CFR 23.1147 - Mixture controls.
Code of Federal Regulations, 2010 CFR
2010-01-01
... 14 Aeronautics and Space 1 2010-01-01 2010-01-01 false Mixture controls. 23.1147 Section 23.1147... Accessories § 23.1147 Mixture controls. (a) If there are mixture controls, each engine must have a separate control, and each mixture control must have guards or must be shaped or arranged to prevent confusion...
16 CFR 1500.5 - Hazardous mixtures.
Code of Federal Regulations, 2010 CFR
2010-01-01
... 16 Commercial Practices 2 2010-01-01 2010-01-01 false Hazardous mixtures. 1500.5 Section 1500.5... HAZARDOUS SUBSTANCES AND ARTICLES; ADMINISTRATION AND ENFORCEMENT REGULATIONS § 1500.5 Hazardous mixtures. For a mixture of substances, the determination of whether the mixture is a “hazardous substance”...
14 CFR 23.1147 - Mixture controls.
Code of Federal Regulations, 2013 CFR
2013-01-01
... 14 Aeronautics and Space 1 2013-01-01 2013-01-01 false Mixture controls. 23.1147 Section 23.1147... Accessories § 23.1147 Mixture controls. (a) If there are mixture controls, each engine must have a separate control, and each mixture control must have guards or must be shaped or arranged to prevent confusion...
16 CFR 1500.5 - Hazardous mixtures.
Code of Federal Regulations, 2011 CFR
2011-01-01
... 16 Commercial Practices 2 2011-01-01 2011-01-01 false Hazardous mixtures. 1500.5 Section 1500.5... HAZARDOUS SUBSTANCES AND ARTICLES; ADMINISTRATION AND ENFORCEMENT REGULATIONS § 1500.5 Hazardous mixtures. For a mixture of substances, the determination of whether the mixture is a “hazardous substance”...
14 CFR 23.1147 - Mixture controls.
Code of Federal Regulations, 2011 CFR
2011-01-01
... 14 Aeronautics and Space 1 2011-01-01 2011-01-01 false Mixture controls. 23.1147 Section 23.1147... Accessories § 23.1147 Mixture controls. (a) If there are mixture controls, each engine must have a separate control, and each mixture control must have guards or must be shaped or arranged to prevent confusion...
14 CFR 23.1147 - Mixture controls.
Code of Federal Regulations, 2012 CFR
2012-01-01
... 14 Aeronautics and Space 1 2012-01-01 2012-01-01 false Mixture controls. 23.1147 Section 23.1147... Accessories § 23.1147 Mixture controls. (a) If there are mixture controls, each engine must have a separate control, and each mixture control must have guards or must be shaped or arranged to prevent confusion...
16 CFR 1500.5 - Hazardous mixtures.
Code of Federal Regulations, 2013 CFR
2013-01-01
... 16 Commercial Practices 2 2013-01-01 2013-01-01 false Hazardous mixtures. 1500.5 Section 1500.5... HAZARDOUS SUBSTANCES AND ARTICLES; ADMINISTRATION AND ENFORCEMENT REGULATIONS § 1500.5 Hazardous mixtures. For a mixture of substances, the determination of whether the mixture is a “hazardous substance”...
14 CFR 23.1147 - Mixture controls.
Code of Federal Regulations, 2014 CFR
2014-01-01
... 14 Aeronautics and Space 1 2014-01-01 2014-01-01 false Mixture controls. 23.1147 Section 23.1147... Accessories § 23.1147 Mixture controls. (a) If there are mixture controls, each engine must have a separate control, and each mixture control must have guards or must be shaped or arranged to prevent confusion...
16 CFR 1500.5 - Hazardous mixtures.
Code of Federal Regulations, 2012 CFR
2012-01-01
... 16 Commercial Practices 2 2012-01-01 2012-01-01 false Hazardous mixtures. 1500.5 Section 1500.5... HAZARDOUS SUBSTANCES AND ARTICLES; ADMINISTRATION AND ENFORCEMENT REGULATIONS § 1500.5 Hazardous mixtures. For a mixture of substances, the determination of whether the mixture is a “hazardous substance”...
Additive attacks on speaker recognition
NASA Astrophysics Data System (ADS)
Farrokh Baroughi, Alireza; Craver, Scott
2014-02-01
Speaker recognition is used to identify a speaker's voice from among a group of known speakers. A common method of speaker recognition is a classification based on cepstral coefficients of the speaker's voice, using a Gaussian mixture model (GMM) to model each speaker. In this paper we try to fool a speaker recognition system using additive noise such that an intruder is recognized as a target user. Our attack uses a mixture selected from a target user's GMM model, inverting the cepstral transformation to produce noise samples. In our 5 speaker data base, we achieve an attack success rate of 50% with a noise signal at 10dB SNR, and 95% by increasing noise power to 0dB SNR. The importance of this attack is its simplicity and flexibility: it can be employed in real time with no processing of an attacker's voice, and little computation is needed at the moment of detection, allowing the attack to be performed by a small portable device. For any target user, knowing that user's model or voice sample is sufficient to compute the attack signal, and it is enough that the intruder plays it while he/she is uttering to be classiffed as the victim.
Deuterium separation by infrared-induced addition reaction
Marling, John B.
1977-01-01
A method for deuterium enrichment by the infrared-induced addition reaction of a deuterium halide with an unsaturated aliphatic compound. A gaseous mixture of a hydrogen halide feedstock and an unsaturated aliphatic compound, particularly an olefin, is irradiated to selectively vibrationally excite the deuterium halide contained therein. The excited deuterium halide preferentially reacts with the unsaturated aliphatic compound to produce a deuterated addition product which is removed from the reaction mixture.
Rabbit Neonates and Human Adults Perceive a Blending 6-Component Odor Mixture in a Comparable Manner
Sinding, Charlotte; Thomas-Danguin, Thierry; Chambault, Adeline; Béno, Noelle; Dosne, Thibaut; Chabanet, Claire; Schaal, Benoist; Coureaud, Gérard
2013-01-01
Young and adult mammals are constantly exposed to chemically complex stimuli. The olfactory system allows for a dual processing of relevant information from the environment either as single odorants in mixtures (elemental perception) or as mixtures of odorants as a whole (configural perception). However, it seems that human adults have certain limits in elemental perception of odor mixtures, as suggested by their inability to identify each odorant in mixtures of more than 4 components. Here, we explored some of these limits by evaluating the perception of three 6-odorant mixtures in human adults and newborn rabbits. Using free-sorting tasks in humans, we investigated the configural or elemental perception of these mixtures, or of 5-component sub-mixtures, or of the 6-odorant mixtures with modified odorants' proportion. In rabbit pups, the perception of the same mixtures was evaluated by measuring the orocephalic sucking response to the mixtures or their components after conditioning to one of these stimuli. The results revealed that one mixture, previously shown to carry the specific odor of red cordial in humans, was indeed configurally processed in humans and in rabbits while the two other 6-component mixtures were not. Moreover, in both species, such configural perception was specific not only to the 6 odorants included in the mixture but also to their respective proportion. Interestingly, rabbit neonates also responded to each odorant after conditioning to the red cordial mixture, which demonstrates their ability to perceive elements in addition to configuration in this complex mixture. Taken together, the results provide new insights related to the processing of relatively complex odor mixtures in mammals and the inter-species conservation of certain perceptual mechanisms; the results also revealed some differences in the expression of these capacities between species putatively linked to developmental and ecological constraints. PMID:23341948
Odour suppression in binary mixtures.
Cashion, Larry; Livermore, Andrew; Hummel, Thomas
2006-10-01
It has been suggested that odours causing stronger trigeminal activation suppress weaker trigeminal stimuli and that mixed olfactory-trigeminal stimuli suppress odorants that only activate one of these systems. Volunteer normosmic participants (n=20) were exposed to six odorants with varying trigeminal impact to test the hypothesis that more intense "trigeminal" odorants would suppress weaker trigeminal stimuli in binary odour mixtures. It was also hypothesised that stronger trigeminal odorants would dominate six-odour mixtures. The predicted linear pattern of suppression was not seen, with a quadratic model emerging from the data. Stronger trigeminal stimuli failed to dominate six-odour mixtures. Despite the fact that the major hypothesis was not supported, it can be hypothesised from this experiment that the effect of suppression in binary mixtures is reliant upon two major effects: (1) the association formed between odours and the multiple memory systems that they interact with during the encoding and recognition processes, and (2) the balance between activation of the olfactory and trigeminal systems.
Uphill diffusion in multicomponent mixtures.
Krishna, Rajamani
2015-05-21
Molecular diffusion is an omnipresent phenomena that is important in a wide variety of contexts in chemical, physical, and biological processes. In the majority of cases, the diffusion process can be adequately described by Fick's law that postulates a linear relationship between the flux of any species and its own concentration gradient. Most commonly, a component diffuses down the concentration gradient. The major objective of this review is to highlight a very wide variety of situations that cause the uphill transport of one constituent in the mixture. Uphill diffusion may occur in multicomponent mixtures in which the diffusion flux of any species is strongly coupled to that of its partner species. Such coupling effects often arise from strong thermodynamic non-idealities. For a quantitative description we need to use chemical potential gradients as driving forces. The transport of ionic species in aqueous solutions is coupled with its partner ions because of the electro-neutrality constraints; such constraints may accelerate or decelerate a specific ion. When uphill diffusion occurs, we observe transient overshoots during equilibration; the equilibration process follows serpentine trajectories in composition space. For mixtures of liquids, alloys, ceramics and glasses the serpentine trajectories could cause entry into meta-stable composition zones; such entry could result in phenomena such as spinodal decomposition, spontaneous emulsification, and the Ouzo effect. For distillation of multicomponent mixtures that form azeotropes, uphill diffusion may allow crossing of distillation boundaries that are normally forbidden. For mixture separations with microporous adsorbents, uphill diffusion can cause supra-equilibrium loadings to be achieved during transient uptake within crystals; this allows the possibility of over-riding adsorption equilibrium for achieving difficult separations.
Uphill diffusion in multicomponent mixtures.
Krishna, Rajamani
2015-05-21
Molecular diffusion is an omnipresent phenomena that is important in a wide variety of contexts in chemical, physical, and biological processes. In the majority of cases, the diffusion process can be adequately described by Fick's law that postulates a linear relationship between the flux of any species and its own concentration gradient. Most commonly, a component diffuses down the concentration gradient. The major objective of this review is to highlight a very wide variety of situations that cause the uphill transport of one constituent in the mixture. Uphill diffusion may occur in multicomponent mixtures in which the diffusion flux of any species is strongly coupled to that of its partner species. Such coupling effects often arise from strong thermodynamic non-idealities. For a quantitative description we need to use chemical potential gradients as driving forces. The transport of ionic species in aqueous solutions is coupled with its partner ions because of the electro-neutrality constraints; such constraints may accelerate or decelerate a specific ion. When uphill diffusion occurs, we observe transient overshoots during equilibration; the equilibration process follows serpentine trajectories in composition space. For mixtures of liquids, alloys, ceramics and glasses the serpentine trajectories could cause entry into meta-stable composition zones; such entry could result in phenomena such as spinodal decomposition, spontaneous emulsification, and the Ouzo effect. For distillation of multicomponent mixtures that form azeotropes, uphill diffusion may allow crossing of distillation boundaries that are normally forbidden. For mixture separations with microporous adsorbents, uphill diffusion can cause supra-equilibrium loadings to be achieved during transient uptake within crystals; this allows the possibility of over-riding adsorption equilibrium for achieving difficult separations. PMID:25761383
Tichý, M; Borek-Dohalský, V; Matousová, D; Rucki, M; Feltl, L; Roth, Z
2002-03-01
The aim of this contribution is to support our proposal of the procedure for predicting acute toxicity of binary mixtures by QSAR analysis techniques. The changes of a mixture composition are described by molar ratio R and visualized in the R-plot (QCAR--quantitative composition-activity relationships). The approach was inspired by Rault and Dalton's laws, their positive and negative deviations in the behavior of a mixture of real gases, by Loewe and Muischnek isoboles and by the Finney test of additivity. Acute toxicity was determined by the laboratory test with woms Tubifex tubifex. The additivity of the acute toxicity in the binary mixture benzene + nitrobenzene was confirmed and a new interaction is described: "mixed interaction" with the binary mixture aniline + ethanol. The "mixed interaction" means that depending on mixture composition, both potentiation and inhibition can occur. As the first physicochemical descriptor of the changes caused by the changing composition of binary mixtures, the gas/liquid equilibrium was studied and a composition of the gaseous phase was determined by a gas chromatographic method. The method for determination of concentrations in the gaseous phase was described. The gaseous phase composition of benzene + nitrobenzene. benzene + ethanol, benzene + aniline and ethanol + aniline mixtures was analyzed. It was found that if the concentrations of the mixture's components in the gaseous phase behave nonideally (they are not additive), the acute toxicity of the same mixture is not additive as well. Another descriptor to distinguish between potentiation and inhibition will be, however, necessary. The properties, both gaseous phase composition and the acute toxicity, of the benzene + nitrobenzene mixture are additive. In mixtures with the mixed interaction, the R-plot of the composition of the gaseous phase is complex with a large variation of results.
Modeling phase equilibria in mixtures containing hydrogen fluoride and halocarbons
Lencka, M. ); Anderko, A. Polish Academy of Sciences, Warszawa )
1993-03-01
Recently, much attention has been focused on the production of environmentally acceptable refrigerants, which not only offer desirable physico-chemical properties, but do not deplete the ozone layer and do not cause the greenhouse effect. The production of such refrigerants involves the separation of multicomponent mixtures containing hydrogen fluoride, hydrogen chloride, and various chlorinated and fluorinated hydrocarbons. Therefore, it is indispensable to know the phase behavior of these mixtures. While the phase behavior of refrigerant mixtures can be adequately modeled in the absence of HF using standard thermodynamic techniques, drastically increases the complexity of the mixture because of its unusually strong association. The association of HF manifests itself in its significantly reduced gas-phase compressibility factor and the strong nonideality of mixtures containing HF and hydrocarbons or halocarbons. In this work, the authors develop an accurate, yet simple, association model for HF and compare it with simulation data. The model is combined with a simple equation of state to yield a closed-form expression that is applicable to both pure fluids and mixtures. In addition to representing the pure-component data for HF, the theory accurately predicts phase equilibria in HF + halocarbon systems.