Diffusion of pentane isomers in faujasite-type zeolites : NMR and molecular dynamics study

Diffusion of pentane isomers in zeolites NaX has been investigated using pulsed field gradient nuclear magnetic resonance (PFG-NMR) and molecular dynamics (MD) techniques respectively. Temperature and concentration dependence of diffusivities have been studied. The diffusivities obtained from NMR are roughly an order of magnitude smaller than those obtained from MD. The dependence of diffusivity on loading at high temperatures exhibits a type I behavior according to the classification of Karger and Pfeifer 1]. NMR diffusivities of the isomers exhibit the order D(n-pentane) > D(isopentane) > D(neopentane). The results from MD suggest that the diffusivities of the isomers follow the order D(n-pentane) < D(isopentane) < D(neopentane). The activation energies from NMR show E-a(n-pentane) < E-a(isopentane) < E-a(neopentane) whereas those from MD suggest the order E-a(n-pentane) > (isopentane) > E-a(neopentane). The latter follows the predictions of levitation effect whereas those of NMR appears to be due to the presence of defects in the zeolite crystals. The differences between diffusivities estimated by NMR and MD are attributed to the longer time and length scales sampled by the NMR technique, as compared to MD. (C) 2012 Elsevier Inc. All rights reserved.

Diffusion in tungsten silicides

Experiments are conducted in the W-Si system to understand the diffusion mechanism of the species. The activation energies from integrated diffusion coefficients are calculated as 152 +/- 7 and 301 +/- 40 kJ/mol in the WSi2 and W5Si3 phases, respectively. In both the phases, Si has a much higher diffusion rate compared to W. This is not surprising to find in the WSi2 phase, if we consider the number of nearest neighbors for both the elements in the crystal. The diffusion of W in this phase indicates the presence of W antisites. The faster diffusion rate of Si in the W5Si3 phase indicates the presence of higher concentration of vacancies on the Si sublattice compared to W sublattice.

Generalized eigenvalue decomposition of the field autocorrelation in correlation diffusion of photons in turbid media

We propose a novel numerical method based on a generalized eigenvalue decomposition for solving the diffusion equation governing the correlation diffusion of photons in turbid media. Medical imaging modalities such as diffuse correlation tomography and ultrasound-modulated optical tomography have the (elliptic) diffusion equation parameterized by a time variable as the forward model. Hitherto, for the computation of the correlation function, the diffusion equation is solved repeatedly over the time parameter. We show that the use of a certain time-independent generalized eigenfunction basis results in the decoupling of the spatial and time dependence of the correlation function, thus allowing greater computational efficiency in arriving at the forward solution. Besides presenting the mathematical analysis of the generalized eigenvalue problem on the basis of spectral theory, we put forth the numerical results that compare the proposed numerical method with the standard technique for solving the diffusion equation.

The diffusion and relaxation of Gaussian chains in narrow rectangular slits

The confinement of a polymer to volumes whose characteristic linear dimensions are comparable to or smaller than its bulk radius of gyration R-G,R-bulk can produce significant changes in its static and dynamic properties, with important implications for the understanding of single-molecule processes in biology and chemistry. In this paper, we present calculations of the effects of a narrow rectangular slit of thickness d on the scaling behavior of the diffusivity D and relaxation time tau(r) of a Gaussian chain of polymerization index N and persistence length l(0). The calculations are based on the Rouse-Zimm model of chain dynamics, with the pre-averaged hydrodynamic interaction being obtained from the solutions to Stokes equations for an incompressible fluid in a parallel plate geometry in the limit of small d. They go beyond de Gennes' purely phenomenological analysis of the problem based on blobs, which has so far been the only analytical route to the determination of chain scaling behavior for this particular geometry. The present model predicts that D similar to dN(-1) ln(N/d(2)) and tau(r) similar to N(2)d(-1) ln(N/d(2))(-1) in the regime of moderate confinement, where l(0) << d < R-G,R-bulk. The corresponding results for the blob model have exactly the same power law behavior, but contain no logarithmic corrections; the difference suggests that segments within a blob may actually be partially draining and not non-draining as generally assumed.

Study on important diffusion parameters of binary Ni3Sn4 phase

Important diffusion parameters, such as-parabolic growth constant, integrated diffusivity, ratio of intrinsic diffusivities of species Ni and Sn, Kirkendall marker velocity and the activation energy for diffusion kinetics of binary Ni3Sn4 phase have been investigated with the help of incremental diffusion couple technique (Sn/Ni0.57Sn0.43) in the temperature range 200-150 degrees C. Low activation energy extracted from Arrhenius plot indicates grain boundary controlled diffusion process. The species Sn is three times faster than Ni at 200 degrees C. Further, the activation energy of Sn tracer diffusivity is greater than that of Ni.

Predictability and chaotic nature of daily streamflow

The predictability of a chaotic series is limited to a few future time steps due to its sensitivity to initial conditions and the exponential divergence of the trajectories. Over the years, streamflow has been considered as a stochastic system in many approaches. In this study, the chaotic nature of daily streamflow is investigated using autocorrelation function, Fourier spectrum, correlation dimension method (Grassberger-Procaccia algorithm) and false nearest neighbor method. Embedding dimensions of 6-7 obtained indicates the possible presence of low-dimensional chaotic behavior. The predictability of the system is estimated by calculating the system's Lyapunov exponent. A positive maximum Lyapunov exponent of 0.167 indicates that the system is chaotic and unstable with a maximum predictability of only 6 days. These results give a positive indication towards considering streamflow as a low dimensional chaotic system than as a stochastic system.

Li diffusion through doped and defected graphene

We investigate the effect of nitrogen and boron doping on Li diffusion through defected graphene using first principles based density functional theory. While a high energy barrier rules out the possibility of Li-diffusion through the pristine graphene, the barrier reduces with the incorporation of defects. Among the most common defects in pristine graphene, Li diffusion through the divacancy encounters the lowest energy barrier of 1.34 eV. The effect of nitrogen and boron doping on the Li diffusion through doped defected-graphene sheets has been studied. N-doping in graphene with a monovacancy reduces the energy barrier significantly. The barrier reduces with the increasing number of N atoms. On the other hand, for N doped graphene with a divacancy, Li binds in the plane of the sheet, with an enhanced binding energy. The B doping in graphene with a monovacancy leads to the enhancement of the barrier. However, in the case of B-doped graphene with a divacancy, the barrier reduces to 1.54 eV, which could lead to good kinetics. The barriers do not change significantly with B concentration. Therefore, divacancy, B and N doped defected graphene has emerged as a better alternative to pristine graphene as an anode material for Li ion battery.

Combining indentation and diffusion couple techniques for combinatorial discovery of high temperature shape memory alloys

We demonstrate the possibility of accelerated identification of potential compositions for high-temperature shape memory alloys (SMAs) through a combinatorial material synthesis and analysis approach, wherein we employ the combination of diffusion couple and indentation techniques. The former was utilized to generate smooth and compositionally graded inter-diffusion zones (IDZs) in the Ni-Ti-Pd ternary alloy system of varying IDZ thickness, depending on the annealing time at high temperature. The IDZs thus produced were then impressed with an indenter with a spherical tip so as to inscribe a predetermined indentation strain. Subsequent annealing of the indented samples at various elevated temperatures, T-a, ranging between 150 and 550 degrees C allows for partial to full relaxation of the strain imposed due to the shape memory effect. If T-a is above the austenite finish temperature, A(f), the relaxation will be complete. By measuring the depth recovery, which serves as a proxy for the shape recovery characteristic of the SMA, a three-dimensional map in the recovery temperature composition space is constructed. A comparison of the published Af data for different compositions with the Ta data shows good agreement when the depth recovery is between 70% and 80%, indicating that the methodology proposed in this paper can be utilized for the identification of promising compositions. Advantages and further possibilities of this methodology are discussed.

Exponential compact higher order scheme and their stability analysis for unsteady convection-diffusion equations

Exponential compact higher-order schemes have been developed for unsteady convection-diffusion equation (CDE). One of the developed scheme is sixth-order accurate which is conditionally stable for the Peclet number 0 <= Pe <= 2.8 and the other is fourth-order accurate which is unconditionally stable. Schemes for two-dimensional (2D) problems are made to use alternate direction implicit (ADI) algorithm. Example problems are solved and the numerical solutions are compared with the analytical solutions for each case.

Scalar transport in diffusion flame wrapped up by an air and fuel side vortex

The present work involves a computational study of soot (chosen as a scalar which is a primary pollutant source) formation and transport in a laminar acetylene diffusion flame perturbed by a convecting line vortex. The topology of soot contours resulting from flame vortex interactions has been investigated. More soot was produced when vortex was introduced from the air side in comparison to the fuel side. Also, the soot topography was spatially more diffuse in the case of air side vortex. The computational model was found to be in good agreement with the experimental work previously reported in the literature. The computational simulation enabled a study of various parameters like temperature, equivalence ratio and temperature gradient affecting the soot production and transport. Temperatures were found to be higher in the case of air side vortex in contrast to the fuel side one. In case of fuel side vortex, abundance of fuel in the vortex core resulted in fuel-rich combustion zone in the core and a more discrete soot topography. Besides, the overall soot production was observed to be low in the fuel side vortex. However, for the air side vortex, air abundance in the core resulted in higher temperatures and greater soot production. Probability density functions (PDFs) have been introduced to investigate the spatiotemporal variation of soot yield and transport and their dependence on temperature and acetylene concentration from statistical view point. In addition, the effect of flame curvature on soot production is also studied. The regions convex to fuel stream side witnessed thicker soot layer. All numerical simulations have been carried out on Fluent 6.3.26. (C) 2013 Elsevier Ltd. All rights reserved.

The diffusion and relaxation of Gaussian chains in narrow rectangular slits

The confinement of a polymer to volumes whose characteristic linear dimensions are comparable to or smaller than its bulk radius of gyration R-G,R-bulk can produce significant changes in its static and dynamic properties, with important implications for the understanding of single-molecule processes in biology and chemistry. In this paper, we present calculations of the effects of a narrow rectangular slit of thickness d on the scaling behavior of the diffusivity D and relaxation time tau(r) of a Gaussian chain of polymerization index N and persistence length l(0). The calculations are based on the Rouse-Zimm model of chain dynamics, with the pre-averaged hydrodynamic interaction being obtained from the solutions to Stokes equations for an incompressible fluid in a parallel plate geometry in the limit of small d. They go beyond de Gennes' purely phenomenological analysis of the problem based on blobs, which has so far been the only analytical route to the determination of chain scaling behavior for this particular geometry. The present model predicts that D similar to dN(-1) ln(N/d(2)) and tau(r) similar to N(2)d(-1) ln(N/d(2))(-1) in the regime of moderate confinement, where l(0) << d < R-G,R-bulk. The corresponding results for the blob model have exactly the same power law behavior, but contain no logarithmic corrections; the difference suggests that segments within a blob may actually be partially draining and not non-draining as generally assumed. (C) 2013 AIP Publishing LLC.

Scaling of turbulent flame speed for expanding flames with Markstein diffusion considerations

In this paper we clarify the role of Markstein diffusivity, which is the product of the planar laminar flame speed and the Markstein length, on the turbulent flame speed and its scaling, based on experimental measurements on constant-pressure expanding turbulent flames. Turbulent flame propagation data are presented for premixed flames of mixtures of hydrogen, methane, ethylene, n-butane, and dimethyl ether with air, in near-isotropic turbulence in a dual-chamber, fan-stirred vessel. For each individual fuel-air mixture presented in this work and the recently published iso-octane data from Leeds, normalized turbulent flame speed data of individual fuel-air mixtures approximately follow a Re-T,f(0.5) scaling, for which the average radius is the length scale and thermal diffusivity is the transport property of the turbulence Reynolds number. At a given Re-T,Re-f, it is experimentally observed that the normalized turbulent flame speed decreases with increasing Markstein number, which could be explained by considering Markstein diffusivity as the leading dissipation mechanism for the large wave number flame surface fluctuations. Consequently, by replacing thermal diffusivity with the Markstein diffusivity in the turbulence Reynolds number definition above, it is found that normalized turbulent flame speeds could be scaled by Re-T,M(0.5) irrespective of the fuel, equivalence ratio, pressure, and turbulence intensity for positive Markstein number flames.

Mechanistic Insights into a Non-Classical Diffusion Pathway for the Formation of Hollow Intermetallics: A Route to Multicomponent Hollow Structures

Hollow nanostructures are used for various applications including catalysis, sensing, and drug delivery. Methods based on the Kirkendall effect have been the most successful for obtaining hollow nanostructures of various multicomponent systems. The classical Kirkendall effect relies on the presence of a faster diffusing species in the core; the resultant imbalance in flux results in the formation of hollow structures. Here, an alternate non-Kirkendall mechanism that is operative for the formation of hollow single crystalline particles of intermetallic PtBi is demonstrated. The synthesis method involves sequential reduction of Pt and Bi salts in ethylene glycol under microwave irradiation. Detailed analysis of the reaction at various stages indicates that the formation of the intermetallic PtBi hollow nanoparticles occurs in steps. The mechanistic details are elucidated using control experiments. The use of microwave results in a very rapid synthesis of intermetallics PtBi that exhibits excellent electrocatalytic activity for formic acid oxidation reaction. The method presented can be extended to various multicomponent systems and is independent of the intrinsic diffusivities of the species involved.

Bivariate frequency analysis of floods using a diffusion based kernel density estimator

Recent focus of flood frequency analysis (FFA) studies has been on development of methods to model joint distributions of variables such as peak flow, volume, and duration that characterize a flood event, as comprehensive knowledge of flood event is often necessary in hydrological applications. Diffusion process based adaptive kernel (D-kernel) is suggested in this paper for this purpose. It is data driven, flexible and unlike most kernel density estimators, always yields a bona fide probability density function. It overcomes shortcomings associated with the use of conventional kernel density estimators in FFA, such as boundary leakage problem and normal reference rule. The potential of the D-kernel is demonstrated by application to synthetic samples of various sizes drawn from known unimodal and bimodal populations, and five typical peak flow records from different parts of the world. It is shown to be effective when compared to conventional Gaussian kernel and the best of seven commonly used copulas (Gumbel-Hougaard, Frank, Clayton, Joe, Normal, Plackett, and Student's T) in estimating joint distribution of peak flow characteristics and extrapolating beyond historical maxima. Selection of optimum number of bins is found to be critical in modeling with D-kernel.