A distribution kinetics approach for crystallization of polymer blends.

The cluster distribution approach is extended to investigate the crystallization kinetics of miscible polymer blends. Mixture effects of polymer-polymer interactions are incorporated into the diffusion coefficient. The melting temperature, activation energy of diffusion, and phase transition enthalpy also depend on the blending fraction and lead to characteristic kinetic behavior of crystallization. The influence of different blending fractions is presented through the time dependence of polymer concentration, number and size of crystals, and crystallinity (in Avrami plots). Computational results indicate how overall crystallization kinetics can be expressed approximately by the Avrami equation. The nucleation rate decreases as the blending fraction of the second polymer component increases. The investigation suggests that blending influences crystal growth rate mainly through the deposition-rate driving force and growth-rate coefficient. The model is further validated by simulating the experimental data for the crystallization of a blend of poly(vinylidenefluoride)[PVDF] and poly(vinyl acetate)[PVAc] at various blending fractions.

Cluster kinetics model of particle separation in vibrated granular media.

We model the Brazil-nut effect (BNE) by hypothesizing that granules form clusters that fragment and aggregate. This provides a heterogeneous medium in which the immersed intruder particle rises (BNE) or sinks (reverse BNE) according to relative convection currents and buoyant and drag forces. A simple relationship proposed for viscous drag in terms of the vibrational intensity and the particle to grain density ratio allows simulation of published experimental data for rise and sink times as functions of particle radius, initial depth of the particle, and particle-grain density ratio. The proposed model correctly describes the experimentally observed maximum in risetime.

Kinetics of nonisothermal polymer crystallization.

We adopt a cluster size distribution model to investigate the kinetics of nonisothermal polymer crystallization. The time dependencies of polymer concentration, number and size of crystals, and crystallinity (in Avrami plots) are presented for different cooling rates. The incubation period is also investigated at different cooling rates and initial temperatures. The relationship between cooling rates and incubation time is presented graphically and compared with experimental measurements. The initial temperature (relative to melting point) has a significant effect on nonisothermal crystallization. A comparison of moment and numerical solutions of the population balance equations shows the influence of Ostwald ripening. Agreement between modeling results and experimental measurements at different cooling rates supports the application of the distribution kinetics model for nonisothermal crystallization.

Evolution of power law distributions in science and society.

Power law distributions have been observed in numerous physical and social systems; for example, the size distributions of particles, aerosols, corporations, and cities are often power laws. Each system is an ensemble of clusters, comprising units that combine with or dissociate from the cluster. Constructing models and investigating their properties are needed to understand how such clusters evolve. To describe the growth of clusters, we hypothesize that a distribution obeys a governing population dynamics equation based on a reversible association-dissociation process. The rate coefficients are considered to depend on the cluster size as power expressions, thus providing an explanation for the asymptotic evolution of power law distributions.

Cluster aggregation and fragmentation kinetics model for gelation.

Gelation can occur in polymer, hydrogel, and colloid systems that undergo reversible aggregation-fragmentation (crosslinking accompanied by breakage). Gelation, characterized by rapid divergence of weight-average molecular weight and viscosity due to initial network formation, can be reversed if conditions change. In this paper, reversible aggregation and fragmentation in the pre-gelation time period are modeled with distribution kinetics. Moment equations are obtained from the population balance equation, and solved for eight different rate kernels. We identify the cases for which gelation is possible and obtain the critical values for the rate constants that allow gelation. The model provides a good simulation of published experimental data for aggregation and degradation of plasticized wheat gluten during thermo-mechanical treatments. We also evaluate two closure approximations based on Gamma and log-normal distributions, and conclude that log-normal closure predicts all five possible steady states, in agreement with the Vigil-Ziff criterion, and Gamma closure predicts only three. However, Gamma closure approximates the steady state either closely or exactly, whereas log-normal closure only poorly approximates the steady-state distribution.

Cluster kinetics of density relaxation in granular materials.

Of the many complex processes of granular materials, vibrational settling and compaction are common phenomena that have attracted much attention. In this work, we investigate vibrational, or tapping, compaction, and propose that the underlying kinetics involves clusters fragmenting and aggregating, and individual grains attaching and dissociating at cluster surfaces. The periodic vibrations cause cluster breakage and interchange between individual free grains and the clusters. The population balance equations for the concurrent kinetics are solved by a moment method, yielding easily solved differential equations. The compaction ratio defined in terms of the mass moments agrees well with experimental data [Knight et al., Phys. Rev. E. 51, 3957 (1995); Nowak et al., ibid. 57, 1972 (1998)] and other models. A change in tapping acceleration can produce reversible or irreversible transitions between densities, depending on the number of clusters that have evolved.

Numerical and similarity solutions for reversible population balance equations with size-dependent rates.

Population balance equations (PBEs) for reversible aggregation-fragmentation processes are important to particle agglomeration and dissolution, polymerization and degradation, liquid droplet coalescence and breakup, and floc coagulation and disintegration. Moment solutions provide convenient solutions to the PBEs, including steady state and similarity solutions, but may not be feasible for complex forms of size-dependent rate coefficients and stoichiometric kernels. Numeric solutions are thus necessary not only for applications, but also for the study of the mathematics of PBEs. Here we propose a numerical method to solve PBEs and compare the results to moment solutions. The numeric results are consistent with known steady state and asymptotic long-time similarity solutions and show how processes can be approximated by self-similar formulations.

Distribution kinetics of Ostwald ripening at large volume fraction and with coalescence.

Condensation phase transitions from metastable fluids occur by nucleation with accompanying particle growth and eventual Ostwald ripening. During ripening the subcritical particles dissolve spontaneously while larger particles grow and possibly coalesce if their volume fraction is large enough. The classical diffusion-influenced rates are also affected by large particle concentrations and are here described by mass-dependent rates. We represent the kinetics of ripening through growth, dissolution, and biparticle coalescence by a new population dynamics equation for the particle size distribution (PSD). Numerical solutions of the scaled governing equations show that coalescence plays a major role in influencing the PSD when the scaled mass concentration (volume fraction) or number concentration is relatively large. The solution describes the time range from initial conditions to the final narrowing of polydispersity. We show that the time dependence of the average particle mass in the asymptotic period of ripening has a power-law increase dependent on rate expressions for particle growth and coalescence at large values of volume fraction.

Formulation of a soil-pesticide transport model based on a compartmental approach.

A semianalytical soil-pesticide transport model is formulated based on a compartmental approach to determine spatial and temporal variations of pesticide residues across a soil profile. The compartmental model is implemented by drawing an analogy between a series of continuous-flow stirred tank reactors and a soil horizon that consists of multiple perfectly mixed compartments. The analogy is strengthened by exploiting a relation between the compartment series and the conventional convective-dispersive equation (CDE) for vertical transport in the soil. Consequently, the number of compartments in the model formulation is not free, but dictated as a function of transport parameters. The model formulation allows consideration of arbitrary boundary value specifications and also, for some cases, spatially varying initial concentration profiles. Sorption kinetics is represented via a two-site model that involves a linear sorption isotherm and a first-order irreversible sorption or a radial diffusive penetrating model. For these three cases, analysis of the compartmental model allows the resultant concentration profiles to be expressed in terms of the Poisson distribution. When a nonlinear kinetic sorption model is used to simulate the sorption processes, an analytical solution is not found and a numerical approach is required.

Cluster kinetics model for mixtures of glassformers.

For glassformers we propose a binary mixture relation for parameters in a cluster kinetics model previously shown to represent pure compound data for viscosity and dielectric relaxation as functions of either temperature or pressure. The model parameters are based on activation energies and activation volumes for cluster association-dissociation processes. With the mixture parameters, we calculated dielectric relaxation times and compared the results to experimental values for binary mixtures. Mixtures of sorbitol and glycerol (seven compositions), sorbitol and xylitol (three compositions), and polychloroepihydrin and polyvinylmethylether (three compositions) were studied.

Cluster kinetics and dynamics during spinodal decomposition.

Spinodal decomposition (barrierless phase transition) is a spontaneous phase separation caused by conditions that force the system to become thermodynamically unstable. We consider spinodal decomposition to occur under conditions of large supersaturation S and/or small ratio of interfacial to thermal energies omega, such that the computed number of monomers in a critical nucleus xi*=(omega/ln S)3 is less than unity. The small critical nucleus size is consistent with a negligible energy barrier for initiating condensation. Thus, in contrast to conventional opinion, it is suggested that the spinodal decomposition is related to the homogeneous nucleation of metastable fluids. Population balance equations show how clusters aggregate and rapidly lead to phase separation. Different mass dependences of aggregation rate coefficients are proposed to investigate the fundamental features of spinodal decomposition. When the mass dependency is an integer, the equations are solved by the moment technique to obtain analytical solutions. When the mass dependency is a noninteger, the general cases are solved numerically. All solutions predict the two time regimes observed experimentally: the average length scale of condensed-phase domains increases as a power law with an exponent of 1/3 at early times, followed by a linear increase at longer times.

Cluster kinetics of pressure-induced glass formation.

A prior correlation model for glass formation based on cluster-size distribution kinetics is here extended to account for pressure effects as well as temperature effects. The model describes how rapidly cooling or compressing a liquid or colloid leads to structural arrest and a consequent sharp rise in viscosity or dielectric relaxation time. In addition to activation energies, we include activation volumes in the rate coefficients for monomer-cluster addition and dissociation and cluster aggregation and breakage. The approach leads to scaled pressure correlations and plots for viscosity that reveal strong and fragile glass behavior, and agree with experimental data. A simple relationship among viscosity, attractive interparticle energy, and particle volume fraction displays how hard spheres with attractive forces can vitrify at small particle densities.

Distribution kinetics of polymer crystallization and the Avrami equation.

Cluster distribution kinetics is adopted to explore the kinetics of polymer crystallization. Population balance equations based on crystal size distribution and concentration of amorphous polymer segments are solved numerically and the related dynamic moment equations are also solved. The model accounts for heterogeneous or homogeneous nucleation and crystal growth. Homogeneous nucleation rates follow the classical surface-energy nucleation theory. Different mass dependences of growth and dissociation rate coefficients are proposed to investigate the fundamental features of nucleation and crystal growth. A comparison of moment solutions with numerical solutions examines the validity of the model. The proposed distribution kinetics model provides a different interpretation of the familiar Avrami equation.

Temperature effects for isothermal polymer crystallization kinetics.

We adopt the cluster size distribution model to investigate the effect of temperature on homogeneous nucleation and crystal growth for isothermal polymer crystallization. The model includes the temperature effects of interfacial energy, nucleation rate, growth and dissociation rate coefficients, and equilibrium solubility. The time dependencies of polymer concentration, number and size of crystals, and crystallinity (in Avrami plots) are presented for different temperatures. The denucleation (Ostwald ripening effect) is also investigated by comparing moment and numerical solutions of the population balance equations. Agreement between the model results and temperature-sensitive experimental measurements for different polymer systems required strong temperature dependence for the crystal-melt interfacial energy.

A New Population Balance Model for Crystal Size Distributions: Reversible, Size-Dependent Growth and Dissolution.

A new approach to crystal growth and dissolution, based on a population balance equation (PBE) similar to models of reversible chain polymerization, describes reversible solute addition to crystal surfaces. The PBE, in combination with a mass balance for solute, can be solved for mass moments of the crystal size distribution (CSD). The first three moments provide the number, average mass, and CSD variance, which allow representation of the CSD by two-parameter, normalized statistical distributions, such as lognormal or gamma distributions. With realistic initial conditions, operating parameters, and rate coefficients, the new theory describes crystal growth, dissolution, and recrystallization (Ostwald ripening) processes. Size-dependent interfacial energy affects solubility and nucleation and determines the driving force for growth or dissolution. Because the model is reversible, the CSD evolves appropriately to equilibrium. The moment equations are readily solved and show properties consistent with observed crystal growth behavior. Copyright 2001 Academic Press.

Lattice-Boltzmann simulation of coalescence-driven island coarsening.

A two-dimensional lattice-Boltzmann model (LBM) with fluid-fluid interactions was used to simulate first-order phase separation in a thin fluid film. The intermediate asymptotic time dependence of the mean island size, island number concentration, and polydispersity were determined and compared with the predictions of the distribution-kinetics model. The comparison revealed that the combined effects of growth, coalescence, and Ostwald ripening control the phase transition process in the LBM simulations. However, the overall process is dominated by coalescence, which is independent of island mass. As the phase transition advances, the mean island size increases, the number of islands decrease, and the polydispersity approaches unity, which conforms to the predictions of the distribution-kinetics model. The effects of the domain size on the intermediate asymptotic island size distribution, scaling form of the island size distribution, and the crossover to the long-term asymptotic behavior were elucidated.