On stability of rapid granular shear flows

We study stability properties of rapid granular flows that are described by the balance laws of mass, momentum and fluctuation energy with phenomenological relationships based upon dimensional arguments [12, 13]. Small disturbances propagating perpendicular to the shear plane are only studied. Calculations show that such flows are stable at small free path lengths of the granules but unstable if free path lengths are large. Received June 17, 1997     

On flows of granular materials

This article reviews the behavior of materials made up of a large assemblage of solid particles under rapid and quasi static deformations. The focus is on flows at relatively high concentrations and for conditions when the interstitial fluid plays an insignificant role. The momentum and energy exchange processes are then primarily governed by interparticle collisions and Coulomb-type frictional contact. We first discuss some physical behavior —dilatancy, internal friction, fluidization and particle segregation — that are typical to the understanding of granular flows. Bagnold's seminal Couette flow experiments and his simple stress analysis are then used to motivate the first constitutive theories that use a microstructural variable — the fluctuation energy or granular temperature — governing the subscale fluctuating motion. The kinetic theories formalize the derivation of the field equations of bulk mass, momentum and energy, and permit derivation of constitutive relations for stress, flux of fluctuation energy and its dissipation rate for simple particle assemblages and when frictional rubbing contact can be ignored. These statistical considerations also show that formulation of boundary conditions needs special attention. The frictional-collisional constitutive behavior in which both Coulomb-type rubbing contact and collisional encounters are significant are discussed. There is as yet no rigorous formulation. We finally present a phenomenological approach that describes rapid flows of granular materials under simultaneous transport of heat and close with a summary of stability analyses of the basic flow down an inclined plane.Dedicated to Professor Dr.-Ing. Franz Gustav Kollmann on the occasion of his sixtieth brithday     

Dividing a complex reaction involving a hypervalent iodine reagent into three limiting mechanisms by ab initio molecular dynamics

The electrophilic N‐trifluoromethylation of MeCN with a hypervalent iodine reagent to form a nitrilium ion, that is rapidly trapped by an azole nucleophile, is thought to occur via reductive elimination (RE). A recent study showed that, depending on the solvent representation, the S_N2 is favoured to a different extent over the RE. However, there is a discriminative solvent effect present, which calls for a statistical mechanics approach to fully account for the entropic contributions. In this study, we perform metadynamic simulations for two trifluoromethylation reactions (with N‐ and S‐nucleophiles), showing that the RE mechanism is always favoured in MeCN solution. These computations also indicate that a radical mechanism (single electron transfer) may play an important role. The computational protocol based on accelerated molecular dynamics for the exploration of the free energy surface is transferable and will be applied to similar reactions to investigate other electrophiles on the reagent. Based on the activation parameters determined, this approach also gives insight into the mechanistic details of the trifluoromethylation and shows that these commonly known mechanisms mark the limits within which the reaction proceeds. © 2015 Wiley Periodicals, Inc.     

A Variational Principle for the Revised Goodman–Cowin Theory with Internal Length

In the present study a variational principle is proposed for the revised Goodman–Cowin theory with internal length for cohesionless granular materials (Fang et al. in Continuum Mech Thermodyn in press). The balance equations of the internal variables employed in the theory in equilibrium states, the equilibrium expressions of the constitutive variables and the corresponding natural boundary conditions are derived by use of the proposed variational principle for both cases of compressible and incompressible grains. It is demonstrated that the derived results coincide with those obtained by use of the thermodynamic analysis. The current work serves as a supplementary variational verification of the constitutive theory proposed in Fang et al. (in Continuum Mech Thermodyn in press).     

A variational approach to a micro-structured theory of solid-fluid mixtures

Summary In this paper, we present a micro-structured model for describing global deformations of heterogeneous mixtures. In particular, for a saturated solid-fluid mixture, we regard the solid volume fraction as a microstructural parameter so as to enlarge the space of admissible deformations with respect to the classical theory of mixtures. According to the variational approach, the governing equations are obtained as the stationarity of a suitable action functional. The micro-structured model is then forced to establish a second-gradient mixture theory, by introducing among the considered state parameters a suitable internal constraint. Finally, we determine under which (integrability) conditions the additional balance laws, typically employed to close the theory of porous media endowed with the volume fraction, can fit the variational framework. The authors wish to thank Prof. Francesco dell'Isola from University of Rome La Sapienza for his constructive criticism about the variational approach to continuum mechanics and the interpretation of the volume-fraction balance law.     

Extracting elements of molecular structure from the all-particle wave function

Structural information is extracted from the all-particle (non-Born-Oppenheimer) wave function by calculating radial and angular densities derived from n-particle densities. As a result, one- and two-dimensional motifs of classical molecular structure can be recognized in quantum mechanics. Numerical examples are presented for three- (H(-), Ps(-), H(2)(+)), four- (Ps(2), H(2)), and five-particle (H(2)D(+)) systems.     

On the thermodynamic consistency of the equivalence principle in continuum damage mechanics

We consider theories of continuum damage mechanics involving damage effect variables of different tensorial ranks. It turns out that orthotropic damage together with the use of Lemaitre's equivalence principle for the elastic part does not allow thermodynamic potentials such as the free enthalpy to exist. As the existence of these potentials is, however, a strict thermodynamic requirement, a theory employing orthotropic damage in this way is inconsistent. We show that the use of a rank-4 damage effect variable allows a consistent use of the equivalence principle.