Depletion effects and gelation in a binary hard-sphere fluid

L. Lue, L. V. Woodcock

Research output: Contribution to journalArticle

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Abstract

A study of the binary hard-sphere fluid with size ratio sigma(B)/sigma(A)= 0.1 is reported. Molecular dynamics and Monte Carlo simulations have been carried out over the mole fraction (x(A)) range 0.002-0.1and over the high density range where several recent authors have predicted a thermodynamic demixing transition on the basis of integral equations. In this region, there is no evidence of such first-order thermodynamic phase separation, or two fluid phases. The effect of the depletion force, arising from the entropic exclusion of B spheres from between two A spheres, as x(B) is increased at constant packing fraction y(A), is to cause a large increase in the partial pressure of A and the radial distribution function of A at contact, a reduction on the mobility of A, and eventually, at a sufficient x(B), the gelation of component A to an open, low coordination, amorphous structure.This gelation transition of A shows discontinuities similar to a glass transition; it can be traced back to the hard sphere glass formation as x(B) approaches zero. Thermodynamic properties are reported over the range studied; and used to evaluate the predictions of current theories and the accuracy of equations of state. The Boublik-Mansoori-Carnahan-Starling-Leland equation is found to be remarkably accurate in this region,over the whole fluid range, but shows systematic deviations at high packing densities.
LanguageEnglish
Pages1435-1443
Number of pages9
JournalMolecular Physics
Volume96
Issue number9
DOIs
Publication statusPublished - 10 May 1999

Fingerprint

gelation
Gelation
Thermodynamics
depletion
Glass
Fluids
fluids
Starlings
Partial Pressure
Molecular Dynamics Simulation
thermodynamics
glass
packing density
exclusion
Equations of state
radial distribution
Phase separation
Partial pressure
Integral equations
Distribution functions

Keywords

  • 5th virial-coefficient
  • density-functional theory
  • phase- separation
  • integral-equation
  • computer-simulation
  • core mixtures
  • monte-carlo
  • consistent
  • colloids

Cite this

Lue, L. ; Woodcock, L. V. / Depletion effects and gelation in a binary hard-sphere fluid. In: Molecular Physics. 1999 ; Vol. 96, No. 9. pp. 1435-1443.
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Depletion effects and gelation in a binary hard-sphere fluid. / Lue, L.; Woodcock, L. V.

In: Molecular Physics, Vol. 96, No. 9, 10.05.1999, p. 1435-1443.

Research output: Contribution to journalArticle

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