2013 | P. Douglas Godfrin, Néstor E. Valadez-Pérez, Ramon Castañeda-Priego, Norman J. Wagner and Yun Liu
This is an Accepted Manuscript, which has been through the Royal Society of Chemistry peer review process and has been accepted for publication. Accepted Manuscripts are published online shortly after acceptance, before technical editing, formatting and proof reading. Using this free service, authors can make their results available to the community, in citable form, before we publish the edited article. We will replace this Accepted Manuscript with the edited and formatted Advance Article as soon as it is available.
The paper investigates the generalized phase behavior of cluster formation in colloidal dispersions with competing interactions. Monte Carlo simulations are performed for two physically meaningful inter-particle potentials across a broad range of interaction parameters, temperatures and volume fractions to locate the conditions where clustered states are found. A corresponding states phase behavior is identified when normalized by the critical point of an appropriately selected reference attractive fluid. Clustered fluid states and cluster percolated states are found exclusively within the two phase region of the state diagram for a reference attractive fluid, confirming the underlying intrinsic relation between clustered states and bulk phase separation. Clustered and cluster percolated states consistently exhibit an intermediate range order peak in their structure factors with a magnitude above 2.7, leading to a semi-empirical rule for identifying clustered fluids in scattering experiments.
The study explores the transition from a dispersed fluid to a clustered fluid by examining a wide range of potential parameters and different potential shapes. Simulations are performed utilizing two functional forms of SALR interaction potentials with varying parameters, temperature and volume fraction. A corresponding states diagram is found for the reference attractive potentials and this is used to create a generalized state diagram for clustered fluids. Published results are also included and shown to be consistent with the proposed generalized corresponding states phase diagram.
The paper discusses the role of long-range repulsion in the formation of clustered states and the effect of varying the range of repulsion on the applicability of the generalized state diagram. The results indicate that the phase behavior of a broad range of physically meaningful SALR systems collapses onto a single state diagram when normalized by the critical point of an appropriately defined reference system. The reference system's potential is comprised of the excluded volume and short range attraction of the corresponding SALR potential. The liquid state binodals for these reference potentials are very similar and follow the extended law of corresponding states themselves.
The paper concludes that the existence of a generalized corresponding states phase diagram for systems with physically meaningful potentials comprised of excluded volume with short range attraction and long range repulsion (SALR) is a significant finding. Four distinct types of states are distinguished as dispersed fluid, clustered fluid, random percolated, and cluster percolated states. Most significantly, cluster fluids are located within the binodal of the reference system and in the one-phase region of the HSDY system. This supports the intuitive notion that cluster fluids are what otherwise would be phase separated fluids that are frustrated by the repulsive interactions. The study provides three semi-empirical criteria necessary for cluster formationThis is an Accepted Manuscript, which has been through the Royal Society of Chemistry peer review process and has been accepted for publication. Accepted Manuscripts are published online shortly after acceptance, before technical editing, formatting and proof reading. Using this free service, authors can make their results available to the community, in citable form, before we publish the edited article. We will replace this Accepted Manuscript with the edited and formatted Advance Article as soon as it is available.
The paper investigates the generalized phase behavior of cluster formation in colloidal dispersions with competing interactions. Monte Carlo simulations are performed for two physically meaningful inter-particle potentials across a broad range of interaction parameters, temperatures and volume fractions to locate the conditions where clustered states are found. A corresponding states phase behavior is identified when normalized by the critical point of an appropriately selected reference attractive fluid. Clustered fluid states and cluster percolated states are found exclusively within the two phase region of the state diagram for a reference attractive fluid, confirming the underlying intrinsic relation between clustered states and bulk phase separation. Clustered and cluster percolated states consistently exhibit an intermediate range order peak in their structure factors with a magnitude above 2.7, leading to a semi-empirical rule for identifying clustered fluids in scattering experiments.
The study explores the transition from a dispersed fluid to a clustered fluid by examining a wide range of potential parameters and different potential shapes. Simulations are performed utilizing two functional forms of SALR interaction potentials with varying parameters, temperature and volume fraction. A corresponding states diagram is found for the reference attractive potentials and this is used to create a generalized state diagram for clustered fluids. Published results are also included and shown to be consistent with the proposed generalized corresponding states phase diagram.
The paper discusses the role of long-range repulsion in the formation of clustered states and the effect of varying the range of repulsion on the applicability of the generalized state diagram. The results indicate that the phase behavior of a broad range of physically meaningful SALR systems collapses onto a single state diagram when normalized by the critical point of an appropriately defined reference system. The reference system's potential is comprised of the excluded volume and short range attraction of the corresponding SALR potential. The liquid state binodals for these reference potentials are very similar and follow the extended law of corresponding states themselves.
The paper concludes that the existence of a generalized corresponding states phase diagram for systems with physically meaningful potentials comprised of excluded volume with short range attraction and long range repulsion (SALR) is a significant finding. Four distinct types of states are distinguished as dispersed fluid, clustered fluid, random percolated, and cluster percolated states. Most significantly, cluster fluids are located within the binodal of the reference system and in the one-phase region of the HSDY system. This supports the intuitive notion that cluster fluids are what otherwise would be phase separated fluids that are frustrated by the repulsive interactions. The study provides three semi-empirical criteria necessary for cluster formation