A large body of experimental work has established that athermal colloid/polymer mixtures undergo a sequence of transitions from a disordered fluid state to a colloidal crystal to a second disordered phase with increas...A large body of experimental work has established that athermal colloid/polymer mixtures undergo a sequence of transitions from a disordered fluid state to a colloidal crystal to a second disordered phase with increasing polymer concentration.These transitions are driven by polymer-mediated interparticle attraction,which is a function of both the polymer density and size.It has been posited that the disordered state at high polymer density is a consequence of strong interparticle attractions that kinetically inhibit the formation of the colloidal crystal,i.e.,the formation of a non-equilibrium gel phase interferes with crystallization.Here we use molecular dynamics simulations and density functional theory on polymers and nanoparticles(NPs)of comparable size and show that the crystal-disordered phase coexistence at high polymer density for sufficiently long chains corresponds to an equilibrium thermodynamic phase transition.While the crystal is,indeed,stabilized at intermediate polymer density by polymer-induced intercolloid attractions,it is destabilized at higher densities because long chains lose significant configurational entropy when they are forced to occupy all of the crystal voids.Our results are in quantitative agreement with existing experimental data and show that,at least in the nanoparticle limit of sufficiently small colloidal particles,the crystal phase only has a modest range of thermodynamic stability.展开更多
基金supported by the Office of Science of the U.S.Department of Energy under Contract No.DE-AC02-05CH11231the Advanced Scientific Computing Research(ASCR)Leadership Computing Challenge(ALCC)Financial support was received from the National Science Foundation(Collaborative Research Award CBET-1403049 at Columbia and CBET-1402166 at Princeton)is gratefully acknowledged.
文摘A large body of experimental work has established that athermal colloid/polymer mixtures undergo a sequence of transitions from a disordered fluid state to a colloidal crystal to a second disordered phase with increasing polymer concentration.These transitions are driven by polymer-mediated interparticle attraction,which is a function of both the polymer density and size.It has been posited that the disordered state at high polymer density is a consequence of strong interparticle attractions that kinetically inhibit the formation of the colloidal crystal,i.e.,the formation of a non-equilibrium gel phase interferes with crystallization.Here we use molecular dynamics simulations and density functional theory on polymers and nanoparticles(NPs)of comparable size and show that the crystal-disordered phase coexistence at high polymer density for sufficiently long chains corresponds to an equilibrium thermodynamic phase transition.While the crystal is,indeed,stabilized at intermediate polymer density by polymer-induced intercolloid attractions,it is destabilized at higher densities because long chains lose significant configurational entropy when they are forced to occupy all of the crystal voids.Our results are in quantitative agreement with existing experimental data and show that,at least in the nanoparticle limit of sufficiently small colloidal particles,the crystal phase only has a modest range of thermodynamic stability.
