title: Nanoscale colloids in a freely adsorbing polymer solution: a Monte Carlo simulation study.
abstract: A key issue in nanoscale materials and chemical processing is the need for thermodynamic and kinetic models covering colloid-polymer systems over the mesoscopic length scale (approximately 1-100 nm). We have applied Monte Carlo simulations to attractive nanoscale colloid-polymer mixtures toward developing a molecular basis for models of these complex systems. The expanded ensemble Monte Carlo simulation method is applied to calculate colloid chemical potentials (micro(c)) and polymer adsorption (gamma) in the presence of freely adsorbing Lennard-Jones (LJ) homopolymers (surface modifiers). gamma and micro(c) are studied as a function of nanoparticle diameter (sigma(c)), modifier chain length (n) and concentration, and colloid-polymer attractive strength over 0.3 < Rg/sigma(c) < 6 (Rg is the polymer radius of gyration). In the attractive regime, nanocolloid chemical potential decreases and adsorbed amount increases as sigma(c), or n is increased. The scaling of gamma with n from the simulations agrees with the theory of Aubouy and Raphael (Macromolecules 1998, 31, 4357) in the extreme limits of Rg/sigma(c). When Rg/sigma(c) is large, the "colloid" approaches a molecular size and interacts only locally with a few polymer segments and gamma approximately n. When Rg/sigma(c) is small, the system approaches the conventional colloid-polymer size regime where multiple chains interact with a single particle, and gamma approximately sigma(c)2, independent of n. In contrast, adsorption in the mesoscopic range of Rg/sigma(c) investigated here is represented well by a power law gamma approximately n(p), with 0 < p < 1 depending on concentration and LJ attractive strength. Likewise, the chemical potential from our results is fitted well with micro(c) approximately n(q)sigma(c)3, where the cubic term results from the sigma(c) dependence of particle surface area (approximately sigma(c)2) and LJ attractive magnitude (approximately sigma(c)). The q-exponent for micro(c) (micro(c) approximately n(q)) varies with composition and LJ attractive strength but is always very close to the power exponent for gamma (gamma approximately n(p)). This result leads to the conclusion that in attractive systems, polymer adsorption (and thus polymer-colloid attraction) dominates the micro(c) dependence on n, providing a molecular interpretation of the effect of adsorbed organic layers on nanoparticle stability and self-assembly.
authors.affiliation: School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332-0100, USA.
authors.forename: Krishna Tej
authors.initials: KT
authors.lastname: Marla
authors.forename: J Carson
authors.initials: JC
authors.lastname: Meredith