Many body effects on the phase separation and structure of dense polymer-particle melts.

Liquid state theory is employed to study phase transitions and structure of dense mixtures of hard nanoparticles and flexible chains (polymer nanocomposites). Calculations are performed for the first time over the entire compositional range from the polymer melt to the hard sphere fluid. The focus is on polymers that adsorb on nanoparticles. Many body correlation effects are fully accounted for in the determination of the spinodal phase separation instabilities. The nanoparticle volume fraction at demixing is determined as a function of interfacial cohesion strength (or inverse temperature) for several interaction ranges and nanoparticle sizes. Both upper and lower critical temperature demixing transitions are predicted, separated by a miscibility window. The phase diagrams are highly asymmetric, with the entropic depletion-like lower critical temperature occurring at a nanoparticle volume fraction of approximately 10%, and a bridging-induced upper critical temperature at approximately 95% filler loading. The phase boundaries are sensitive to both the spatial range of interfacial cohesion and nanoparticle size. Nonmonotonic variations of the bridging (polymer-particle complex formation) demixing boundary on attraction range are predicted. Moreover, phase separation due to many body bridging effects occurs for systems that are fully stable at a second order virial level. Real and Fourier space pair correlations are examined over the entire volume fraction regime with an emphasis on identifying strong correlation effects. Special attention is paid to the structure near phase separation and the minimum in the potential of mean force as the demixing boundaries are approached. The possibility that nonequilibrium kinetic gelation or nanoparticle cluster formation preempts equilibrium phase separation is discussed.