A New Self-Consistent Field Model of Polymer/Nanoparticle Mixture

Abstract

Field-theoretical method is efficient in predicting assembling structures of polymeric systems. However, it’s challenging to generalize this method to study the polymer/nanoparticle mixture due to its multi-scale nature. Here, we develop a new field-based model which unifies the nanoparticle description with the polymer field within the self-consistent field theory. Instead of being “ensemble-averaged” continuous distribution, the particle density in the final morphology can represent individual particles located at preferred positions. The discreteness of particle density allows our model to properly address the polymer-particle interface and the excluded-volume interaction. We use this model to study the simplest system of nanoparticles immersed in the dense homopolymer solution. The flexibility of tuning the interfacial details allows our model to capture the rich phenomena such as bridging aggregation and depletion attraction. Insights are obtained on the enthalpic and/or entropic origin of the structural variation due to the competition between depletion and interfacial interaction. This approach is readily extendable to the study of more complex polymer-based nanocomposites or biology-related systems, such as dendrimer/drug encapsulation and membrane/particle assembly.

Modeling the Morphology and Phase Behavior of One-Component Polymer-Grafted Nanoparticle Systems

“…Here, we attempt to utilize SCF-DFT while minimizing the particle deformation and overlap. We follow the ideas of Chen et al, 71 who proposed to add a "particle cohesive energy" term in the free energy. The addition of this term results in sharpening the peaks of ρ P (r) and preserving the spherical shapes of individual particles.…”

Surface Segregation of Cyclic Chains in Binary Melts of Thin Polymer Films: The Influence of Constituent Concentration

“…At this peculiar distance from the interface, attraction between cyclic molecules generates geometrical constraints (we will discuss this aspect later), thus preventing close packing of cyclic chains in the bulk of the blend. In the recent literature [40,41], preferential adsorption of polymer components at the interface (in the absence of preferential interaction energies with the medium at the interface) was shown to arise from competition between configurational energy and entropic packing effects. Here, we show that concentration can also be another important parameter affecting enhancement/depletion of polymer species of a blend at the interface.…”

Effect of Chain Architecture on Phase Behavior of Giant Surfactant Constructed from Nanoparticle Monotethered by Single Diblock Copolymer Chain

“…However, in the current version of the SCFT/DFT method, the NPs will overlap with each other and with polymers to a certain degree. A potential way to avoid this drawback has been discussed recently by Chen et al and Ginzburg . Readers who are interested in this problem can refer to refs and .…”

“…A potential way to avoid this drawback has been discussed recently by Chen et al and Ginzburg . Readers who are interested in this problem can refer to refs and .…”

“…However, in the current version of the SCFT/DFT method, the NPs will overlap with each other and with polymers to a certain degree. A potential way to avoid this drawback has been discussed recently by Chen et al 45 and Ginzburg. 46 Readers who are interested in this problem can refer to refs 45 and 46. In this work, we employed the combinatorial screening algorithm proposed by Drolet and Fredrickson to solve the self-consistent field equations.…”