Polymer-grafted nanoparticles (PGNPs) can provide property profiles that cannot be obtained individually by polymers or nanoparticles (NPs). Here, we have studied the mixing-demixing transition of symmetric copolymer melts of polymer-grafted spherical nanoparticles by means of coarse-grained molecular dynamics simulation and a theoretical mean-field model. We find that a larger size of NPs leads to higher stability for a given number of grafted chains and chain lengths, reaching a point where demixing is not possible. Most importantly, the increase in the number of grafted chains, Ng, can initially favour the phase separation of PGNPs, but a further increase can lead to more difficult demixing. The reason is the increasing impact of an effective core that forms as the grafting density of the tethered polymer chains around the NPs increases. The range and exact values of Ng where this change in behaviour takes place depend on the NP size and the chain length of the grafted polymer chains. Our study elucidates the phase behaviour of PGNPs and in particular the influence of the grafting density on the phase behaviour of the systems, anticipating that it will open new doors in the understanding of these systems with implications in materials science and medicine.
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http://dx.doi.org/10.1039/c9sm01639b | DOI Listing |
Eur Phys J E Soft Matter
September 2023
Department of Physics, McGill University, 3600 University Street, Montreal, QC, H3A 2T8, Canada.
We use molecular dynamics simulation to probe the non-equilibrium physics of two nanochannel-confined semiflexible polymers in a homogeneous flow field. We find that for sufficiently stiff chains the internal organization of the two chains takes the form of interwoven folds and circular coils. This organization can lead to mixing or demixing depending on chain stiffness and flow speed.
View Article and Find Full Text PDFJ Chem Phys
January 2022
Laboratoire Charles Coulomb (L2C), UMR 5221 CNRS-Universitè de Montpellier, F-34095 Montpellier, France.
Motivated by observations of the heterogeneous domain structure on the surface of cells and vesicles and by domain formation due to the adsorption of complex molecules onto composite membranes, we consider a minimal quasi-2D model to describe the structure of binary mixtures on the surface of a spherical particle. We study the effect of miscibility and adsorbing particle (AP) addition on the mixture structure. We define a new scalar quantity, the geodesic mixing parameter Ξ, through which we detail the effect of miscibility and the role of preferential affinity of APs with one of the two components of the mixture, distinguishing unambiguously between mixing and demixing solely induced by APs.
View Article and Find Full Text PDFPhys Chem Chem Phys
April 2021
COMP Centre of Excellence, Department of Applied Physics, Aalto University, Espoo, Finland.
Complex fluids made of liquid crystals (LCs) and small molecules, surfactants, nanoparticles or 1D/2D nanomaterials show novel and interesting features, making them suitable materials for various applications starting from optoelectronics to biosensing. While these additives (impurities) introduce new features in the complex fluids, they may also alter the phase transition behaviour of LCs depending on the physiochemical properties of the added impurity. This article reports on the phase transition of 4-cyano-4'-alkylbiphenyl (nCB) LCs in the presence of an associative impurity, i.
View Article and Find Full Text PDFSoft Matter
January 2020
Department of Chemical Engineering, Imperial College London, South Kensington Campus, SW7 2AZ London, UK.
Polymer-grafted nanoparticles (PGNPs) can provide property profiles that cannot be obtained individually by polymers or nanoparticles (NPs). Here, we have studied the mixing-demixing transition of symmetric copolymer melts of polymer-grafted spherical nanoparticles by means of coarse-grained molecular dynamics simulation and a theoretical mean-field model. We find that a larger size of NPs leads to higher stability for a given number of grafted chains and chain lengths, reaching a point where demixing is not possible.
View Article and Find Full Text PDFSci Rep
May 2019
Department of Applied Science and Technology and u.d.r. CNISM, Politecnico di Torino, I-10129, Torino, Italy.
We derive the complete mixing-demixing phase-diagram relevant to a bosonic binary mixture confined in a ring trimer and modeled within the Bose-Hubbard picture. The mixing properties of the two quantum fluids, which are shown to be strongly affected by the fragmented character of the confining potential, are evaluated by means of a specific indicator imported from Statistical Thermodynamics and are shown to depend only on two effective parameters incorporating the asymmetry between the heteronuclear species. To closely match realistic experimental conditions, our study is extended also beyond the pointlike approximation of potential wells by describing the systems in terms of two coupled Gross-Pitaevskii equations.
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