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Internal Microstructure Dictates Interactions of Polymer-grafted Nanoparticles in Solution.

ABSTRACT: Understanding the effects of polymer brush architecture on particle interactions in solution is requisite to enable the development of functional materials based on self-assembled polymer-grafted nanoparticles (GNPs). Static and dynamic light scattering of polystyrene-grafted silica particle solutions in toluene reveals that the pair interaction potential, inferred from the second virial coefficient, A ₂, is strongly affected by the grafting density, σ, and degree of polymerization, N, of tethered chains. In the limit of intermediate σ (∼0.3 to 0.6 nm^-2) and high N, A ₂ is positive and increases with N. This confirms the good solvent conditions and can be qualitatively rationalized on the basis of a pair interaction potential derived for grafted (brush) particles. In contrast, for high σ > 0.6 nm^-2 and low N, A ₂ displays an unexpected reversal to negative values, thus indicating poor solvent conditions. These findings are rationalized by means of a simple analysis based on a coarse-grained brush potential, which balances the attractive core-core interactions and the excluded volume interactions imparted by the polymer grafts. The results suggest that the steric crowding of polymer ligands in dense GNP systems may fundamentally alter the interactions between brush particles in solution and highlight the crucial role of architecture (internal microstructure) on the behavior of hybrid materials. The effect of grafting density also illustrates the opportunity to tailor the physical properties of hybrid materials by altering geometry (or architecture) rather than a variation of the chemical composition.

SUBMITTER: Gury L

PROVIDER: S-EPMC8361431 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:We describe a successful strategy to substantially enhance cell nucleation efficiency in polymer foams by using designer nanoparticles as nucleating agents. Bare and poly(dimethylsilane) (PDMS)-grafted raspberry-like silica nanoparticles with diameters ranging from ∼80 nm to ∼200 nm were synthesized and utilized as highly efficient cell nucleators in CO2-blown nanocellular polymethyl methacrylate (PMMA) foams. The successful synthesis of core-shell nanoparticles was confirmed by Fourier transform infrared spectroscopy, thermogravimetric analysis, Brunauer-Emmett-Teller measurements, and transmission electron microscopy. The cell size and cell density of the obtained PMMA micro- and nanocellular foams were determined by scanning electron microscopy. The results show that increased surface roughness enhances the nucleation efficiency of the designer silica particles. This effect is ascribed to a decreased nucleation free energy for foam cell nucleation in the nanocavities at the melt-nucleator interface. For PDMS grafted raspberry-like silica nanoparticles with diameters of 155 and 200 nm, multiple cell nucleation events were observed. These hybrid particles had nucleation efficiencies of 3.7 and 6.2, respectively. The surprising increase in nucleation efficiency to above unity is ascribed to the significant increase in CO2 absorption and capillary condensation in the corresponding PMMA during saturation. This increase results in the presence of large amounts of the physical blowing agent close to energetically favorable nucleation points. Additionally, it is shown that as a consequence of cell coalescence, the increased number of foam cells is rapidly reduced during the first seconds of foaming. Hence, the design of highly efficient nucleating particles, as well as careful selection of foam matrix materials, seems to be of pivotal importance for obtaining polymer cellular materials with cell dimensions at the nanoscale. These findings contribute to the fabrication of polymer foams with high thermal insulation capacity and have relevance in general to the area of cellular materials.

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Internal Microstructure Dictates Interactions of Polymer-grafted Nanoparticles in Solution.

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