Polymer-based membranes play a key role in several industrially important gas separation technologies, e.g., removing CO 2 from natural gas, with enormous economic and environmental impact. Here, we develop a novel hybrid membrane construct comprised entirely of nanoparticles grafted with polymers. These membranes are shown to have broadly tunable separation performance through variations in graft density and chain length. Computer simulations show that the optimal NP packing forces the grafted polymer layer to distort, yielding regions of measurably lower polymer density. Multiple experimental probes confirm that these materials have the predicted increase in "polymer free volume", which explains their improved separation performance. These polymer-grafted NP materials thus represent a new template for rationally designing membranes with desirable separation abilities coupled with improved aging characteristics in the glassy state and enhanced mechanical behavior.
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Two different classes of hairy self-suspended nanoparticles in the melt state, polymer-grafted nanoparticles (GNPs) and star polymers, are shown to display universal dynamic behavior across a broad range of parameter space. Linear viscoelastic measurements on well-characterized silica-poly(methyl acrylate) GNPs with a fixed core radius (R core) and grafting density (or number of arms f) but varying arm degree of polymerization (N arm) show two distinctly different regimes of response. The colloidal Regime I with a small N arm (large core volume fraction) is characterized by predominant low-frequency solidlike colloidal plateau and ultraslow relaxation, while the polymeric Regime II with a large N arm (small core volume fractions) has a response dominated by the starlike relaxation of partially interpenetrated arms. The transition between the two regimes is marked by a crossover where both polymeric and colloidal modes are discerned albeit without a distinct colloidal plateau. Similarly, polybutadiene multiarm stars also exhibit the colloidal response of Regime I at very large f and small N arm. The star arm retraction model and a simple scaling model of nanoparticle escape from the cage of neighbors by overcoming a hopping potential barrier due to their elastic deformation quantitatively describe the linear response of the polymeric and colloidal regimes, respectively, in all these cases. The dynamic behavior of hairy nanoparticles of different chemistry and molecular characteristics, investigated here and reported in the literature, can be mapped onto a universal dynamic diagram of f/[R core 3/ν0)1/4] as a function of (N armν0 f)/(R core 3), where ν0 is the monomeric volume. In this diagram, the two regimes are separated by a line where the hopping potential ΔU hop is equal to the thermal energy, k B T. ΔU hop can be expressed as a function of the overcrowding parameter x (i.e., the ratio of f to the maximum number of unperturbed chains with N arm that can fill the volume occupied by the polymeric corona); hence, this crossing is shown to occur when x = 1. For x > 1, we have colloidal Regime I with an overcrowded volume, stretched arms, and ΔU hop > k B T, while polymeric Regime II is linked to x < 1. This single-material parameter x can provide the needed design principle to tailor the dynamics of this class of soft materials across a wide range of applications from membranes for gas separation to energy storage.
It is demonstrated that the addition of nanoparticles can decrease the viscosity of an entangled polymer matrix (plasticization). While there has been considerable effort in understanding the role of bare nanoparticles on viscosity, the corresponding study on grafted particles is nascent. Two nanometer radius zirconia fillers with a bimodal population of grafted PDMS is used. Two fillers are considered: one has grafted chains with a molecular weight, Mg, less than the entanglement M, Mg < Me (ZrO2 1k 10k), and the other filler has grafted chains M > Mc (the critical Me) (ZrO2 1k 36k). The ZrO2 1k 10k composites exhibit plasticization for large matrix molecular weight Mm. The ZrO2 1k 36k composites, in contrast, have Einstein‐like behavior. The plasticization effects are either due to: the small filler size relative to the tube diameter or an increase in chain mobility at the interface due to autophobic dewetting.
Membranes made purely from nanoparticles (NPs) grafted with polymer chains show increased gas permeability relative to the analogous neat polymer films, with this effect apparently being tunable with systematic variations in polymer graft density and molecular weight. To explore the structural origins of these unusual transport results, we use small angle scattering (neutron, X-ray) on the dry nanocomposite film and to critically examine in situ the structural effects of absorbed solvent. The relatively low diffusion coefficients of typical solvents (∼10 −12 m 2 /s) restricts us to thin films (≈1 μm in thickness) if solute concentration profiles are to equilibrate on the 1 s time scale. The use of such thin films, however, renders them as weak scatterers. Inspired by our nearly two decades old previous work, we address these conflicting requirements through the use of a custom designed flow cell, where stacks of 10 individual ≈1 μm thick supported films are used, while ensuring that each film is individually exposed to solvent vapor. By using isotopically labeled solvents, we study the solvent distribution within the film and show surprisingly that the solvent homogeneously swells the polymer under all conditions that we examined. These results are not anticipated by current theories, but they suggest that, at least under some conditions, the free volume increases due to the grafting of chains to nanoparticles is apparently distributed isotropically in these materials.
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