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Understanding the role of interparticle interactions in jamming phenomena is essential for gaining insights into the intriguing glass transition behavior observed in atomic and molecular systems. In this study, we investigate the jamming behavior of colloids with tunable interparticle interactions during evaporation-induced assembly (EIA). By manipulating the interaction among charged colloids using cationic polyethyleneimine (PEI) through electro-sorption and subsequent free polymer induced repulsion, we observe distinct jamming behavior in silica colloids during EIA, depending on the interparticle interactions. Silica colloids with strong repulsive interactions exhibit a repulsive colloidal glass state with a volume fraction of silica colloids in supraparticle ϕ ∼ 0.70. On the other hand, PEI-mediated attractive interactions among silica colloids lead to an attractive colloidal glass phase with a significantly lower ϕ ∼ 0.43. Free polymer induced repulsion of colloids at higher PEI concentration once again results in a repulsive glassy state with ϕ ∼ 0.61. Furthermore, we revealed that interparticle interactions not only influence the jamming behavior but also play a significant role in shaping the morphology of self-assembled structures during EIA, and the assembled structure undergoes a morphological reentrant transition from a doughnut-like shape to a spherical form and again back to a doughnut-like configuration. Jamming-dependent evolution of micropores and dynamics of the confined PEI have been probed using positron annihilation lifetime spectroscopy (PALS) and broadband dielectric spectroscopy (BDS). PALS reveals distinct variations in the micropores of the supraparticles with different PEI loadings, confirming the impact of jamming on the evolution of the micropores within the supraparticles. BDS measurements uncover non-monotonic dynamics of PEI molecules confined in the evolved pore network. It is revealed that the reentrant jamming behavior of colloids, modulated by PEI, holds profound significance for the long-term stability of supraparticles.

For various industrial processes, the stabilization of an oil phase is crucial and demands a proper balance of complex interactions in an emulsion system. In Pickering emulsions, this is achieved by introducing nanoparticles, which become organized at the oil-water interface. The influence of interparticle interactions towards the formation of a stable emulsion and the ordering of the stabilizing nanoparticles is intriguing and needs attention. In this work, the role of amphiphilic interactions between hydrophilic silica nanoparticles and the Pluronic F127 tri-block co-polymer towards the spontaneous formation of a fairly stable Pickering emulsion has been studied using small-angle X-ray scattering. Unlike the usual random arrangements of the nanoparticles in a conventional Pickering emulsion, we observed highly organized silica nanoparticles at the oil-water interface. The established standard raspberry structural model of the Pickering emulsion fails to explain such strong ordering as observed in the present case. A plausible formation mechanism of the present Pickering emulsion with a high on-surface silica correlation is elucidated on the basis of the combined interactions of the block co-polymer and silica particles. A computer model is developed to elucidate the effects of size and distribution of the surface-decorating nanoparticles and their positional correlation.

We report a detailed study of hierarchically organized silica-polyethylenimine (PEI) microspheres achieved through evaporation-induced assembly. Due to complex interactions between oppositely-charged silica nanoparticles and PEI, non-monotonic jamming of the colloidal particles is manifested. With an increase in the polymer concentration, the local volume fraction of the silica particles decreases from 0.68 to 0.43 and then increases to 0.55 with further increase. The unusual jamming behaviour of the silica colloids in the presence of PEI provides an avenue for immobilizing PEI without reducing the porosity and specific area in contrast to the conventional impregnation approach. The resultant composite microspheres show good thermal stability and CO 2 sorption characteristics. For a 33 wt% PEI loading, the microspheres exhibit a significant CO 2 capture capacity of 65 mg g -1 even at room temperature and it is increased to 90 mg g -1 at 75 °C. The variation in the CO 2 capture capacity at 0 °C as a function of PEI loading also demonstrated the signature of non-monotonicity owing to the structural modification in the silica-PEI microspheres. The composite microspheres demonstrated fast adsorption kinetics reaching 70% of the total capture capacity in one minute during the CO 2 capture. The CO 2 cycling adsorption-desorption studies showed good regeneration capability up to 20 cycles.

The kinetics of liquid solvent sorption in polymeric systems and their nanocomposites often deviate from normal Fickian behaviour. This needs to be understood and interpreted, in terms of their underlying mechanistic origins. In the present study, the results of time dependent toluene sorption measurements in model segmented polyurethane-urea/clay nanocomposites have been analysed at room temperature. The studies revealed pronounced S-shaped sorption curves and unusually higher swelling of the nanocomposites compared to the neat polyurethane-urea matrix. Dynamic mechanical analysis (DMA) and small angle X-ray scattering (SAXS) measurements on the nanocomposites in the dry and liquid toluene saturated state have been carried out. The DMA studies revealed a significant decrease in the α relaxation temperature and storage modulus of the nanocomposites in the swollen state compared to the dry samples. The SAXS results showed that the nanoclay dispersion morphology transformed from intercalation in the dry state to exfoliation in the swollen state and the interdomain distance between hard segments increased upon swelling. Thermodynamic analysis of the Flory-Huggins interaction parameter (χ) of nanocomposite/toluene systems revealed increasingly negative χ values with increased clay loading. These results imply a significant plasticization effect of toluene on the nanocomposites. An interpretation of these data, which relates the abovementioned results, is presented in the framework of differential swelling stress (DSS) induced deviation from Fickian transport characteristics. We expect that these findings and methods may provide new insight into the analysis of the solvent diffusion process in heterogeneous polymers and their nanocomposites.