A Gibbs monolayer of jammed, or nearly jammed, spherical nanoparticles was imaged at a liquid surface in real time by in-situ scanning electron microscopy performed at the single-particle level. At nanoparticle areal fractions above that for the onset of two-dimensional crystallization, structural reorganizations of the mobile polymer-coated particles were visualized after a stepwise areal compression. When the compression was small, slow shearing near dislocations and reconfigured nanoparticle bonding were observed at crystal grain boundaries. At larger scales, domains grew as they rotated into registry by correlated but highly intermittent motions. Simultaneously, the areal density in the middle of the monolayer increased. When the compression was large, the jammed monolayers exhibited out-of-plane deformations such as wrinkles and bumps. Due to their large interfacial binding energy, few (if any) of the two-dimensionally mobile nanoparticles returned to the liquid subphase. Compressed long enough (several hours or more), monolayers transformed into solid nanoparticle films, as evidenced by their cracking and localized rupturing upon subsequent areal expansion. These observations provide mechanistic insights into the dynamics of a simple model system that undergoes jamming/unjamming in response to mechanical stress.
The relaxation and aging of an assembly of spherical nanoparticles (NPs) at a water−oil interface are characterized in situ by grazing incidence X-ray photon correlation spectroscopy. The dynamics of the interfacial assembly is measured while the interface saturates with NPs. Weak attractions between NPs lead to gel-like structures in the assembly, where the in-plane ordering is inhibited by the broad size distribution of the NPs. Structural rearrangements on the length scale of the NP−NP center-to-center distances proceed by intermittent fluctuations instead of continuous cooperative motions. The coexistence of rapid and slow NP populations is confirmed, as commonly observed in soft glass-forming materials. Dynamics are increasingly slowed as the NPs initially segregate to the locally clustered interface. The structural relaxation of the NPs in these localized clusters is 5 orders of magnitude slower than that of free particles in the bulk. When the interface is nearly saturated, the time for relaxation increases suddenly due to the onset of local jamming, and the dynamics slow exponentially afterward until the system reaches collective jamming by cooperative rearrangements. This investigation provides insights into structural relaxations near the glass transition and the evolution of the structure and dynamics of the assemblies as they transition from an isotropic liquid to a dense disordered film.
Bottlebrush polymer surfactants (BPSs), formed by the interfacial interactions between bottlebrush polymers (BPs) with poly(acrylic acid) side chains dissolved in an aqueous phase and amine-functionalized ligands dissolved in the oil phase, assemble and bind strongly to the fluid−fluid interface. The ratio between N BB (backbone degree of polymerization) and N SC (side chain degree of polymerization) defines the initial assembly kinetics, interface packing efficiency, and stress relaxation. The equilibrium interfacial tension (γ) increases when N BB < N SC , but decreases when N BB ≫ N SC , correlating to a pronounced change in the effective shape of the BPs from being spherical to worm-like structures. The apparent surface coverage (ASC), i.e., the interfacial packing efficiency, decreases as N BB increases. The dripping-to-jetting transition of an injected polymer solution, as well as fluorescence recovery after photobleaching experiments, revealed faster initial assembly kinetics for BPs with higher N BB . Euler buckling of BPS assemblies with different N BB values was used to characterize the stress relaxation behavior and bending modulus. The stress relaxation behavior was directly related to the ASC, reflecting the strong influence of macromolecular shape on packing efficiency. The bending modulus of BPSs decreases for N BB < N SC , but increased when N BB ≫ N SC , showing the effect of molecular architecture and multisite anchoring. All-liquid printed constructs with lower N BB BPs yielded more stable structured liquids, underscoring the importance of macromolecular packing efficiency at fluid interfaces. Overall, this work elucidates fundamental relationships between nanoscopic structures and macroscopic properties associated with various bottlebrush polymer architectures, which translate to the stabilization of all-fluidic printed constructs.
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