Samanvaya Srivastava

25th Anniversary Article: Polymer–Particle Composites: Phase Stability and Applications in Electrochemical Energy Storage

Polymer-particle composites are used in virtually every field of technology. When the particles approach nanometer dimensions, large interfacial regions are created. In favorable situations, the spatial distribution of these interfaces can be controlled to create new hybrid materials with physical and transport properties inaccessible in their constituents or poorly prepared mixtures. This review surveys progress in the last decade in understanding phase behavior, structure, and properties of nanoparticle-polymer composites. The review takes a decidedly polymers perspective and explores how physical and chemical approaches may be employed to create hybrids with controlled distribution of particles. Applications are studied in two contexts of contemporary interest: battery electrolytes and electrodes. In the former, the role of dispersed and aggregated particles on ion-transport is considered. In the latter, the polymer is employed in such small quantities that it has been historically given titles such as binder and carbon precursor that underscore its perceived secondary role. Considering the myriad functions the binder plays in an electrode, it is surprising that highly filled composites have not received more attention. Opportunities in this and related areas are highlighted where recent advances in synthesis and polymer science are inspiring new approaches, and where newcomers to the field could make important contributions.

Tethered Nanoparticle–Polymer Composites: Phase Stability and Curvature

Phase behavior of poly(ethylene glycol) (PEG) tethered silica nanoparticles dispersed in PEG hosts is investigated using small-angle X-ray scattering. Phase separation in dispersions of densely grafted nanoparticles is found to display strikingly different small-angle X-ray scattering signatures in comparison to phase-separated composites comprised of bare or sparsely grafted nanoparticles. A general diagram for the dispersion state and phase stability of polymer tethered nanoparticle-polymer composites incorporating results from this as well as various other contemporary studies is presented. We show that in the range of moderate to high grafting densities the dispersion state of nanoparticles in composites is largely insensitive to the grafting density of the tethered chains and chemistry of the polymer host. Instead, the ratio of the particle diameter to the size of the tethered chain and the ratio of the molecular weights of the host and tethered polymer chains (P/N) are shown to play a dominant role. Additionally, we find that well-functionalized nanoparticles form stable dispersions in their polymer host beyond the P/N limit that demarcates the wetting/dewetting transition in polymer brushes on flat substrates interacting with polymer melts. A general strategy for achieving uniform nanoparticle dispersion in polymers is proposed.

Phase stability and dynamics of entangled polymer–nanoparticle composites

Nanoparticle–polymer composites, or polymer–nanoparticle composites (PNCs), exhibit unusual mechanical and dynamical features when the particle size approaches the random coil dimensions of the host polymer. Here, we harness favourable enthalpic interactions between particle-tethered and free, host polymer chains to create model PNCs, in which spherical nanoparticles are uniformly dispersed in high molecular weight entangled polymers. Investigation of the mechanical properties of these model PNCs reveals that the nanoparticles have profound effects on the host polymer motions on all timescales. On short timescales, nanoparticles slow-down local dynamics of the host polymer segments and lower the glass transition temperature. On intermediate timescales, where polymer chain motion is typically constrained by entanglements with surrounding molecules, nanoparticles provide additional constraints, which lead to an early onset of entangled polymer dynamics. Finally, on long timescales, nanoparticles produce an apparent speeding up of relaxation of their polymer host.

Self-assembling peptide-based building blocks in medical applications ☆

Abstract Peptides and peptide‐conjugates, comprising natural and synthetic building blocks, are an increasingly popular class of biomaterials. Self‐assembled nanostructures based on peptides and peptide‐conjugates offer advantages such as precise selectivity and multifunctionality that can address challenges and limitations in the clinic. In this review article, we discuss recent developments in the design and self‐assembly of various nanomaterials based on peptides and peptide‐conjugates for medical applications, and categorize them into two themes based on the driving forces of molecular self‐assembly. First, we present the self‐assembled nanostructures driven by the supramolecular interactions between the peptides, with or without the presence of conjugates. The studies where nanoassembly is driven by the interactions between the conjugates of peptide‐conjugates are then presented. Particular emphasis is given to in vivo studies focusing on therapeutics, diagnostics, immune modulation and regenerative medicine. Finally, challenges and future perspectives are presented. Graphical abstract Figure. No Caption available.

Structure and rheology of nanoparticle–polymer suspensions

Structure and rheology of oligomer-tethered nanoparticles suspended in low molecular weight polymeric host are investigated at various particle sizes and loadings. Strong curvature effects introduced by the small size of the nanoparticle cores are found to be important for understanding both the phase stability and rheology of the materials. Small angle X-ray scattering (SAXS) and transmission electron microscopy measurements indicate that PEG–SiO2/PEG suspensions are more stable against phase separation and aggregation than expected from theory for interacting brushes. SAXS and rheology measurements also reveal that at high particle loadings, the stabilizing oligomer brush is significantly compressed and produces jamming in the suspensions. The jamming transition is accompanied by what appears to be a unique evolution in the transient suspension rheology, along with large increments in the zero-shear, Newtonian viscosity. The linear and nonlinear flow responses of the jammed suspensions are discussed in the framework of the Soft Glassy Rheology (SGR) model, which is shown to predict many features that are consistent with experimental observations, including a two-step relaxation following flow cessation and a facile method for determining the shear-thinning coefficient from linear viscoelastic measurements. Finally, we show that the small sizes of the particles have a significant effect on inter-particle interactions and rheology, leading to stronger deviations from expectations based on planar brushes and hard-sphere suspension theories. In particular, we find that in the high volume fraction limit, tethered nanoparticles interact in their host polymer through short-range forces, which are more analogous to those between soft particles than between spherical polymer brushes.

High energy lithium–oxygen batteries – transport barriers and thermodynamics

We show that it is possible to achieve higher energy density lithium–oxygen batteries by simultaneously lowering the discharge overpotential and increasing the discharge capacity via thermodynamic variables alone. By assessing the relative effects of temperature and pressure on the cell discharge profiles, we characterize and diagnose the critical roles played by multiple dynamic processes that have hindered implementation of the lithium–oxygen battery.

Size-Dependent Particle Dynamics in Entangled Polymer Nanocomposites

Polymer-grafted nanoparticles with diameter d homogeneously dispersed in entangled polymer melts with varying random coil radius R0, but fixed entanglement mesh size a(e), are used to study particle motions in entangled polymers. We focus on materials in the transition region between the continuum regime (d > R0), where the classical Stokes-Einstein (S-E) equation is known to describe polymer drag on particles, and the noncontinuum regime (d < a(e)), in which several recent studies report faster diffusion of particles than expected from continuum S-E analysis, based on the bulk polymer viscosity. Specifically, we consider dynamics of particles with sizes d ≥ a(e) in entangled polymers with varying molecular weight M(w) in order to investigate how the transition from noncontinuum to continuum dynamics occur. We take advantage of favorable enthalpic interactions between SiO2 nanoparticles tethered with PEO molecules and entangled PMMA host polymers to create model nanoparticle-polymer composites, in which spherical nanoparticles are uniformly dispersed in entangled polymers. Investigation of the particle dynamics via X-ray photon correlation spectroscopy measurements reveals a transition from fast to slow particle motion as the PMMA molecular weight is increased beyond the entanglement threshold, with a much weaker M(w) dependence for M(w) > M(e) than expected from S-E analysis based on bulk viscosity of entangled PMMA melts. We rationalize these observations using a simple force balance analysis around particles and find that nanoparticle motion in entangled melts can be described using a variant of the S-E analysis in which motion of particles is assumed to only disturb subchain entangled host segments with sizes comparable to the particle diameter.

Electric field induced microstructures in thin films on physicochemically heterogeneous and patterned substrates.

We study by nonlinear simulations the electric field induced pattern formation in a thin viscous film resting on a topographically or chemically patterned substrate. The thin film microstructures can be aligned to the substrate patterns within a window of parameters where the spinodal length scale of the field induced instability is close to the substrate periodicity. We investigate systematically the change in the film morphology and order when (i) the substrate pattern periodicity is varied at a constant film thickness and (ii) the film thickness is varied at a constant substrate periodicity. Simulations show two distinct pathway of evolution when the substrate-topography changes from protrusions to cavities. The isolated substrate defects generate locally ordered ripplelike structures distinct from the structures on a periodically patterned substrate. In the latter case, film morphology is governed by a competition between the pattern periodicity and the length scale of instability. Relating the thin film morphologies to the underlying substrate pattern has implications for field induced patterning and robustness of inter-interface pattern transfer, e.g., coding-decoding of information printed on a substrate.

Gel phase formation in dilute triblock copolyelectrolyte complexes

Assembly of oppositely charged triblock copolyelectrolytes into phase-separated gels at low polymer concentrations (<1% by mass) has been observed in scattering experiments and molecular dynamics simulations. Here we show that in contrast to uncharged, amphiphilic block copolymers that form discrete micelles at low concentrations and enter a phase of strongly interacting micelles in a gradual manner with increasing concentration, the formation of a dilute phase of individual micelles is prevented in polyelectrolyte complexation-driven assembly of triblock copolyelectrolytes. Gel phases form and phase separate almost instantaneously on solvation of the copolymers. Furthermore, molecular models of self-assembly demonstrate the presence of oligo-chain aggregates in early stages of copolyelectrolyte assembly, at experimentally unobservable polymer concentrations. Our discoveries contribute to the fundamental understanding of the structure and pathways of complexation-driven assemblies, and raise intriguing prospects for gel formation at extraordinarily low concentrations, with applications in tissue engineering, agriculture, water purification and theranostics.

Embedded Microstructures by Electric-Field-Induced Pattern Formation in Interacting Thin Layers

Electric-field-induced interfacial instabilities and pattern formation in a pair of interacting thin films are analyzed on the basis of linear stability analysis and long-wave nonlinear simulations. The films are coated onto two parallel plate electrodes and separated by an air gap between them. A linear stability analysis (LSA) is carried out for viscoelastic films to show that the ratios of material properties to films thickness control the length scale and timescale significantly and the presence of the second layer increases the overall capacitance and thus can lead to a smaller length scale as compared to the instability in a single film. Long-wave nonlinear analysis for interacting viscous layers indicates that the instabilities are always initiated by the antiphase squeezing rather than the in-phase bending mode of deformation at the interfaces. Nonlinear simulations on patterned electrodes show that this novel geometry for electric field patterning can be employed to generate intricate, embedded 3-D periodic patterns and to miniaturize patterns. Simulations are presented for e-molding of a number of periodic self-organized patterns such as pincushion structures, straight/corrugated embedded microchannels, and microbubbles. A few interesting examples are also shown where (1) the pathway of evolution changes without altering the equilibrium morphology when kinetic parameters such as viscous forces are changed and (2) the self-organized equilibrium morphology does not reproduce the underlying patterns on the electrodes.