Effects of the polymer glass transition on the stability of nanoparticle dispersions.

In addition to the repulsive and attractive interaction forces described by Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, many charged colloid systems are stabilized by non-DLVO contributions stemming from specific material attributes. Here, we investigate non-DLVO contributions to the stability of polymer colloids stemming from the intra-particle glass transition temperature (Tg). Flash nanoprecipitation is used to fabricate nanoparticles (NPs) from a library of polymers and dispersion stability is studied in the presence of both hydrophilic and hydrophobic salts. When adding KCl, stability undergoes a discontinuous decrease as Tg increases above room temperature, indicating greater stability of rubbery NPs over glassy NPs. Glassy NPs are also found to interact strongly with hydrophobic phosphonium cations (PR4+), yielding charge inversion and intermediate aggregation while rubbery NPs resist ion adsorption. Differences in the lifetime of ionic structuration within mobile surface layers is presented as a potential mechanism underlying the observed phenomenon.

Rapid Precipitation of Ionomers for Stabilization of Polymeric Colloids.

Polymeric colloids have shown potential as "building blocks" in applications ranging from formulations of Pickering emulsions and drug delivery systems to advanced materials, including colloidal crystals and composites. However, for applications requiring tunable properties of charged colloids, obstacles in fabrication can arise through limitations in process scalability and chemical versatility. In this work, the capabilities of flash nanoprecipitation (FNP), a scalable nanoparticle (NP) fabrication technology, are expanded to produce charged polystyrene colloids using sulfonated polystyrene ionomers as a new class of NP stabilizers. Through experimental exploration of formulation parameters, increases in the ionomer content are shown to reduce the particle size, mitigating a significant trade-off between the final particle size and inlet concentration; thus, expanding the processable material throughput of FNP. Further, the degree of sulfonation is found to impact stabilization with optimal performance achieved by selecting ionomers with intermediate (2.45-5.2 mol %) sulfonation. Simulations of single ionomer chains and their arrangement in multicomponent NPs provide molecular insights into the assembly and structure of NPs wherein the partitioning of ionomers to the particle surface depends on the polymer molecular weight and degree of sulfonation. By combining the insights from simulations with diffusion-limited growth kinetics and parametric fits to experimental data, a simple design formulation relation is proposed and validated. This work highlights the potential of ionomer-based stabilizers for controllably producing charged NP dispersions in a scalable manner.

Evolution of Polymer Colloid Structure During Precipitation and Phase Separation.

Polymer colloids arise in a variety of contexts ranging from synthetic to natural systems. The structure of polymeric colloids is crucial to their function and application. Hence, understanding the mechanism of structure formation in polymer colloids is important to enabling advances in their production and subsequent use as enabling materials in new technologies. Here, we demonstrate how the specific pathway from precipitation to vitrification dictates the resulting morphology of colloids fabricated from polymer blends. Through continuum simulations, free energy calculations, and experiments, we reveal how colloid structure changes with the trajectory taken through the phase diagram. We demonstrate that during solvent exchange, polymer-solvent phase separation of a homogeneous condensate can precede polymer-polymer phase separation for blends of polymers that possess some degree of miscibility. For less-miscible, higher-molecular-weight blends, phase separation and kinetic arrest compete to determine the final morphology. Such an understanding of the pathways from precipitation to vitrification is critical to designing functional structured polymer colloids.

Writing Highly Ordered Macroscopic Patterns in Cylindrical Block Polymer Thin Films via Raster Solvent Vapor Annealing and Soft Shear.

Block polymers (BPs) potentially can be used to template large arrays of nanopatterns for advanced nanotechnologies. However, the practical utilization of directed BP self-assembly typically requires guide patterns of relatively small size scales. In this work, the macroscopic alignment of block polymer cylinders on a template-free substrate is achieved through raster solvent vapor annealing combined with soft shear (RSVA-SS). Spatial control over nanoscale structures is realized by using a solvent vapor delivery nozzle, poly(dimethylsiloxane) shearing pad, and motorized stage. Complex patterns including dashes, crossed lines, and curves are demonstrated, along with the ability for large area alignment and scale-up for industry applications. The unique ability to directly write macroscopic patterns with microscopically aligned BP nanostructures will open new avenues of applied research in nanotechnology.

Cooperative ordering at liquid crystal interfaces and its role in orientational memory.

Orientational memory in interfacial liquid crystal films occurs when cells heated above the isotropic transition temperature return to their initial ordered texture upon cooling. First observed over 80 years ago, the origins of orientational memory, which is sometimes called the surface memory effect, remain poorly understood. In this study, films of the thermotropic liquid crystal 4'-octyl-4-cyanobiphenyl on graphite were studied by scanning tunneling and polarizing optical microscopy. Strong orientational memory was observed despite relatively weak molecule-surface interactions of the kind previously thought to be responsible for this effect. By preparing cells in a uniformly oriented initial reference state and separately measuring bulk and surface order parameters as systems were thermally disordered, cooperative interactions were found to play an important role, leading to the recovery of long-range order that neither the bulk nor surface layers alone retained. When the surface and bulk layers were partially decoupled using a magnetic field, orientational memory in the surface layer almost disappeared. The findings provide a new interpretation of the origins of orientational memory in liquid crystal films and underscore the potentially important role of cooperativity in bulk <--> interfacial liquid crystal interactions.