Shock compression of semiflexible polymers.

We employ molecular dynamics simulations to investigate the shock compression of linear semiflexible polymers. While the propagation velocity of a shock primarily depends on density, both chain rigidity and chain orientation significantly influence the shock width and the final temperature of the system. In general, the shock wave triggers molecular buckling in chains oriented perpendicular to the compression front. Following the passage of the front, the semiflexible chains buckle with a wavelength that decreases with the compression speed as λm ∼ up-0.2, and subsequent relaxation leads to a banana-like liquid crystal phase. In ordered systems with molecules oriented perpendicular to the compression front, the shock width increases by a factor of up to 10 compared to a similar isotropic system, resulting in enhanced shock energy absorption. These findings indicate that chain stiffness plays a critical role in the impact absorption properties of polymeric materials.

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.

Estimating the Segregation Strength of Microphase-Separated Diblock Copolymers from the Interfacial Width.

The ever-growing catalog of monomers being incorporated into block polymers affords exceptional control over phase behavior and nanoscale structure. The segregation strength, χN, is the fundamental link between the molecular-level detail and the thermodynamics. However, predicting phase behavior mandates at least one experimental measurement of χN for each pair of blocks. This typically requires access to the disordered state. We describe a method for estimating χN from small-angle X-ray scattering measurements of the interfacial width between lamellar microdomains, tx, in the microphase-separated melt. The segregation strength is determined by comparing tx to self-consistent field theory calculations of the intrinsic interfacial width, ti, as a function of the mean-field χN. The method is validated using a series of independent experimental measurements of tx and χN, measured via the order-disorder transition temperature, TODT. The average absolute relative difference between χN calculated from tx and the value calculated from TODT is a modest 11%. Corrections for nonplanarity of the interfaces are investigated but do not improve the agreement between the experiments and theory. Published 2019. This article is a U.S. Government work and is in the public domain in the USA.

Curvature as a Guiding Field for Patterns in Thin Block Copolymer Films.

Experimental data on thin films of cylinder-forming block copolymers (BC)-free-standing BC membranes as well as supported BC films-strongly suggest that the local orientation of the BC patterns is coupled to the geometry in which the patterns are embedded. We analyze this phenomenon using general symmetry considerations and numerical self-consistent field studies of curved BC films in cylindrical geometry. The stability of the films against curvature-induced dewetting is also analyzed. In good agreement with experiments, we find that the BC cylinders tend to align along the direction of curvature at high curvatures. At low curvatures, we identify a transition from perpendicular to parallel alignment in supported films, which is absent in free-standing membranes. Hence both experiments and theory show that curvature can be used to manipulate and align BC patterns.

Direct Measurement of the Local Glass Transition in Self-Assembled Copolymers with Nanometer Resolution.

Nanoscale compositional heterogeneity in block copolymers can impart synergistic property combinations, such as stiffness and toughness. However, until now, there has been no experimental method to locally probe the dynamics at a specific location within these structured materials. Here, this was achieved by incorporating pyrene-bearing monomers at specific locations along the polymer chain, allowing the labeled monomers' local environment to be interrogated via fluorescence. In lamellar-forming poly(butyl methacrylate-b-methyl methacrylate) diblock copolymers, a strong gradient in glass transition temperature, Tg, of the higher-Tg block, 42 K over 4 nm, was mapped with nanometer resolution. These measurements also revealed a strongly asymmetric influence of the domain interface on Tg, with a much smaller dynamic gradient being observed for the lower-Tg block.

Rapid Production of Internally Structured Colloids by Flash Nanoprecipitation of Block Copolymer Blends.

Colloids with internally structured geometries have shown great promise in applications ranging from biosensors to optics to drug delivery, where the internal particle structure is paramount to performance. The growing demand for such nanomaterials necessitates the development of a scalable processing platform for their production. Flash nanoprecipitation (FNP), a rapid and inherently scalable colloid precipitation technology, is used to prepare internally structured colloids from blends of block copolymers and homopolymers. As revealed by a combination of experiments and simulations, colloids prepared from different molecular weight diblock copolymers adopt either an ordered lamellar morphology consisting of concentric shells or a disordered lamellar morphology when chain dynamics are sufficiently slow to prevent defect annealing during solvent exchange. Blends of homopolymer and block copolymer in the feed stream generate more complex internally structured colloids, such as those with hierarchically structured Janus and patchy morphologies, due to additional phase separation and kinetic trapping effects. The ability of the FNP process to generate such a wide range of morphologies using a simple and scalable setup provides a pathway to manufacturing internally structured colloids on an industrial scale.

Role of Chain Connectivity across an Interface on the Dynamics of a Nanostructured Block Copolymer.

Fluorescence labeling enables component- and location-specific measurements of the glass transition temperature (T_{g}) in complex polymer systems. Here we characterize the T_{g} of fluorescently labeled poly(methyl methacrylate) homopolymers (PMMA-py) blended at low concentrations into an unlabeled lamellar poly(n-butyl methacrylate-b-methyl methacrylate) diblock copolymer (PBMA-PMMA). In this system, the PMMA-py homopolymer is sequestered within the PMMA domains of the diblock copolymer and subject to soft confinement by the domains of the lower-T_{g} PBMA block, which lowers the homopolymer T_{g} by ∼5 K beyond the contribution of segmental mixing. In contrast to the PMMA block in the diblock copolymer, the PMMA-py homopolymer is not covalently bound to the interdomain interface. A comparison of T_{g} for the homopolymers in the blends to T_{g} for diblock copolymers with equivalent labeled segment density profiles reveals that the homopolymer's T_{g} is consistently ∼10 K higher than for diblock segments at the same location within the domain structure, highlighting the dominant contribution of a covalent bond across the interface to the perturbation of the chain dynamics in the block copolymer.

Synthesis of Narrow-Distribution, High-Molecular-Weight ROMP Polycyclopentene via Suppression of Acyclic Metathesis Side Reactions.

Methods for the preparation of narrow-distribution ROMP polycyclopentene are developed to suppress the rate of acyclic metathesis: reaction between the active metal-carbene chain end and an acyclic olefin in the reaction medium. In particular, we investigate interchain metathesis, which generates linear polymers with "scrambled" chain lengths, and we demonstrate the formation of ring polymers by intrachain backbiting and quantify their content in the reaction product. By controlling the relative rates of propagation versus these side reactions, we prepare ROMP polycyclopentene with low dispersity to substantially higher molecular weights than have been reported previously. Polymerization kinetics are quantitatively described by a kinetic model, which accounts for the reversible binding of added trimethylphosphine to the active chain end.

Wrinkles and splay conspire to give positive disclinations negative curvature.

Recently, there has been renewed interest in the coupling between geometry and topological defects in crystalline and striped systems. Standard lore dictates that positive disclinations are associated with positive Gaussian curvature, whereas negative disclinations give rise to negative curvature. Here, we present a diblock copolymer system exhibiting a striped columnar phase that preferentially forms wrinkles perpendicular to the underlying stripes. In free-standing films this wrinkling behavior induces negative Gaussian curvature to form in the vicinity of positive disclinations.

Living Vinyl Addition Polymerization of Substituted Norbornenes by a t-Bu3P-Ligated Methylpalladium Complex.

The vinyl addition polymerization of substituted norbornene (NB) monomers, via (t-Bu3P)PdMeCl activated by [Li(OEt2)2.5]B(C6F5)4, is investigated. NB monomers bearing alkyl, aryl, fluoroaryl, and even hexafluoroisopropanol substituents yield polymers exhibiting monomodal and narrow molecular weight distributions, with molecular weight controlled by reaction time and monomer to initiator ratio, demonstrating the living nature of these polymerizations. These polymers are soluble in common organic solvents and possess excellent thermal stability. Block copolymers are also prepared via sequential monomer addition; these are the first examples of well-defined block copolymers of substituted NB monomers enchained by vinyl addition polymerization.

Defect formation and coarsening in hexagonal 2D curved crystals.

In this work we study the processes of defect formation and coarsening of two-dimensional (2D) curved crystal structures. These processes are found to strongly deviate from their counterparts in flat systems. In curved backgrounds the process of defect formation is deeply affected by the curvature, and at the onset of a phase transition the early density of defects becomes highly inhomogeneous. We observe that even a single growing crystal can produce varying densities of defects depending on its initial position and local orientation with regard to the substrate. This process is completely different from flat space, where grain boundaries are formed due to the impingement of different propagating crystals. Quenching the liquid into the crystal phase leads to the formation of a curved polycrystalline structure, characterized by complex arrays of defects. During annealing, mechanisms of geodesic curvature-driven grain boundary motion and defect annihilation lead to increasing crystalline order. Linear arrays of defects diffuse to regions of high curvature, where they are absorbed by disclinations. At the early stage of coarsening the density of dislocations is insensitive to the geometry while the population of isolated disclinations is deeply affected by curvature. The regions with high curvature act as traps for the diffusion of different structures of defects, including disclinations and domain walls.

Large-area nanosquare arrays from shear-aligned block copolymer thin films.

While block copolymer lithography has been broadly applied as a bottom-up patterning technique, only a few nanopattern symmetries, such as hexagonally packed dots or parallel stripes, can be produced by spontaneous self-assembly of simple diblock copolymers; even a simple square packing has heretofore required more intricate macromolecular architectures or nanoscale substrate prepatterning. In this study, we demonstrate that square, rectangular, and rhombic arrays can be created via shear-alignment of distinct layers of cylinder-forming block copolymers, coupled with cross-linking of the layers using ultraviolet light. Furthermore, these block copolymer arrays can in turn be used as templates to fabricate dense, substrate-supported arrays of nanostructures comprising a wide variety of elements: deep (>50 nm) nanowells, nanoposts, and thin metal nanodots (3 nm thick, 35 nm pitch) are all demonstrated.

Thin films of homopolymers and cylinder-forming diblock copolymers under shear.

We study thin films of homopolymers (PS) and monolayers of cylinder-forming diblock copolymers (PS­PHMA) under shear. To this end, we employed both experiments and computer simulations that correctly take into account hydrodynamic interactions and chain entanglements. Excellent quantitative agreement for static as well as dynamic properties in both the homopolymer and diblock copolymer cases was achieved. In particular, we found that the homopolymer thin films exhibit a distinct shear thinning behavior, which is strongly correlated with the disentanglement and shear alignment of the constituent polymer chains. For the PS­PHMA films, we show that shear can be employed to induce long-range ordering to the spontaneously self-assembled microdomains, which is required for many applications such as the fabrication of nanowire arrays. We found that the impact of chemical incompatibility on the viscosity is only minor in shear-aligned films. Once the domains were aligned, the films exhibited an almost Newtonian response to shear because the cylindrical microdomains acted as guide rails, along which the constituent copolymer chains could simply slide. Furthermore, we developed a model for predicting the onset of shear alignment based on equilibrium dynamics data, and found good agreement with our shear simulations. The employed computational method holds promise for a faster and more cost-effective route for developing custom tailored materials.

Creating controlled thickness gradients in polymer thin films via flowcoating.

Flowcoating is a popular technique for generating thin (5-200 nm), substrate-supported polymer films. In this process, a reservoir of coating fluid is held between the horizontal substrate and a nearly horizontal blade above the substrate; a film of fluid is drawn out of the reservoir by moving the substrate. Accelerating the substrate produces a film with a thickness gradient, particularly useful for high-throughput measurements where film thickness is an important parameter. The present work compares experimental film thickness profiles with a model based on a Landau-Levich treatment to identify the experimental parameters which govern film thickness. The key parameters are the capillary number and the radius of curvature of the reservoir's static meniscus, which is set by the blade angle, gap height, solution reservoir volume, and contact angles of the fluid with the blade and substrate. The results show excellent quantitative agreement with the first-principles model; the model thus provides a design approach which allows a user to produce polymer thin films of virtually any desired thickness profile.

Metal-containing block copolymer thin films yield wire grid polarizers with high aspect ratio.

Highly selective etch masks are formed by thin films of a polystyrene-b-poly(ferrocenylisopropylmethylsilane) diblock copolymer, PS-PFiPMS, containing hemicylindrical domains of PFiPMS. These domains, with a period of 35 nm, are readily aligned through mechanical shear. Aligned PS-PFiPMS templates are employed to fabricate high-aspect-ratio nanowire grids from amorphous silicon, which can polarize deep ultraviolet radiation, including 193 nm, at >90% efficiency.

Crystallization dynamics on curved surfaces.

We study the evolution from a liquid to a crystal phase in two-dimensional curved space. At early times, while crystal seeds grow preferentially in regions of low curvature, the lattice frustration produced in regions with high curvature is rapidly relaxed through isolated defects. Further relaxation involves a mechanism of crystal growth and defect annihilation where regions with high curvature act as sinks for the diffusion of domain walls. The pinning of grain boundaries at regions of low curvature leads to the formation of a metastable structure of defects, characterized by asymptotically slow dynamics of ordering and activation energies dictated by the largest curvatures of the system. These glassylike ordering dynamics may completely inhibit the appearance of the ground-state structures.

Flexible piezoelectric PMN-PT nanowire-based nanocomposite and device.

Piezoelectric nanocomposites represent a unique class of materials that synergize the advantageous features of polymers and piezoelectric nanostructures and have attracted extensive attention for the applications of energy harvesting and self-powered sensing recently. Currently, most of the piezoelectric nanocomposites were synthesized using piezoelectric nanostructures with relatively low piezoelectric constants, resulting in lower output currents and lower output voltages. Here, we report a synthesis of piezoelectric (1 - x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 (PMN-PT) nanowire-based nanocomposite with significantly improved performances for energy harvesting and self-powered sensing. With the high piezoelectric constant (d33) and the unique hierarchical structure of the PMN-PT nanowires, the PMN-PT nanowire-based nanocomposite demonstrated an output voltage up to 7.8 V and an output current up to 2.29 µA (current density of 4.58 µA/cm(2)); this output voltage is more than double that of other reported piezoelectric nanocomposites, and the output current is at least 6 times greater. The PMN-PT nanowire-based nanocomposite also showed a linear relationship of output voltage versus strain with a high sensitivity. The enhanced performance and the flexibility of the PMN-PT nanowire-based nanocomposite make it a promising building block for energy harvesting and self-powered sensing applications.