Mobility gradients yield rubbery surfaces on top of polymer glasses.

Many emerging materials, such as ultrastable glasses1,2 of interest for phone displays and OLED television screens, owe their properties to a gradient of enhanced mobility at the surface of glass-forming liquids. The discovery of this surface mobility enhancement3-5 has reshaped our understanding of the behaviour of glass formers and of how to fashion them into improved materials. In polymeric glasses, these interfacial modifications are complicated by the existence of a second length scale-the size of the polymer chain-as well as the length scale of the interfacial mobility gradient6-9. Here we present simulations, theory and time-resolved surface nano-creep experiments to reveal that this two-scale nature of glassy polymer surfaces drives the emergence of a transient rubbery, entangled-like surface behaviour even in polymers comprised of short, subentangled chains. We find that this effect emerges from superposed gradients in segmental dynamics and chain conformational statistics. The lifetime of this rubbery behaviour, which will have broad implications in constraining surface relaxations central to applications including tribology, adhesion, and surface healing of polymeric glasses, extends as the material is cooled. The surface layers suffer a general breakdown in time-temperature superposition (TTS), a fundamental tenet of polymer physics and rheology. This finding may require a reevaluation of strategies for the prediction of long-time properties in polymeric glasses with high interfacial areas. We expect that this interfacial transient elastomer effect and TTS breakdown should normally occur in macromolecular systems ranging from nanocomposites to thin films, where interfaces dominate material properties5,10.

Ultrastable Glassy Polymer Films with an Ultradense Brush Morphology.

Glassy polymer films with extreme stability could enable major advancements in a range of fields that require the use of polymers in confined environments. Yet, from a materials design perspective, we now know that the glass transition temperature (Tg) and thermal expansion of polymer thin films can be dramatically different from those characteristics of the bulk, i.e., exhibiting confinement-induced diminished thermal stability. Here, we demonstrate that polymer brushes with an ultrahigh grafting density, i.e., an ultradense brush morphology, exhibit a significant enhancement in thermal stability, as manifested by an exceptionally high Tg and low expansivity. For instance, a 5 nm thick polystyrene brush film exhibits an ∼75 K increase in Tg and ∼90% reduction in expansivity compared to a spin-cast film of similar thickness. Our results establish how morphology can overcome confinement and interfacial effects in controlling thin-film material properties and how this can be achieved by the dense packing and molecular ordering in the amorphous state of ultradense brushes prepared by surface-initiated atom transfer radical polymerization in combination with a self-assembled monolayer of initiators.

Interfacial Engineering to Tailor the Properties of Multifunctional Ultralight Weight hBN-Polymer Composite Aerogels.

A common feature of aerogels is that they are brittle and suffer from poor mechanical properties. The development of high-performance, lightweight, and mechanically robust polymer composite aerogels may find use in a broad range of applications such as packaging, transportation, construction, electronics, and aerospace. Most aerogels are made of ceramic materials, such as silica, alumina, and carbide. These aerogels are dense and brittle. Two-dimensional (2D) layered nanostructures such as graphene, graphene oxide and hexagonal boron nitride (hBN) have promising potential in emerging technologies including those involved in extreme environmental conditions because they can withstand high temperatures, harsh chemical environments, and corrosion. Here, we report the development of highly porous, ultralightweight, and flexible aerogel composites made by the infiltration of various polymers into 2D hBN aerogels. The 2D hBN aerogels in which pore size could be controlled were fabricated using a unique self-assembly approach involving polystyrene nanoparticles as templates for ammonia borane into desired structures. We have shown that the physical, mechanical, and thermal properties of hBN-polymer composite aerogels can be tuned by the infiltration of different additives. We also performed theoretical calculations to gain insight into the interfacial interactions between the hBN-polymer structure, as the interface is critical in determining key material properties.

Local Disorder Facilitates Chain Stretching in Crowded Polymer Brushes.

Intermolecular crowding of densely tethered polymers promotes chain extension and anisotropy that induces many unique properties. In this study, we used conformation-sensitive infrared spectroscopy to determine that chain extension in a polymer brush is associated with local conformation rearrangements, i.e., contraction of side groups and increased proportion of gauche twists in the backbone, which served to increase molecular disorder at or below the segmental scale. This conformational transition points to a particular molecular mechanism for chain extension in densely tethered polymers, wherein increased local disorder facilitates global chain ordering (i.e., chain extension) and therefore supplements our current understanding of chain orientation at a molecular level.

Revealing Interfacial Interactions in Random Copolymer Adsorbed Layers by Solvent Leaching.

Annealing a supported polymer film in the melt state results in the growth of an irreversibly adsorbed layer, which has been shown to influence thin film properties such as diffusion and glass transition temperature. Adsorbed layer growth is attributed to many simultaneous interactions between individual monomer units and the substrate, stabilizing chains against desorption. In this study, adsorbed layers of polystyrene (PS), poly(methyl methacrylate) (PMMA), and their random copolymers are isolated by select solvents. While PS adsorbed layer thickness is largely unaffected by the choice of washing solvent, the PMMA adsorbed layer completely desorbs when washed with tetrahydrofuran and chloroform, as opposed to toluene. Scaling relationships between adsorbed layer thickness and degree of chain adsorption at the substrate enable the use of adsorbed layer thickness to probe specific polymer-substrate interactions. Composition-dependent desorption trends indicate non-preferential adsorption between styrene and methyl methacrylate repeat units at the substrate, despite differences in substrate interaction strength. This insight contributes to the developing mechanism for the adsorption of random copolymers during melt-state annealing, further extending the ability to predict processing-inducted changes to the properties of polymer thin films to heterogeneous systems.

Polyladderane Constructed from a Gemini Monomer through Photoreaction.

Polyladderane, the first polymer to contain the ladderane functional group, was synthesized from a gemini monomer through photoreaction in the solid state. The modular design of the gemini monomers used to create polyladderane allowed specific structural modification, resulting in the formation of two distinct polymer products. Monomers were synthesized by connecting two photoreactive units, either sorbic acids (monomer I) or 2-furanacrylic acids (monomer II), with a 1,4-butanediol linker. Single-crystal X-ray diffraction analysis of the monomers confirmed that they packed in the desired head-to-tail orientation and within a viable distance for photoreaction by electronically complementary interaction. Pre-organized gemini monomers were irradiated with UV light and monitored by FT-IR. Two polyladderanes with cis,anti,cis-[3]-ladderane as a characteristic functional group were constructed stereospecifically in 24-36 hours.