Doubly Threaded Slide-Ring Polycatenane Networks.

Crosslinking in polymer networks leads to intrinsic structural inhomogeneities that result in brittle materials. Replacing fixed covalent crosslinks with mobile ones in mechanically interlocked polymers (MIPs), such as in slide-ring networks (SRNs) in which interlocked crosslinks are formed when polymer chains are threaded through crosslinked rings, can lead to tougher, more robust networks. An alternative class of MIPs is the polycatenane network (PCN), in which the covalent crosslinks are replaced with interlocked rings that introduce the unusual catenane's mobility elements (elongation, rotation, and twisting) as connections between polymer chains. A slide-ring polycatenane network (SR-PCN), with doubly threaded rings embedded as crosslinks in a covalent network, combines the mobility features of both the SRNs and PCNs, where the catenated ring crosslinks can slide along the polymer backbone between the two limits of network bonding (covalent and interlocked). This work explores using a metal ion-templated doubly threaded pseudo[3]rotaxane (P3R) crosslinker, combined with a covalent crosslinker and a chain extender, to access such networks. A catalyst-free nitrile-oxide/alkyne cycloaddition polymerization was used to vary the ratio of P3R and covalent crosslinker to yield a series of SR-PCNs that vary in the amount of interlocked crosslinking units. Studies on their mechanical properties show that metal ions fix the rings in the network, leading to similar behavior as the covalent PEG gels. Removal of the metal ion frees the rings resulting in a high-frequency transition attributed to the additional relaxation of polymer chains through the catenated rings while also increasing the rate of poroelastic draining at longer timescales.

Linear, Graft, and Beyond: Multiblock Copolymers as Next-Generation Compatibilizers.

Properly addressing the global issue of unsustainable plastic waste generation and accumulation will require a confluence of technological breakthroughs on various fronts. Mechanical recycling of plastic waste into polymer blends is one method expected to contribute to a solution. Due to phase separation of individual components, mechanical recycling of mixed polymer waste streams generally results in an unsuitable material with substantially reduced performance. However, when an appropriately designed compatibilizer is used, the recycled blend can have competitive properties to virgin materials. In its current state, polymer blend compatibilization is usually not cost-effective compared to traditional waste management, but further technical development and optimization will be essential for driving future cost competitiveness. Historically, effective compatibilizers have been diblock copolymers or in situ generated graft copolymers, but recent progress shows there is great potential for multiblock copolymer compatibilizers. In this perspective, we lay out recent advances in synthesis and understanding for two types of multiblock copolymers currently being developed as blend compatibilizers: linear and graft. Importantly, studies of appropriately designed copolymers have shown them to efficiently compatibilize model binary blends at concentrations as low as ∼0.2 wt %. These investigations pave the way for studies on more complex (ternary or higher) mixed waste streams that will require novel compatibilizer architectures. Given the progress outlined here, we believe that multiblock copolymers offer a practical and promising solution to help close the loop on plastic waste. While a complete discussion of the implementation of this technology would entail infrastructural, policy, and social developments, they are outside the scope of this perspective which instead focuses on material design considerations and the technical advancements of block copolymer compatibilizers.

Translocation of soft phytoglycogen nanoparticles through solid-state nanochannels.

Phytoglycogen nanoparticles are soft, naturally-derived nanomaterials with a highly uniform size near 35 nm. Their interior is composed of a highly-branched polysaccharide core that contains more than 200% of its dry mass in water. In this work, we measure the translocation of phytoglycogen particles by observing blockade events they create when occluding solid-state nanochannels with diameters between 60 and 100 nm. The translocation signals are interpreted using Poisson-Nernst-Planck calculations with a "hardness parameter" that describes the extent to which solvent can penetrate through the interior of the particles. Theory and experiment were found to be in quantitative agreement, allowing us to extract physical characteristics of the particles on a per particle basis.

Structural evolution during mechanical deformation in high-barrier PVDF-TFE/PET multilayer films using in situ X-ray techniques.

Poly(vinylidene fluoride-co-tetrafluoroethylene) (PVDF-TFE) is confined between alternating layers of poly(ethylene terephthalate) (PET) utilizing a unique multilayer processing technology, in which PVDF-TFE and PET are melt-processed in a continuous fashion. Postprocessing techniques including biaxial orientation and melt recrystallization were used to tune the crystal orientation of the PVDF-TFE layers, as well as achieve crystallinity in the PET layers through strain-induced crystallization and thermal annealing during the melt recrystallization step. A volume additive model was used to extract the effect of crystal orientation within the PVDF-TFE layers and revealed a significant enhancement in the modulus from 730 MPa in the as-extruded state (isotropic) to 840 MPa in the biaxially oriented state (on-edge) to 2230 MPa in the melt-recrystallized state (in-plane). Subsequently, in situ wide-angle X-ray scattering was used to observe the crystal structure evolution during uniaxial deformation in both the as-extruded and melt-recrystallized states. It is observed that the low-temperature ferroelectric PVDF-TFE crystal phase in the as-extruded state exhibits equatorial sharpening of the 110 and 200 crystal peaks during deformation, quantified using the Hermans orientation function, while in the melt-recrystallized state, an overall increase in the crystallinity occurs during deformation. Thus, we correlated the mechanical response (strain hardening) of the films to these respective evolved crystal structures and highlighted the ability to tailor mechanical response. With a better understanding of the structural evolution during deformation, it is possible to more fully characterize the structural response to handling during use of the high-barrier PVDF-TFE/PET multilayer films as commercial dielectrics and packaging materials.