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1. Atomistic mechanisms of adhesion and shear strength in graphene oxide-polymer interfaces

   Jin Y. Choi, Xu Zhang (January 2021, Journal of the mechanics and physics of solids)

   Combining experimental and computational studies of nanocomposite interfaces is highly needed to gain insight into their performance. However, there are very few literature reports, combining well-controlled atomic force microscopy experiments with molecular dynamic simulations, which explore the role of polymer chemistry and assembly on interface adhesion and shear strength. In this work, we investigate graphene oxide (GO)-polymer interfaces prevalent in nanocomposites based on a nacre-like architectures. We examine the interfacial strength resulting from van der Waals and hydrogen bonding interactions by comparing the out-of-plane separation and in-plane shear deformations of GO-polyethylene glycol (PEG) and GO-polyvinyl alcohol (PVA). The investigation reveals an overall better mechanical performance for the anhydrous GO-PVA system in both out-of-plane and in-plane deformation modes, highlighting the benefits of the donor-acceptor hydrogen bond formation present in GO-PVA. Such bond formation results in interchain hydrogen bond networks leading to stronger interfaces. By contrast, PEG, a hydrogen bond acceptor only, relies primarily on van der Waals inter-chain interactions, typically resulting in weaker interactions. The study also predicts that water addition increases the adhesion of GOPEG but decreases the adhesion of GO-PVA, and slightly increases the shear strength in both systems. Furthermore, by comparing simulations and experiments, we show that the CHARMM force field has enough accuracy to capture the effect of polymer content, water distribution, and to provide quantitative guidance for achieving optimum interfacial properties. Therefore, the study demonstrates an effective methodology, in the Materials Genome spirit, toward the design of 2D materials-polymer nanocomposites system for applications demanding mechanical robustness. 

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2. Hierarchically hydrogen-bonded graphene/polymer interfaces with drastically enhanced interfacial thermal conductance

   https://doi.org/10.1039/C8NR08760A  

   Zhang, Lin; Liu, Ling (February 2019, Nanoscale)

   Interfacial thermal transport is a critical physical process determining the performance of many material systems with small-scale features. Recently, self-assembled monolayers and polymer brushes have been widely used to engineer material interfaces presenting unprecedented properties. Here, we demonstrate that poly(vinyl alcohol) (PVA) monolayers with hierarchically arranged hydrogen bonds drastically enhance interfacial thermal conductance by a factor of 6.22 across the interface between graphene and poly(methyl methacrylate) (PMMA). The enhancement is tunable by varying the number of grafted chains and the density of hydrogen bonds in the unique hierarchical hydrogen bond network. The extraordinary enhancement results from a synergy of hydrogen bonds and other structural and thermal factors including molecular morphology, chain orientation, interfacial vibrational coupling and heat exchange. Two types of hydrogen bonds, i.e. PVA–PMMA hydrogen bonds and PVA–PVA hydrogen bonds, are analyzed and their effects on various structural and thermal properties are systematically investigated. These results are expected to provide new physical insights for interface engineering to achieve tunable thermal management and energy efficiency in a wide variety of systems involving polymers and biomaterials. 

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3. Emulsion Assembly of Graphene Oxide/Polymer Composite Membranes

   https://doi.org/10.1021/acsami.3c02636  

   Ngo, Quynh P; Yuan, Weize; Wu, You-Chi Mason; Swager, Timothy M (May 2023, ACS Applied Materials & Interfaces)

   Graphene oxide/polymer composite water filtration membranes were developed via coalescence of graphene oxide (GO) stabilized Pickering emulsions around a porosity-generating polymer. Triptycene poly(ether ether sulfone)-CH2NH2:HCl polymer interacts with the GO at the water−oil interface, resulting in stable Pickering emulsions. When they are deposited and dried on polytetrafluoroethylene substrate, the emulsions fuse to form a continuous GO/polymer composite membrane. X-ray diffraction and scanning electron microscopy demonstrate that the intersheet spacing and thickness of the membranes increased with increasing polymer concentration, confirming the polymer as the spacer between the GO sheets. The water filtration capability of the composite membranes was tested by removing Rose Bengal from water, mimicking separations of weak black liquor waste. The composite membrane achieved 65% rejection and 2500 g m−2 h−1 bar−1. With high polymer and GO loading, composite membranes give superior rejection and permeance performance when compared with a GO membrane. This methodology for fabrication membranes via GO/polymer Pickering emulsions produces membranes with a homogeneous morphology and robust chemical separation strength. 

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4. In situ alignment of graphene nanoplatelets in poly(vinyl alcohol) nanocomposite fibers with controlled stepwise interfacial exfoliation

   https://doi.org/10.1039/C9NA00191C  

   Xu, Weiheng; Jambhulkar, Sayli; Verma, Rahul; Franklin, Rahul; Ravichandran, Dharneedar; Song, Kenan (July 2019, Nanoscale Advances)

   Hierarchically microstructured tri-axial poly(vinyl alcohol)/graphene nanoplatelet (PVA/GNP) composite fibers were fabricated using a dry-jet wet spinning technique. The composites with distinct PVA/GNPs/PVA phases led to highly oriented and evenly distributed graphene nanoplatelets (GNPs) as a result of molecular chain-assisted interfacial exfoliation. With a concentration of 3.3 wt% continuously aligned GNPs, the composite achieved a ∼73.5% increase in Young's modulus (∼38 GPa), as compared to the pure PVA fiber, and an electrical conductivity of ∼0.38 S m −1 , one of the best mechanical/electrical properties reported for polymer/GNP nanocomposite fibers. This study has broader impacts on textile engineering, wearable robotics, smart sensors, and optoelectronic devices. 

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5. Oxidative regulation of the mechanical strength of a C–S bond

   https://doi.org/10.1039/D0SC04381H  

   Lin, Yangju; Craig, Stephen L. (October 2020, Chemical Science)

   null (Ed.)

   The mechanical strength of individual polymer chains is believed to underlie a number of performance metrics in bulk materials, including adhesion and fracture toughness. Methods by which the intrinsic molecular strength of the constituents of a given polymeric material might be switched are therefore potentially useful both for applications in which triggered property changes are desirable, and as tests of molecular theories for bulk behaviors. Here we report that the sequential oxidation of sulfide containing polyesters ( PE-S ) to the corresponding sulfoxide ( PE-SO ) and then sulfone ( PE-SO2 ) first weakens (sulfoxide), and then enhances (sulfone), the effective mechanical integrity of the polymer backbone; PE-S ∼ PE-SO2 > PE-SO . The relative mechanical strength as a function of oxidation state is revealed through the use of gem -dichlorocyclopropane nonscissile mechanophores as an internal standard, and the observed order agrees well with the reported bond dissociation energies of C–S bonds in each species and with the results of CoGEF modeling. 

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