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1. Release, detection and toxicity of fragments generated during artificial accelerated weathering of CdSe/ZnS and CdSe quantum dot polymer composites

   https://doi.org/10.1039/C8EN00249E  

   Gallagher, Miranda J. ; Buchman, Joseph T. ; Qiu, Tian A. ; Zhi, Bo ; Lyons, Taeyjuana Y. ; Landy, Kaitlin M. ; Rosenzweig, Zeev ; Haynes, Christy L. ; Fairbrother, D. Howard ( January 2018 , Environmental Science: Nano)

   Next generation displays and lighting applications are increasingly using inorganic quantum dots (QDs) embedded in polymer matrices to impart bright and tunable emission properties. The toxicity of some heavy metals present in commercial QDs ( e.g. cadmium) has, however, raised concerns about the potential for QDs embedded in polymer matrices to be released during the manufacture, use, and end-of-life phases of the material. One important potential release scenario that polymer composites can experience in the environment is photochemically induced matrix degradation. This process is not well understood at the molecular level. To study this process, the effect of an artificially accelerated weathering process on QD–polymer nanocomposites has been explored by subjecting CdSe and CdSe/ZnS QDs embedded in poly(methyl methacrylate) (PMMA) to UVC irradiation in aqueous media. Significant matrix degradation of QD–PMMA was observed along with measurable mass loss, yellowing of the nanocomposites, and a loss of QD fluorescence. While ICP-MS identified the release of ions, confocal laser scanning microscopy and dark-field hyperspectral imaging were shown to be effective analytical techniques for revealing that QD-containing polymer fragments were also released into aqueous media due to matrix degradation. Viability experiments, which were conducted with Shewanella oneidensis MR-1, showed a statistically significant decreasemore »in bacterial viability when the bacteria were exposed to highly degraded QD-containing polymer fragments. Results from this study highlight the need to quantify not only the extent of nanoparticle release from a polymer nanocomposite but also to determine the form of the released nanoparticles ( e.g. ions or polymer fragments).« less
2. Effect of Filler–Polymer Interface on Elastic Properties of Polymer Nanocomposites: A Molecular Dynamics Study

   Chi Ma, 1 Tuo ( September 2017 , Tire science & technology)

   A coarse-grained model has been built to study the effect of the interfacial interaction between spherical filler particles and polymer on the mechanical properties of polymer nanocomposites. The polymer is modeled as bead-spring chains, and nano-fillers grafted with coupling agent are embedded into the polymer matrix. The potential parameters for polymer and filler are optimized to maximally match styrene-butadiene rubber reinforced with silica particles. The results indicated that, to play a noticeable role in mechanical reinforcement, a critical value exists for the grafting density of the filler–polymer coupling agent. After reaching the critical value, the increase of grafting density can substantially enhance mechanical properties. It is also observed that the increase of grafting density does not necessarily increase the amount of independent polymer chains connected to fillers. Instead, a significant amount of increased grafting sites serve to further strengthen already connected polymer and filler, indicating that mechanical reinforcement can occur through the locally strengthened confinement at the filler–polymer interface. These understandings based on microstructure visualization shed light on the development of new filler polymer interfaces with better mechanical properties.
3. Review and reproducibility of forming adsorbed layers from solvent washing of melt annealed films

   https://doi.org/10.1039/D0SM00565G  

   Thees, Michael F. ; McGuire, Jennifer A. ; Roth, Connie B. ( June 2020 , Soft Matter)

   Recent studies suggest chain adsorption in the melt may be responsible for a number of property changes in thin films by making correlations between the residual adsorbed layer thickness h ads ( t ) measured after a given solvent washing procedure as a function of annealing time t of the film at an elevated temperature prior to this solvent rinse. This procedure, frequently called “Guiselin's experiment”, refers to the thought experiment proposed in a 1992 theoretical treatment by Guiselin that assumed chain segments in contact with the surface are irreversibly adsorbed whereby unadsorbed chains could be washed away by solvent without disturbing the adsorbed substrate contact points in the melt. In the present work, we review this recent literature, identifying and experimentally testing a common protocol for forming adsorbed layers h ads ( t ) from solvent washing melt films. We find h ads ( t ) curves to be far less reproducible and reliable than implied in the literature, strongly dependent on solvent washing and substrate cleaning conditions, and annealing at elevated temperatures is unnecessary as densification of films sitting at room temperature makes the glassy film harder to wash off, leaving behind h ads of comparable thickness. Thismore »review also summarizes literature understanding developed over several decades of study on polymer adsorption in solution, which experimentally demonstrated that polymer chains in solution are highly mobile, diffusing and exchanging on the surface even in the limit of strong adsorption, contradicting Guiselin's assumption. Preformed adsorbed layers of different thicknesses h ads are shown to not affect the average glass transition temperature or physical aging of 30 nm thick films. In summary, a number of open questions and implications are discussed related to thin films and polymer nanocomposites.« less
4. Effect of graphene on the absorption of methanol and crack healing in poly(methyl methacrylate)-based composites

   https://doi.org/10.1039/c8sm01454j  

   Lin, Zu-wen ; Yang, Fuqian ; Lee, Sanboh ( January 2018 , Soft Matter)

   This work is focused on the mass transport of methanol and the methanol-assisted crack healing in poly(methyl methacrylate) (PMMA)–graphene composites at different temperatures. The effect of the fraction of graphene on the mass transport of methanol and the methanol-assisted crack healing is also studied. The experimental results reveal that adding graphene to the PMMA matrix increases the resistance to the migration/diffusion of methanol and polymer chains in the PMMA matrix, and the absorption of methanol follows anomalous diffusion. The activation energies for the case I transport and case II transport in the PMMA–graphene composites are relatively independent of the fraction of graphene, and are larger than the corresponding ones in pure PMMA. Increasing the healing time and healing temperature allows for more polymer chains to migrate/diffuse across fractured surfaces, leading to the increase in the fracture strength of the crack-healed PMMA–graphene composites.
5. Covalently integrated silica nanoparticles in poly(ethylene glycol)-based acrylate resins: thermomechanical, swelling, and morphological behavior

   https://doi.org/10.1039/D1SM01377G  

   Hocken, Alexis ; Beyer, Frederick L. ; Lee, Jae Sang ; Grim, Bradley J. ; Mithaiwala, Husain ; Green, Matthew D. ( February 2022 , Soft Matter)

   Nanocomposites integrate functional nanofillers into viscoelastic matrices for electronics, lightweight structural materials, and tissue engineering. Herein, the effect of methacrylate-functionalized (MA-SiO 2 ) and vinyl-functionalized (V-SiO 2 ) silica nanoparticles on the thermal, mechanical, physical, and morphological characteristics of poly(ethylene glycol) (PEG) nanocomposites was investigated. The gel fraction of V-SiO 2 composites decreases upon addition of 3.8 wt% but increases with further addition (>7.4 wt%) until it reaches a plateau at 10.7 wt%. The MA-SiO 2 induced no significant changes in gel fraction and both V-SiO 2 and MA-SiO 2 nanoparticles had a negligible impact on the nanocomposite glass transition temperature and water absorption. The Young's modulus and ultimate compressive stress increased with increasing nanoparticle concentration for both nanoparticles. Due to the higher crosslink density, MA-SiO 2 composites reached a maximum mechanical stress at a concentration of 7.4 wt%, while V-SiO 2 composites reached a maximum at a concentration of 10.7 wt%. Scanning electron microscopy, transmission electron microscopy, and small-angle X-ray scattering revealed a bimodal size distribution for V-SiO 2 and a monomodal size distribution for MA-SiO 2 . Although aggregates were observed for both nanoparticle surface treatments, V-SiO 2 dispersion was poor while MA-SiO 2 were generally well-dispersed. Thesemore »findings lay the framework for silica nanofillers in PEG-based nanocomposites for advanced manufacturing applications.« less