Fragmentation and release of pristine and functionalized carbon nanotubes from epoxy-nanocomposites during accelerated weathering

There is an increasing volume of nano-enabled materials in the market. Once composites containing nano-additives are disposed of, weathering could deteriorate their structures, releasing nanoparticles and risking exposure of humans and aquatic organisms. Composite degradation due to environmental aging continues, including structural deterioration resulting in cracking, fragmentation, and release of microplastics and nano-additives to the environment. This research aims to study the degradation and release of initially embedded nanomaterials (NMs) from composites and their toxicity. The molecular interaction of carbon nanotube (CNT)/polymer composites is critical for modifying the polymer properties. This study investigated the interactions of functional multiwalled carbon nanotube (MWCNT) composites which affect their release during accelerated weathering processes. Different epoxy-MWCNT composites were prepared by filling a polymer with pure MWCNTs and MWCNTs functionalized with acid (<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:mo>-</mml:mo><mml:mtext>COOH</mml:mtext></mml:mrow></mml:math>) and amine (<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:mo>-</mml:mo><mml:msub><mml:mrow><mml:mtext>NH</mml:mtext></mml:mrow><mml:mn>2</mml:mn></mml:msub></mml:mrow></mml:math>) groups. The physical and chemical changes of aged composites were characterized by gravimetric analysis, contact angle measurements, FTIR, SEM, and laser confocal microscopy. A loss of hydrophobicity was observed for composite surfaces long before surface cracks materialized. Released polymer fragments and nanoparticles were analyzed in wash water using TEM, FTIR and Raman spectroscopy. The environmental risks for long-term use of CNT-polymer composites and the influence of fillers on the extent of chemical photodegradation depended on the combination of polymer and fillers. If nanoparticles are released from the matrix, the high surface-to-volume ratio and reactivity of NMs make them highly dynamic in environmental systems. Exposure to these released NMs could negatively affect human health and the environment. This study provides fragmentation and CNT particle release data that could describe how molecular-level interactions between functionalized CNTs and epoxy polymers affect the aging and release of CNTs. A toxicity assessment based on a reactive oxygen species (ROS) formation assay and MTS assay for cell viability and activity of the released polymer and CNT fragments and leachate showed moderate levels of cytotoxicity of released materials as compared to pristine epoxy plates.