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Abstract |
This thesis initiates an inquiry into the intricate interplay between confinement and material behaviors, addressing cutting-edge topics in nanomechanics and interfacial physics. Each section explores how confinement significantly alters material properties compared to their bulk counterparts, extending the investigation into the nuanced realm of thermodynamic properties at interfaces. We first demonstrate the breakdown of a previously acknowledged universal aspect ratio (height versus diameter) in nanometer-sized bubbles within graphene, laying the groundwork for a detailed examination of adhesion energies. Further, the indentation of graphene nanobubbles reveals failure points reminiscent of viral shells through analysis using the Föppl–von Kármán (FvK) dimensionless number. Additionally, phase transitions of encapsulated noble gases are explored, exhibiting intriguing behaviors under varying temperatures. The formation of anomalous shapes in flat nanobubbles encapsulated by hexagonal boron nitride is also investigated, highlighting the influence of heating rates and hydrogen bonding. The cation-controlled permeation of charged polymers through nano-capillaries is examined, revealing distinct effects of monovalent cations on polymer transmission speed. The ability to manipulate permeation is elucidated based on the differing surface versus bulk preferences of various alkali cations in the presence of an external electric field, offering valuable insights into the interplay between ionic dynamics and nano-confinement effects. The exploration continues with an assessment of the accuracy of the Kelvin equation in nanoscale capillaries, proposing a revision based on disjoining pressure. Finally, critical commentary on the Shuttleworth equation corrects misconceptions and contributes to a comprehensive understanding of interfacial thermodynamics. |
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