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Dropwise condensation is favorable for numerous industrial and heat/mass transfer applications due to the enhanced heat transfer performance that results from efficient condensate removal. Organofunctional silane self-assembled monolayer (SAM) coatings are one of the most common ultrathin low surface energy materials used to promote dropwise condensation of water vapors because of their minimal thermal resistance and scalable synthesis process. These SAM coatings typically degrade (i.e., condensation transitions from the efficient dropwise mode to the inefficient filmwise mode) rapidly during water vapor condensation. More importantly, the condensation-mediated coating degradation/failure mechanism(s) remain unknown and/or unproven. In this work, we develop a mechanistic understanding of water vapor condensation-mediated organofunctional silane SAM coating degradation and validate our hypothesis through controlled coating synthesis procedures on silicon/silicon dioxide substrates. We further demonstrate that a pristine organofunctional silane SAM coating resulting from a water/moisture-free coating environment exhibits superior long-term robustness during water vapor condensation. Our molecular/nanoscale surface characterizations, pre- and post-condensation heat transfer testing, indicate that the presence of moisture in the coating environment leads to uncoated regions of the substrate that act as nucleation sites for coating degradation. By elucidating the reasons for formation of these degradation nuclei and demonstrating a method to suppress such defects, this study provides new insight into why low surface energy silane SAM coatings degrade during water vapor condensation. The proposed approach addresses a key bottleneck (i.e., coating failure) preventing the adoption of efficient dropwise condensation methods in industry, and it will facilitate enhanced phase-change heat transfer technologies in industrial applications.

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