Papers › Water cavitation results from the kinetic competition of bulk, surface and...
Water cavitation results from the kinetic competition of bulk, surface and surface-defect nucleation events
Philip Loche, Matej Kanduč, Emanuel Schneck, Roland R. Netz
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Water at negative pressures can remain in a metastable state for a surprisingly long time before it reaches equilibrium by cavitation, i.e. by the formation of vapor bubbles. The wide spread of experimentally measured cavitation pressures depending on water purity, surface contact angle and surface quality implicates the relevance of water cavitation in bulk, at surfaces and at surface defects for different systems. We formulate a kinetic model that includes all three different cavitation pathways and determine the needed nucleation attempt frequencies in bulk, at surfaces and at defects from atomistic molecular dynamics simulations. Our model reveals that cavitation occurs in pure bulk water only for defect-free hydrophilic surfaces with wetting contact angles below 50{\deg} to 60{\deg} and at pressures of the order of $-$100 MPa, depending only slightly on system size and observation time. Cavitation on defect-free surfaces occurs only for higher contact angles, with the typical cavitation pressure rising to about $-$30 MPa for very hydrophobic surfaces. Nanoscopic hydrophobic surface defects act as very efficient cavitation nuclei and can dominate the cavitation kinetics in a macroscopic system. In fact, a nanoscopic defect that hosts a pre-existing vapor bubble can raise the critical cavitation pressure much further. Our results explain the wide variation of experimentally observed cavitation pressures in synthetic and biological systems and highlight the importance of surface and defect mechanisms for the nucleation of metastable systems.
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