A covalent network of polymer can imbibe a solvent to form a gel. In a cavity on the surface of the gel, capillary force may suck the solvent out of the gel to form a pure liquid phase. We show that such osmocapillary phase separation occurs when capillarity balances osmosis, and when the diffusion of solvent in the gel prevails over the condensation of solvent from the vapor. Osmocapillary phase separation can occur even when the gel is isolated from the vapor, or when the solvent is nonvolatile.
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