Generality of anomalous expansion of polymer chains in supercritical fluids

By using in-situ neutron reflectivity, we have investigated swelling isotherms of solvophilic and solvophobic end-grafted/non-grafted polymer chains on solid substrates in supercritical carbon dioxide and supercritical ethane. It was found that anomalous expansion of the polymer chains associated with excess absorption of the fluid molecules occurs in the large compressible regions of both supercritical fluids (SCFs) regardless of the polymer–fluid interactions. In addition, we found that the excess expansion of the solvophobic polymer chains in both SCFs collapse onto one master curve under the same magnitude of density fluctuations in the fluids. A simple thermodynamic two-state model along with the experimental results proposes that polymer chains are expanded independently of the polymer–fluid interactions to further change solvent density fluctuations around the polymer chains, thereby lowering the free energy of the polymer/SCF systems.