Solvent Dynamics in Solutions of PNIPAM in Water/Methanol Mixtures-A Quasi-Elastic Neutron Scattering Study.

ABSTRACT

The solvent dynamics of concentrated solutions of poly(N-isopropylacrylamide) (PNIPAM, 25 wt %) in water/methanol mixtures (8515 v/v) are measured with the aim of shedding light onto the cononsolvency effect. Quasi-elastic neutron scattering (QENS) with contrast variation has been carried out at temperatures below and above the cloud point by using in the first set of experiments the mixture H2Od-MeOD (d-MeOD denotes fully deuterated methanol) as a solvent and in the second set of experiments the mixture D2OMeOH (MeOH denotes methanol). As a reference, bulk H2O, bulk MeOH and the mixtures H2Od-MeOD and D2OMeOH (both 8515 v/v) have been investigated as well. In the PNIPAM solution in H2Od-MeOD, two water populations are identified, namely strongly and less strongly arrested water. At the cloud point, the former is partially released from PNIPAM. The diffusion coefficient of the latter one is similar to the one in the water/methanol mixture, and its residence time decreases at the cloud point. The PNIPAM solution in D2OMeOH reveals similar dynamics to the one in H2Od-MeOD which may reflect that the dynamics of MeOH near the PNIPAM chain is similar to the one of H2O. The similarity may, however, partially be due to H/D exchange between D2O and MeOH. In both PNIPAM solutions, the mean-square displacement of the PNIPAM chain decreases gradually above the cloud point.