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Water Sorption Thermodynamics and Mass Transport in Poly(ϵ‐Caprolactone): Interactional Issues Emerging from Vibrational Spectroscopy
Author(s) -
Musto Pellegrino,
Galizia Michele,
Scherillo Giuseppe,
Mensitieri Giuseppe
Publication year - 2013
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.201300030
Subject(s) - sorption , gravimetric analysis , chemistry , hydrogen bond , polymer chemistry , fourier transform infrared spectroscopy , thermodynamics , molecule , caprolactone , polymer , chemical engineering , organic chemistry , adsorption , physics , engineering , copolymer
Water sorption and transport in poly‐(ϵ‐caprolactone) (PCL) is studied by FTIR spectroscopy in transmission mode, providing information at the molecular level on equilibrium sorption and the diffusion mechanism. Coupling of spectroscopic and gravimetric data allows the equilibrium absorbance to be correlated with the water concentration in PCL. The analysis of the ν (OH) spectral region reveals the presence of two species of absorbed water (i.e., molecules directly interacting with the carbonyl group of PCL and self‐associated water). Sorption thermodynamics are interpreted using an equation of state approach routed on a compressible lattice fluid framework, accounting for self‐ and cross‐hydrogen‐bond formation. Assuming that only the carbonyl group acts as a proton acceptor group on the polymer backbone, theoretical predictions are found to be in close agreement with the experimental results.