Free-Volume Studies in Polycaprolactone/Poly(propylene oxide) Urethane/Urea Membranes by Positron Lifetime Spectroscopy

Positron annihilation lifetime spectroscopy was used to study the free volume parameters in polypropylene oxide-based tri-isocyanate terminated prepolymer/polycaprolactone diol bi-soft urethane/urea membranes (PU/PCL) with PCL content from 5 up to 25 wt%. Positron annihilation lifetime spectroscopy measurements carried out in the temperature range 298-324 K mirrored the phase separation of the various soft and hard segments present in the membranes. The size and amount of free volume holes determined by positron annihilation lifetime spectroscopy appear to be correlated with the CO2 gas permeability through the membranes.