Positron Annihilation Spectroscopy (PAS), proton Nuclear Magnetic Relaxation (NMR) and hydration kinetics measurements were applied to study the free volume formation process in the initial stages of bean cotyledons imbibition. These methods allowed us to analyse the behaviour of bound water in the bean cotyledon molecular structure, and to observe free volume regions formed there. They also made it possible to describe their dimensions and concentration quantitatively. Good correlation was found between the increase of the free volume radius and the amount of water bound to the bean cotyledon solid matrix.
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