Pore size determination of TEMPO-oxidized cellulose nanofibril films by positron annihilation lifetime spectroscopy.

Wood cellulose nanofibril films with sodium carboxylate groups prepared from a 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized pulp exhibited an extremely low oxygen permeability of 0.0008 mL μm m(-2) day(-1) kPa(-1) at 0% relative humidity (RH). Positron annihilation lifetime spectroscopy (PALS) was used to determine the pore sizes in wood and tunicate TEMPO-oxidized cellulose nanofibril (TOCN-COONa) films in a vacuum (i.e., at 0% RH). PALS analysis revealed that the pore size of the wood TOCN-COONa films remained nearly at 0.47 nm from the film surface to the interior of the film. This is probably the cause of this high oxygen-barrier properties at 0% RH. The crystalline structure of TOCN-COONa also contributes to the high oxygen-barrier properties of the wood TOCN-COONa films. However, the oxygen permeability of the wood TOCN-COONa films increased to 0.17 mL μm m(-2) day(-1) kPa(-1) at 50% RH, which is one of the shortcomings of hydrophilic TOCN-COONa films.