R. Rabago et al., EFFECTS OF INCORPORATION OF FLUOROCARBON AND HYDROCARBON SURFACTANTS INTO PERFLUOROSULFONIC ACID (NAFION) MEMBRANES, Chemistry of materials, 6(7), 1994, pp. 947-951
Significant permeability improvements can be made to perfluorinated io
nomer films by incorporating sulfonated surfactants of suitable size i
nto the membrane microstructure. A variety of 20-mum composite Nafion/
surfactant membranes were prepared from DMF casting solutions containi
ng Nafion and the sodium salts of perfluoro-1-butanesulfonic acid (per
f-ButSO3Na), perfluoro-1-octanesulfonic acid (perf-OctSO3Na) and 1-oct
anesulfonic acid (OctSO3Na). The time required for 50% extraction of t
he surfactants from the membranes into water was 1 min for OctSO3Na, 5
min for perf-ButSO3Na, and approximately 3 days for perf-OctSO3Na. Ex
traction of perf-OctSO3Na into isooctane contacting solutions was not
observable over periods of days. For membranes containing surfactants
and exchanged with silver(I) ion, 3-fold permeability improvements can
be obtained for the separation of 1,5-hexadiene from 1-hexene and n-h
exane without any decreases in separation factors. Observed flux impro
vements are larger than the increase in ion-exchange site density and
are attributed to increased mobility of olefins between carrier sites
due to the presence of specific surfactants. Results indicate that mov
ement of olefins in Nafion occurs primarily through an interfacial reg
ion of the film structure. The ability of a surfactant to improve tran
sport performance is dependent on its ability to partition into the in
terfacial region.