Fa. Bottino et al., XPS STUDY ON SURFACE SEGREGATION IN POLY(ETHYLENE-ISO TEREPHTHALATE)-PERFLUOROPOLYETHER BLOCK-COPOLYMERS/, Macromolecules, 31(22), 1998, pp. 7814-7819
Samples of poly(ethylene-iso/terephthalate)-perfluoro polyether multib
lock copolymers with perfluoropolyether (PFPE) segments of different l
engths have been characterized for surface composition by XPS and angu
lar dependent XPS in order to determine the influence of the length of
the PFPE blocks on the surface segregation of fluorine moieties. The
results indicated that there was a high surface excess of PFPE when th
e PFPE blocks had molecular weight (MW) of 2200; far a bulk content of
PFPE of about 8%, the amount of PFPE at the surface was 94 wt %. When
the MW of PFPE blocks was 3400 or 1200, for the same bulk content of
PFPE of about 8%, the surface showed a more limited excess of PFPE (ab
out 46 and 30 wt % for MW 3400 and 1200 respectively). The segregation
capability of PFPE blocks was also influenced by the length of polyes
ter segments to which the PFPE blocks are bonded. So, when the fractio
n of PFPE bonded to very short segments of polyesters was extracted, t
he surface enrichment was reduced, and for a bulk, composition of PFPE
of about 6%, the surface amount of PFPE was of 15, 45, and 29% for PF
PE with MW of 1200, 2200, and 3400, respectively. These data suggest t
hat surface segregation depends on the MW of the initial PFPE and of t
he polyester segments bonded to PFPE after polymerization and that the
re is an optimum MW for PFPE surface segregation; the most favorable c
onditions are met for PFPE with MW 2200.