According to a common viewpoint the surface of the binary polymer mixture A
/B could be enriched only in one component, say A, regardless of the value
of its bulk volume fraction phi(bulk). From recent theoretical analyses and
Monte Carlo simulations one can expect however that some mixtures can exhi
bit surface segregation in the minority blend component, i.e. enrichment in
the component A for phi(bulk) < 50% and in the component B for phi(bulk) >
50%- Using composition-depth profiling techniques, we have observed both t
ypes of the segregation with only one- or both-blend component(s) preferred
at the surface. These results were obtained for model mixtures composed of
partly deuterated (dx) and protonated (hx) random olefinic copolymers of t
he structure -[C4H8](1-x)[C2H3(C2H5)](x)-. A simple mean-field model is pre
sented to explain both situations. (C) 1999 Published by Elsevier Science L
td. All rights reserved.