  Temperature-responsive properties of surface-attached
poly(N-isopropylacrylamide) (PNIPAM) network films with well-controlled
chemistry are investigated. The synthesis consists of cross-linking and
grafting preformed ene-reactive polymer chains through thiol--ene click
chemistry. The formation of surface-attached and cross-linked polymer films has
the advantage of being wellcontrolled without any caution of no-oxygen
atmosphere or addition of initiators. PNIPAM hydrogel films with same
cross-link density are synthesized on a wide range of thickness, from
nanometers to micrometers. The swelling-collapse transition with temperature is
studied by using ellipsometry, neutron reflectivity, and atomic force
microscopy as complementary surface-probing techniques. Sharp and high
amplitude temperature-induced phase transition is observed for all
submicrometric PNIPAM hydrogel films. For temperature above LCST,
surface-attached PNIPAM hydrogels collapse similarly but without complete
expulsion of water. For temperature below LCST, the swelling of PNIPAM
hydrogels depends on the film thickness. It is shown that the swelling is
strongly affected by the surface attachment for ultrathin films below $\sim$150
nm. For thicker films above 150 nm (to micrometers), surface-attached polymer
networks with the same cross-link density swell equally. The density profile of
the hydrogel films in the direction normal to the substrate is confronted with
in-plane topography of the free surface. It results that the free interface
width is much larger than the roughness of the hydrogel film, suggesting
pendant chains at the free surface.
