The present study describes the surface tailoring of a polymeric substrate
by a multistep process using two consecutive plasma treatments, followed by
derivatization reactions. The chemical concept of this approach is present
ed in this paper, using a poly(ethylene terephthalate) (PET) substrate. In
the first step, tetrafluoroethylene (TFE) was plasma polymerized, generatin
g a highly cross-linked perfluoric surface layer. The next step introduced
amine groups into the plasma polymer, by exposing the surface to plasma of
ammonia. The reactive amine moieties were then used as anchoring sites for
further derivatization. Finally, poly(ethylene glycol) (PEG) chains were gr
afted onto the surface via a hexamethylene diisocyanate (HDI) spacer. The E
SCA spectrum of treated PET revealed that the surface chemistry obtained af
ter plasma polymerizing TFE was one clearly dominated by CF2 and CF moietie
s, as demonstrated by the large peaks appearing at 291.1 and 289.5 eV, resp
ectively. As expected, substantial amounts of nitrogen could be seen after
exposing the surface to a plasma of ammonia, as revealed by the large N 1s
peak at 402.0 eV. ESCA also demonstrated the presence of PEG chains bound t
o the sur face. These findings were confirmed by FTIR spectroscopy and supp
orted by water contact angle measurements. Special attention was given to t
he absorption bands of the CF groups and ether bonds belonging to the fluor
inated plasma polymer and the PEG chains, respectively, as well as to the c
haracteristic N=C=O band (2272 cm(-1)). While the water contact angle of un
treated PET was 76 degrees, it increased sharply after the fluorinated laye
r was created (93 degrees), decreasing drastically (to less than 20 degrees
) once the highly hydrophilic PEG chains were grafted on the surface.