A model polymer−solid interface, aluminum- (Al-) carboxylated
polybutadiene (cPBD), was
designed to investigate the influence of the sticker group (−COOH) on
the fracture energy (G
IC). A
model
polymer, cPBD, was synthesized through high-pressure carboxylation of
polybutadiene (PBD) and
contained −COOH randomly distributed along the length of the polymer
chains. T-peel tests were used
to evaluate the interfacial fracture energy. The effect of the
concentration of the sticker groups (φ) on
the fracture energy was examined, and a critical concentration
(φc), around 3 mol %, was found to give
a maximum bonding strength, which was an order of magnitude stronger
than the same interface without
sticker groups. The fracture energy of Al−cPBD−Al interfaces
increased over a range of 10−1000 min
annealing time, t, which is much longer than the
characteristic relaxation time of PBD at room
temperature. The fastest adhesion occurred for sticker group
concentrations at φc, whereas chains with
sticker groups at φc ± 1% required much longer surface
rearrangement times. The dynamics of adhesion
was found to be comparable to time-dependent surfaces restructuring,
using dynamic contact angle studies.
Many of these results could be understood from a self-consistent
lattice model developed by Theodorou,
which we used to investigate how the sticker groups affect the
structure of the interfacial chains. Sticker
groups were found to have a strong tendency to segregate to the solid
surface, resulting in a large
concentration gradient near the solid surface. This phenomenon,
together with the extremely slow surface
restructuring process of cPBD chains, which relax like tethered chains,
partially accounts for the long
time dependence of the fracture energy of Al−cPBD−Al interfaces.
Modeling also showed that the chain
shape and the chain connectivity close to the solid surface was
modified. With increasing concentration
of sticker groups, the flatness of the chains near the solid substrate
decreased at first and then increased,
indicating an optimum concentration for efficient chain connectivity
within the interfaces. These modeling
results predicted a critical concentration of sticker groups for
optimum bonding in the sense of cohesive
strength, agreeing well with experimental results.