  The present communication reports the first direct measurement of the
conformation of a polymer corona grafted around silica nano-particles dispersed
inside a nanocomposite, a matrix of the same polymer. This measurement
constitutes an experimental breakthrough based on a refined combination of
chemical synthesis, which permits to match the contribution of the neutron
silica signal inside the composite, and the use of complementary scattering
methods SANS and SAXS to extract the grafted polymer layer form factor from the
inter-particles silica structure factor. The modelization of the signal of the
grafted polymer on nanoparticles inside the matrix and the direct comparison
with the form factor of the same particles in solution show a clear-cut change
of the polymer conformation from bulk to the nanocomposite: a transition from a
stretched and swollen form in solution to a Gaussian conformation in the matrix
followed with a compression of a factor two of the grafted corona. In the
probed range, increasing the interactions between the grafted particles (by
increasing the particle volume fraction) or between the grafted and the free
matrix chains (decreasing the grafted-free chain length ratio) does not
influence the amplitude of the grafted brush compression. This is the first
direct observation of the wet-to-dry conformational transition theoretically
expected to minimize the free energy of swelling of grafted chains in
interaction with free matrix chains, illustrating the competition between the
mixing entropy of grafted and free chains, and the elastic deformation of the
grafted chains. In addition to the experimental validation of the theoretical
prediction, this result constitutes a new insight for the nderstanding of the
general problem of dispersion of nanoparticles inside a polymer matrix for the
design of new nanocomposites materials.
