Macromolecules, Vol.35, No.17, 6650-6664, 2002
Arm relaxation in deformed H-polymers in elongational flow by SANS
We present a small-angle neutron scattering (SANS) investigation of the relaxation process of branched polymer melts under deformation. The selected model polymer is an H-shaped polyisoprene having deuterium-labeled blocks at the dangling tips of the arms. The melt is step strained in a strain rig especially built for that purpose, where the sample temperature and its deformation conditions are precisely controlled. Uniaxial extensions to values of 2 and 3 are performed at a temperature above the polymer glass transition temperature T-g. The sample is then allowed to relax during a given time before being quenched to below its T-g in order to freeze the chains conformation to perform the SANS experiments. Very large anisotropies in S(q) develop on time scales corresponding to the relaxation of the dangling arms. The experimental structure function is then compared to theoretical ones obtained by the random phase approximation applied to the tube model. While theory describes well the scattering for short times, it seems not to be able to describe the increase of intensity in the direction parallel to the strain at higher times, even when highly nonaffine processes such as arm retraction and branch point withdrawal are taken into account.