Muon spin relaxation will be used to study the dynamical properties of the polymer polydimethylsiloxane. This has emerged as an excellent model system for the study of polymer dynamics and the polymer glass transition using muon techniques. Previous work has allowed both bulk and surface dynamics to be studied using the diamagnetic muon probe states. The present study aims to extend these measurements by making use of the additional paramagnetic muonium fraction that forms the larger part of the set of implanted muon states. Understanding the contribution to the observed relaxation from possible transitions between diamagnetic and paramagnetic states is a key to interpreting the muon data. Such transitions may be measured using radio frequency MUSR techniques. In particular a slow forming diamagnetic signal can easily be revealed, as we have previously demonstrated in polybutadiene.