Neutron scattering from equilibrium-swollen networks.

Small-angle neutron scattering measurements were performed on end-linked poly (dimethylsiloxane) (PDMS) networks swollen to equilibrium with d-benzene. Comparison was made with equivalent concentration PDMS solutions. Equilibrium-swollen networks consistently displayed a linear scattering regime at low q followed by a good-solvent-like scaling regime at high q in agreement with the predictions of the Gel Tensile Blob (GTB) model. Data are fit using the unified function modified for the GTB model (3-parameter fit). Equilibrium-swollen networks display a base structural size, the gel tensile-blob size, xi, that was found to be independent of the molecular weight between crosslinks for the series of molecular weights studied, consistent with the predictions of the model. The length of the extended tensile structure, L, can be larger than the length of the fully extended network strand. The predicted scaling relationship for L, L approximately Q(1/2)N(avg), where N(avg) = (1/fN(c)(2) + 1/4N(e)(2), Q is the equilibrium swelling ratio, N(c) is the molecular weight between crosslinks, N(e) is the entanglement molecular weight and f is the crosslink functionality is in agreement with experimental results for the networks studied.