The NMR response of a polymeric fluid to the application of shear field has been studied
by using specially designed shearing devices conforming to a couette geometry. We show that an air-driven high-resolution liquids sample spinning arrangement, available on any high-resolution liquid-state NMR spectrometer, is easily adapted to set up a couette cell and impart shear rates (γ̇) of ca. 18−450 s-1 on polymer solutions of low viscosity. This simple but elegant method has allowed us to conduct
in situ rheo-NMR relaxation experiments on poly(acrylamide) solution where we observe large changes
in proton spin−lattice relaxation times in the sheared state of the polymer. The enhanced relaxation
rates are rationalized on the basis of the release of entanglements due to breaking of intermolecular
hydrogen bonds, which decrease the rotational correlation times for the molecular motions. By identifying
from the 2-D NOESY experiments that the molecular mobility occurs in the long correlation regime (ω0τc
≫ 1), we gather evidence from in situ rheo-NMR measurements that the imposition of shear reduces the
motional correlation time τc with increasing shear rate. We also find that the restoration of relaxation
times, upon cessation of shear, is seen to occur over a much larger time scale (ca. 20 h). This has been
interpreted by taking recourse to the postulate of the slow re-formation process in the framework of the
energetically cross-linked transient network model (ECTN) proposed recently by our school.