Secondary relaxation processes in binary glass formers: emergence of "islands of rigidity"

In addition to the primary α-process, some neat glass formers show a well resolved secondary β-process (type-B) or solely an excess wing (type-A). We investigate two binary glass forming systems composed of a type-A and a type-B component. (2)H nuclear magnetic resonance (NMR) spectroscopy is selectively applied to the type-B component in order to characterize the β-process over a large range of mole fractions x in the glassy state. We demonstrate that for x ≳ 0.75 the apparent relaxation strength is constant, i.e., all molecules of type-B participate in the β-process and the time constant τβ(T) is independent of concentration. For x < 0.75, however, the apparent relaxation strength decreases abruptly, which we interpret in terms of population: below this concentration a fraction ξ of type-B molecules still exhibits essentially the β-process of the neat system (in terms of time scale and mechanism), while others have been immobilized. The arise of such a scenario is verified by 2D and spin-lattice relaxation (2)H NMR techniques. In selective (2)H NMR experiments on the type-A component we observe a contribution to the β-process of the type-B molecules at medium concentrations. The latter finding and the rather sharp threshold occurring at x ≈ 0.75 may indicate that the β-process is a cooperative process.