Mechanical spectroscopy is a powerful tool for the investigation of molecular dynamics of amorphous polymers over a large temperature range and frequency scale. In this work, by using high precision shear mechanical spectroscopy tool, we have investigated the segmental dynamics from local segmental relaxation to sub-Rouse modes in a series of amorphous polymers. We have demonstrated the existence of sub-Rouse modes slower than the local segmental motion in amorphous polymers. The sub-Rouse modes exhibit a similar change of dynamics at the same temperature TB ~1.2 Tg, as the local segmental relaxation through the temperature dependence of relaxation time and relaxation strength. Furthermore, the crossover relaxation time of the sub-Rouse modes at TB is almost the same for all the polymers investigated, i.e. τα'(TB) = 10-1±0.5 s, which is independent of molecular weight and molecular structure. This remarkable finding indicates that solely the time scale of the relaxation determines the change in dynamics of the sub-Rouse modes. According to the coupling model, the crossover is suggested to be caused by the onset of strong intermolecular cooperativity below TB. Hence the results suggest that the sub-Rouse modes and their properties are generally found in amorphous polymers by mechanical spectroscopy, and reveal the cooperative nature of the sub-Rouse modes.

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A new technique, direct photodegradation of self-assembled monolayers (SAM), to obtain surface energy gradients on Si substrates was demonstrated. The gradient surface, with hydrophobic to hydrophilic gradients, was prepared by two steps: Firstly, a homogeneous fluoroalkylsilane SAM film was deposited by a chemical vapor deposition on a Si substrate. Secondly, a controlled photodegradation technique was directly applied to the homogeneous FAS-SAM surface. The surface energy gradient was then obtained due to the different intensity of photoirradiation in the different positions along the photodegraded path on the SAM surfaces. The resulting surface displayed a gradient of wettability (with the contact angle of water changing from 55° to 18°) over a distance of 4.2 mm. The water droplet was driven by surface energy gradient and spontaneously moved from the hydrophobic to hydrophilic surface. During the moving process, the water droplet accelerated firstly and then decelerated. The peak velocity was about 23.3 mm/s. The velocity is dependent on the gradient of the surface energy.