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β-Relaxation of PMMA: Tip Size and Stress Effects in Friction Force Microscopy.

The kinetic signature of the β-relaxation of poly(methyl methacrylate) (PMMA) is investigated by friction force microscopy. The variation in friction force was measured as a function of scan velocity, temperature (300 K-410 K), and applied load using both sharp and blunt probe tips. The friction data show distinct maxima, which can be ascribed to the β-relaxation of PMMA. The contact area was varied over the ranges of approximately 20 to 70 nm(2) and 12,000 to 43,000 nm(2) through the use of probe tips with radii of approximately 15, 18, 1350, and 2650 nm. Kinetic analysis shows that the apparent activation energy of the β-relaxation decreases with the tip radius. Accompanying finite element simulations indicate that for the sharp tips a substantial subvolume of the polymer underneath the tip exceeds the yield stress of PMMA. This suggests that for small contact sizes and high stresses the activation barrier of the β-process decreases through the activation of the α-process by material yielding.