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<sup>2</sup> and 12 000 to 43 000 nm<sup>2</sup> 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.