Glass and Structural Transitions Measured at Polymer Surfaces on the Nanoscale

This paper reviews our recent progress in determining the surface glass transition temperature, T_g, of free and substrate confined amorphous polymer films. We will introduce novel instrumental approaches and discuss surface and bulk concepts of T_g. The T_g of surfaces will be compared to the bulk, and we will discuss the effect of interfacial interactions (confinements), surface energy, disentanglement, adhesion forces, viscosity and structural changes on the glass transition. Measurements have been conducted with scanning force microscopy in two different shear modes: dynamic friction force mode and locally static shear modulation mode. The applicability of these two nano-contact modes to T_g will be discussed.This revised version was published online in November 2005 with corrections to the Cover Date.     

Shear modulation force microscopy study of near surface glass transition temperatures

We report results of glass transition (T(g)) measurements for polymer thin films using atomic force microscopy (AFM). The AFM mode, shear modulation force microscopy (SMFM), involves measuring the temperature-dependent shear force on a tip modulated parallel to the sample surface. Using this method we have measured the surface T(g) of thin (17-500 nm) polymer films and found that T(g) is independent of film thickness (t>17 nm), strength of substrate interactions, or even presence of substrate.     

Investigations of heterogeneous ultrathin blends using lateral force microscopy

In order to study the glass transition of thin film polymer blends, high spatial resolution and temperature sensitivity is needed. In this paper, we emphasize the importance of the calibration of scanning parameters such as load and speed when measuring the glass transition temperature of polymers using lateral force microscopy. Once calibrated, this method is ideal for investigations of heterogeneous samples such as blends and co‐polymers. We present an analysis technique for lateral force imaging using a fast and stable cooling/heating stage. This approach involves mapping the friction forces over a certain area and identifying regions of different frictional properties. The difference in the average friction force can then be plotted as a function of temperature. The friction force is expected to vary around the glass transition. Therefore, the glass transition temperature can be defined as the temperature at which the difference in the average friction force undergoes a slope change. We present investigations of blends using polystyrene mixed with poly(butylmethacrylate). The transition temperatures obtained are in good agreement with the bulk values of corresponding homopolymeric films.