Interdiffusion kinetics of miscible polymer/polymer laminates investigated by atomic force microscopy

The miscibility of poly(vinyl chloride)/poly(n-butyl methacrylate) (PVC/PnBMA) blend and the interdiffusion kinetics of PVC/PnBMA laminates have been investigated by differential scanning calorimetry (DSC) and atomic force microscopy (AFM), respectively. This blend exhibited a lower critical solution temperature behavior. Below 120 °C, DSC results showed each blend with different PVC contents exhibited only a single glass transition temperature which increased with PVC content, indicating that PVC and PnBMA were miscible. After PVC/PnBMA laminates were annealed at different temperature for different time, a smooth cross-section across interface was prepared by ultramicrotoming. Combined with topography and phase images of tapping mode AFM, the relative concentration profile, interface width and the relationship between interface width and annealing time could be obtained. In a regime of rubbery/rubbery interdiffusion, the diffusion obeyed a typical Fickian Case-I behavior where the interface width was proportional to the square root of annealing time. The mutual diffusion coefficient was in good agreement with that obtained from DSC and positron annihilation lifetime spectroscopy. However, in the regime of glassy/rubbery interdiffusion, the diffusion followed a typical Case-II behavior where the interface width was proportional to annealing time. These results imply that AFM is a reliable and powerful tool for the investigation of polymer/polymer interdiffusion at a level of polymer chain size.