The optical and mechanical performance of polymer articles is often very strongly influenced by the crystallinity and degree of molecular orientation in the polymer. It is therefore important to have available techniques for measuring and mapping these parameters over article surfaces and through wall thicknesses, on scales from centimetres to microns. It is also desirable that these techniques do not in themselves perturb the morphology of the polymer, for example by introducing excess orientation or crystallinity through sectioning.

In this paper we will show how Raman microscopy can provided a useful approach for mapping polymer crystallinity on the micron scale, particularly when coupled with multivariate calibration techniques for data analysis. The acquisition and treatment of data to obtain crystallinity information will be described in detail. We will also describe the development and application of polarised FTIR specular reflectance and attenuated total reflection (ATR) microbeam techniques for quantifying and mapping surface orientation of polymer articles.