For the first time, four different methods to determine the degree of molecular orientation from polarized Raman spectroscopy measurements are compared. The great influence of molecular orientation on the properties of polymers has driven the development of multiple experimental techniques and procedures. This study is based on the C1-C4 ring stretching vibration of poly(propylene terephthalate) (PPT) at 1614 cm-1. It is shown that simply ratioing the band intensity obtained with the polarization parallel and perpendicular to the unique axis of the sample provides a good qualitative method to observe the evolution of orientation in a series of similar samples. To quantitatively compare the degree of orientation one needs to utilize a more complex method yielding the second- and fourth-order parameters of the orientation distribution function (P2 and P4, respectively). To date, most studies have been based on the assumption of a cylindrically symmetric polarizibility tensor. It is shown that this assumption is highly questionable although this method has been used fairly successfully in the past. This method results in orientation parameters that are clearly different from those obtained with the two more complex procedures. The most complex method, both theoretically and experimentally, requires the most measurements per sample. Major problems have occurred when trying to calculate the desired parameters, in particular for samples with high birefringence. These problems are related to experimental complexities occurring for measurements when the samples are tilted with respect to the polarization direction of the incident light. These measurements are replaced by a simple determination of depolarization ratio in the third method. This method assumes that the depolarization ratio is independent of changes in molecular orientation and structure. It was found that this assumption is not correct. Thus, the most complex method is the method of choice to quantitatively determine the second- and fourth-order parameters of the orientation distribution function, unless one has knowledge of the depolarization ratio of each sample being studied. That knowledge permits the use of an experimentally simpler method to obtain the desired parameters.
S. Frisk, R. M. Ikeda, D. B. Chase, and J. F. Rabolt, "Determination of the Molecular Orientation of Poly(propylene terephthalate) Fibers Using Polarized Raman Spectroscopy: A Comparison of Methods," Appl. Spectrosc. 58, 279-286 (2004)