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 C(1)-C(4) 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 (P(2) and P(4), 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.

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A prototype, no-moving-parts, plane array infrared spectrograph (PA-IR) capable of routine spectral acquisition in the 3400 to 2000 cm−1 region has been constructed. The instrument includes a continuous source, Czerney–Turner type monochromator system and an infrared camera that incorporates a 320 × 256 pixel InSb focal plane array detector cooled with liquid nitrogen. PA-IR spectra (∼3400 to 2550 cm−1) of polystyrene (PS) and poly(ethylene naphthalate) (PEN) films have been obtained at a resolution of ∼8 cm−1 with excellent signal-to-noise ratios (SNR). Peak-to-peak noise levels of ∼1 × 10−3 absorbance units are observed for single acquisition spectra with 1.5 ms integration times and 17 ms total acquisition times. Integration times as low as 10 μs are possible (with good SNR); however, data acquisition is limited by the frame rate (60 frames/s) of the software acquisition package currently used. In this work, an apertured image of the source is displayed over ∼20 rows of the array and the expected square root improvement in SNR is observed when multiple rows and/or frames are averaged. We have also shown that a square root improvement in SNR continues to occur with further signal averaging, providing noise levels as low as 1.5 × 10−5 absorbance units. Several additional advantages and options associated with the PA-IR method are discussed, including time-resolved spectroscopy, real-time monitoring, and spectroscopic mapping.