Quantitative analysis of polymers by attenuated total reflectance fourier-transform infrared spectroscopy: Vinyl acetate and methyl content of polyethylenes

A comparison was made between the transmission and attenuated total reflectance (ATR) infrared spectroscopic techniques for the determination of the vinyl acetate content of poly(ethylene–vinyl acetate) copolymers and methyl content of polyethylene. It was demonstrated that the transmission and ATR calibration curves for ratios of absorbances of bands with maxima at very similar wavelength were coincident, while those for ratios of absorbances of bands with maxima at significantly dissimilar wavelength were shifted apart. The explanation of this behavior is based on the wavelength dependence of the interaction of the IR radiation in ATR, compared to the wavelength independence of the interaction in transmission IR. The effect of polarized radiation was investigated in each type of analysis with the ATR technique. It was found that essentially the same results were obtained with the IR radiation polarized at 0° or 90°, relative to the plane of incidence, as compared to spectra obtained with unpolarized radiation. However, larger scatter was observed with polarized radiation. The effect of clamping pressure was also investigated. It was found that a minimum clamping torque of 5 in. lb is necessary to assure good physical contact in ATR work.