Dynamic infrared linear dichroism (DIRLD) measurements of films of a thermo-plastic polyester/polyurethane random copolymer (Estane 5703, B. F. Goodrich) are reported. Step-scan Fourier transform infrared (FT-IR) is used for dynamic measurements, and a photoelastic modulator (PEM) is used to create broadband polarization modulation as the carrier frequency for the strain modulation. A novel modulation/demodulation strategy has been employed that simplifies the triple-modulation experiment into a double-modulation experiment; the theory is thoroughly discussed. Both static and dynamic dichroic absorption difference spectra have been measured on the prestretched polymer film. The results are of high signal-to-noise ratio (SNR) and clearly indicate the static and dynamic orientation of the transition dipole moments due to the tensile deformation. The dynamic orientation responses are primarily in phase with the perturbation. The orientation magnitudes of the infrared absorption bands are quantified and compared, and the orientations of the hard and soft domains are differentiated. To assist in the interpretation of the dynamically measured data, we also describe a static linear dichroic measurement using a wire-grid polarizer and FT-IR in the rapid-scan mode for a sample incrementally drawn until the point of breaking. The orientation functions of selected bands have been calculated, and the static results agree with the dynamic data, indicating the dependency of the dynamic orientation response on the preorientation state.

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