Dichroic ratio thin films

Normal incidence transmission IRLD measurements are used to study thin films (typically 100 pm thickness and less, depending on the molar extinction coefficient of the bands) with in-plane uniaxial orientation. Two spectra are recorded sequentially with the radiation polarized parallel (p) and perpendicular (s) to the principal (machine) direction of the sample. The order parameter of the transition moment of the studied vibration is calculated from either the dichroic ratio (R — Ap/As) or the dichroic difference (AA = Ap—As) as ... 

Fig. 22(b) shows polarized visible absorption spectra of mixed LB films of MS-C2o binary and MS-C20-AL18 ternary systems prepared by using an aqueous subphase containing Cd2+ ions, where the ratio in the mixed system is [MS] [C20] [AL18] = l 2 x (x — 0 and 1) [77-84]. The thick and thin lines in Fig. 22(b) refer to the spectra, Atl and A , measured by linearly polarized light with the electric vector parallel and perpendicular to the dipping direction of the substrate, respectively. For x = 0, a sharp absorption peak is observed at 590 nm, which is red-shifted from the MS monomer peak at around 540 nm. The dichroic ratio R of the 590 nm band is R> 1, where R is defined as A /A . For x= 1.0, on the other hand, a sharp blue-shifted band with R< 1 appears at 505 nm. Fig. 22(c) refers to the cases of the corresponding binary and ternary systems fabricated under the subphase without the Cd2+ ions [84], Unlike the results in Fig. 22(b), remarkably red- and blue-shifted bands are not observed... 

Measurements f dichroic ratios at fundamental absorption frequencies usually require very thin specimens or films (typical thickness range 2 too. to 0-1 mm) in order to avoid complete absorption of the radiation. Such specimens require careful preparation using either melt... 

The value of the approach using dichroic ratios coupled with a knowledge of the assignments of peaks is further illustrated by measurements on plain polyethylene films [2]. The production process leads to a rather complex orientation pattern. The molten polymer is extruded as a thin, hollow cylinder, in what may be termed the machine direction. It is simultaneously expanded in a plane perpendicular to the machine direction by the application of internal pressure. Additional variables are the extrusion temperature and the rate at which the blown film has been cooled. The resulting orientation behaviour is best studied by x-ray diffraction pole figure measurements [3,4,5] but the infrared approach provides a relatively simple means for obtaining a useful amount of information, particularly for the behaviour of chains in amorphous regions. 

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