It has been well documented that the use of dry optics in depth profiling by confocal Raman microspectroscopy significantly distorts the laser focal volume, thus negatively affecting the spatial resolution of the measurements. In that case, the resulting in-depth confocal profile is an outcome of several contributions: the broadening of the laser spot due to instrumental factors and diffraction, the spreading of the illuminated region due to refraction of the laser beam at the sample surface, and the influence of the confocal aperture in the collection path of the laser beam. Everall and Batchelder et al. developed simple models that describe the effect of the last two factors, i.e., laser refraction and the diameter of the pinhole aperture, on the confocal profile. In this work, we compare these theoretical predictions with experimental data obtained on a series of well-defined planar interfaces, generated by contact between thin polyethylene (PE) films (35, 53, 75, and 105 microm thickness) and a much thicker poly(methyl methacrylate) (PMMA) piece. We included two refinements in the above-mentioned models: the broadening of the laser spot due to instrumental factors and diffraction and a correction for the overestimation in the decay rate of collection efficiency predicted by Batchelder et al. These refinements were included through a semiempirical approach, consisting of independently measuring the Raman step-response in the absence of refraction by using a silicon wafer and the actual intensity decay of a thick and transparent polymer film. With these improvements, the model reliably reproduces fine features of the confocal profiles for both PE films and PMMA substrates. The results of this work show that these simple models can not only be used to assist data interpretation, but can also be used to quantitatively predict in-depth confocal profiles in experiments carried out with dry optics.
We examine mechanistic aspects of the diffusion between a series of liquid polystyrenes (PS) and a glassy poly(phenylene oxide) (PPO) matrix, through the use of confocal Raman microspectroscopy. The results show that the diffusion kinetics has Fickean characteristics, similar to those found in liquid‐liquid polymer diffusion. No signatures of the linear regime typical of the case‐II diffusion mechanism were found. Overall, these observations are consistent with the claim that case‐II is unlikely to occur in liquid‐glassy polymer diffusion.magnified image
Summary: We explored the diffusion mechanisms in a series of liquid/glassy polymer interphases. The diffusion experiments were performed in a unique way: the temperature range studied encompassed the glass transition temperature (Tg) of the glassy matrices. We observed that the diffusion behavior of the liquid polymer was remarkably continuous when passing through the matrix Tg, and that the diffusion modes at the liquid/glassy interphases were very similar to those observed in liquid/liquid polymer diffusion.
Thermoplastic composites were made from polypropylene (PP) and long sisal fibers (SF) by using different processing techniques. Four sets of composites specimens were made with a 60/40 (wt/wt) SF/PP ratio: the first set was made by melt-blending PP and SF and compression molding 2-mm-thick flat sheets; a second set was made by melt-blending PP, SF, and maleic anhydride grafted polypropylene (MA-g-PP); the third set was made by compression molding knitted SF yarns, preimpregnated with PP, between PP sheets; the fourth set was also made by compression molding knitted SF yarns, preimpregnated with diluted MA-g-PP, between PP sheets. The bidirectional array of fibers, containing 60% of SF well-impregnated with a small quantity of MA-g-PP, increases the flexural modulus by 600%, the tensile modulus by 475%, and the tensile strength by 300% compared with unfilled PP. The composites sheets were successfully thermoformed with small wall thickness reductions to obtain a three-dimensional (3D) shape with very low forming energy, outstanding mechanical properties, and excellent surface finish. POLYM. ENG. SCI., 45:976 -983, 2005.
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