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Polarization-dependent vibrational shifts on dielectric substrates

2020, Yang, C., Wang, W., Nefedov, A., Wang, Y., Mayerhöfer, T.G., Wo¨ll, C.

The interaction of light with matter at surfaces of dielectrics strongly depends on polarization. Here, we present the first infrared spectroscopic evidence for significant polarization effects in the spectroscopic detection of adsorbate vibrational frequencies. In addition to much larger peak intensities for p-polarized light relative to s-polarization, a small but distinct blue shift was identified for CO adsorbed at the surfaces of two prototype dielectric substrates, CeO2(111) and CaCO3(10.4). A simulation using a layer model yields very good agreement with experiment.

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The Tensile Behaviour of Highly Filled High-Density Polyethylene Quaternary Composites: Weld-Line Effects, DIC Curiosities and Shifted Deformation Mechanisms

2021, Viljoen, David, Fischer, Matthieu, Kühnert, Ines, Labuschagné, Johan

The interactive effects between additives and weld lines, which are frequent injection-moulding defects, were studied in high-density polyethylene (HDPE) and compared to weld-line-free reference samples. These materials were formulated around a D- and I-optimal experimental design, based on a quadratic Scheffé polynomial model, with up to 60 wt% calcium carbonate, masterbatched carbon black and a stabiliser package. Where reasonable and appropriate, the behaviours of the systems were modelled using statistical techniques, for a better understanding of the underlying trends. The characterisations were performed through the use of conventional tensile testing, digital image correlation (DIC) and scanning electron microscopy (SEM). A range of complex interactive effects were found during conventional tensile testing, with DIC used to better understand and explain these effects. SEM is used to better understand the failure mechanics of some of these systems through fractography, particularly regarding particle effects. A measure is introduced to quantify the deviation of the pre-yield deformation curve from the ideal elastic case. Novel analysis of DIC results is proposed, through the use of combined time-series plots and measures quantifying the extent and localisation of peak deformation. Through this, it could be found that strong shifts in the deformation mechanisms occur as a function of formulation and the presence/absence of weld lines. Primarily, changes are noted in the onset of continuous inter- and intralamellar slip and cavitation/fibrillation, seen through the onset of localised deformation and stress-whitening.

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Biowaste chicken eggshell powder as a potential cure modifier for epoxy/anhydride systems: competitiveness with terpolymer-modified calcium carbonate at low loading levels

2017, Saeb, Mohammad Reza, Ghaffari, Mehdi, Rastin, Hadi, Khonakdar, Hossein Ali, Simon, Frank, Najafi, Farhood, Goodarzi, Vahabodin, Vijayan P., Poornima, Puglia, Debora, Asl, Farzaneh Hassanpour, Formela, Krzysztof

Biowaste chicken eggshell (ES) powder was applied as a potential cure modifier in epoxy/anhydride systems. Cure behaviour and kinetics of composites filled with very low content (0.1 wt% based on epoxy resin) of ES, calcium carbonate (CaCO3), and terpolymer-modified fillers, mES and mCaCO3, were discussed comparatively. Surface analysis was performed by X-ray photoelectron spectroscopy. Cure kinetics was investigated by differential (Friedman) and integral (Ozawa and Kissinger-Akahira-Sunose) isoconversional methods using dynamic differential scanning calorimetry (DSC) data. Overall, protein precursors naturally existing in the structure of pristine ES facilitated crosslinking of epoxy and hardener of anhydride with functional groups resulting from terpolymer attachment to CaCO3 particles. Accelerated/hindered cure was observed depending on the filler type and surface characteristics, as investigated via the autocatalytic/non-catalytic nature of reactions and comparison of activation energy values of four types of composites. An enhanced cure was identified for composites containing untreated ES, which could be inferred on account of the lower competitive cure of carboxyl groups in the terpolymer backbone with epoxy compared to peptide groups existing in microporous pristine ES. On the other hand, mCaCO3 revealed low values of activation energy compared to pristine CaCO3, but still of the same order as ground biowaste ES.