Engineering Polypropylene-Calcium Sulfate (Anhydrite II) Composites: The Key Role of Zinc Ionomers via Reactive Extrusion

工程聚丙烯-硫酸钙(硬石膏 II)复合材料:锌离子在反应挤出过程中的关键作用

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作者:Marius Murariu, Yoann Paint, Oltea Murariu, Fouad Laoutid, Philippe Dubois

Abstract

Polypropylene (PP) is one of the most versatile polymers widely used in packaging, textiles, automotive, and electrical applications. Melt blending of PP with micro- and/or nano-fillers is a common approach for obtaining specific end-use characteristics and major enhancements of properties. The study aims to develop high-performance composites by filling PP with CaSO4 β-anhydrite II (AII) issued from natural gypsum. The effects of the addition of up to 40 wt.% AII into PP matrix have been deeply evaluated in terms of morphology, mechanical and thermal properties. The PP-AII composites (without any modifier) as produced with internal mixers showed enhanced thermal stability and stiffness. At high filler loadings (40% AII), there was a significant decrease in tensile strength and impact resistance; therefore, custom formulations with special reactive modifiers/compatibilizers (PP functionalized/grafted with maleic anhydride (PP-g-MA) and zinc diacrylate (ZnDA)) were developed. The study revealed that the addition of only 2% ZnDA (able to induce ionomeric character) leads to PP-AII composites characterized by improved kinetics of crystallization, remarkable thermal stability, and enhanced mechanical properties, i.e., high tensile strength, rigidity, and even rise in impact resistance. The formation of Zn ionomers and dynamic ionic crosslinks, finer dispersion of AII microparticles, and better compatibility within the polyolefinic matrix allow us to explain the recorded increase in properties. Interestingly, the PP-AII composites also exhibited significant improvements in the elastic behavior under dynamic mechanical stress and of the heat deflection temperature (HDT), thus paving the way for engineering applications. Larger experimental trials have been conducted to produce the most promising composite materials by reactive extrusion (REx) on twin-screw extruders, while evaluating their performances through various methods of analysis and processing.

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