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

Abstract

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.