The development of new materials for bone substitution has been of great interest for the scientific community in the last years. High‐density polyethylene (HDPE) and hydroxyapatite (HA) composites have been used in biomedical applications without any inflammatory response. However, the differences in nature of both materials have motivated the use of coupling agents to improve their interfacial interactions. In this work, the effects of adding three different commercial coupling agents (NZ12, Lica01, Lica12) to high‐density polyethylene (HDPE)/hydroxyapatite (HA) composites were studied. Composites containing 20 parts per hundred (phr) of HA previously treated with the already mentioned coupling agents were characterized by mechanical tests and their morphologies were analyzed afterwards. Composites with 0.3 and 0.5 wt% of NZ12 unfolded an increase in their Young's modulus and tensile strength, as a consequence of an improved dispersion of the filler into the polymeric matrix. Analysis of the samples by XPS showed that the zirconate coupling agent interacted more with the HA, as reflected in the lower binding energies of the corresponding oxygen atoms, which agrees with their better performance from the mechanical point of view.
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