Abstract

In this work, nanohydroxyapatite (HAp) was functionalized with poly(ε-caprolactone) (PCL), using 1,6-hexamethylene diisocyanate (HDI) as a coupling agent, and then incorporated into the polyoxymethylene copolymer (POM) matrix using the extrusion technique. The obtained POM/HAp-g-PCL composites were investigated using FTIR, DSC, TOPEM DSC, and TG methods. Mechanical properties were studied using destructive and non-destructive ultrasonic methods, wettability, and POM crystallization kinetics in the presence of HAp-g-PCL. Moreover, preliminary bioactivity evaluation of the POM/HAp-g-PCL composites was performed using the Kokubo method. It was found that the introduction of HAp-g-PCL to the POM matrix has a limited effect on the phase transitions of POM as well as on its degree of crystallinity. Importantly, HAp grafted with PCL caused a significant increase in the thermal stability of the POM, from 292 °C for pristine POM to 333 °C for POM modified with 2.5% HAp-g-PCL. If unmodified HAp was used, a distinct decrease in the thermal stability of the POM was observed. Crystallization kinetic studies confirmed that HAp-g-PCL, in small amounts, can act as a nucleating agent for the POM crystallization process. Moreover, incorporation of HAp-g-PCL, although slightly decreasing the mechanical properties of POM composites, improved the crucial parameter in biomedical applications, namely the in vitro bioactivity.

Highlights

  • Published: 3 March 2022Polyoxymethylene (POM) is a well-known thermoplastic engineering resin that exhibits good mechanical properties, stiffness, creep and fatigue resistance, moldability, and excellent chemical resistance [1]

  • We found that HAp functionalization by poly(ethylene glycol) (PEG) grafting leads—through blocking of polyoxymethylene copolymer (POM) basic active sites—to significant improvements in the thermal stability of polyoxymethylene [8,9]

  • This is due to the fact that the kinetics of crystallization is strongly influenced by the nucleation process close to the temperature Tm

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Summary

Introduction

Polyoxymethylene (POM) is a well-known thermoplastic engineering resin that exhibits good mechanical properties, stiffness, creep and fatigue resistance, moldability, and excellent chemical resistance [1]. Due to its excellent mechanical properties in the latter field, POM can be applied in bone tissue replacement [4]. To make POM more biocompatible and bioactive in bone tissue engineering applications, it can be modified with hydroxyapatite (HAp), which is the compound most similar to the mineral part of human bonds [5,6]. In our previous work, it has been revealed that the incorporation of higher amounts of HAp into the POM matrix leads to a significant decrease in POM thermal stability. We found that HAp functionalization by poly(ethylene glycol) (PEG) grafting leads—through blocking of POM basic active sites—to significant improvements in the thermal stability of polyoxymethylene [8,9]

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