Overview Biological Materials ScienceHydroxyapatite (HA)-reinforced polymer biocomposites offer a robust system to engineer synthetic bone substitutes with tailored mechanical, biological, and surgical functions. The basic design rationale has been to reinforce a tough, biocompatible polymer matrix with a bioactive HA filler. A large number of studies have investigated modifications to the biocomposite structure and composition, aimed at improving the mechanical properties, often through modified or novel processing methods. In this article, the effects of the polymer composition and molecular orientation; the HA/polymer interface; and the HA-reinforcement content, morphology, preferred orientation, and size are reviewed with respect to mechanical properties, drawing frequent comparisons between various HA-reinforced polymer composites and bone tissue.
Hydroxyapatite (HA) whiskers have been synthesized using a number of chemical solution methods, including the chelate decomposition method. Numerous previous studies have investigated the effects of the reagents, reagent concentrations, solution pH, and reaction temperature on HA whisker morphology and composition. However, purely kinetic effects, such as the reaction heating and stirring rates, have not been rigorously investigated and are rarely reported in the literature. Therefore, the objective of this study was to investigate kinetic effects on the morphology of HA whiskers synthesized using the chelate decomposition method. In order to study the kinetic effects on the morphology of HA whiskers, three experimental parameters were varied independently: the reaction heating rate (0.36°–3.0°C/min), stirring rate (0–250 rpm), and temperature (80°–200°C). At all heating and stirring rates, precipitated whiskers were confirmed by XRD and FT‐IR to comprise phase‐pure, calcium‐deficient HA (Ca/P=1.57–1.62). The length and aspect ratio of HA whiskers increased with decreased heating rate, decreased stirring rate, and increased reaction temperature. The mean length and aspect ratio of HA whiskers increased approximately twofold with decreased heating rate over the range studied, following a power‐law relationship. Therefore, the reaction heating rate is a key variable that can be used to tailor the morphology of HA whiskers and ought to be reported in the literature. The reaction heating rate and temperature had relatively little effect on the width of HA whiskers. However, the precipitate morphology was altered significantly from micro‐scale whiskers to nano‐scale plates with increased stirring rate. These results offered new insights and provided clarification regarding the reaction mechanism, which is discussed in detail.
A micromechanical model was developed to predict the elastic moduli of hydroxyapatite (HA) whisker reinforced polymer biocomposites based upon the elastic properties of each phase and the reinforcement volume fraction, morphology, and preferred orientation. The effects of the HA whisker volume fraction, morphology, and orientation distribution were investigated by comparing model predictions with experimentally measured elastic moduli for HA whisker reinforced high-density polyethylene composites. Predictions using experimental measurements of the HA whisker aspect ratio distribution and orientation distribution were also compared to common idealized assumptions. The best model predictions were obtained using the experimentally measured HA whisker aspect ratio distribution and orientation distribution.
The anisotropic elastic constants of human cortical bone were predicted using a specimen-specific micromechanical model that accounted for structural parameters across multiple length scales. At the nano-scale, the elastic constants of the mineralized collagen fibril were estimated from measured volume fractions of the constituent phases, namely apatite crystals and Type I collagen. The elastic constants of the extracellular matrix (ECM) were predicted using the measured orientation distribution function (ODF) for the apatite crystals to average the contribution of misoriented mineralized collagen fibrils. Finally, the elastic constants of cortical bone tissue were determined by accounting for the measured volume fraction of Haversian porosity within the ECM. Model predictions using the measured apatite crystal ODF were not statistically different from experimental measurements for both the magnitude and anisotropy of elastic constants. In contrast, model predictions using common idealized assumptions of perfectly aligned or randomly oriented apatite crystals were significantly different from the experimental measurements. A sensitivity analysis indicated that the apatite crystal volume fraction and ODF were the most influential structural parameters affecting model predictions of the magnitude and anisotropy, respectively, of elastic constants.
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