Surface potential change in bioactive polymer during the process of biomimetic apatite formation in a simulated body fluid

A bioactive polyethylene substrate can be produced by incorporation of sulfonic functional groups (-SO3H) on its surface and by soaking in a calcium hydroxide saturated solution. Variation of the surface potential of the polyethylene modified with -SO3H groups with soaking in a simulated body fluid (SBF) was investigated using a laser electrophoresis zeta-potential analyzer. To complement the study using laser electrophoresis, the surface was examined by X-ray photoelectron spectroscopy (XPS), thin film X-ray diffraction (TF-XRD), field-emission scanning electron microscopy (FE-SEM) and energy-dispersive electron X-ray spectroscopy (EDS). Comparing the zeta potential of sulfonated and Ca(OH)2-treated polyethylene with its surface structure at each interval of these soaking times in SBF, it is apparent that the polymer has a negative surface potential when it forms -SO3H groups on its surface. The surface potential of the polymer increases when it forms amorphous calcium sulfate. The potential decreases when it forms amorphous calcium phosphate, revealing a constant negative value after forming apatite. The XPS and zeta potential analysis demonstrated that the surface potential of the polyethylene was highly negatively charged after soaking in SBF for 0.5 h, increased for higher soaking times (up to 48 h), and then decreased. The negative charge of the polymer at a soaking time of 0.5 h is attributed to the presence of -SO3H groups on the surface. The initial increase in the surface potential was attributed to the incorporation of positively charged calcium ions to form calcium sulfate, and then the subsequent decrease was assigned to the incorporation of negatively charged phosphate ions to form amorphous calcium phosphate, which eventually transformed into apatite. These results indicate that the formation of apatite on bioactive polyethylene in SBF is due to electrostatic interaction of the polymer surface and ions in the fluid.