Date of Award

Spring 2007

Document Type

Dissertation

Degree Name

Doctor of Philosophy in Chemical Engineering - (Ph.D.)

Department

Chemical Engineering

First Advisor

Marino Xanthos

Second Advisor

Treena Livingston Arinzeh

Third Advisor

Michael Jaffe

Fourth Advisor

Laurent Simon

Fifth Advisor

Jing Wu

Abstract

In spite of numerous publications on the potential use of combinations of aliphatic polyester composites containing bioactive fillers for bone regeneration, little information exists on the combined in vitro mechanisms involving simultaneously diffusion for polymer degradation and bioactivity through nucleation and growth of apatite in simulated body fluid (SBF) solution. The objective of this study is to contribute to the understanding of the fundamentals in designing non-porous, solid materials for bone regeneration, from experimental data along with their engineering interpretation.

Bioactivity, in terms of apatite growth, was assessed through several experimental methods such as scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), X-ray-diffraction (XRD) and changes in ion concentration. In the case of the six neat fillers evaluated, the filler shape, form and chemical structure showed significant differences in bioactivity response. Bioglass and calcium silicate fillers showed faster nucleation and growth rates in the screening experiments.

Composites at 30 % by weight filler were prepared by solution and/or melt mixing. Polycaprolactone (PCL) composites containing five different fillers were evaluated. Solution processed PCL/calcium silicate (CS) samples showed faster bioactivity, as determined by apatite growth, compared to melt mixed samples. The onset time for bioactivity was different for all PCL composites. The limited bioactivity in the PCL composites over longer periods of time could be attributed to the PCL hydrophobicity leading to a slow polymer degradation rate, and also to the lack of SBF replenishment. For both polylactic acid (PLA) composites containing CS and bioglass, significant growth was observed after one week and in the case of CS was still evident after four weeks immersion. However, at prolonged time periods no further bioactivity was observed, although ion release results indicated a faster release rate that would eventually lead to a faster polymer degradation and possibly continuing bioactivity.

The presence of silicate fillers enhanced the hydrolytic degradation rate of both PCL and PLA as shown from kinetic data calculations based on molecular weight measurements. Unfilled PLA samples showed significant embrittlement after two weeks immersion, whereas for the CS filled system more significant changes could be observed in the compressive strength and modulus after the same time period.

Experimental data were also fitted into an equation proposed to calculate erosion number; in the case of unfilled PLA predictions were found to agree with literature results suggesting bulk erosion. By assuming impermeable, randomly dispersed glass flakes, water transport in a composite system, prior to significant polymer degradation could be modeled. However, modeling of transport in the case of the composite consisting of a degrading polymer and a reactive decaying filler was challenging, particularly in the case of directional bioactive reinforcements, due to the occurrence of simultaneous time dependent diffusion phenomena that altered the integrity of the sample.

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