A Dissertation Entitled Synthesis of Amorphous Alkaline Earth

A Dissertation entitled Synthesis of Amorphous Alkaline Earth Phosphate and its Applications in Orthopedics by Elham Babaie Submitted to the Graduate Faculty as partial fulfillment of the requirements for the Doctor of Philosophy Degree in Biomedical Engineering ________________________________________ Dr. Sarit B Bhaduri , Committee Chair ________________________________________ Dr. A. Champa Jayasuriya, Committee Member ______________________________________ Dr. Vijay K. Goel, Committee Member ________________________________________ Dr. Mehdi Pourazady, Committee Member _______________________________________ Dr. Arunan Nadarajah, Committee Member _______________________________________ Dr. Amanda Bryant-Friedrich, Dean College of Graduate Studies The University of Toledo December 2016 Copyright 2016, Elham Babaie This document is copyrighted material. Under copyright law, no parts of this document may be reproduced without the expressed permission of the author. An Abstract of Synthesis of Amorphous Alkaline Earth Phosphate and its Applications in Orthopedics by Elham Babaie Submitted to the Graduate Faculty as partial fulfillment of the requirements for the Doctor of Philosophy Degree in Biomedical Engineering The University of Toledo December 2016 The focus of this dissertation is synthesis and applications of amorphous alkaline earth phosphate such as magnesium-calcium phosphate and magnesium phosphate. Phosphates of alkaline earths such as calcium phosphates, are of great interest as bone replacement materials because they are biocompatible and resorbable in physiological conditions. As such, they have been studied for a long time. With growing research interest in magnesium alloys, magnesium phosphates have been gaining attention as a bone substitute material with comparable or in some cases, better properties than calcium phosphates. The compositional similarities between calcium phosphates (Ca Ps) and natural bone matrix prompted vigorous research activities in calcium phosphates. By comparison, research on magnesium-calcium phosphates are rare. Among the Ca P, amorphous calcium phosphates (ACP), have found applications as an important class of materials since their presence is important in commercial products such as plasma sprayed coatings on implants to self-setting CaP cements, or the fact that amorphous phase is as an intermediate phase in the synthesis of various iii crystalline phases of CaP. On the other hand, an understanding of the amorphous phases of magnesium phosphate or magnesium-calcium phosphate, or their transformation into their relevant crystalline phases is rare. For instance, it is shown that doping magnesium (small amount) in calcium phosphate can stabilize amorphous calcium phosphate prior to conversion to hydroxyapatite, However, not much information is available on amorphous magnesium phosphate as reports of synthesis of amorphous magnesium phosphate is scarce in the literature. Accordingly, this dissertation is broadly divided into five sub-sections. The first section reviews the state-of-the-art on processing of porous biomaterials. Porous biomaterials are an important class of materials and important goal of this research is to be able fabricate them in a cost-effective way. The second section discusses the synthesis and applications of amorphous magnesium-calcium phosphate, and amorphous magnesium phosphate as promising biomaterials in comparison to amorphous calcium phosphates or other relevant crystalline phases of calcium phosphates. The focus is on the mechanisms of formation and functional properties such as biocompatibility. In general, several methods have been proposed on the synthesis of amorphous phase, including synthesis from aqueous medium (wet route), using high energy processing or high temperatures (dry route) etc. Among them precipitation (wet route) was chosen in this study, because it is relatively simple and reproducible. Additionally, based on the method of the formation and experimental conditions (solution supersaturation, pH, etc.) different ratios of Ca/P, Mg/P, (Ca+Mg)/P ranging from 1 to 2 or even higher can be produced. iv The as-synthesized materials were characterized using Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD), and Fourier Transform Infrared Spectroscopy (FTIR). In vitro studies were conducted on mouse osteoblasts, and SEM was used as the imaging methods. In the next of the work, the theme is to investigate the applications of amorphous magnesium-calcium phosphate, and amorphous magnesium phosphate as dense bodies (sintered bioceramic), as cement and also as porous cement scaffold in orthopedic applications. We show that amorphous magnesium phosphate, and amorphous magnesium-calcium phosphate can be produced through ethanol-assisted precipitation method. They are also shown to be biocompatible for relevant applications. The sinterability of amorphous magnesium-calcium phosphate and magnesium phosphate was studied. The results indicate that the amorphous phase of magnesium magnesium- calcium phosphates was able to transform into relevant crystalline phases upon sintering using microwave sintering technique. Next, the development of cement composite consisting of amorphous magnesium phosphate and hydrophilic poly vinyl alcohol (PVA) biopolymer, was carried. Finally, the ability of amorphous magnesium phosphate in fabrication of macroporous composite scaffold through gas-foaming technique was studied. Biodegradable Mg-particles were used as the porogen to produce macroporous structure. This method uses the fast corrosion kinetics of Mg to create macro pores in real time during the setting of the cement. v To my parents Acknowledgements My deepest gratitude is to my advisor, Dr. Sarit Bhaduri. I have been amazingly fortunate to have an advisor who gave me his continual support, guidance, and motivation throughout my dissertation. Without the mentoring of him, I could not have completed this work. I am beholden to Ohio Third Frontier grant and Department of Bioengineering TA Support. I would like to thank my committee members Dr. Arunan Nadarajah, Dr. A. Champa Jayasuriya, Dr. Mehdi Pourazady, and Dr. Vijay Goel for their guidance. I am grateful to Dr. Sam Imaniye for his help in material characterizations. Also, I am thankful for Tamara Phares in the Bioengineering Department for her help in biological aspects. I would like to thank my fellow friends in UT, especially Mr. Yufu Ren for the support and cooperation during my studies. Finally, I am grateful to my parents for all of their love, and strength all these years. vii Table of Content Abstract ............................................................................................................................ iii Acknowledgements ........................................................................................................ vii Table of Content ............................................................................................................ viii List of Tables .................................................................................................................. xv Lists of Figures ............................................................................................................. xvii List of Abbreviations .................................................................................................... xxii Chapter 1 Introduction ...................................................................................................... 1 1. Introduction ............................................................................................................. 1 1.1 Overview .......................................................................................................... 1 Chapter 2- Introduction .................................................................................................... 5 2. Fabrication and biological aspects of porous biomaterials in orthopedic applications: A review ...................................................................................................... 5 2.1 Introduction ...................................................................................................... 5 2.1.1 Description of bone as a porous material ....................................... 12 2.2 Creation of random porosity .......................................................................... 16 2.2.1 Partial sintering .............................................................................. 16 2.2.2 Porosity using transient porogen .................................................... 19 viii 2.2.3 Dissolution ..................................................................................... 21 2.2.4 Porosity using a liquid pore forming agent .................................... 24 2.2.4.1 Freeze-casting/ freezedrying………….......……25 2.2.4.2 Reverse freeze casting......................................... 28 2.2.5 Porosity formation using gas bubble.............................................. 29 2.2.6 Porosity using polymeric sponge replication ................................. 33 2.2.7 Gel casting ..................................................................................... 34 2.3 Other fabrication methods............................................................................. 37 2.3.1 Bioglass .......................................................................................... 37 2.3.1.1 Melt-quenching route .......................................... 37 2.3.1.2 Sol-gel ................................................................

Load more