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UUnniivveerrssiittyy ooff KKeennttuucckkyy UUKKnnoowwlleeddggee University of Kentucky Master's Theses Graduate School 2010 MMUULLTTIIWWAALLLL CCAARRBBOONN NNAANNOOTTUUBBEESS AALLTTEERR TTHHEE TTHHEERRMMAALL PPRROOFFIILLEE AANNDD AANNTTIIBBIIOOTTIICC EELLUUTTIIOONN OOFF OORRTTHHOOPPAAEEDDIICC BBOONNEE CCEEMMEENNTT Alison Carroll Tickle University of Kentucky, [email protected] RRiigghhtt cclliicckk ttoo ooppeenn aa ffeeeeddbbaacckk ffoorrmm iinn aa nneeww ttaabb ttoo lleett uuss kknnooww hhooww tthhiiss ddooccuummeenntt bbeenneefifittss yyoouu.. RReeccoommmmeennddeedd CCiittaattiioonn Tickle, Alison Carroll, "MULTIWALL CARBON NANOTUBES ALTER THE THERMAL PROFILE AND ANTIBIOTIC ELUTION OF ORTHOPAEDIC BONE CEMENT" (2010). University of Kentucky Master's Theses. 76. https://uknowledge.uky.edu/gradschool_theses/76 This Thesis is brought to you for free and open access by the Graduate School at UKnowledge. It has been accepted for inclusion in University of Kentucky Master's Theses by an authorized administrator of UKnowledge. For more information, please contact [email protected]. ABSTRACT OF THESIS MULTIWALL CARBON NANOTUBES ALTER THE THERMAL PROFILE AND ANTIBIOTIC ELUTION OF ORTHOPAEDIC BONE CEMENT Multiwall carbon nanotubes (MWNTs) have extraordinary mechanical and thermal transport properties. They significantly improve the static and dynamic mechanical properties of acrylic orthopaedic bone cement when added to the dry cement polymer powder. Understanding the role MWNTs play on bone cement polymerization temperatures will lead to improved mechanical integrity of the cement-bone interface in joint arthroplasties. It was determined through thermal testing that MWNTs increased the polymerization time of the methylmethacrylate by 45-460% and decreased the peak exothermic temperature of bone cement with and without antibiotics. The flow of heat produced during polymerizing cement was reduced 25-85% with the addition of MWNTs to the cement powder. This decreases the probability of thermal necrosis and “hot” spots  caused by high exothermic polymerization temperatures that can destroy the bone adjacent to the cement. These high temperatures also affect the potency and range of antibiotics used in arthroplasty. Isothermal and elution studies determined that MWNTs altered the heat flow and amount of antibiotic release from bone cement during polymerization. Antibiotic elution from bone cement containing MWNTs could match the elution seen in pure cement. The alteration of the flow of heat from bone cement leads to new options for heat-labile antibiotics in total joint arthroplasty. KEYWORDS: Multiwall Carbon Nanotubes, Orthopaedic Bone Cement, Bone Cement Polymerization Temperature, Bone Cement Isothermal Reactions, Antibiotic Elution _______Alison C. Tickle______ ________April 19, 2010_______ iii MULTIWALL CARBON NANOTUBES ALTER THE THERMAL PROFILE AND ANTIBIOTIC ELUTION OF ORTHOPAEDIC BONE CEMENT By Alison Carroll Tickle ________David Pienkowski_________ Director of Thesis _______Abhijit Patwardhan_________ Director of Graduate Studies __________May 3, 2010____________ iv RULES FOR THE USE OF THESES Unpublished theses submitted for the Master’s degree and deposited in the University of  Kentucky Library are as a rule open for inspection, but are to be used only with due regard to the rights of the authors. Bibliographical references may be noted, but quotations or summaries of parts may be published only with the permission of the author, and with the usual scholarly acknowledgments. Extensive copying or publication of the thesis in whole or in part also requires the consent of the Dean of the Graduate School of the University of Kentucky. A library that borrows this thesis for use by its patrons is expected to secure the signature of each user. Name Date ________________________________________________________________________ ________________________________________________________________________ ________________________________________________________________________ ________________________________________________________________________ ________________________________________________________________________ ________________________________________________________________________ ________________________________________________________________________ ________________________________________________________________________ ________________________________________________________________________ ________________________________________________________________________ ________________________________________________________________________ v THESIS Alison Carroll Tickle The Graduate School University of Kentucky 2010 vi MULTIWALL CARBON NANOTUBES ALTER THE THERMAL PROFILE AND ANTIBIOTIC ELUTION OF ORTHOPAEDIC BONE CEMENT ________________________________ THESIS ________________________________ A thesis submitted in partial fulfillment of the requirements for the degree of Master of Science in Biomedical Engineering in the Graduate School at the University of Kentucky By Alison Carroll Tickle Lexington, Kentucky Director: Dr. David Pienkowski, Associate Professor of Biomedical Engineering Lexington, Kentucky 2010 Copyright ©Alison C. Tickle 2010 vii ACKNOWLEDGMENTS The following thesis, while an individual work, benefited from the insights and direction of several people. First, my Thesis Chair, David Pienkowski, exemplifies the high quality scholarship to which I aspire. In addition, Mauro Giordani and Brock Marrs provided timely and instructive comments and evaluation at every stage of the thesis process, allowing me to complete this project on schedule. Next, I wish to thank the complete Thesis Committee: David Puleo and Rodney Andrews. Along the way, I also received guidance and help from Rebecca Peyyala and Stephen Duncan. Each individual provided insights that guided and challenged my thinking, substantially improving the finished product. I’d also like to thank the Center for Applied Energy Research, the  Center for Biomedical Engineering, the Department of Orthopaedic Surgery, the Center for Oral Health Research, and the Clinical Laboratories at the University of Kentucky for their continued support of this work. In addition to the technical and instrumental assistance above, I received equally important assistance from family and friends. My parents, Robert and Debbie Tickle, supported my desire to achieve a Master’s degree and knew from an early age that I would be attending graduate school. It was a result of your guidance and encouragement that I succeeded in furthering my education. Finally, I wish to thank my colleagues in the Biomedical Engineering department who helped me along the road to achieving my goal as well as all my friends who supported and encouraged me throughout my studies. viii TABLE OF CONTENTS ACKNOWLEDGMENTS ............................................................................................... viii LIST OF TABLES ............................................................................................................. xi LIST OF FIGURES .......................................................................................................... xii Chapter 1 - Background ...................................................................................................... 1 Section 1.1 Arthroplasty ........................................................................................... 1 Section 1.1.1 History and Functions ............................................................................. 1 Section 1.1.2 Current Clinical Data .............................................................................. 2 Section 1.2 Bone Cement ......................................................................................... 5 Section 1.2.1 Composition and Structure ...................................................................... 5 Section 1.2.2 Polymerization Process ........................................................................... 6 Section 1.2.3 Properties ................................................................................................. 8 Section 1.2.4 Antibiotic Laden Bone Cement ............................................................. 11 Section 1.2.5 Variations and Adaptations ................................................................... 14 Section 1.3 Carbon Nanotubes ............................................................................... 17 Section 1.3.1 History and Properties ........................................................................... 17 Section 1.3.2 Carbon Nanotube Composites ............................................................... 19 Section 1.4 Objectives ............................................................................................ 27 Chapter 2 – Polymerization Kinetics of Acrylic Bone Cement with MWNTs................. 28 Section 2.1 Introduction ......................................................................................... 28 Section 2.2 Methods ............................................................................................... 32 Section 2.2.1 Polymerization Kinetics ........................................................................ 33 Section 2.2.2 Isothermal Heating ................................................................................ 36 Section 2.2.2.1 Simplex Bone Cement ........................................................................ 37 Section 2.2.2.2 Palacos Bone Cement ......................................................................... 38 ix Section 2.3 Results ................................................................................................. 47 Section 2.3.1 Polymerization Kinetics Results ........................................................... 47 Section 2.3.2 Isothermal Heating Results ................................................................... 51 Section 2.3.2.1 Simplex Results ................................................................................... 51 Section 2.3.2.2 Palacos Results .................................................................................... 57 Section 2.3.2.3 Comparison of Simplex and Palacos Bone Cement ............................ 61 Section 2.4 Discussion ............................................................................................ 64 Section 2.4.1 Polymerization Kinetics Conclusions ................................................... 64 Section 2.4.2 Isothermal Heating Conclusions ........................................................... 66 Chapter 3 - Elution Properties of Antibiotic Bone Cement with MWNTs ....................... 68 Section 3.1 Background .......................................................................................... 68 Section 3.2 Methods ............................................................................................... 72 Section 3.3 Results ................................................................................................. 75 Section 3.4 Discussion ............................................................................................ 82 Chapter 4 - Conclusions and Future Work ....................................................................... 84 Section 4.1 Conclusions ............................................................................................. 84 Section 4.2 Future Work ............................................................................................ 85 References ......................................................................................................................... 87 VITA ................................................................................................................................. 93    x LIST OF TABLES Table 1.1 Current Bone Cements……………………………………………....................9 Table 1.2 Properties of Carbon Nanotubes……………………………………………...19 Table 2.1 Activation Energies, Frequency Factors, Areas, and Control Polymerization Values……………….…………………………………..………………………..……...50 Table 2.2 Maximum Heat Flow and Duration for MWNT and Tobramycin Loaded Simplex Bone Cement…………………………………..………………………..……...52 Table 2.3 Maximum Heat Flow and Duration for MWNT and Cefazolin Loaded Simplex Bone Cement…………...…………………………………………………..…………….56 Table 2.4 Maximum Heat Flow and Duration for MWNT and Gentamicin Loaded Palacos. Bone Cement ………...………………………………………………………...59 Table 2.5 Maximum Heat Flow and Duration for all MWNT Palacos Bone Cement Samples………………………………………………………………………….........….60 Table 2.6 Heat Flow Maximum and Duration Comparison for Palacos and Simplex Bone Cement ………………………………………………….……………………..………...63 Table 3.1 Food and Drug Administration-Approved Premixed Antibiotic Bone Cements Used in Study ………………………………………………….………………………...70 Table 3.2  Elution Amounts and Rates for Each Sample………………………………...76 Table 3.3 Total Elution Amount and Elution Rates for Each Sample Type…………….79       xi

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Antibiotics in bone cement leach out of the hardened plastic material by diffusion. The idea is that the antibiotics are released from the cement gradually over
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