carbonated hydroxyapatite carbonated - pan stanford · fleet carbonated hydroxyapatite “as...

FleetCarbonated H

ydroxyapatite

“As interest in apatite continues to rise, this timely book is an absolute must-read for all apatite researchers, regardless of discipline. Professor Fleet collects a large body of research on carbonated apatite, from many disparate disciplines, and synthesizes it exceptionally well. This book now becomes the authoritative reference on carbonated apatite.”

Prof. John M. HughesUniversity of Vermont, USA

“This is an authoritative and comprehensive review of our current knowledge about carbonate-bearing hydroxylapatite, the main mineral constituent of bones and teeth in vertebrates. Much has been learned in recent years about the detailed structure and chemistry of this mineral and methods for use in biomaterials. The author is one of the world’s leading researchers on the structure and chemistry of apatite group minerals.”

Prof. John RakovanMiami University, USA

“This book, written by the world’s foremost expert on carbonated hydroxylapatite, provides comprehensive accounts of the state-of-the-art knowledge, the latest approaches, and new research directions about this bone mineral. The book will be of particular interest to all researchers and graduate students of biomaterials.”

Prof. Yuanming PanUniversity of Saskatchewan, Canada

This book introduces recent advances in understanding the crystal structure of carbonate hydroxylapatite (also known as bone mineral), which forms the hard tissue of bones and teeth. Bone mineral is the reservoir for carbon dioxide in the body and maintains the concentration of mineral ions in body fluids at homeostasis. The detailed structure of bone mineral has remained obscure more than 80 years after publication of the basic apatite structure, because of the nanoscale size and poor quality of bone mineral crystals. An entirely new approach to the determination of carbonate apatite structures has resulted in a greatly expanded role for the c-axis channel of bone mineral crystals in the control of metabolic acidosis and blood pH.

The book includes chapters on apatite mineralogy and geochemistry, synthesis methods, X-ray structure, infrared spectroscopy, crystal chemistry of carbonate hydroxylapatite, and biological apatites. There are 74 illustrations, 25 tables of data, and 3 appendixes. Discussion of the new research is supported by an outline of the theory behind the methods of investigation and reviews of previous research on hydroxylapatite materials, for the benefit of non-specialist students and researchers.

Michael Fleet was educated at Manchester University, UK, and enjoyed a scholarly career in the Department of Earth Sciences at the University of Western Ontario, Canada, where he is currently professor emeritus. He has published extensively in the general area of earth material science, using X-ray crystallography, laboratory synthesis and experimentation, and chemical spectroscopy as his primary research tools. Prof. Fleet’s research interests have encompassed metal sulfides, geochemistry of gold, nickel, and platinum,

high-pressure silicates, apatite, rare earth silicates, mica minerals, and boron. He is the author of Micas, volume 3A in the Rock-Forming Minerals series. He was elected Fellow of the Royal Society of Canada in 1996, awarded the Past Presidents’ Medal of the Mineralogical Association of Canada in 1997, and appointed honorary professor at Jilin University, Changchun, P. R. China, in 2006.

ISBN 978-981-4463-67-6V413

Carbonated Hydroxyapatite

Michael Fleet

Materials, Synthesis, and Applications

for the WorldWind PowerThe Rise of Modern Wind Energy

Preben MaegaardAnna KrenzWolfgang Palz

editors

Pan Stanford Series on Renewable Energy — Volume 2


Michael Fleet

Materials, Synthesis, and Applications

October 14, 2014 17:10 PSP Book - 9in x 6in 00-Michael-Fleet-prelims

Published by

Pan Stanford Publishing Pte. Ltd.

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British Library Cataloguing-in-Publication DataA catalogue record for this book is available from the British Library.

Carbonated Hydroxyapatite: Materials, Synthesis, and Applications

Copyright c© 2015 Pan Stanford Publishing Pte. Ltd.

All rights reserved. This book, or parts thereof, may not be reproduced in anyform or by any means, electronic or mechanical, including photocopying,recording or any information storage and retrieval system now known or tobe invented, without written permission from the publisher.

For photocopying of material in this volume, please pay a copying

fee through the Copyright Clearance Center, Inc., 222 Rosewood Drive,

Danvers, MA 01923, USA. In this case permission to photocopy is not

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ISBN 978-981-4463-67-6 (Hardcover)

ISBN 978-981-4463-68-3 (eBook)

Printed in the USA


Contents

Preface ix

1 Introduction 1

2 Apatite-Type Structure 72.1 Introduction 7

2.2 Fluorapatite 9

2.3 Hydroxylapatite and Chlorapatite 13

2.4 Other Space Groups 16

3 Crystal Chemistry and Geochemistry 173.1 Apatite Crystal Chemistry 17

3.1.1 Introduction 17

3.1.2 A-Site Cations 20

3.1.3 BO4n− Complex Ions 23

3.1.4 Channel (X) Anions 26

3.1.5 Substitution Mechanisms 26

3.2 Geochemical Aspects of Calcium Phosphate Apatites 28

3.2.1 P-T-X Stability 28

3.2.2 Igneous and Metamorphic Rocks 29

3.2.3 Rare Earths (RE) 31

3.2.4 Phosphorite 33

4 Synthesis of Carbonate Apatites 414.1 Introduction 41

4.2 HAP 42

4.3 Type A CHAP 43

4.4 Type B and Type AB CHAP 44

4.5 Sodium-Bearing Type AB CHAP 46


vi Contents

4.6 Type B CFAP with Acetate Impurity 47

4.7 Francolite 47

4.8 Synthesis at High Pressure and Temperature 48

4.8.1 Early High-Pressure Research 48

4.8.2 Experiments at The University of Western

Ontario (UWO) 48

4.8.2.1 Sodium-free type A and type AB CHAP 49

4.8.2.2 Sodium-bearing type AB CHAP 51

4.8.2.3 Sodium-bearing type AB CCLAP 53

4.8.2.4 Sodium-bearing type AB CFAP 53

5 X-Ray Structures 555.1 Introduction 55

5.2 Theoretical Aspects 56

5.2.1 Crystal Structures from X-ray Diffraction 56

5.2.2 Rietveld Method for Powder Patterns 60

5.2.3 Practical Problems 61

5.2.4 Rigid Body Refinement of Channel Carbonate

Ion 64

5.3 Unit-Cell Parameters for CHAP 67

5.4 Structural Information from X-Ray Powder Patterns 71

5.5 Single-Crystal X-Ray Structures 77

5.5.1 Apatite Host Structures 79

5.5.2 Type A Carbonate Ion 80

5.5.3 Type A2 Carbonate Ion 91

5.5.4 Type B Carbonate 93

6 Chemical Spectroscopy 976.1 Introduction 97

6.2 Infrared Spectroscopy 98

6.2.1 Overview 98

6.2.2 Carbonate Apatite Spectra 101

6.2.3 Asymmetric Stretch (ν3) Bands 108

6.2.4 Sodium-Bearing CHAP 111

6.2.5 Annealing Experiments 118

6.2.6 Out-of-Plane Bend (ν2) Bands 123

6.2.7 Polarized Infrared Spectra 130

6.2.8 Vitreous State 132

6.3 Nuclear Magnetic Resonance Spectroscopy 136


Contents vii

7 Carbonate Apatite Crystal Chemistry 1417.1 Introduction 141

7.2 Symmetry of Type A CHAP 141

7.3 Location of Type B Carbonate Ion 145

7.4 Proportion of A and B Carbonate from ν2 Band Areas 149

7.5 Coupling of Sodium and A and B Carbonate

Substituents 151

7.5.1 Evidence for Coupling 151

7.5.1.1 Introduction 151

7.5.1.2 Accommodation of B carbonate 153

7.5.1.3 Contents of sodium, A and B carbonate 155

7.5.1.4 Common ν3 profile 156

7.5.1.5 Extent of ordering 157

7.5.2 Influence of Alkali Metals 157

7.6 Hydrogencarbonate CHAP 164

7.7 Mobility of Carbonate Species 172

7.7.1 Aging Experiments on Hydrogencarbonate

CHAP 172

7.7.2 Annealing Experiments on Sodium-Free AB

CHAP 175

7.8 Monohydrogen Phosphate Ion 181

7.9 Pressure Stability of the A2 Carbonate Ion 183

7.10 Isothermal Bulk Modulus of CHAP 190

7.11 Excess Fluorine in Francolite 193

8 Biological Apatites 1998.1 Introduction 199

8.2 Calcium Phosphates in the Body 200

8.3 Crystal Size and Crystallinity 205

8.3.1 Size of Nanocrystals 205

8.3.2 Crystallinity 208

8.4 Crystal Structure of CHAP 210

8.5 Structure of Bone Mineral and Other Biological

Apatites 213

8.5.1 Composition and Asymmetric Stretch (ν3)

Spectra 213

8.5.2 Proportion of A and B Carbonate Ions 220

8.5.3 Sodium and Large-Cation Vacancies 222


viii Contents

8.5.4 Monohydrogen Phosphate Ions 223

8.5.5 Labile Carbonate Fraction 226

8.5.6 Channel Hydroxyl Ions 229

8.6 Mobility of Carbonate Ions in Bone Mineral 230

Appendix I 235

Appendix II 237

Appendix III 239

References Cited 243

Index 261


Preface

This book introduces recent advances in understanding the crys-

tal structure of the inorganic component of bone, which is a

carbonate-bearing calcium phosphate apatite known as “carbonate

hydroxylapatite” or “bone mineral.” Nanoscale crystals of carbonate

hydroxylapatite form the hard tissue of bones and teeth and

numerous other calcified structures in the body. They are the

reservoir for carbon dioxide in the body and have an important role

in maintaining the concentration of mineral ions in the extracellular

fluid at homeostasis, which is critical for a variety of physiological

functions, including control of acidosis and blood pH. Information

on the crystal structure of carbonate hydroxylapatite is an essential

starting point for understanding the physiological functions of bone.

Although the basic structure of hydroxylapatite has been known

for more than 80 years, the location of the carbonate ions has

remained obscure due to the nanoscale size and poor quality of bone

mineral crystals. An entirely new approach to the determination

of carbonate apatite structures has been developed over the last

decade, and is described in this book. This research uses the

single-crystal X-ray structure method in combination with infrared

spectroscopy and crystals of carbonate hydroxylapatite synthesized

from carbonate-rich calcium phosphate melts at high pressure

and temperature. The book predicts an expanded role for the

c-axis channel of bone mineral crystals in communicating with the

extracellular fluid.

Research interest in hydroxylapatite biomaterials, and in bone

mineral in particular, encompasses a broad swath of scientific

disciplines, including health sciences, biology, materials chemistry,

bioengineering, agricultural science, and earth sciences. Hydro-

xylapatite, and calcium phosphates in general, are among the


x Preface

most actively studied biomaterials, with interest spanning bone

physiology, prostheses and pastes for repairing damaged bone

tissue, and dental enamel.

The laboratory research for this project was funded by grants

from the Natural Sciences and Engineering Research Council

(NSERC) of Canada. I thank Xiaoyang Liu and Xi Liu for the high-

pressure synthesis experiments and collection of infrared spectra,

Michael Jennings and the Department of Chemistry at the University

of Western Ontario for collection of single-crystal X-ray intensity

data, and Joan Fleet for reading the manuscript.

Michael FleetLondon, Ontario

July 2014

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