CALCIUM PHOSPHATES

IN BIOLOGICAL

ANDINDUSTR~LSYSTEMS

CALCIUM PHOSPHATES

IN BIOLOGICAL

AND INDUSTRIAL SYSTEMS

edifed by

Zahid Amjad Ph.D. The BFGoodrich Company

~.

" SPRINGER SCIENCE+BUSINESS MEDIA, LLC

ISBN 978-1-4613-7521-0 ISBN 978-1-4615-5517-9 (eBook) DOI 10.1007/978-1-4615-5517-9

Library of Congress Cataloging-in-Publication Data

A c.I.P. Catalogue record for this book is available from the Library of Congress.

Copyright © 1998 by Springer Science+Business Media New York Originally published by Kluwer Academic Publishers. in 1998

* Chapter 4 copyright© 1998 by Laurence C. Chowand Milenko Markovic

All rights reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, mechanical, photo­copying, recording, or otherwise, without the prior written permission of the publisher, Springer Science+Business Media, LLC.

Printed on acid-free paper.

To my devoted family,

Rukhsana and Naureen,

with all my love

CONTENTS

LIST OF CONTRIBUTORS ..... ............ ..... ......................... .... ix

PREFACE ............................................................................................... Xlli

Part I GENERAL

1. Calcium Phosphates: Structures, Composition, Solubility and Stability Ming S. Tung ........................................................................................ .

2. Amorphous Calcium Phosphate: Thermodynamic and Kinetic Considerations Edward D. Eanes ................................................................................... 21

3. Growth of Calcium Phosphates on Different Substrates: Epitaxial Considerations Petros G. Koutsoukos ............................................................................ 41

4. Physicochemical Properties of Fluorapatite Laurence C. Chow and Milenko Markovic ..... .... .......... .... ........... ......... 67

5. Interfacial Properties of Calcium Phosphates P. Somasundaran and Berislav Markovic ................................................ 85

6. Nuclear Magnetic Resonance Spectroscopy of Calcium Phosphates James P. Yesinowski .............................................................................. 103

Part II CALCIUM PHOSPHATES IN BIOLOGICAL SYSTEMS

7. Influence of Metal Ions on the Crystal Growth of Calcium Phosphates Petros G. Koutsoukos ............................................................................. 145

8. Structure I Performance Relationships of Phosphorous and Carboxyl Containing Additives as Calcium Phosphate Crystal Growth Inhibitors John D. Sallis ......................................................................................... 173

9. Crystal Growth of Calcium Phosphates in the Presence of Polymeric Inhibitors Saburo Shimabayashi and Tadayuki Uno ................................................ 193

viii

10. Calcium Phosphates for Medical Applications Christian Rey ......................................................................................... 217

11. Importance of Calcium Phosphates in the Development of Calcium Urolithiasis Saeed R. Khan ......... ............. ................................................................. 253

12. Calcium Pyrophosphate Crystal Formation and Dissolution Kenneth P. H. Pritzker ........................................................................... 277

13 Calcium Phosphates in Pharmaceutical Product Development Mansoor A. Khan and Indra K. Reddy................................................... 303

14. Recent Advances in Dentifrice Technologies Abdul Gaffar and John Afflitto ............................................................... 325

15. Preparation and Application of Calcium Phosphate Fibers Koji Ioku ... ........ ... ... ....... ....... ........ .... .... .......... ... .................................... 357

Part III CALCIUM PHOSPHATES IN INDUSTRIAL SYSTEMS

16. Development of Calcium Phosphate Inhibiting Polymers for Cooling Water Applications

Zahid Amjad ................ ....................... ......................... ........ ....... ........... 371

17. Mechanism of Calcium Phosphate Scale Formation and Inhibition in Cooling Systems Libardo A. Perez .......................................................... ............... ........... 395

18. The Role of Calcium Phosphate in Internal Boiler Water Treatment Jasbir S. Gill .......................................................................................... 417

19. Equipment Fouling in the Dairy Application: Problem and Pretreatment Georges Daufin and Jean-Pierre Labbe ................................................... 437

20. Phosphate Removal from Waste Water M. M. Seckler, O. S. L. Bruinsma and G. M. Van Rosmalen .................. 465

21. Phosphorous Speciation in Sediments and its Release Control Kazuaki Ito and Mitsumasa Okada ......................................................... 479

22. Mechanistic Aspects of Calcium Phosphonates Precipitation Lynn M. Frostman, Amy T. Kan and Mason B. Tomson ........................ 493

INDEX ...................................................................................................... 507

CONTRIBUTORS

John Afllitto, Colgate-Palmolive Company, 909 River Road, P. O. Box 1343, Piscataway, New Jersey 08855-1343 USA

Zahid Amjad, The Advanced Technology Group, The BFGoodrich Company, 9921 Brecksville Road, Brecksville, Ohio 44141 USA

O.S.L. Bruinsma, Delft University of Technology, Laboratory for Process Equipment, Leeghwaterstraat 44,2628, CA Delft, The Netherlands

Laurence C. Chow, American Dental Association Health Foundation, Paffenbarger Research Center, National Institute of Science and Technology, Gaithersburg, Maryland 20899 USA

Georges Daufin, National Institute for Agriculture, INRA, Dairy Technology Research Laboratory, LRTL, 65 rue de Saint-Brieuc, 35042 Rennes Cedex, France

Edward D. Eanes, Mineral Chemistry and Structure Section, National Institute of Dental Research, National Institutes of Health, Building 30, Room 106, MSC-4320, Bethesda, Maryland 20892 USA

Lynn M. Frostman, Baker Petrolite, 1600 Industrial Boulevard, Sugarland, Texas 77448 USA

Abdul Gaffar, Colgate-Palmolive Company, 909 River Road, P. O. Box 1343, Piscataway, New Jersey 08855-1343 USA

Jasbir S. Gill, Calgon Corporation, P. O. Box 1346, Pittsburgh, Pennsylvania 15230 USA

Koji Ioku, Department of Advanced Materials Science and Engineering, Faculty of Engineering, Yamaguchi University, 2557 Tokiwadai, Ube-Shi, Yamaguchi 755 Japan

Kazuaki Ito, Department of Environmental Science, Faculty of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima 739, Japan

Amy T. Kan, Rice University, Environmental Science and Engineering MS 317, 600 S. Main Street, Houston, Texas 77005-1892 USA

x

Mansoor A. Khan, College of Pharmacy and Health Sciences, Northeast Louisiana University, Monroe, Louisiana 71209 USA

Saeed R. Khan, Department of Pathology, College of Medicine, P. O. Box J-275, JHMHC, University of Florida, Gainesville, Florida 32610-0275 USA

Petros G. Koutsoukos, Institute of Chemical Engineering and High Temperature Chemical Processes, P. O. Box 1414, Department of Chemical Engineering, University ofPatras, GR-26500 Patras, Greece

Jean-Pierre Labbe, National School of Chemistry of Paris, 11 rue Pierre et Marie Curie, 75231 Paris Cedex 05, France

Berislav Markovic, Langmuir Center for Colloid and Interfaces, School of Engineering and Applied Sciences, Columbia University, New York, New York 10027 USA

Milenko Markovic, American Dental Association Health Foundation, Paffenbarger Research Center, National Institute of Science and Technology, Gaithersburg, Maryland 20899 USA

Mitsumasa Okada, Department of Environmental Science, Faculty of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima 739, Japan

Libardo A. Perez, BetzDearbom Water Management Group, I Quality Way, Trevose, Pennsylvania 19053 USA

Kenneth P. B. Pritzker, Pathology and Laboratory Medicine, Mount Sinai Hospital, University of Toronto, 600 University Avenue, Toronto, Ontario, Canada M5G lX5

Indra K. Reddy, College of Pharmacy and Health Sciences, Northeast University, Monroe, Louisiana 71209 USA

Christian Rey, Laboratoire des Matereriaux, Physico-chimie des Phosphates, Ecole Nationale Superieure de Chimie, CNRS 5071, 38 rue des 36 Ponts - 31400 Toulouse, France

G.M. van Rosmalen, Delft university of Technology, Laboratory for Process Equipment, Leeghwaterstraat 44, 2628 CA Delft, The Netherlands

John D. Sallis, University of Tasmania, Department of Biochemistry, P. O. Box 252-58 GPO Hobart, Tasmania, Australia 7001

M.M. Seckler, IPT Institute for Technological Research of the State of sao Paulo, sao Paulo, S. P., Brazil

xi

Saburo Shimabayashi, Faculty of Pharmaceutical Sciences, The University of Tokushima, Sho-machi 1-78-1, Tokushima 770, Japan

P. Somasundaran, Langmuir Center for Colloids and Interfaces, School of Engineering and Applied Science, Columbia University, New York, New York 10027 USA

Mason B. Tomson, Rice University, Department of Environmental Science and Engineering - MS 317, 6100 S. Main Street, Houston, Texas 77005-1892 USA

Ming S. Tung, American Dental Association Health Foundation, Paffenbarger Research Center, National Institute of Science and Technology, Gaithersburg, Maryland 20899 USA

Tadayuki Uno, Faculty of Pharmaceutical Sciences, The University of Tokushima, Tokushima, Sho-machi 1-78-1, Tokushima 770, Japan

James P. Yesinowski, Naval Research Laboratory, Washington DC 20375-5342 USA

ABOUT THE EDITOR

Zahid Amjad was born in Lahore, Pakistan; received his M.Sc. from Punjab University (Lahore) and Ph.D. from Glasgow University, Glasgow, Scotland. He is presently a Research Fellow in the Advanced Technology Group of The BFGoodrich Company in Brecksville, Ohio where he has served since 1982. Dr. Amjad was Lecturer at the Institute of Chemistry of Punjab University, and was Assistant Research Professor at the State University of New York at Buffalo (1977 -79) before joining the Calgon Corporation. His areas of research include: the adsorption of polyelectrolytes at solid-liquid interface, crystal growth and inhibition, development and applications of water soluble/swellable polymers, and the control and removal of foulants from water treatment systems.

Dr. Amjad has authored or coauthored more than 90 technical publications and is a holder of 29 patents. He is also the editor of two books: Reverse Osmosis: Membrane Technology, Water Chemistry, and Industrial Applications (Van Nostrand Reinhold, New York, 1993) and Mineral Scale Formation and Inhibition (Plenum Press, New York, 1995). He has been inducted into the National Hall of Corporate Inventors and is listed in American Men and Women of Sciences, Who's Who in Technology, and Who's Who of American Inventors. Dr. Amjad is a recipient of 1997 EDI Innovation Award. He is a member of several professional organizations.

PREFACE

Research on calcium phosphates has attracted considerable attention in recent years. Calcium phosphates are the major inorganic constituents of biological hard tissues such as teeth and bones and other pathological minerals. Calcium phosphates have been widely produced in industry, in such forms as, ceramics, nutrient supplements, medicines, dentifrices, and stabilizers for plastics. They are utilized in solid state chemistry as fluorescent lamp phosphors and play a role in waste water treatment processes. Calcium phosphates are important in industrial water treatment (Le., boiler and cooling) where deposition of these salts on heat exchanger surfaces can lead to loss of system efficiency, overheating, unscheduled shutdown time, and ultimately heat exchanger failures. Effective control of calcium phosphate deposits continue to challenge the industrial scientist. Calcium phosphate deposits have also been encountered during pasteurization of milk.

Calcium phosphates of interest include: dicalcium phosphate dihydrate (DCPD, CaHP04-2H20), brushite; dicalcium phosphate anhydrous (DCP, CaHP04), monetite; octacalcium phosphate (OCP, CasH2(P04)6-SH20); tricalcium phosphate (TCP, Ca3(P04h), whitlockite; and hydroxyapatite (HAP, Cas(P04h0H). Other calcium compounds of biological and industrial interest include: amorphous calcium phosphate (ACP); fluorapatite (FAP, CaS(P04)~); calcium pyrophosphate dihydrate (CPPD, Ca2P20 7-2H20); calcium fluoride; and calcium phosphonates.

This book is intended to provide a comprehensive discussion on calcium phosphates in the diverse areas of their investigations. The authors were selected because they are the specialists in their particular fields, possessing wide knowledge and experience and and able to analyze recent results and relate them to their respective areas of expertise. New information, as well as review of current concepts, generally highlights the individual contributions. Due to the broad scope of the subject covered and the large number of contributions, this book is divided into three parts. While each section contains a basic theme, there is a considerable overlapping of ideas and approaches. This reflects the considerable excitement and interdisciplinary nature of investigations by researchers interested in dissimilar aspects of calcium phosphates.

The book begins with an introduction to calcium phosphates in chapter 1 including a brief review of structural and solubility aspects of calcium phosphates. Chapter 2 deals with amorphous calcium phosphate, first addressing the thermodynamics and kinetics, followed by its role in the earlier stages of calcification. Chapter 3 covers the growth of calcium phosphates from epitaxial perspective. In chapter 4, physiochemical properties of fluorapatite is presented and compared with

xiv

hydroxyapatite. The influence of various ions on the interfacial properties of synthetic and natural hydroxyapatite is discussed in chapter 5. In chapter 6, various NMR techniques for the studies of calcium phosphate surfaces are reviewed.

The focus of the second section is the mechanistic aspects of precipitation and inhibition of calcium phosphates and calcium pyrophosphate, especially in biological systems. Also included in this section is a discussion of the medical and industrial applications of calcium phosphates. Chapters 7-9 present discussion of the inhibition of calcium phosphates by metal ions, polymeric, and non-polymeric materials. Chapter 10 outlines the methods for the preparation of calcium phosphates and their unique properties as biomaterials for medical applications. Chapter 11 discusses the importance of calcium phosphates in urinary stones. In chapter 12, the crystal growth and dissolution of calcium pyrophosphate is reviewed. Chapter 13 and 14 cover the role of calcium phosphates in pharmaceutical and dentifrice applications. The final chapter of this section presents discussion on the medical and industrial applications of calcium phosphate fibers.

The final section concentrates on calcium phosphate scales commonly encountered in industrial systems and presents discussion on the removal of phosphate from waste water. Chapters 16-19 cover calcium phosphate scaling problem in cooling, boiler, and dairy industries. Included also in these chapters is the discussion of the important role played by polymeric inhibitors to control the deposition of calcium phosphates on heat exchanger and membrane surfaces. Phosphate removal methods for treating waste water as well as various phosphorous species present in sediments and their release control are reviewed in chapter 21. A discussion of the solution chemistry of various calcium phosphonates concludes the book.

Considering the general interest in calcium phosphates, this publication is directed to an audience ofresearchers in the fields of biology, chemistry, dentistry, geology, chemical engineering, environmental engineering, and medicine. It will also be useful to technology-focused researchers in industry whose investigations might be related directly or indirectly to calcium phosphates. It is my hope that this book will contribute to the better understanding of the role calcium phosphates play in a number of interesting fields including, but not limited to, biological, environmental, industrial, and medical applications.

I wish to thank all of the contributors and their institutions for making this book possible. I sincerely appreciate the support of The BFGoodrich Company, especially Dr. Victoria F. Haynes, for allowing me the opportunity to edit this book. Thanks are also extended to the editorial staff of the K1uwer Publishing Company for their patience and professionalism. Finally, a special thanks to my wife, Rukhsana, for her support and great patience during the completion of this book.

August, 1997 ZahidAmjad