Table Of Content“As interest in apatite continues to rise, this timely book is an absolute must-read for all apatite
“As rinetseeraerscth ienr sa, preagtiaterd cleosnst ionfu deiss ctiop lriinsee., Pthroisf etsismoerl Fy lbeeoto cko ilsle catns aa blsaorgluet eb omduys ot-fr reeasde afrocrh aolnl acaprabtioten ated
“As interest in apatite continues to rise, this timely book is an absolute must-read for all apatite
reseaarpcahteirtes,, frreogma rmdlaensys doifs dpiasrcaipteli dnies.c Piprloinfeesss,o arn Fd lseyent tchoelsliezcetss iat elaxcrgepe tbioondayl loyf wreeslle.a Trhchis obno ocka rnboown abteecdo mes C
researchers, regardless of discipline. Professor Fleet collects a large body of research on carbonated
apatittheae,p faarutoitmtheo ,m rfriaotanmtyi vmdeias rpneayfe rdraietsenp cdaeir saoctniep cdliainsrecbsiop, nalianntdee sds, y aanpntahdte sistyeinz.e”ths eist iezxecse ipt teixocneaplltyio wnaellll.y T wheisll .b Tohoiks nboowo kb necoowm beesc omes CaC
the authoritative reference on carbonated apatite.” Prof. John M. Hughes
the authoritative reference on carbonated apatite.” UPrnoivf.e Jrosihtyn o Mf V. eHrumgohnets, USA ara
Prof. John M. Hughes rb
University of Vermont, USA r
“This is an authoritative and comprehensive review of our current knowledgUe nabivoeurts ictayr obfo Vneartme-boenatr, iUnSgA bob
“Thish y“isdT arhonixs a yiusla tahpnoa rtaiiutteat,ht iovthreie ta anmtidva ceino a mnmdpi rcneoehmreanpls riecvhoeen rnsetsviitivueeew rn eot vfoi oefuw rb o ocfnu oerurse rn actnu kdrn reotenwetl tkehnd oginwe lavebedorgtueet b acrbaaortbeusot .nc aaMrtebu-ocbhne aahtreai-nsb geb aereinn g ono
hydrolexhayyrldnarepodax tyiintlea r,p eatchteiente t,m y etahaienr sm maabinioneu rtam tlhi nece odrneastlta iictluoeendns stt ittrouufe cnbtuto rnoee fa s nbadon ncdeh se tmeaenitsdhtr ytien oe ftv hteh riitnse bmvrieanrteteersba. rl Maatneudsc. h m Mehtuahcso hdb seh efaonsr buesee n nan
learnined b iino mreacteenrita yles.a Trsh ae baouutht othre i sd eotnaei loefd t shter uwcoturlrde’ sa nleda cdhinegm risetsreya orcf htheriss monin tehrea sl taruncdt umreet haondds c fhoerm uissetr y of
in bioampleaaattrietnere igadrl ison.u Trpeh mcee iannute tyrhaeoalrsr .si”s a obnoeu ot ft hthe ed wetoarilledd’s slteraudcitnugre r easneda rcchheemriss otrny tohfe t hstirsu mctiunreer aaln adn cdh emmeitshtordy so ffo r use ata
in biomaterials. The author is one of the world’s leading researchers on the structure and chemistry of
apatitea pgartoiutep gmroinuepr amlisn.”erals.” Prof. John Rakovan tet
ProMf.i aJPomrhoi nfU. JRnoiavhkenors vRiataynk, UovSAan ede
MiamMi Uianmivei Ursnitiyv,e UrsSiAty, USA d d
“This book, written by the world’s foremost expert on carbonated hydroxylapatite, provides H
“Thisc o“mbTohpoirske ,h bewonosrikivt,te e nwa cricbtoyteu nnt htseb yo wf ttohhreel d s’wsta otrfeol-droe’sfm- thofoesr-t eamretxo pksnet rotew xlopened rgtec ,a ortnhb eo nclaaartteebdsot n ahapytepddrr ooaxhycylhdaerposa,x tyaitlnead,p anpteirtwoev , irdepesreso avricdhe s Hy H
compdrierehcetniosinvse aabcocouut nthtsi so fb othnee smtaitnee-roaf-l.t hTeh-aer tb okonko wwleildl gbee, tohfe plaartetisctu alaprp rionatecrheesst, taon da lln erwes eraesrecahrecrhs and
direcgtircoaondmsu paartbeeho seutnut sdtihevniest sab coocfn obeui onmmtsi naoetefr ratihla.e l sTs.h”taet eb-ooof-kt hwe-iallr tb ek noofw pleadrgtiec,u tlhaer liantteesrte sat ptpor oaalcl hreess,e aarncdh enresw a rneds earch ydy
directions about this bone mineral. The book will be of particular interest to all researchers and
graduate students of biomaterials.” Prof. Yuanming Pan drd
graduate students of biomaterials.”
University oPfr oSaf.s Ykuatacnhmewinagn ,P Caannada ro
Prof. Yuanming Pan r
UniveUrsnitiyv eorfs Sitays okfa tScahsekwatacnh,e Cwaanna,d Caanada oxo
This book introduces recent advances in understanding the crystal structure of carbonate
This hbyodorokx yinlatproadtiutec e(sa lsroe ckennot wand vaas nbcoens ei nm iunnedraelr),s twanhdicihn gfo rtmhes tchryes htaalr ds ttriusscutuer eo f obfo ncaersb aonnda ttee eth. xyx
hydrBoToxhynlieas pmbaitonioteekr a(ali nlissto rto hkdenu orcewessne rravesoc iebr nofton rea cdmavriabnnoecnrea sld) ,i oiwnx hiduicenh di nfe ortrshmtea snb dtohidneyg h aatnhrdde mtcisarsyiunsettaa oli nfs sbt rtouhnceet ucso raenn cdoe fn ttecreaattrhibo.o nn oatf e yay
hydroxylapatite (also known as bone mineral), which forms the hard tissue of bones and teeth.
Bonem Bminoiennreea rlma ilo ininse str hainel ibsre otsdheyer vfroleuisried frsov rao tcir ah froobmro cnea odrsbitooaxnsiid sd.e iT oihnxei dt hdeee i tnba oitlheddey bsatnoruddcy mt auanriedn tomafi nabison ntthaeie nm sc oitnnhecere acnlo thnraacstei ornentmr aoatfii onne do f apa
mineorbals ciounres mino breo tdhya fnlu 8i0d sy eaatr hs oafmteero psutabsliics.a Ttihoen doef tthaiele bda ssitcr uacptautritee o sft rbuoctnuer em, bineecraaul shea osf rtehme naianneods cale p
mineral ions in body fluids at homeostasis. The detailed structure of bone mineral has remained ap
obscsuizree manodre p tohoarn q8u0a yleitayr so af fbteorn peu mbliincaetriaol nc royfs tthaels b. aAsnic e anptairteitlye snteruwc tauprper, obaeccha utsoe t ohfe t hdee tnearnmoisncaatlieo n of
size acanordbb sopcnouaoretre mq auoparaelitt itythe ao snft rb8uo0c nytuee ramerssi nahfeatresa rrl e pcsuruyblstltiecadals ti.in oA nan o gefrn ethtaietrle ybl yae sxnipce aawnp daapetidpte rr osotalrecuh fco tturo rt ehth,e be ce d-caeaxtuiessr ecmh oiafn ntahnteieo lnn oa fon bfo oscnael e ata
carbomscniianazretebe rao aannlp cdaart typeist oateoap slrast q rtiuinutce att hlsuitterrye uc sooc hftn uabtrrsoeo rnsle eohs fuam mslt ierneedetsa ruianbllt o aecl dirgcy r isaentca aaitld slgyo. rAseeixnsap taelanynn detdi xrbeepldloay onr noddle eepwd Hfo ra.rop tlpeh refoo car- cathhx eitso cc -thahaxenis nd ceehlt aeonrfm nbeionl naoetfi obno noef tiitt
minermal icnreyrsatla clsr yinst tahlse i nco tnhter oclo onft rmoel otaf bmoelitca abcoidlico saicsi adnodsi sb alonodd b ploHo.d pH. teit
The book includes chapters on apatite mineralogy and geochemistry, synthesis methods, X-ray e
e
The sbtoruockt uinrec,l uidnefrsa rcehda pspteercst roons caoppayt,i tcer ymstianle rcahleomgyis atrnyd o gf ecoacrhbeomnaistter yh, ysdyrnotxhyelsaips amtiteet,h aondds, bXi-oraloyg ical
The book includes chapters on apatite mineralogy and geochemistry, synthesis methods, X-ray
strucatpuareti,t einsf. rTahreedre s pareec t7ro4 siclloupsytr, actrioynstsa, l 2c5h etambilsetsr yo fo fd acatarb, oanndat e3 haypdpreonxdyilxaepsa. tDiteis, caunsdsi obnio olof gtihcea l new Carbonated
structure, infrared spectroscopy, crystal chemistry of carbonate hydroxylapatite, and biological
apatriteesse. aTrhche ries saurpe p7o4r tielldu sbtyra atnio onus,t l2in5e toafb tlhees tohfe doaryta b, eahnidn d3 t hape pmeentdhioxedss. oDf iisncvuessstiiogna toiof nt haen dn reewvi ews Carbonated
apatites. There are 74 illustrations, 25 tables of data, and 3 appendixes. Discussion of the new Carbonated
reseaorfc hp ries vsiuopups orretseeda rbcyh a onn o huytldinroex oyfl athpea ttihtee omrya tbeerhiailns,d f tohre t hmee btheondesf iot fo ifn vneosnt-igspaeticoinal iasnt ds truedvieenwtss and
research is supported by an outline of the theory behind the methods of investigation and reviews
of prreevsieoaurcs hreersse.arch on hydroxylapatite materials, for the benefit of non-specialist students and
of previous research on hydroxylapatite materials, for the benefit of non-specialist students and
researchers.
researchers.
Hydroxyapatite
Michael Fleet was educated at Manchester University, UK, and enjoyed a HHyyddroroxxyyaappaatittiete
Michsachelo lFarlelye tc awreaesr eidnu cthatee dD eapt aMrtmanecnhte sotfe rE aUrnthiv eSrcsiietyn, ceUsK , ata ntdh ee nUjnoyiveedr siaty of
Michael Fleet was educated at Manchester University, UK, and enjoyed a F
schoWlaerlsyt ecranr eOenr tainri ot,h eC aDnaedpaa,r twmheenrte ohfe Eiasr tchu rSrecnietnlyc epsr oafte stshoer eUmnievreitrusist.y Hoef has
Westpesurcnbh lioOslhanertldayr ieocx,a treCenaesnri vaiednlay , t ihnwe ht heDeree gp ehanrete mrisae l ncatur eroraef n oEtfl ayer atprhtr hoS fmeciseasntoecrr eiaes lm asect ireittnhucese. ,U Hunesii vnhegar ssXi t-yra yo f FleF
Western Ontario, Canada, where he is currently professor emeritus. He has l
publcisrhysetda leloxgteranpsihvye,l y lainb othraet ogreyn esrayln athreeas iso f aenardt h emxpateerrimiale snctiaetniocne,, uasnindg Xc-hraeym ical eel
crystsappclleruoycbgsttrlriaaoslphslocheogydp,r aeypxl aahtbesy no,h sriaislvat eopblrroyyi mr iantas oyrtyhrny etr h egesseyesninasert chrhaaeln s tiadosr oelaeas nx.o pPdfer eoraeifm.rx tFpehleen mretiatma’tsite oernnerits,a aelt aaisornccnidhe, ninccaehtne,ed rum essiictnchsag elh mXa-virceaa yl etee Materials, Synthesis, and Applications
specetrnsopcseoccmotprpoyas sacsose pdhyi s am pse rhitmaisla prsyrui mrlfeiadsereyas r,r cehgs eetaoorcochlhse . mtPoriosoltfsr.. y FP lerooeff t. ’sgF loreeledste, ’sa nrrciechsk eeinal,rt ceharen isdnt tse phrleaasvttiesn uhmav, e tt MaMteartiearlsia, lSsy, nSythnethsies,s iasn, adn Adp Applipcalitciaotniosns
high-pressuree nsicloicmatpeas,s saepda timtee, traalr es uelafirdthes ,s ilgiceaotechs,e mmiicsatr ym ionfe rgaolsl,d a, nndi cbkoerl,o na.n Hde pisla tthineu mau, thor
encompassed metal sulfides, geochemistry of gold, nickel, and platinum,
higho-phf riMegshisc-uaprsre,e svssoiulliucream teseis li,3 caAapt eainst, i ttaehp, ear atRirtoeec , ekra-aFrrotehr m esaiinlritcgha tMesisilni, cemartaieclssa, smmeriicnieaes r.m aHlsine, eawrnaadlss , beaolnerdoct neb.d oH rFeoe nlil.s o Hwthe e oi sfa utthhtheeo aRr uotyhaol r Michael Fleet
of MSicooacfs i,eM tviyco aolusf, m Cvaeon l3uaAdm aei ni n 3 tA1h9 ei9 n6R ,ot hacwek -aFRroodrcemkd-i Fntohgre m MPiainnsget rPMarlesins isederearinlests s.s’ eMHrieee dsw.a alH soe f e twlheaecst M eediln eFecertaellldoo wgF iecolalfol wtAhs eso ofRc otiahyteaio l Rno oyfa l MiMchicahela Felle Felteet
SocieCtayn oafd Caa inna d1a9 9in7 ,1 a9n9d6 , aapwpaordinetde dth heo Pnaosrta Prrye spirdoefnetsss’o Mr eadt aJli loinf tUhen iMveinrseitrya,l oCghicaanlg Acshsuonc,i aPt.i oRn. oCfh ina,
Society of Canada in 1996, awarded the Past Presidents’ Medal of the Mineralogical Association of
Canaind a2 0in0 61. 997, and appointed honorary professor at Jilin University, Changchun, P. R. China,
Canada in 1997, and appointed honorary professor at Jilin University, Changchun, P. R. China,
in 2006. V413
in 2006.
ISBN 978-981-V4446133-67-6
V413
ISBN 978-981-4463-67-6
ISBN 978-981-4463-67-6
Carbonated
Hydroxyapatite
Pan Stanford Series on Renewable Energy — Volume 2
Carbonated
Hydroxyapatite
Materials, Synthesis, and Applications
editors
Michael Fleet
Preben Maegaard
Anna Krenz
Wolfgang Palz
The Rise of Modern Wind Energy
Wind Power
for the World
CRC Press
Taylor & Francis Group
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Boca Raton, FL 33487-2742
© 2015 by Taylor & Francis Group, LLC
CRC Press is an imprint of Taylor & Francis Group, an Informa business
No claim to original U.S. Government works
Version Date: 20141126
International Standard Book Number-13: 978-981-4463-68-3 (eBook - PDF)
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October14,2014 17:10 PSPBook-9inx6in 00-Michael-Fleet-prelims
Contents
Preface ix
1 Introduction 1
2 Apatite-TypeStructure 7
2.1 Introduction 7
2.2 Fluorapatite 9
2.3 HydroxylapatiteandChlorapatite 13
2.4 OtherSpaceGroups 16
3 CrystalChemistryandGeochemistry 17
3.1 ApatiteCrystalChemistry 17
3.1.1 Introduction 17
3.1.2 A-SiteCations 20
3.1.3 BO n−ComplexIons 23
4
3.1.4 Channel(X)Anions 26
3.1.5 SubstitutionMechanisms 26
3.2 GeochemicalAspectsofCalciumPhosphateApatites 28
3.2.1 P-T-XStability 28
3.2.2 IgneousandMetamorphicRocks 29
3.2.3 RareEarths(RE) 31
3.2.4 Phosphorite 33
4 SynthesisofCarbonateApatites 41
4.1 Introduction 41
4.2 HAP 42
4.3 TypeACHAP 43
4.4 TypeBandTypeABCHAP 44
4.5 Sodium-BearingTypeABCHAP 46
October14,2014 17:10 PSPBook-9inx6in 00-Michael-Fleet-prelims
vi Contents
4.6 TypeBCFAPwithAcetateImpurity 47
4.7 Francolite 47
4.8 SynthesisatHighPressureandTemperature 48
4.8.1 EarlyHigh-PressureResearch 48
4.8.2 ExperimentsatTheUniversityofWestern
Ontario(UWO) 48
4.8.2.1 Sodium-freetypeAandtypeABCHAP 49
4.8.2.2 Sodium-bearingtypeABCHAP 51
4.8.2.3 Sodium-bearingtypeABCCLAP 53
4.8.2.4 Sodium-bearingtypeABCFAP 53
5 X-RayStructures 55
5.1 Introduction 55
5.2 TheoreticalAspects 56
5.2.1 CrystalStructuresfromX-rayDiffraction 56
5.2.2 RietveldMethodforPowderPatterns 60
5.2.3 PracticalProblems 61
5.2.4 RigidBodyRefinementofChannelCarbonate
Ion 64
5.3 Unit-CellParametersforCHAP 67
5.4 StructuralInformationfromX-RayPowderPatterns 71
5.5 Single-CrystalX-RayStructures 77
5.5.1 ApatiteHostStructures 79
5.5.2 TypeACarbonateIon 80
5.5.3 TypeA2CarbonateIon 91
5.5.4 TypeBCarbonate 93
6 ChemicalSpectroscopy 97
6.1 Introduction 97
6.2 InfraredSpectroscopy 98
6.2.1 Overview 98
6.2.2 CarbonateApatiteSpectra 101
6.2.3 AsymmetricStretch(ν )Bands 108
3
6.2.4 Sodium-BearingCHAP 111
6.2.5 AnnealingExperiments 118
6.2.6 Out-of-PlaneBend(ν )Bands 123
2
6.2.7 PolarizedInfraredSpectra 130
6.2.8 VitreousState 132
6.3 NuclearMagneticResonanceSpectroscopy 136
October14,2014 17:10 PSPBook-9inx6in 00-Michael-Fleet-prelims
Contents vii
7 CarbonateApatiteCrystalChemistry 141
7.1 Introduction 141
7.2 SymmetryofTypeACHAP 141
7.3 LocationofTypeBCarbonateIon 145
7.4 ProportionofAandBCarbonatefromν BandAreas 149
2
7.5 CouplingofSodiumandAandBCarbonate
Substituents 151
7.5.1 EvidenceforCoupling 151
7.5.1.1 Introduction 151
7.5.1.2 AccommodationofBcarbonate 153
7.5.1.3 Contentsofsodium,AandBcarbonate 155
7.5.1.4 Commonν profile 156
3
7.5.1.5 Extentofordering 157
7.5.2 InfluenceofAlkaliMetals 157
7.6 HydrogencarbonateCHAP 164
7.7 MobilityofCarbonateSpecies 172
7.7.1 AgingExperimentsonHydrogencarbonate
CHAP 172
7.7.2 AnnealingExperimentsonSodium-FreeAB
CHAP 175
7.8 MonohydrogenPhosphateIon 181
7.9 PressureStabilityoftheA2CarbonateIon 183
7.10IsothermalBulkModulusofCHAP 190
7.11ExcessFluorineinFrancolite 193
8 BiologicalApatites 199
8.1 Introduction 199
8.2 CalciumPhosphatesintheBody 200
8.3 CrystalSizeandCrystallinity 205
8.3.1 SizeofNanocrystals 205
8.3.2 Crystallinity 208
8.4 CrystalStructureofCHAP 210
8.5 StructureofBoneMineralandOtherBiological
Apatites 213
8.5.1 CompositionandAsymmetricStretch(ν )
3
Spectra 213
8.5.2 ProportionofAandBCarbonateIons 220
8.5.3 SodiumandLarge-CationVacancies 222
October14,2014 17:10 PSPBook-9inx6in 00-Michael-Fleet-prelims
viii Contents
8.5.4 MonohydrogenPhosphateIons 223
8.5.5 LabileCarbonateFraction 226
8.5.6 ChannelHydroxylIons 229
8.6 MobilityofCarbonateIonsinBoneMineral 230
AppendixI 235
AppendixII 237
AppendixIII 239
ReferencesCited 243
Index 261
October14,2014 17:10 PSPBook-9inx6in 00-Michael-Fleet-prelims
Preface
This book introduces recent advances in understanding the crys-
tal structure of the inorganic component of bone, which is a
carbonate-bearingcalciumphosphateapatiteknownas“carbonate
hydroxylapatite”or“bonemineral.”Nanoscalecrystalsofcarbonate
hydroxylapatite form the hard tissue of bones and teeth and
numerous other calcified structures in the body. They are the
reservoirforcarbondioxideinthebodyandhaveanimportantrole
inmaintainingtheconcentrationofmineralionsintheextracellular
fluid at homeostasis, which is critical for a variety of physiological
functions, including control of acidosis and blood pH. Information
onthecrystalstructureofcarbonatehydroxylapatiteisanessential
startingpointforunderstandingthephysiologicalfunctionsofbone.
Although the basic structure of hydroxylapatite has been known
for more than 80 years, the location of the carbonate ions has
remainedobscureduetothenanoscalesizeandpoorqualityofbone
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-crystalX-raystructuremethodincombinationwithinfrared
spectroscopyandcrystalsofcarbonatehydroxylapatitesynthesized
from carbonate-rich calcium phosphate melts at high pressure
and temperature. The book predicts an expanded role for the
c-axischannelofbonemineralcrystalsincommunicatingwiththe
extracellularfluid.
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
