Unravelling the specific site preference in doping of calcium hydroxyapatite with strontium from ab initio investigations and Rietveld analyses

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dc.contributor.authorZeglinski, Jacek
dc.contributor.authorNolan, Michael
dc.contributor.authorBredol, Michael
dc.contributor.authorSchatte, Andrea
dc.contributor.authorTofail, Syed A. M.
dc.contributor.funderUniversity of Limericken
dc.contributor.funderWestfälische Wilhelms-Universität Münsteren
dc.contributor.funderEuropean Commissionen
dc.contributor.funderScience Foundation Irelanden
dc.contributor.funderHigher Education Authorityen
dc.date.accessioned2017-12-18T16:37:03Z
dc.date.available2017-12-18T16:37:03Z
dc.date.issued2012-01-19
dc.date.updated2017-12-18T16:28:19Z
dc.description.abstractStrontium can be substituted into the calcium sublattice of hydroxyapatite without a solubility limit. However, recent ab initio simulations carried out at 0 K report endothermic nature of this process. There is also striking discrepancy between experimentally observed preference of Sr doping at Ca-II sites and the first principles calculations, which indicate that a Ca-I site is preferred energetically for the Sr substitution. In this paper we combine insights from Density Functional Theory simulations and regular configurational entropy calculations to determine the site preference of Sr doping in the range of 0-100 at% at finite temperatures. In addition, samples of Sr-HA are synthesized and refinement of the relevant structural information provides benchmark information on the experimental unit cell parameters of Sr-HA. We find that the contribution of the entropy of mixing can efficiently overcome the endothermic excess energy at a temperature typical of the calcining step in the synthesis route of hydroxyapatite (700-950 degrees C). We observe that the most preferential substitution pattern is mixed substitution of Sr regardless of the concentration. For a wet chemical method, carried out at a moderate temperature (90 degrees C), the mixed doping is still slightly favourable at higher Sr-concentrations, except the range at 20% Sr, where Site II substitution is not restricted energetically and equally possible as the mixed doping. We observe a close correspondence between our theoretical results and available experimental data. Hence it should be possible to apply this theory to other divalent dopants in HA, such as Zn2+, Mg2+, Pb2+, Cu2+, Ba2+, Cd2+ etc.en
dc.description.sponsorshipEuropean Commission (Bilateral Socrates-Erasmus Exchange Programme between University of Limerick and University of Münster); Science Foundation Ireland and Higher Education Authority (Irish Centre for High Performance Computing)en
dc.description.statusPeer revieweden
dc.description.versionAccepted Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.citationZeglinski, J., Nolan, M., Bredol, M., Schatte, A. and Tofail, S. A. M. (2012) 'Unravelling the specific site preference in doping of calcium hydroxyapatite with strontium from ab initio investigations and Rietveld analyses', Physical Chemistry Chemical Physics, 14(10), pp. 3435-3443. doi:10.1039/c2cp23163hen
dc.identifier.doi10.1039/c2cp23163h
dc.identifier.endpage3443en
dc.identifier.issn1463-9076
dc.identifier.journaltitlePhysical Chemistry Chemical Physicsen
dc.identifier.startpage3435en
dc.identifier.urihttps://hdl.handle.net/10468/5191
dc.identifier.volume14en
dc.language.isoenen
dc.publisherRoyal Society of Chemistryen
dc.rights© the Owner Societies 2012. This is the accepted manuscript version of an article published in Physical Chemistry Chemical Physics. The version of record is available at http://dx.doi.org/10.1039/C2CP23163Hen
dc.subjectTotal-energy calculationsen
dc.subjectAugmented-wave methoden
dc.subjectDoped hydroxyapatiteen
dc.subjectBasis-seten
dc.subjectPhosphatesen
dc.subjectSubstitutionen
dc.subjectNanocrystalsen
dc.subjectResorptionen
dc.subjectMetalsen
dc.subjectHydroxyapatiteen
dc.subjectStrontiumen
dc.subjectDurapatiteen
dc.subjectEntropyen
dc.subjectQuantum Theoryen
dc.titleUnravelling the specific site preference in doping of calcium hydroxyapatite with strontium from ab initio investigations and Rietveld analysesen
dc.typeArticle (peer-reviewed)en
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