The deposition of strontium and zinc Co-substituted hydroxyapatite coatings

L. Robinson, K. Salma-Ancane, L. Stipniece, Brian Meenan, A. R. Boyd

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The in vitro and in vivo performance of hydroxyapatite (HAp) coatings can be modified by the addition of different trace ions, such as silicon (Si), lithium (Li), magnesium (Mg), zinc (Zn) or strontium (Sr) into the HAp lattice, to more closely mirror the complex chemistry of human bone. To date, most of the work in the literature has considered single ion-substituted materials and coatings,with limited reports on co-substituted calcium phosphate systems. The aim of this study was to investigate the potential of radio frequency magnetron sputtering to deposit Sr and Zn co-substituted HAp coatings using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction(XRD) and X-ray photoelectron spectroscopy (XPS). The FTIR and XPS results highlight that all of the Sr, Zn and Sr-Zn co-substituted surfaces produced are all dehydroxylated and are calcium deficient. All of the coatings contained HPO4 2− groups, however; only the pure HAp coating andthe Sr substituted HAp coating contained additional CO3 2− groups. The XRD results highlight that none of the coatings produced in this study contain any other impurity CaP phases, showing peaks corresponding to that of ICDD file #01-072-1243 for HAp, albeit shifted to lower 2θ valuesdue to the incorporation of Sr into the HAp lattice for Ca (in the Sr and Sr-Zn co-substituted surfaces only). Therefore, the results here clearly show that RF magnetron sputtering offers a simple means to deliver Sr and Zn co-substituted HAp coatings with enhanced surface properties.
Original languageEnglish
Pages (from-to)1-14
JournalJournal of Materials Science: Materials in Medicine
Issue number51
Early online date14 Feb 2017
Publication statusPublished - 31 Mar 2017

Bibliographical note

Compliant in UIR; evidence uploaded to 'Other files'

Date: Jan 04, 2017
To: "Adrian Boyd"
From: "Journal of Materials Science: Materials in Medicine (JMSM)"
Subject: JMSM-D-16-00530R1 - Editor Decision

Dear Dr. Boyd,

We are pleased to inform you that your manuscript, "The Deposition of Strontium and Zinc Co-substituted Hydroxyapatite Coatings", has been accepted for publication in

Journal of Materials Science: Materials in Medicine.

You will receive an e-mail from Springer in due course with regards to the following items:


2.Colour figures

3.Transfer of Copyright

Please remember to quote the manuscript number, JMSM-D-16-00530R1, whenever inquiring about your manuscript.

Best regards,
Divya Ananthanarayanan
Springer Journals Editorial Office
Journal of Materials Science: Materials in Medicine
Reference text: 1. Dorozhkin SV. Calcium orthophosphates: Applications in Nature,
Biology, and Medicine. Singapore: Pan Stanford Publishing;
2. Kokubo T. Bioceramics and their clinical applications. England:
Woodhead Publishing; 2008.
3. Ben-Nissan B, Choi AH, Roest R, Latella BA, Bendavid A.
Adhesion of hydroxyapatite on titanium medical implants. In:
Mucalo M, editor. Hydroxyapatite (HAp) for biomedical applications.
Cambridge: Woodhead publishing series in biomaterials;
2015. pp. 21–52.
4. Zhang BGX, Myers DE, Wallace GG, Brandt M, Choong PFM.
Bioactive coatings for orthopaedic implants—recent trends in
development of implant coatings. Int J Mol Sci.
5. Drevet R, Benhayoune H. Pulsed electrodeposition for the
synthesis of strontium-substituted calcium phosphate coatings
with improved dissolution properties. Mater Sci Eng C Mater Biol
Appl. 2013;33:4260–5.
6. Lindahl C, Pujari-Palmer S, Hoess A, Ott M, Engqvist H, Xia W.
The influence of Sr content in calcium phosphate coatings. Mater
Sci Eng C. 2015;53:322–30.
7. Shepherd JH, Shepherd DV, Best SM. Substituted hydroxyapatites
for bone repair. J Mater Sci: Mater Med.
8. Mourińo V, Cattalini JP, Boccaccini AR. Metallic ions as therapeutic
agents in tissue engineering scaffolds: an overview of their
biological applications and strategies for new developments. J
Roy Soc Interface. 2012;9:401–19.
9. Boanini E, Gazzano M, Bigi A. Ionic substitutions in calcium
phosphates synthesized at low temperature. Acta Biomater.
10. Stanić V, Dimitrijević S, Antić-Stanković J, Mitrić M, Jokić B,
Plećaš IB, et al. Synthesis, characterization and antimicrobial
activity of copper and zinc-doped hydroxyapatite nanopowders.
Appl Surf Sci. 2010;256:6083–9.
11. Shanmugam S, Gopal B. Copper substituted hydroxyapatite and
fluorapatite: synthesis, characterization and antimicrobial properties.
Ceram Int. 2014;40:15655–62.
12. Feng QL, Cui FZ, Kim TN, Kim JW. Ag-substituted hydroxyapatite
coatings with both antimicrobial effects and biocompatibility.
J Mater Sci Lett. 1999;18:559–61.
13. Gopi D, Shinyjoy E, Kavitha L. Synthesis and spectral characterization
of silver/magnesium co-substituted hydroxyapatite for
biomedical applications. Spectrochim Acta—Part A Mol Biomol
Spectrosc. 2014;127:286–91.
14. Kannan S, Goetz-Neunhoegffer F, Neubauer J, Ferreira JMF.
Cosubstituition of zinc and strontium in β-triclacium phosphate:
synthesis and charaterisation. Jn Amer Cer Soc. 2011;94:230–5.
15. Tang XL, Xiao XF, Liu RF. Structural characterization of siliconsubstituted
hydroxyapatite synthesized by a hydrothermal method.
Mater Lett. 2005;59(29-30):3841–6.
16. Tian T, Jiang D, Zhang J, Lin Q. Synthesis of Si-substituted
hydroxyapatite by a wet mechanochemical method. Mater Sci Eng
C. 2008;28(1):57–63.
17. Wakamura M, Kandori K, Ishikawa T. Surface structure and
composition of calcium hydroxyapatites substituted with
Al(III), La(III) and Fe(III) ions. Colloids Surf A. 2000;164(2-3):
18. Lou W, Dong Y, Zhang H, Jin Y, Hu X, Ma J, et al. Preparation
and characterization of lanthanum-incorporated hydroxyapatite
coatings on titanium substrates. Int J Mol Sci. 2015;16
19. Zhang L, Li H, Li K, Zhang Y, Lu J, Li W. La and F cosubstituted
hydroxyapatite bioactive coating reinforced by SiC
nanowire/ZrO2 hybrid materials for carbon/carbon composites.
Ceram Int. 2016;42:2164–9.
20. Bianco A, Cacciotti I, Lombardi M, Montanaro L, Bemporad E,
Sebastiani M. F-substituted hydroxyapatite nanopowders: thermal
stability, sintering behaviour and mechanical properties. Ceram
Int. 2010;36(1):313–22.
21. Rodriguez-Valencia C, Lopez-Alvarez M, Cochon-Cores B, Pereiro
I, Serra J, Gonzalez P. Novel selnium doped hydroxyapatite
coatings for biomaedical applications. J Biomed Mater Res A.
22. Kaygili O, Dorozhkin SV, Keser S. Synthesis and characterization
of Ce-substituted hydroxyapatite by sol-gel method. Mater Sci
Eng C. 2014;42:78–82.
23. Nasiri-Tabrizi B, Pingguan-Murphy B, Basirun WJ, Baradaran S.
Crystallization behavior of tantalum and chlorine co-substituted
hydroxyapatite nanopowders. J Ind Eng Chem. 2016;33:316–25.
24. Kannan S, Rebelo A, Ferreira JMF. Novel synthesis and structural
characterization of fluorine and chlorine co-substituted hydroxyapatites.
J Inorg Biochem. 2006;100(10):1692–7.
25. Sang Cho J, Um SH, Su Yoo D, Chung YC, Hye Chung S, Lee
JC, et al. Enhanced osteoconductivity of sodium-substituted
hydroxyapatite by system instability. J Biomed Mater Res—Part
B Appl Biomater. 2014;102(5):1046–62.
26. Zyman Z, Tkachenko M. Sodium-carbonate co-substituted
hydroxyapatite ceramics. Process Appl Ceram. 2013;7(4):153–7.
27. Kannan S, Ventura JMG, Ferreira JMF. Synthesis and thermal
stability of potassium substituted hydroxyapatites and hydroxyapatite/
β-tricalciumphosphate mixtures. Ceram Int. 2007;33
28. Nordström E, Karlsson K. Chemical characterization of a
potassium hydroxyapatite prepared by soaking in potassium
chloride and carbonate solutions. Biomed Mater Eng. 1992;
29. Yasukawa A, Ueda E, Kandori K, Ishikawa T. Preparation and
characterization of carbonated barium-calcium hydroxyapatite
solid solutions. J Colloid Interface Sci. 2005;288(2):468–74.
51 Page 12 of 14 J Mater Sci: Mater Med (2017) 28:51
30. Hanna AA, Sherief MA, Aboelenin RM, Mousa SM. Preparation
and characterizations of barium hydroxyapatite as ion exchanger.
Can J Pure Appl Sci. 2010;4:1087–93.
31. Merry JC, Gibson IR, Best SM, Bonfield W. Synthesis and
characterization of carbonate hydroxyapatite. J Mater Sci Mater
Med. 1998;9(12):779–83.
32. Aligul B, Koseoglu NC, Aslan MH, Oral AY. Microstructural
study of Mn and Si co-substituted hydroxyapatite thin films
produced by a sol–gel method. Adv. Eng. Mater. 2009;11:
33. Ignjatović N, Ajduković Z, Savić V. Nanoparticles of cobaltsubstituted
hydroxyapatite in regeneration of mandibular osteoporotic
bones. J Mater Sci Mater Med. 2013;24(2):343–54.
34. Swain S, Rautray TR, Narayanan R. Sr, Mg, and Co substituted
hydroxyapatite coating on TiO2 nanotubes formed by electrochemical
methods. Adv Sci Lett. 2016;22:482–7.
35. Melnikov P, Teixeira AR, Malzac A, Coelho MDB. Galliumcontaining
hydroxyapatite for potential use in orthopedics. Mater
Chem and Phy. 2009;117:86–90.
36. Wakamura M. Photocatalysis by calcium hydroxyapatite modified
by Ti (IV). Fujitsu Sci Tech J. 2005;41:181–90.
37. Hu A, Li M, Chang C, Mao D. Preparation and characterization of
a titanium-substituted hydroxyapatite photocatalyst. J Mol Cat A:
Chemical. 2007;267:79–85.
38. Wiglusz RJ, Kedziora A, Lukowiak A, Doroszkiewicz W, Strek
W. Hydroxyapatite and europium (III) doped hydroxyapatite as a
carrier for silver nanoparticles and their antimicrobial activity. J
Biomed Nanotech. 2012;8:605–12.
39. Capanema NSV, Mansur AAP, Carvalho SM, Silva ARP, Ciminelli
VS, Mansur HS. Niobium-doped hydroxyapatite bioceramics:
synthesis, characterization and in vitro
cytocompatibility. Mater. 2015;8:4191–209.
40. Webster TJ, Ergun C, Doremus RH, Bizios R. Hydroxyapatite
with substituted magnesium, zinc, cadmium and yttrium. II
Mechanisms of osteoblast adhesion. J Biomed Mater Res.
41. Terra J, Gonzalez GB, Rossi AM, Eon JG, Ellis DE. Theoretical
and experimental studies of substitution of cadmium into hydroxyapatite.
Phys Chem Chem Phys. 2010;21:15490–500.
42. Kaygili O, Dorozhkin SV, Ates T, Gursoy NC, Keser S, Yakuphanoglu
F, Selçuk AB. Structural and dielectric properties of
yttrium-substituted hydroxyapatites. Mater Sci Eng C Mater Biol
Appl. 2015;47:333–8.
43. Shainburg APM, Valerio P, Zonari A, Oktar FN, Ozyegin LS,
Craca MPF, Leite MF, Goes AM. Attachment and proliferation of
osteoblasts on lithium-hydroxyapatite composites. Adv Mat Sci
Eng. 2012;2012:10. doi:10.1155/2012/650574. Accessed 28 July
44. Alshemary AZ, Goh YF, Akram M, Kadir MRA, Hussain R.
Microwave assisted synthesis of nano sized sulphate doped
hydroxyapatite. Mater Res Bull. 2013;48:2106–10.
45. Ligot S, Godfroid T, Music D, Bousser E, Schneider JM, Snyders
R. Tantalum-doped hydroxyapatite thin films: synthesis and
characterization. Acta Materialia. 2012;60:3435–43.
46. Sishkumar S, Louis K, Shinyjoy E, Gopi D. Tailoring the
Sm/Gd-substituted hydroxyapatite coating on biomedical
AISI 316L SS: exploration of corrosion resistance, protein profiling,
osteocompatibility, and osteogenic differentiation for
orthopedic implant applications. Ind. Eng. Chem. Res.
47. Webster TJ, Massa-Schlueter EA, Smith JL, Slamovich EB.
Osteoblast response to hydroxyapatite doped with divalent and
trivalent cations. Biomater. 2004;25:2111–21.
48. Kong D, Long D, Wu Y, Zhou C. Mechanical properties of
hydroxyapatite-zirconia coatings prepared by magnetron sputtering.
Trans. Nonferrous Met. Soc. China. 2012;22:104–10.
49. Cox SC, Jamshidi P, Grover LM, Mallick KK. Preparation and
characterisation of nanophase Sr, Mg, and Zn substituted hydroxyapatite
by aqueous precipitation. Mater Sci Eng C Mater Biol
Appl. 2014;35:106–14.
50. Aina V, Bergandi L, Lusvardi G, Malavasi G, Imrie FE, Gibson
IR, Cerrato G, Ghigo D. Sr-containing hydroxyapatite: morphologies
of HAp crystals and bioactivity on osteoblast cells. Mater
Sci Eng C Mater Biol Appl. 2013;33:1132–42.
51. Aryal S, Matsunaga K, Ching WY. Ab initio simulation of elastic
and mechanical properties of Zn- and Mg-doped hydroxyapatite
(HAP). J Mech Behav Biomed Mater. 2015;47:135–46.
52. Shepherd D. Zinc-substituted hydroxyapatite for the inhibition of
osteoporosis. In: Mucalo M, editor. Hydroxyapatite (HAp) for
biomedical applications. Cambridge: Woodhead publishing series
in biomaterials; 2015. pp. 107–26.
53. Stipniece L, Salma-Ancane K, Borodajenko N, Sokolova M,
Jakovlevs D, Berzina-Cimdina L. Characterization of Mgsubstituted
hydroxyapatite synthesized by wet chemical method.
Ceram Int. 2014;40:3261–7.
54. Drouet C, Carayon MT, Combes C, Rey C Surface enrichment of
biomimetic apatites with biologically-active ions Mg2+ and Sr2+:
a preamble to the activation of bone repair materials. Mater Sci
and Eng C. 2008;28:1544–50.
55. Ravi ND, Balu R, Kumar TTS. Strontium-substituted calcium
deficient hydroxyapatite nanoparticles: synthesis, characterization,
and antibacterial properties. J Am Ceram Soc. 2012;95:
56. Kaygili O, Keser S, Komc M, Eroksuz Y, Dorozhkin SV, Ates T,
Ozercan IH, Tatar C, Yakuphanoglu F. Strontium substituted
hydroxyapatites: synthesis and determination of their structural
properties, in vitro and in vivo performance. Mater Sci Eng C
Mater Biol Appl. 2015;55:538–46.
57. Landi E, Tampieri A, Celotti G, Sprio S, Sandri M, Logroscino G.
Sr-substituted hydroxyapatites for osteoporotic bone replacement.
Acta Biomaterialia. 2007;3:961–9.
58. Kumar GS, Thamizhavel A, Yokogawa Y, Kalkura SN, Girija EK.
Synthesis, characterization and in vitro studies of zinc and carbonate
co-substituted nano-hydroxyapatite for biomedical applications.
Mater Chem Phys. 2012;134:1127–35.
59. Ramya JR, Arul KT, Elayaraja K, Kalkura SN. Physicochemical
and biological properties of iron and zinc ions co-doped nanocrystalline
hydroxyapatite, synthesized by ultrasonication. Ceram
Int. 2014;40:16707–17.
60. Gopi D, Ramyaa S, Rajeswaria D, Karthikeyana P, Kavitha L.
Strontium, cerium co-substituted hydroxyapatite nanoparticles:
synthesis, characterization, antibacterial activity towards prokaryotic
strains and in vitro studies. Colloid Surface A. 2014;
61. Huang Y, Zhang X, Mao H, Li T, Zhao R, Yan Y, Pang X.
Osteoblastic cell responses and antibacterial efficacy of Cu/Zn cosubstituted
hydroxyapatite coatings on pure titanium using electrodeposition
method. RSC Adv. 2015;5:17076–86.
62. Kaygili O, Keser S. Sol–gel synthesis and characterization of Sr/
Mg, Mg/Zn and Sr/Zn co-doped hydroxyapatites. Mater Lett.
63. Huang T, Xiao Y, Wang S, Huang Y, Liu X, Wu F, Gu Z.
Nanostructured Si, Mg, CO3
2− substituted hydroxyapatite coatings
deposited by liquid precursor plasma spraying: synthesis and
characterization. J Thermal Spray Tech. 2011;20:829–36.
64. O’Sullivan C, O’Hare P, O’Leary ND, Crean AM, Ryan K,
Dobson ADW, O’Neill L. Deposition of substituted apatites with
anticolonizing properties onto titanium surfaces using a novel
blasting process. J. Biomed. Mat. Res B: Appl. Biomater.
65. van Dijk K, Schaeken HG, Wolke JGC, Maree CHM, Habraken
FHPM, Verhoeven J, Jansen JA. Influence of discharge power
J Mater Sci: Mater Med (2017) 28:51 Page 13 of 14 51
level on the properties of hydroxyapatite films deposited on
Ti6A14V with RF magnetron sputtering. J Biomed Mat Res.
66. Yonggang Y, Wolke JGC, Yubao L, Jansen JA. The influence of
discharge power and heat treatment on calcium phosphate coatings
prepared by RF magnetron sputtering deposition. J Mater Sci:
Mater Med. 2007;18:1061–9.
67. Boyd AR, Akay M, Meenan BJ. Influence of target surface
degradation on the properties of RF magnetron‐sputtered calcium
phosphate coatings. Surf Inter Anal. 2003;35:188–98.
68. Boyd AR, Meenan BJ, Leyland NS. Surface characterisation of
the evolving nature of radio frequency (RF) magnetron sputter
deposited calcium phosphate thin films after exposure to physiological
solution. Surf Coat Tech. 2006;200:6002–13.
69. Boyd AR, O’Kane C, Meenan BJ. Control of calcium phosphate
thin film stoichiometry using multi-target sputter deposition. Surf
Coat Tech. 2013;233:131–9.
70. Thian ES, Huang J, Best SM, Barber ZH, Bonfield W. Surface
modification of magnetron-sputtered hydroxyapatite thin films via
silicon substitution for orthopaedic and dental applications. Surf
Coat Technol. 2011;205:3472–7.
71. Ozeki K, Hoshino T, Aoki H, Masuzawa T. Phase composition of
sputtered film from a mixture of hydroxyapatite and strontiumapatite.
J Mater Sci Technol. 2013;29:1–6.
72. Boyd A, Randolph LD, Rutledge L, Meenan BJ. Strontiumsubstituted
hydroxyapatite coatings deposited via a co-deposition
sputter technique. Mater Sci & Eng C. 2015;46:290–300.
73. Boyd A, Rutledge L, Randolph LD, Mutreja I, Meenan BJ. The
deposition of strontium-substituted hydroxyapatite coatings. J
Mater Sci: Mater Med. 2015;26:1–14.
74. Li MO, Xiao XF, Liu RF, Chen CY, Huang LZ. Structural characterization
of zinc-substituted hydroxyapatite prepared by hydrothermal
method. J Mater Sci: Mater Med. 2008;19(2):797–803.
75. Quilitz M, Steingröver K, Veith M. Effect of the Ca/P ratio on the
dielectric properties of nanoscaled substoichiometric hydroxyapatite.
J Mater Sci: Mater Med. 2010;21:399–405.
76. Gibson IR, Bonfield W. Novel synthesis and characterization of
an AB-type carbonate-substituted hydroxyapatite. J Biomed Mater
Res. 2002;59:697–708.
77. Fadeeva IV, Bakunova NV, Komlev VS, Medvecký L, Fomin AS,
Gurin AN, Barinov SM. Zinc- and silver- substituted hydroxyapatite:
synthesis and properties. Doklady Akademii Nauk.
78. Thian ES, Konishi T, Kawanobe Y, Lim PN, Choong C, Ho B,
Aizawa M. Zinc-substituted hydroxyapatite: a biomaterial with
enhanced bioactivity and antibacterial properties. J Mater Sci:
Mater Med. 2013;24:437–45.
79. Yu T, Ye J, Wang Y. Preparation and characterization of a novel
strontium-containing calcium phosphate cement with the two-step
hydration process. Acta Biomater. 2009;5:2717–27.
80. Dorozhkin SV. Bioceramics of calcium orthophosphates. Biomater.
81. Yang Y, Perez-Amodio S, Barre‘ re-de Groot FYF, Everts V, van
Blitterswijk CA, Habibovic P. The effects of inorganic additives
to calcium phosphate on in vitro behaviour of osteoblasts and
osteoclasts. Biomater. 2010;31:2976–89.
82. Kim H, Camata RP, Chowdhury S, Vohra YK. In vitro dissolution
and mechanical behavior of c-axis preferentially oriented hydroxyapatite
thin films fabricated by pulsed laser deposition. Acta
Biomater. 2010;6:3234–41.
83. Wopenka B, Pasteris JD. A mineralogical perspective on the
apatite in bone. Mat Sci Eng C. 2005;25:131–43.
84. Suganthi RV, Elayaraja K, Joshy MIA, Chandra VS, Girija EK,
Kalkura SN. Fibrous growth of strontium substituted hydroxyapatite
and its drug release. Mat Sci Eng C. 2010;31:593–9.
85. Ren F, Xin R, Ge X, Leng Y. Characterization and structural
analysis of zinc-substituted hydroxyapatites. Acta Biomaterialia.
86. Vignoles M, Bone G, Young RA. Occurrence of nitrogenous
species in precipitated B-type carbonated hydroxyapatites. Calcif
Tissue Int. 1987;40:64–70.
87. Kavitha M, Subramanian R, Narayanan R, Udhayabanu V.
Solution combustion synthesis and characterization of strontium
substituted hydroxyapatite nanocrystals. Powd Tech.
88. Norhidayu D, Sopyan I, Ramesh S. Development of zinc doped
hydroxyapatite for bone implant applications. ICCBT. 2008;F-
89. Zreiqat H, Ramaswamy Y, Wu C, Paschalidis A, Lu Z, James B,
Birke O, McDonald M, Little D, Dunstan CR. The incorporation
of strontium and zinc into a calcium-silicon ceramic for bone
tissue engineering. Biomater. 2010;31:3175–84.
90. Imrie FE, Aina V, Lusvardi G, Malavasi G, Gibson IR, Cerrato G,
Annaz B. Synthesis and characterisation of strontium and magnesium
co-substituted biphasic calcium phosphates. Key Eng
Mater. 2013;529-30:88–93.


  • RF magnetron sputtering
  • hydroxyapatite coating
  • co-deposition
  • co-substitution
  • strontium
  • zinc


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