Abstract
Nano-hydroxyapatite/poly(l-lactic acid) (nano-HA/PLLA) composites with uniform HA distribution and good mechanical performance were fabricated by a modified in situ precipitation method, using Ca(OH)2 and H3PO4 as precursors for the synthesis of HA phase. This method has solved the aggregation problem of the nano-sized particles in the polymer matrix. The X-ray diffraction, Fourier transform infrared spectroscopy, and transmission electron microscopy were used to characterize the phase composition, chemical interactions and morphology of the composites, while the mechanical properties were determined by compressive measurements. The results show that the rod-like nano-HA particles synthesized by this method were uniformly distributed in the PLLA matrix. The compressive strength and Young’s modulus of the composites were greatly enhanced and reached the values of 155 MPa and 3.6 GPa at 20 wt% HA content, respectively, which are much higher than those of the reference samples fabricated by direct mixing of PLLA with nano-HA particles. This supports the potential of these composites for applications in bone tissue engineering and load bearing bone defects repair.
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs10856-010-4161-y/MediaObjects/10856_2010_4161_Fig1_HTML.gif)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs10856-010-4161-y/MediaObjects/10856_2010_4161_Fig2_HTML.gif)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs10856-010-4161-y/MediaObjects/10856_2010_4161_Fig3_HTML.jpg)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs10856-010-4161-y/MediaObjects/10856_2010_4161_Fig4_HTML.gif)
![](http://media.springernature.com/m312/springer-static/image/art%3A10.1007%2Fs10856-010-4161-y/MediaObjects/10856_2010_4161_Fig5_HTML.gif)
Similar content being viewed by others
References
Murugan R, Ramakrishna S. Development of nanocomposites for bone grafting. Compos Sci Technol. 2005;65:2385–406.
Kusmanto F, Walker G, Gan Q, et al. Development of composite tissue scaffolds containing naturally sourced microporous hydroxyapatite. Chem Eng J. 2008;139:398–407.
Gunatillake PA, Adhikari R. Biodegradable synthetic polymers for tissue engineering. Eur Cells Mater. 2003;5:1–16.
Hench LL, Wilson J. Surface-active biomaterials. Science. 1984;226:630–6.
Hardy DCR, Frayssinet P. Osteointegration of hydroxyapatite coated stems of femoral prostheses. Eur J Orthop Surg Traumatol. 1999;9:75–81.
Shackelford JF. Bioceramics-current status and future trends. Mater Sci Forum. 1999;293:99–106.
Ducheyne P. Bioceramics—material characteristics versus in vivo behavior. J Biomed Mater Res Appl Biomater. 1987;21:219–36.
Heise U, Osborn JF, Duwe F. Hydroxyapatite ceramic as a bone substitute. Int Orthop. 1990;14:329–38.
Kitsugi T, Yamamuro T, Nakamura T, et al. 4 calcium phosphate ceramics as bone substitutes for non-weight-bearing. Biomaterials. 1993;14:216–24.
Best S, Bonfield W. Processing behavior of hydroxyapatite powders with contrasting morphology. J Mater Sci: Mater Med. 1994;5:516–21.
Cleries L, Fernandez Pradas JM, Morenza JL. Behavior in simulated body fluid of calcium phosphate coatings obtained by laser ablation. Biomaterials. 2000;2:1861–5.
Zhang RY, Ma PX. Poly(alpha-hydroxyl acids)/hydroxyapatite porous composites for bone tissue engineering. I. Preparation and morphology. J Biomed Mater Res. 1999;44:446–55.
Maquet V, Jerome R. Design of macroporous biodegradable polymer scaffolds for cell transplantation. Mater Sci Forum. 1997;250:15–42.
Rose FR, Oreffo RO. Bone tissue engineering: hope vs hype. Biochem Biophys Res Commun. 2002;292:1–7.
Oh SH, Kang SG, Kim ES, Cho SH, Lee JH. Fabrication and characterization of hydrophilic poly(lactic-co-glycolic acid)/poly(vinyl alcohol) blend cell scaffolds by melt-molding particulate-leaching method. Biomaterials. 2003;24:4011–21.
Zhang RY, Ma PX. Porous poly(l-lactic acid)/apatite composites created by biomimetic process. J Biomed Mater Res. 1999;45:285–93.
Qiu XY, Hong ZK, Hu JL, et al. Hydroxyapatite surface modified by l-lactic acid and its subsequent grafting polymerization of l-lactide. Biomacromolecules. 2005;6:1193–9.
Plueddemann EP. Silane coupling agents. 2nd ed. New York: Plenum Press; 1991.
Sada E, Kumazawa H, Murakami Y. Hydrothermal synthesis of crystalline hydroxyapatite ultrafine particles. Chem Eng Commun. 1991;103:57–64.
Ignjatovic N, Uskokovic D. Synthesis and application of hydroxyapatite/polylactide composite biomaterial. Appl Surf Sci. 2004;238:314–9.
Kasuga T, Maeda H, Kato K, et al. Preparation of Poly(lactic-acid) composites containing calcium carbonate. Biomaterials. 2003;24:3247–53.
Nikcevic I, Maravic D, Ignjatovic N, et al. The formation and characterization of nanocrystalline phases by mechanical milling of biphasic calcium phosphate/poly-l-lactide biocomposite. Mater Trans. 2006;47:2980–6.
Fang Y, Agrawal DK, Roy DM, et al. Ultrasonically accelerated synthesis of hydroxyapatite. J Mater Res. 1992;7:2294–8.
Borum-Nicholas L, Wilson OC. Surface modification of hydroxyapatite. Part I. Dodecyl alcohol. Biomaterials. 2003;24:3671–9.
Liu Q, Wijn JR, Bakker D, et al. Polyacids as bonding agents in hydroxyapatite polyester-ether (polyactive (TM) 30/70) composites. J Mater Sci: Mater Med. 1998;9:23–30.
Wang XJ, Li YB, Wei J, Groot K. Development of biomimetic nano-hydroxyapatite/poly (hexamethylene adipamide) composites. Biomaterials. 2002;23:4787–91.
Dong GC, Sun JS, Yao CH, Jiang GJ, Huang CW, Lin FH. A study on grafting and characterization of HMDI-modified calcium hydrogen phosphate. Biomaterials. 2001;22:3179–89.
Borum L, Wilson OC. Surface modification of hydroxyapatite. Part II. Silica. Biomaterials. 2003;24:3681–8.
Hong ZK, Qiu XY, Sun JR, Deng MX, Chen XS, **g XB. Grafting polymerization of l-lactide on the surface of hydroxyapatite nano-crystals. Polymer. 2004;45:6699–706.
Tian T, Jiang DL, Zhang JX, Lin QL. Fabrication of bioactive composite by develo** PLLA onto the framework of sintered HA scaffold. Mater Sci Eng C. 2008;28:51–6.
Li HY, Chen YF, **e YS. Photo-crosslinking polymerization to prepare polyanhydride/needle-like hydroxyapatite biodegradable nanocomposite for orthopedic application. Mater Lett. 2003;57:2848–54.
Lin XY, Li XD, Fan HS, et al. In situ synthesis of bone-like apatite/collagen nano-composite at low temperature. Mater Lett. 2004;58:3569–72.
Murugan R, Ramakrishna S. In situ formation of recombinant humanlike collagen-hydroxyapatite nanohybrid through bionic approach. Appl Phys Lett. 2006;88:193124.
Lin FH, Yao CH, Huang CW, et al. The bonding behavior of DP-Bioglass and bone tissue. Mater Chem Phys. 1996;46:36–42.
Powder Diffraction File No. 9-432, International Centre of Diffraction Data (ICDD), Newton Square, PA, USA.
Li YB, Groot K, Wijn J, Klein CAPT, Meer SVD. Morphology and composition of nanograde calcium phosphate needle-like crystals formed by simple hydrothermal treatment. J Mater Sci: Mater Med. 1994;5:326–31.
Paschalis EP, Betts F, DiCarlo E, Mendelsohn R, Boskey AL. FTIR microspectroscopic analysis of normal human cortical and trabecular bone. Calcif Tissue Int. 1997;61:480–6.
Gay S, Arostegui S, Lemaitre J. Preparation and characterization of dense nano-hydroxyapatite/PLLA composites. Mater Sci Eng C. 2009;29:172–7.
Ignjatovic N, Delijic K, Vukcevic M, Uskokovic D. Microstructure and mechanical properties of hot-pressed hydroxyapatite/poly-l-lactide biomaterials. Bioceramics. 2000;192:737–40.
Shikinami Y, Okuno M. Bioresorbable devices made of forged composites of hydroxyapatite (HA) particles and poly-l-lactide (PLLA): part I. Basic characteristics. Biomaterials. 1999;20:859–77.
Park J, Lakes R. Biomaterials-an introduction. 2nd ed. New York: Plenum Press; 1992. p. 7–316.
Acknowledgment
The authors wish to thank Dr. Chun Li at Nanchang Hangkong University for her help in the compression experiments.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Zhang, C.Y., Lu, H., Zhuang, Z. et al. Nano-hydroxyapatite/poly(l-lactic acid) composite synthesized by a modified in situ precipitation: preparation and properties. J Mater Sci: Mater Med 21, 3077–3083 (2010). https://doi.org/10.1007/s10856-010-4161-y
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10856-010-4161-y