Rapid Synthesis of Hydroxyapatite Nanorods at Low Temperature Controlled by Sodium Alginate

doi:10.15541/jim20140286

Abstract

Abstract:

Hydroxyapatite (HA) nanorods with uniform morphology and high aspect ratio were prepared by hydrothermal method using alginate (SA) as controlling agent. The samples were characterized by XRD, FTIR, SEM, TEM and TG/DSC to detect the effects of temperature and time on the crystallinity, composition and morphology of the final products. Meanwhile, the growth mechanism of HA nanorods was explored. Experiments showed that uniform HA nanorods with low organic composition could be well synthesized via hydrothermal method at 80°C after 24 h. Investigations on the microstructures of nanorods revealed that their growth could be divided into four stages: initial nucleation, surface regulation, continuous growth and oriented attachment.

Key words: hydroxyapatite, sodium alginate, nanorods, hydrothermal method

CLC Number:

TQ174

MA Li, ZHU Jian-Hua, HUANG Lei. Rapid Synthesis of Hydroxyapatite Nanorods at Low Temperature Controlled by Sodium Alginate[J]. Journal of Inorganic Materials, 2015, 30(3): 311-317.

Figures/Tables 10

Fig. 1 SEM images of synthesized products by hydrothermal method at 60℃ (a), 80℃ (b), 100℃ (c) and 120℃ (d) for 24 h

Table 1 Diameter and length of HA products prepared at various temperatures

Products	60℃	80℃	100℃	120℃
Diameter/nm	—	40-120	50-250	50-250
Length/μm	—	4-6	2-4	1-3

Fig. 2 XRD patterns of synthesized products by hydrothermal method at 60℃ (a), 80℃ (b), 100℃ (c) and 120℃ (d) for 24 h Tick marks below the patterns corresponding to the position of the Bragg reflections of the HA (JCPDS 09-0432)

Fig. 3 FTIR spectra of synthesized products by hydrothermal method at 60℃ (a), 80℃ (b), 100℃ (c) and 120℃ (d) for 24 h

Fig. 4 TEM image (a) and HRTEM image (b) of synthesized products by hydrothermal method at 80℃ for 24 h

Fig. 5 TG/DSC patterns of pure SA and synthesized product by hydrothermal method for 24 h at 80℃:(a) Pure SA; (b) Synthesized product

Fig. 6 SEM (a), TEM (b) and HRTEM (c) images of initial precipitation after 8 h with inset showing the Fast Fourier Transform image (FFT) in (c), and (d-e) SEM (d), TEM (e) and HRTEM (f) images of products after 16 h with inset showing the magnified area in (e)

Fig. 7 XRD patterns of synthesized products by hydrothermal method at 80℃ for 8 h (a), 16 h (b) and 24 h (c)

Fig. 8 FTIR spectra of synthesized products by hydrothermal method at 80℃ for 8 h (a), 16 h (b) and 24 h(c)

Fig. 9 Formation mechanism of HA nanorods

References 30

[1]	PALMER L C, NEWCOMB C J, KALTZ S R, et al.Biomimetic systems for hydroxyapatite mineralization inspired by bone and enamel. Chemical Reviews, 2008, 108(11): 4754-4783.
[2]	MA G B, LIU X Y.Hydroxyapatite: hexagonal or monoclinicCrystal. Growth & Design, 2009, 9(7): 2991-2994.
[3]	LIANG X H, LYNN A D, KING D, et al.Biocompatible interface films deposited within porous polymers by atomic layer deposition (ALD).Applied Materials & Interfaces, 2009, 1(9): 1988-1995.
[4]	YE W, WANG X X.Ribbon-like and rod-like hydroxyapatite crystals deposited on titanium surface with electrochemical method. Materials Letters, 2007, 61(19/20): 4062-4065.
[5]	JIANG S D, YAO Q Z, ZHOU G T, et al.Fabrication of hydroxyapatite hierarchical hollow microspheres and potential application in water treatment.The Journal of Physical Chemistry C, 2012, 116(7): 4484-4492.
[6]	ESCUDERO A, CALVO M E, OCAÑA M, et al. Microwave-assisted synthesis of biocompatible europium-doped calcium hydroxyapatite and fluoroapatite luminescent nanospindles functionalized with poly(acrylic acid). Langmuir, 2013, 29(6): 1985-1994.
[7]	VISWANATH B, RAVISHANKAR N.Controlled synthesis of plate-shaped hydroxyapatite and implications for the morphology of the apatite phase in bone. Biomaterials, 2008, 29(36): 4855-4863.
[8]	NEIRA I S, KOLENKO Y V, LEBEDEV O I, et al.An effective morphology control of hydroxyapatite crystals via hydrothermal synthesis.Crystal Growth & Design, 2008, 9(1): 466-474.
[9]	CHEN J D, WANG Y J, WEI K, et al.Self-organization of hydroxyapatite nanorods through oriented attachment.Biomaterials, 2007, 28(14): 2775-2280.
[10]	ZHANG Y J, LU J J.A mild and efficient biomimetic synthesis of rodlike hydroxyapatite particles with a high aspect ratio using polyvinylpyrrolidone as capping agent.Crystal Growth & Design, 2008, 8(7): 2011-2017.
[11]	WANG A, LIU D, YIN H B, et al.Size-controlled synthesis of hydroxyapatite nanorods by chemical precipitation in the presence of organic modifiers.Materials Science and Engineering C, 2007, 27(4): 865-869.
[12]	LIANG Y H, LIU C H, LIAO S H, et al.Co-synthesis of cargo-loaded hydroxyapatite/alginate core-shell nanoparticles (HAP@Alg) as pH-responsive nanovehicles by a pre-gel method.Applied Materials & Interfaces, 2012, 4(12): 6720-6727.
[13]	WANG L, SHELTON R M, COPPER P R, et al.Evaluation of sodium alginate for bone marrow cell tissue engineering.Biomaterials, 2003, 20(24): 3475-3481.
[14]	ANDERSEN T, MELVIK J E, ALSBERG E, et al.Ionically gelled alginate foams: physical properties controlled by operational and macromolecular parameters. Biomacromolecules, 2012, 13(11): 3703-3710.
[15]	XIE M, ZHANG Z B, ANDREASSEN J P, et al.Biocomposites prepared by alkaline phosphatase mediated mineralization of alginate microbeads,Advances, 2012, 2: 1457-1465.
[16]	IWASAKI N, YAMANE S T, MAJIMA T, et al.Feasibility of polysaccharide hybrid materials for scaffolds in cartilage tissue engineering: evaluation of chondrocyte adhesion to polyion complex fibers prepared from alginate and chitosan.Biomacromolecules, 2004, 5(3): 828-833.
[17]	MOURIÑO V, NEWBY P, PISHBIN F, et al. Physicochemical, biological and drug-release properties of gallium crosslinked alginate/nanoparticulate bioactive glass composite films.Soft Matter, 2011, 7(14): 6705-6712.
[18]	LENG B X, JIANG F G, LU K B, et al.Growth of calcium carbonate mediated by slowly released alginate.Crystal Engineering Communication, 2010, 12(3): 730-736.
[19]	VALLET-REGÍ, GONZÁLEZ-CALBET J M. Calcium phosphates as substitution of bone tussues,Progress in Solid State Chemistry, 2004, 32(1): 1-31.
[20]	ZHANG X J, LIN D Y, YAN X H, et al.Evolution of the magnesium incorporated amorphous calcium phosphate to nano-crystallized hydroxyapatite in alkaline solution.Journal of Crystal Growth, 2011, 336(1): 60-66.
[21]	CAO M, WANG Y, GUO C, et al.Preparation of ultrahigh-aspect-ratio hydroxyapatite nanofibers in reverse micelles under hydrothermal conditions.Langmuir, 2004, 20(11): 4784-4786.
[22]	HAO LI-JING, YANG HUI, ZHAO NA- RU, et al.Hydrothermal synthesis of hydroxyapatite fibers precipitated by propionmide.Journal of Inorganic Materials, 2013, 28(1): 63-68.
[23]	DING H C, PAN H H, XU X R, et al.Toward a detailed understanding of magnesium ions on hydroxyapatite crystallization inhibition.Crystal Growth & Desigin, 2014, 14(2): 763-769.
[24]	ZENG H C.Synthetic architecture of interior space for inorganic nanostructures. Journal of Materials Chemistry, 2006, 16: 649-662.
[25]	ZHANG Y J, LU J J, WANG J Q, et al.Synthesis of nanorod and needle-like hydroxyapatite crystal and role of pH adjustment.Journal of Crystal Growth, 2009, 311(23/24): 4740-4746.
[26]	CHEN H F, TANG Z, CLARKSON B H, et al.Acellular synthesis of a human enamel-like microstructure.Advanced Materials, 2006, 18(14): 1846-1851.
[27]	XU A W, MA Y R, CÖLFEN H. Biomimetic mineralization.Journal of Materials Chemistry, 2007, 17: 415-449.
[28]	KIM H W, NOH Y J, KOH Y H, et al.Effect of CaF2 on desification and properites of hydroxyapapite-zirconia composites for biomedical applications.Biomaterials, 2002, 23(20): 4113-4121.
[29]	BERTONI E, BIGI A, FALINI G, et al.Hydroxyapatite/polyacrylic acid nanocrystals.Journal of Materials Chemistry, 1999, 9: 779-782.
[30]	DONNERS J J J M, NOLTE R J M, SOMMERDIJK N A J M. Dendrimer-based hydroxyapatite composites with remarkable materials properties.Advanced Materials, 2003, 15(4): 313-316.