Materials Letters 96 (2013) 177–180

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Surfactant-assisted synthesis of oriented hydroxyapatite nanoclusters by

reflux method
Shen Yang a, Jingdi Chen a,n, Zihao Wang a, Hui Zhang a, Qiqing Zhang a,b,nn
a
Institute of Biomedical and Pharmaceutical Technology & College of Chemistry and Chemical Engineering, Fuzhou University, Fuzhou 350002, China
b
Institute of Biomedical Engineering, Chinese Academy of Medical Science & Peking Union Medical College, Tianjin 300192, China

a r t i c l e i n f o abstract

Article history: Oriented hydroxyapatite nanoclusters were achieved by reflux method in the presence of non-
Received 18 October 2012 poisonous and well dissolved surfactant (potassium polyoxyethylene laurylether phosphate, MAEPK).
Accepted 12 January 2013 Transmission electron microscopy (TEM) demonstrated uniform sizes of nanorods arranged in parallel
Available online 23 January 2013
to each other along the c-axis and formed partially oriented nanoclusters in the presence of MAEPK. The
Keywords: sizes of each nanoparticle were about 60–80 nm in length and 20 nm in width. MAEPK had an
Hydroxyapatite important impact on the morphology of product due to the structure of surfactant and a strong
Crystal growth electrostatic interaction between ionized MAEPK and Ca2 þ ions. The regulating formation mechanism
Oriented of hydroxyapatite nanoclusters by MAEPK may extend the understanding of biomineralization process
Template
for the preparation of biomimetic materials.
Nanoparticles
& 2013 Elsevier B.V. All rights reserved.
Biomimetic

1. Introduction provide the driving force for spontaneous oriented attachment

[18]. To obtain products with excellent bioactivity and biocom-
Hydroxyapatite (Ca10(PO4)6(OH)2, HAp) is the main inorganic patibility, templates with mild, innoxious, degradative and envir-
mineral component of teeth and bones. Due to its outstanding onmental performance are expected. Furthermore, reflux method
bioactivity and biocompatibility, it has been widely used as bone based on the normal pressure is a convenient preparing process,
cavity filling, metallic implant coating [1–3] and bone graft in which the reactors can mix well. It seems that the combination
substitute [4,5]. Many chemical methods have been used to
synthesize HAp, such as co-precipitation [6], microemulsion
method [7], hydrothermal method [8], solid-state reactions [9]
and sol-gel synthesis [10]. Recently, surfactant based organic
template with complex functionalization patterns are found to
control the nucleation, growth and alignment of inorganic crys-
tals, which has been widely applied for biomimetic synthesis of
inorganic materials with controllable morphology and arrange-
ment [11–13]. Due to the geometric, electrostatic and stereoche-
mical complementarities between the functionalized substrates
and the incipient nuclei [14–17], controllable morphology and
arrangement of crystal can be achieved by introducing appro-
priate organic template to change the free energies to alter their
growth rates. As introducing ions to the negatively charged
substrates, it will lead to a substantial reduction in the surface
free energy, accelerate the nucleation and growth of HAp and

n
Corresponding author at: Institute of Biomedical and Pharmaceutical Technol-
ogy, Fuzhou University, No. 523 Gongye Road, Fuzhou 350002, China
Tel./fax: þ86 591 83725260.
nn
Corresponding author at: Institute of Biomedical Engineering, Chinese Acad-
emy of Medical Science & Peking Union Medical College, Tianjin 300192, China.
E-mail addresses: ibptcjd@fzu.edu.cn (J. Chen), zhangqiq@126.com (Q. Zhang). Fig. 1. XRD spectra of (a) sample and (b) control.

0167-577X/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.matlet.2013.01.062
178 S. Yang et al. / Materials Letters 96 (2013) 177–180
of proper template and reflux method, the manipulation of nano-
HAp particles may be achieved.
Here, we report a new kind of surfactant (potassium polyox-
yethylene laurylether phosphate, MAEPK) as template to synthesize
Fig. 2. FTIR spectra of (a) sample and (b) control.
Fig. 3. TEM images of (a) HAp precursors and corresponding selected area electron diffraction (SAED), (b) partially oriented HAp precursors, (c) HRTEM of HAp products,
(d) control.
oriented and size-controllable nano-HAp through the reflux method
in normal pressure system. The effect of MAEPK on the morphology
of HAp has been investigated.
2. Experimental
Materials and method: In this study, analytical grade calcium
nitrate tetrahydrate (Ca(NO3)2d4H2O) and ammonium hydrogen
phosphate ((NH3)2HPO4) were used as calcium and phosphorus
sources. Absolute ethylalcohol (AR) and distilled water were used as
solvent. Sodium hydroxide (NaOH, AR) (6 mol/l) was used to vary the
pH of reaction solution. These reagents above were purchased from
Sinopharm Chemical Reagent Co., Ltd. MAEPK (C.P., Guangzhou
Flower’s Song Fine Chemical., Ltd, china) was used as template. The
products were achieved as follows: 15 ml distilled water and 30 ml
absolute ethyl alcohol was added to 10 g MAEPK and stirred at room
temperature for 15 min. After 11.8 g calcium nitrate tetrahydrate (Ca
(NO3)2d4H2O) was dissolved into 15 ml distilled water, the MAEPK
solution was added. The mixture was stirred for 20 min at room
temperature. Subsequently, 3.96 g ammonium hydrogen phosphate
((NH3)2HPO4) with 30 ml distilled water was added dropwise into
the above mixture reaction under vigorous stirring and yielded
a milky suspension. The suspension was stirred for half an hour at
room temperature. NaOH solution was added to adjust the pH to 10.
The suspension continuously stirred for 4 h and then refluxing
at 90 1C for 12 h. White powders were obtained after the precipitates
 S. Yang et al. / Materials Letters 96 (2013) 177–180 179

were washed, ultracentrifugated and freeze dried. Product observed

in the absence of MAEPK as control.
Characterization: The phase of the products were analyzed by
X-ray diffraction (XRD, Philips X’Pert Pro MPD, Co Ka radiation).
Fourier Transform infrared spectroscopy (FTIR, Nicolet Nexus
spectrometer) was used to study the composition of the products.
The microstructure, size and morphology of nanorods were
characterized by Transmission electron microscopy (TEM, JEOL
2010, 200 keV).

3. Results and discussion

From the x-ray diffraction (XRD) of as-achieved powders in Fig. 1,

it shows that the diffraction peaks of sample and control correspond-
ing to the standard characteristic peaks of HAp. The crystal phases of
as-achieved powders can be indexed to hexagonal structured hydro-
xyapatite (HAp) (JCPDS 09-0432). The broad peaks of sample dis-
played in Fig. 1a indicate that the crystallinity of crystal is low.
Fig. 2 shows the FTIR spectra of as-achieved powders. Char-
acteristic bands appear at 560, 604, 958, 1031 and 1107 cm  1 are
attributed to phosphate absorption bands. The band at 3436 cm  1
can be assigned to the vibration mode of OH group of H2O
adsorbed or involved in the particles [19,20]. Band at 3582 cm  1
corresponds to the characteristic vibration of O–H in HAp lattice
[21]. The bands at 1468 and 1568 cm  1 ascribed to CO2 3 absorp-
Fig. 4. (a) The chemical structure of MAEPK, (b) the electrostatic interaction
tion bands, the carbonate might caused by carbon dioxide from the
between ionized MAEPK and Ca2 þ ions, (c) schematic formation mechanism of
air while dissolving, stirring and reaction process [22,23]. The hydroxyapatite nanoclusters.
characteristic band for adsorbed water appears at 1650 cm  1.
The C–H stretching vibrations bands can be detected at 2929 and
2855 cm  1, these peaks are aroused by the residual organics in the anion tail groups. The micelles acted as nucleating points for the
precursor. The residual organics may lead to the decrease of growth of HAp nanoparticles [26]. As the MAEPK solution was
crystallinity, which has been proved by the former XRD character- added to the Ca2 þ solution, Ca2 þ ions immediately incorporated
ization (broad peaks of HAp precursors). into the phosphate groups of the organic chains because of the
Fig. 3a shows TEM image with corresponding selected area electrostatic interaction between ionized MAEPK and Ca2 þ ions
electron diffraction (SAED) pattern of the prepared HAp. From the (Fig. 4b). The introduction of Ca2 þ into MAEPK solution resulted
TEM micrograph of Fig. 3a, there are well dispersed nanocrystals in the decrease of surface energy [27], accelerated the nucleation
and some black substances. These black substances can be the and growth of HAp. With the addition of phosphate solution and
residual surfactants, which have been confirmed with the organ- sodium hydroxide solution, the nucleation gradually appeared on
ics peaks got from Fig. 2. The diffused rings in the SAED pattern the surface of these organic chains. In the other words, these
reveal that the crystallinity of HAP precursors is low, which oriented long organic chains were served as nuclear substrates.
corresponded to the broad peaks got from Fig. 1. From Fig. 3a, it With the continuous reaction, nanocrystals grow and attach along
shows that the sample was composed of many clusters and these organic chains to form nanorods. The coalescence of
hundreds of ordered build block-like single crystal fabricated nanorods with the same direction finally formed the partially
the clusters. The high magnification of Fig. 3b shows nanoclusters oriented nanoclusters (Fig. 4c).
assembled by partially oriented nanorods with about 60–80 nm
in length and 20 nm in width. High-resolution transmission
electron microscopy (HRTEM) image of HAp product was dis-
4. Conclusion
played in Fig. 3c. The lattice distance is about 0.36 nm, which is
corresponding to the interplanar spacing of (002) planes for HAp
Partially oriented HAp nanoclusters were achieved by reflux
and indicates that the nanoclusters grows along c-axis direction
method in the existence of MAEPK. Due to the charge complement
of HAp [24]. Fig. 3d shows TEM image with corresponding
and the long organic chains, the HAp crystals nucleated on and
selected area electron diffraction (SAED) pattern of the control
grow oriented along these organic substrates, with the continuous
product, the particles achieved in the absence of MAEPK are
of reaction, partially oriented nanoclusters were formed. The result
inhomogeneous and disordered. Comparing with the control
help to further understand the formation of oriented HAp.
product and sample achieved in presence of template, the later
one is poorly crystalline and ordered, which revealed that the
template may regulate the crystallization of HAp and induce the
oriented arrangement of product. Acknowledgments
In this experiment, MAEPK was acted as organic template
because of its alcohol ether chains and phosphate tail groups This research was supported by National Natural Science
(Fig. 4a). The added surfactant would first bind ions, which could Foundation of China (31100677), Natural Science Foundation of
be then incorporated to the existing nuclei at a steady rate and Fujian Province (2010J05112), Scientific Project of Fujian Educa-
the final shape and size of HAp particles could be well controlled tion Department (JA10053), Scientific Research Foundation in
[25]. When the MAEPK was added to the alcohol–water system, it Fuzhou University (2011-XQ-18 and 022228) and Scientific Major
could be ionized to alcohol ether chains micelles with phosphate Research Project of Fujian Province (2010NZ0001-1).
180 S. Yang et al. / Materials Letters 96 (2013) 177–180

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