Template-assisted synthesis of

Hydroxyapatite Nano-wires
Jinghong Li, Yuanjian Zhang, Lihen Zhou, Naicun
Xue, Di Li
Presented at the 8th International Conference on Electronic
Materials (IUMRS-ICEM 2002, Xian, China, 1014 June
2002)
536
Template-assisted synthesis of Hydroxyapatite Nano-wires
Jinghong Li*, Yuanjian Zhang, Lihen Zhou, Naicun Xue, Di Li
State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of
Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
Abstract
Bone itself is a kind of compound consisting of hydroxyapatite (abbreviated as
HAp) nano-rods embedded in the collagen matrix with the same
crystallographic organization. In the present study, HAp nano-rods precursors
were synthesized via wet chemical method, and then an anodic oxide
aluminum (AAO) as the template was soaked in HAp suspension to assembly
HAp nano-wires. It provides meaningful information of biological molecules
mineralization process.
Key words: hydroxyapatite, template, Nano-wires, bio-mineralization
*To whom correspondence should be addressed
Telephone and fax (86-431-5262243)
E-mail: lijingh@ciac.jl.cn
Advanced Nanomaterials and Nanodevices (IUMRS-ICEM 2002, Xian, China, 1014 June 2002)
537
Introduction
Hydroxyapatite (HApCa
10
(PO
4
)
6
(OH)
2
) is one of the most attractive materials
for bone implant due to its compositional and biological similarity to native
tissues
[1]
. Bone is an inorganicbioorganic composite material consisting
mainly of collagen proteins and HAp, and its properties depend intimately on
its nano-scale structures, which are dictated specifically by the collagen
template
[2-4]
. Anodic oxide aluminum (AAO) is the most widely used porous
template and many materials have been fabricated into nanowires using this
template process, including various inorganic materials Au, Ag, Pt, TiO
2
, MnO
2
,
ZnO, SnO
2
, electronically conductive polymers polypyrrole, polyaniline, and
carbon nanotubes
[5]
. However, to the best of our knowledge, there has no
report on assembling HAp in AAO. Herein we aim at employing AAO as
template to assembly HAp nano-structures and attempt to design artificial
nano-structures that can interact with and replace natural biological materials.
Experimental
Ca(OH)
2
(A.R), H
3
PO
4
(A.R) and NaOH (A.R) were acquired from standard source
and used as received. Water was purified with Milli-Q (18.2 M) water system.
AAO template was prepared as the literature
[6]
. High-purity aluminum sheets
(99.99%) were etched in alkaline solution and rinsed in water and then
electro-polished to provide a smooth surface. The resulting aluminum sheets
were anodized at a constant potential of 150 V in 4% H
3
PO
4
solution. A vigorously
stirred 0.01 mol Ca(OH)
2
was titrated with 0.006 mol H
3
PO
4
at a rate of 1 ml/min.
After aging, washing, filtration, and drying, the HAp precursors were obtained
[7]
.
AAO was further soaked in HAp suspension for a week to assembly the nano-Hap
wires in the pores of template. HAp/AAO membrane was etched in NaOH to
exhibit the HAp in the pores of the cross section before SEM observation.
X-ray diffraction (XRD) was recorded on RIGAKU D/max-IIB X-ray
Diffractometer using Cu K

radiation of 40 kV and 20 mA. Transmission electron

Advanced Nanomaterials and Nanodevices (IUMRS-ICEM 2002, Xian, China, 1014 June 2002)
538
microscopy (TEM) and scanning electron microscopy (SEM) were performed on
JEOL-JE M-2010 and JEOL JXA-840 (JEOL, Japan) electron microscopy,
respectively, operating at 200 kV.
Results and discussion
Fig. 1(a) shows X-ray diffraction patterns of HAp precursors. All peaks
corresponded to hexagonal HAp crystal (JCPDS 9-432). Lattice parameters of c
= 0.6880 nm and a= 0.9431 nm, which were calculated from (002), (211), (300)
and (202) diffraction peaks, were similar to the theoretical values (c=0.6884 nm,
a=0.9418 nm)
[7]
. Its average crystallite size is estimated to be 19.2 nm by the
Sherrer formula
[7,8]
. Fig. 1(c) illustrates XRD patterns of the mixture of 1:1 Al
2
O
3
and HAp (milled for 3 h). Compared with Fig. 1a and 1b, almost all peaks from
the mixture were attributed from hexagonal HAp crystallites or Al
2
O
3
crystallites
respectively, no new phases found. Hence, there is no chemical reaction to
occur as nano-HAp assembled into the pores of AAO.
Fig. 2 shows TEM image of the HAp precursors. Nano-rods of HAp precursors
were observed, which had the diameter of 6-7 nm and the length of 70-100 nm.
Considering the average individual size of crystallite of HAp precursors obtained
by XRD observation, the HAp inclined to grow in the c-axis of HAp lattice
[4,9]
.
Fig. 3(a) shows the SEM image of AAO template of the planar section. The
nano-pores exhibited almost perfect two-dimension arrays with a hexagonal
pattern. The average pore size of 200 nm, mean porosity of 50% and pore
density of 10
9
pores/cm
2
were calculated using Scion Image Beta 4.02
(download from http://www.scioncorp.com). Fig. 3(b) shows the SEM image of
nano-structured HAp of the cross section. The parallel array of HAp was
observed and its average diameter was calculated to be ca.160 nm (less than
the mean pore size of AAO template), and its average length of ca. 10 m. The
ratio of the length to the diameter of HAp nano-rods was ca. 63. Considering the
size of individual HAp precursors, the re-crystallization process probably
Advanced Nanomaterials and Nanodevices (IUMRS-ICEM 2002, Xian, China, 1014 June 2002)
539
occurred during soak and then arranged in the same direction of the template,
which was similar to the mineralization process of biological inorganic molecule
[2,4,10]
. The property of HAp growing along the same orientation as the template
could be of interest in the design of biomaterials, especially those used for bone
tissue repair
[4]
.
Conclusions
In conclusion, nano-HAp assembled in AAO with similar biological vivo
orientation was synthesized via template technology, and characterized with
XRD, TEM and SEM. It is desired to be studied widely and thoroughly to
interact with and replace natural biological materials.
Acknowledgment
This work was finically supported by Outstanding Youth Fund (No. 20125513)
from the National Natural Scientific Foundation of China, 100 People Plan from
Chinese Academy of Sciences and 100 Outstanding Ph D. Thesis Award of
China.
Advanced Nanomaterials and Nanodevices (IUMRS-ICEM 2002, Xian, China, 1014 June 2002)
540
Reference
[1] Weiner S., Addadi L., J.Mater.Chem., 7 (1997) 689-702
[2] Taton T.A., Nature, 412 (2001) 491-492
[3] Service R.F., Science, 294 (2001) 1635-1637
[4] Hartgerink J.D., Beniash E., Stupp S.I., Science, 294 (2001) 1684-1688
[5] P.D. Yang, Y.Y. Wu, R. Fan, Int.J.Nanosci., 1 (2002) 1-39
[6] Miller C.J., Majda M., J.Electroanal.Chem., 207 (1986) 49-72
[7] Slavica L., Slavica Z., Nada M., Slobodan M., Thermochim. Acta, 374 (2001)
13-22
[8] Zhang S., Gonsalves K.E., J.Mater.Sci.: Mater. in Med., 8 (1997) 25-28
[9] Furuzono T., Walsh D., Sato K., J.Mater.Sci.Lett., 20 (2001) 111-114
[10] Daniel M.D., Ilhan A.A., Annu.Rev.Mater.Sci., 30 (2000) 601-622
Legends
Fig. 1 XRD patterns of the HAp precursors (a), Al
2
O
3
powders (b), and the
mixture of HAp/Al
2
O
3
(1:1, milled for 3 h) (c).
symbols * and # corresponded to Al
2
O
3
and HAp peaks respectively.
Fig. 2 TEM image of the HAp precursors.
Fig. 3 SEM images of AAO of the planar section (a) and nano-HAp of the cross
section (b).
Advanced Nanomaterials and Nanodevices (IUMRS-ICEM 2002, Xian, China, 1014 June 2002)
541
Fig. 1
5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90
#
#
#
#
#
#
#
#
(a)
*
*
*
*
*
*
*
(b)
I
n
t
e
n
s
i
t
y
#
(c)
*
* * *
*
*
#
#
#
#
#
#
#
*
2 q
Advanced Nanomaterials and Nanodevices (IUMRS-ICEM 2002, Xian, China, 1014 June 2002)
542
Fig. 2
Advanced Nanomaterials and Nanodevices (IUMRS-ICEM 2002, Xian, China, 1014 June 2002)
543
Fig. 3
(a)
(b)
Advanced Nanomaterials and Nanodevices (IUMRS-ICEM 2002, Xian, China, 1014 June 2002)
544