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Self-Assembly of Hydroxyapatite Nanostructures by Microwave Irradiation
Self-Assembly of Hydroxyapatite Nanostructures by Microwave Irradiation
Self-Assembly of Hydroxyapatite Nanostructures by Microwave Irradiation
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Self-assembly of hydroxyapatite
nanostructures by microwave irradiation
Jingbing Liu, Kunwei Li, Hao Wang1 , Mankang Zhu, Haiyan Xu
and Hui Yan
The College of Materials Science and Engineering, Beijing University of Technology,
Beijing 100022, People’s Republic of China
E-mail: haowang@bjut.edu.cn
211
112
Intensity (a.u.)
300
222
002
213
130
202
321
210
111
132
402
004
102
200
131
322
301
113
20 30 40 50 60
2θ (degree)
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J B Liu et al
(c)
(a)
(b) (d)
Figure 3. (a) Low magnification SEM image showing bowknot-like HAp nanostructures. (b) Higher magnification SEM image of a typical
bundle of the HAp nanostructures. (c) TEM image of a typical bowknot-like bundle of HAp. Inset: SAED pattern taken from an individual
HAp nanorod from the bowknot-like HAp nanostructures. (d) HRTEM image recorded from the tip of the individual sword-like HAp
nanorod.
The SAED pattern taken from a single nanorod shows that with the (100) lattice spacing of HAp, showing that the nanorod
the nanorod was a single crystal of hexagonal HAp (inset in was of uniform crystal structure. Further studies of both the
figure 2). HRTEM image and SAED pattern demonstrate that the growth
The SEM and TEM images of as-prepared HAp axis is the [001] direction of HAp.
nanostructures with a pH of 11 are shown in figure 3. Figure 4 shows the SEM and TEM images of the typical
The overall morphology of the samples which is shown in flower-like HAp nanostructures prepared in the solution of
figure 3(a) indicates that there exist a great many uniform pH 13. The morphology of the obtained HAp is in the
bowknot-like bundles with their two ends fanning out while form of leaf-like flakes of 150–200 nm width and of 1–2 µm
the middle part is tied together. Typical bundles of the HAp length extending radially from the centre. The corresponding
nanocrystals (figure 3(b)) indicate that the bundles consist of SAED pattern (inset in figure 4(c)) taken from individual leaf-
HAp nanorods with a typical width of 150 nm and lengths up to like flake confirms that the flakes are well crystallized single
1–2 µm. After long-period ultrasonic treatment, the bowknot- crystals. The typical HRTEM image (figure 4(d)), recorded
like HAp nanostructures were not destroyed, indicating the from an individual leaf-like flake, reveals a perfect crystal
nanostructures were not due to aggregation. Figure 3(c) shows structure, and unambiguously distinguishes the (100) and (002)
the TEM image of a typical bowknot-like bundle of HAp. It atomic planes of hexagonally structured HAp with interplanar
can be seen from this image that the end of the HAp nanorod spacings of about 0.82 and 0.34 nm, respectively. The (002)
is a cusp like a sword. More detail about the structure of a crystal planes are approximately vertical to the long axis of the
selected nanorod from the bowknot-like HAp was investigated HAp flakes, which shows that the HAp flakes predominantly
by the SAED pattern (inset in figure 3(c)). The highly arrayed grow along the [001] direction.
diffraction spots in the pattern indicate the single-crystalline In order to reveal the growth mechanism and the effect
property of the HAp nanorod. Figure 3(d) shows the HRTEM of EDTA, comparative experiments in the absence of EDTA
image recorded from the sword-like tip of the individual HAp under the same synthesis conditions were studied. When
nanorod shown in figure 3(c). The regular spacing of the CaNO3 solution was added to Na2 HPO4 solution, a mass
observed lattice planes was about 0.82 nm, which is consistent of white precipitate of amorphous calcium phosphate (ACP)
84
Self-assembly of hydroxyapatite nanostructures by microwave irradiation
(c)
(a)
(b) (d)
Figure 4. (a) Low-magnification SEM image showing flower-like HAp nanostructures. (b) Higher magnification SEM image of typical
flower-like HAp nanostructures. (c) TEM image of a typical flower-like HAp. Inset: SAED pattern taken from an individual HAp leaf-like
flake from the flower-like HAp nanostructures. (d) HRTEM image recorded from the edge of the individual leaf-like HAp flake.
85
J B Liu et al
Figure 8. Schematic illustration of major steps involved in the microwave approach to the synthesis of HAp nanostructures.
86
Self-assembly of hydroxyapatite nanostructures by microwave irradiation
− area on the surface of the particles, may bring some novel and
At lower pH value (lower OH concentration), the crystal
growth habit is mainly affected by the interior structure rather unexpected properties. We can foresee the scaling-up of the
than the exterior condition. In this condition, free Ca ions process to form large quantities of this kind of nanomaterial.
can be easily released from Ca–EDTA complexes due to the Further work is under way to study the properties of these novel
poor stability of Ca–EDTA. The free Ca ions will incorporate 3D nanostructures and the possibility of synthesizing other 3D
into the crystal lattice site of the obtained crystallite and the nanostructures.
crystallite will grow according to the anisotropic structure of
HAp. Consequently, HAp nanorods are obtained at a pH References
of 9. However, with increasing pH value, the concentration
of OH− and the stability of the complex increase. At a [1] Shipway N, Katz E and Willner I 2000 Chem. Phys. Chem.
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gives the flower-like form. For the condition of pH equal to 11, [10] Li Y, Wan J H and Gu Z N 2000 Mater. Sci. Eng. A 286 106
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49
In summary, uniform 1D and 3D (bowknot-like and flower- [22] Xu H Y, Wang H, Meng Y Q and Yan H 2004 Solid State
like) HAp nanostructures have been successfully prepared Commun. 130 465
by microwave irradiation without any help of templates. A [23] Liu C S, Huang Y, Shen W and Cui J H 2001 Biomaterials 22
mechanism was proposed to elucidate their formation. The 301
shape of the obtained crystals can be easily controlled by [24] Riman R E, Suchanek W L, Byrappa K, Chen C W, Shuk P
and Oakes C S 2002 Solid State Ion. 151 393
changing the complex stability of Ca–EDTA and the hindrance [25] Christian G D 1986 Analytical Chemistry (New York: Wiley)
effect of OH− on the crystallite facets. These bowknot-like [26] Li W J, Shi E W, Zhong W Z and Yin Z W 1999 J. Cryst.
and flower-like nanostructures, which have a highly specific Growth 203 186
87