Materials and Design 87 (2015) 445–449

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Materials and Design

journal homepage: www.elsevier.com/locate/jmad

Synthesis of hydroxyapatite nanorods from abalone shells via

hydrothermal solid-state conversion
Jingdi Chen a,⁎, Zhenliang Wen a, Shengnan Zhong a, Zihao Wang a, Jiulin Wu a, Qiqing Zhang a,b,⁎⁎
a
Institute of Biomedical and Pharmaceutical Technology, 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 a b s t r a c t

Article history: Hydroxyapatite (HAP) has been widely applied as a biomaterial for repairing or substituting human hard tissues.
Received 8 June 2015 In this paper, HAP nanorods were successfully produced from abalone shell powders via hydrothermal solid-state
Received in revised form 11 August 2015 conversion without surfactants or complex agents. The field emission scanning electron microscopy (FESEM)
Accepted 13 August 2015
showed that the produced HAP exhibited the typical rod-like structure. Based on the X-ray diffraction (XRD)
Available online 18 August 2015
and thermal analysis (thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC)), these
Keywords:
samples contain a small amount of aragonite and calcite crystals, and their content gradually decreases by
Hydroxyapatite nanorods prolonging the hydrothermal time. However, this decrease only slightly changes for the longer times. The Fourier
Abalone shell transform infrared spectroscopy (FTIR) revealed that organic matter was detected in the samples without adding
Solid-state conversion surfactants or complex agents. This study provides a solution to the resource waste and environmental pollution
Hydrothermal caused by abandoned abalone shells, and we also synthesized HAP for potential bone repair materials.
© 2015 Elsevier Ltd. All rights reserved.

1. Introduction and osteoconductivity [11–14]. For this reason, synthetic nano-HAP

As a type of marine mollusk, abalone (Haliotis) is a typical single
shell shellfish. Because of its delicious taste and high nutrition values,
abalone meat is a rare ingredient of traditional Chinese food and one
of the necessary dishes for Chinese banquets. However, the abalone
shell is a great burden to the environment after consumption of the ab-
alone meat. Thousands of tons of shells were found abandoned on an is-
land and around a town (shown in Fig. 1). This not only resulted in
waste of natural resources, but also polluted the environment. Abalone
shell is a natural composite material. It is composed of more than
95 wt.% calcium carbonate [1,2] and less than 5 wt.% organic matter
[3–5]. Thus, abalone shell is a good source of calcium. Until now, there
have been few reports on the efficient use of abalone shells.
Hydroxyapatite (HAP, Ca10(PO4)6(OH)2) is the most stable form of
calcium phosphate and is slightly soluble in water [6–8]. It is the main
inorganic component of mammalian hard tissues, such as bones and
teeth [9,10]. The HAP content of human enamel is about 96 wt.%. Gener-
ally, synthetic biomaterials have excellent bioactivity, biocompatibility
⁎ Correspondence to: J. Chen, Institute of Biomedical and Pharmaceutical Technology,
Fuzhou University, No. 523 Gongye Road, Fuzhou 350002, China.
⁎⁎ Correspondence to: Q. Zhang, Institute of Biomedical Engineering, Chinese Academy
of Medical Science & Peking Union Medical College, Tianjin 300192, China.
E-mail addresses: ibptcjd@fzu.edu.cn (J. Chen), zhangqiq@126.com (Q. Zhang).
has been widely applied as a biomaterial for repairing or substituting
human hard tissues [15–17]. In recent years, methods to prepare
nano-HAP using different forms of the raw material have been reported,
including solid-phase synthesis [12,18], sol–gel method [19,20], tem-
plate synthesis [12,21,22], and the hydrothermal method [12,23–25],
among others. However, the solid-phase synthesis method requires
processing with high temperature. Template synthesis is necessary to
add organic templates; however, it is not easy to degrade after
implanting into the organism, which limits the clinical applications. For-
tunately, the hydrothermal synthesis method can make use of the orig-
inal mineral that is poorly soluble or insoluble. Additionally, ion
exchange and recrystallization occur, which make a smooth solid-
state conversion from one mineral phase to another realizable under
hydrothermal conditions. Moreover, solid-state conversion reduces
the calcination and milling steps. Hence, it is easy to control the reaction
conditions. Thus far, some scholars have reported the synthesis of HAP
using calcium carbonate with different forms [24,26], but it is still a chal-
lenge to synthesize well-organized nano-HAP with an expected compo-
sition and mechanical properties using abalone shell powders under
hydrothermal conditions.
Herein, we utilized abalone shell powders as a calcium source for
HAP. HAP nanorods were successfully synthesized via hydrothermal
solid-state conversion. The crystal phase and morphology of the sam-
ples were characterized using X-ray diffraction (XRD), field emission

http://dx.doi.org/10.1016/j.matdes.2015.08.056
0264-1275/© 2015 Elsevier Ltd. All rights reserved.
446 J. Chen et al. / Materials and Design 87 (2015) 445–449
Fig. 1. Abandoned abalone shells.
scanning electron microscopy (FESEM), Fourier transform infrared
spectroscopy (FTIR), zeta potential measurements (ZP) and a thermo
gravimetric analyzer.
2. Materials and methods
2.1. Materials
The shells of Wrinkles Abalone were collected from the official dock
Ocean Development Co., Ltd (Lianjiang Country in Fujian Province, CN).
Diammonium phosphate ((NH4)2HPO4, ≥ 99%) was purchased from
Sinophar Chemical Reagent Co., Ltd, China. Sodium hydroxide (NaOH,
98%) and acetic acid (CH3COOH, ≥ 99.5%) were purchased from
Shanghai Lianshi Chemical Co., Ltd (Shanghai, CN).
2.2. Preparation of the samples
First, the abalone shell was immersed in 10 vol.% acetic acid solution
to clean off the surface impurities. After rinsing with distilled water and
naturally dying them, the abalone shell was crushed and screened using
a pulverizer (SF-130, Zhong Cheng Pharmaceutical Machinery Factory,
CN). This produced the abalone shell powders.
For the synthesis, abalone shell powders and diammonium phos-
phate ((NH4)2HPO4) were used as the calcium and phosphorous
sources, respectively. The samples were prepared as follows: 2 g of ab-
alone shell powders and 1.5847 g of (NH4)2HPO4 were mixed (Ca/P in
a molar ratio of 1.67:1), and they were dissolved in 20 ml of deionized
water. The pH of the solution was adjusted to 10 using sodium hydrox-
ide solution (NaOH, 1 M) and the mixture was stirred at room temper-
ature for 30 min using a magnetic stirrer. Then, the mixed solution was
transferred to an autoclave, and heated at 150 °C at hydrothermal times
of 6 h, 18 h, and 72 h. After completing the reaction, the final precipitate
was washed with deionized water via centrifugation several times. Fi-
nally, the white latex-like precipitant was freeze-dried to yield white
powders. This produced the samples.
2.3. Characterization of the samples
The phase of the samples was examined using X-ray diffraction
(XRD, X'Pert PRO Panalytical diffractometer) with Cu Kα (λ =
0.154056 nm) incident radiation at a working voltage of 40 keV in the
range of 10° to 70° at a 0.02° step size. The phases were identified by
comparing the data with data reported in the Joint Committee of Powder
Diffraction Standards database (JCPDS no. 09-0432).
For FTIR, (Nicolet 360 intelligent spectrometer, Thermo Nicolet
Corporation, US) studies, we used the KBr pellet method, which was
performed on dried samples.
The microstructure and surface potential of the sample were ana-
lyzed using FESEM, (Nova NanoSEM, FEI, Netherlands) and a potential
instrument (Malvern Zetasizer Nano-ZS90).
A thermogravimetric analyzer (TGA, DIL402C, NETZSCH, Germany)
further determined the composition of the obtained HAP. The samples
were heated to 1000 °C in flowing air at a heating rate of 10 °C/min.
3. Results and discussion
Fig. 2 shows the XRD patterns of the abalone shell powders (A) and
the samples exposed to different hydrothermal times of (B) 6 h,
(C) 18 h, and (D) 72 h. In Fig. 2A, the abalone shell was determined to
be composed of aragonite and calcite. After the hydrothermal treat-
ment, most of the diffraction peaks of the calcium carbonate (aragonite
and calcite) disappeared, whereas the HAP phase diffraction peaks were
detected at 2θ of 25.77°, 31.81°, 32.12°, 34.01°, 39.97°, 46.74°, and
49.38°. Moreover, the intensity of the diffraction peaks is increased as
a function of the prolonged hydrothermal treatment time at 2θ of
25.77°, and 31.81° (shown in Fig. 2D). This suggested that the crystallin-
ity of the samples also increased. Moreover, the weak diffraction peaks
of the calcite and aragonite (at the 2θ of 29.38° and 33.08°, respectively)
were observed even after hydrothermal treatment for 72 h. This may be
due to the natural structure and special composition of the abalone shell
[1,27,28].
To further investigate the composition of the samples exposed to dif-
ferent hydrothermal times of (B) 6 h, (C) 18 h, and (D) 72 h, FTIR anal-
ysis was conducted (Fig. 3). The bands at 1789 cm−1, 1464 cm−1,
862 cm−1 and 710 cm−1 represent CO2− 3 (shown in Fig. 3A), which is
due to the composition of the abalone shell that contains calcium car-
bonate (aragonite and calcite). After the hydrothermal treatment, the
components of all the samples were similar, which showed the pres-
ence of the characteristic groups of the HAP. The characteristic vibration
of the PO3−4 groups was detected at 1037 cm−1, 960 cm−1, 608 cm−1
and 567 cm . The band at 3567 cm−1 was assigned to the stretching
−1
vibration of the OH−. Additionally, the vibration peaks at 1462 cm−1,
1418 cm−1, and 874 cm−1 represent CO2− 3 . These bands are due to cal-
cium carbonate entrapped inside the HAP, which is consistent with the
XRD results. C\\H asymmetric stretching vibration and symmetric
stretching vibration were detected at 2929 cm−1 and 2856 cm−1, re-
spectively. These bands demonstrated that organic matter exists in the
synthesized HAP. This particular organic matter originates from the
Fig. 2. XRD patterns of the abalone shell powders (A) and the samples exposed to different
hydrothermal times: (B) 6 h, (C) 18 h, and (D) 72 h.
 J. Chen et al. / Materials and Design 87 (2015) 445–449
Fig. 3. FTIR spectra of the abalone shell powders (A) and the samples exposed to different
hydrothermal times: (B) 6 h, (C) 18 h, and (D) 72 h.
abalone shell [3,29], and it can play an important role in biological min-
eralization [4,30–35].
The thermal analysis (TGA and DSC) is illustrated in Fig. 4. A weight
loss in the TGA curve corresponds to an absorption peak of the DSC
curve, which represents a phase transition process. In Fig. 4A, we ob-
serve that the major mass loss of the abalone shell powder occurred at
approximately 800 °C, which is due to the thermal decomposition of cal-
cium carbonate to calcium oxide and carbon dioxide. Additionally, the
organic matter degraded in one or several steps between 200 °C and
Fig. 4. TGA–DSC patterns of the abalone shell powders (A) and the samples exposed to different hydrothermal times: (B) 6 h, (C) 18 h, and (D) 72 h.
447
450 °C. The TGA curve also showed a loss of adsorbed H2O at 100 °C.
After the hydrothermal treatment, the TGA–DSC patterns of all of the
samples were similar (shown in Fig. 4B–D). Thus, compared with
Fig. 4A, in all of the samples, we detected the mass loss of adsorbed
H2O, organic matter and carbon dioxide. This suggests that the sample
contained a small amount of calcium carbonate and organic matter,
which is similar to the results of XRD and FTIR. Particularly, slightly
below 700 °C, the sample exhibits an endothermic peak (shown in
Fig. 4B–D). This may be due to the HAP crystallized from the amorphous
calcium phosphate (ACP) of the sample, which is consistent with the re-
sults reported by Suchanek et al. [36].
Fig. 5 shows the FESEM images of the abalone shell cross-section
(A) and the samples exposed to different hydrothermal times of
(B) 6 h, (C) 18 h, and (D) 72 h. In Fig. 5A, the abalone shell consists of
aragonite sheets and prismatic calcite, this composition was consistent
with the XRD analysis (Fig. 2A). After 6 h of hydrothermal treatment,
the morphology of the sample is rod-like or flake-like (shown in
Fig. 5B), similar to the structure of the precursor, but the morphology
and the size of the samples are not uniform. As the hydrothermal time
increased to 18 h, the size and morphology of the samples became
more regular (Fig. 5C). A good rod-like structure and uniform sizes
were obtained for the nano-HAP after a hydrothermal time of 72 h
(shown in Fig. 5D). Fig. 5E is an enlarged image of the red area in
Fig. 5D. As clearly shown, the structure of the obtained HAP is a hexag-
onal rod-like structure, which is similar to the structure reported by
Zhan et al. [6]. Furthermore, the crystal growth schematic diagram of
the HAP hexagonal crystallites is showed in Fig. 5F. The sheet structure
of the HAP gradually reduces, whereas the rod-like structure increases
as a function of the extended hydrothermal time. This result may be at-
tributed to the composition transformation of both aragonite and calcite
to HAP. At the beginning of the hydrothermal process, the amorphous
448 J. Chen et al. / Materials and Design 87 (2015) 445–449

Fig. 5. FESEM images of the abalone shell cross-section (A) and the samples exposed to different hydrothermal times: (B) 6 h, (C) 18 h, and (D) 72 h; The inset (E) is a magnified view of the
selected red area. (F) Schematic diagram of the HAP hexagonal crystallites. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this
article.)

calcium phosphate of the HAP precursor is deposited around the sur-

faces of the aragonite and calcite crystals. With more time, the forma-
tion of the outside layer HAP prevents the phase transformation of the
inside aragonite and calcite. Thus, the content of the internal aragonite
and calcite did not significantly change even after the long hydrother-
mal time. This result agrees with the slight change observed in the ara-
gonite and calcite in Fig. 2B–D and can explain the existence of the small
amount of aragonite and calcite in the produced HAP even though the
hydrothermal treatment time was 72 h (Fig. 2D). According to
previous research, monocrystalline HAP typically grows following the
c-axis of the HAP structure [37]. Hence, the rod-like structure of HAP
was finally formed.
Fig. 6 shows the zeta potential (ZP) value of the abalone shell pow-
ders (A) and the samples exposed to different hydrothermal times of
(B) 6 h, (C) 18 h, and (D) 72 h. We visually observe that the surface po-
tential of the abalone shell powders and the samples exposed to differ-
ent hydrothermal times are very similar, which all have a negative value
of approximately −22 mv. Smith et al. [38] reported that HAP particles
with a negative surface charge favor bone growth and osteoblast forma-
tion. Thus, the samples with a negative surface may be used as potential
bone repair materials to promote bone growth and osteoblast forma-
tion. Moreover, for particles that are small enough, a high zeta potential Fig. 6. Zeta potential patterns of the abalone shell powders (A) and the samples exposed to
will confer stability; thus, the particles will resist aggregation. However, different hydrothermal times: (B) 6 h, (C) 18 h, and (D) 72 h.
 J. Chen et al. / Materials and Design 87 (2015) 445–449
Fig. 7. Formation mechanism of the obtained HAP.
the particles tend to aggregate when the zeta potential is low, and this is
because the attraction exceeds the repulsion [39]. Hence, according to
the above-mentioned results, the stability of the obtained samples is
satisfactory.
Based on the preceding analysis, the formation mechanism of the
obtained HAP is depicted in Fig. 7. First, the aragonite and calcite partly
dissolved, and Ca2+ and CO2− 3 are released. Then, the recrystallization of
− [20] B.A. Allo, A.S. Rizkalla, K. Mequanint, Hydroxyapatite formation on sol–gel derived
Ca2+, PO3−4 and OH occurs around aragonite and calcite via the hydro-
thermal treatment. Meanwhile, the aragonite sheets to form the HAP
nanosheets, while the prismatic calcite forms the HAP nanorods. How-
ever, monocrystalline HAP typically grows following the c-axis of the
HAP structure. Thus, the rod-like HAP increases with prolonged treat-
ment time. Finally, the solid-state conversion process produces the mor-
phological and crystalline characteristics of HAP.
4. Conclusions
We have successfully obtained HAP nanorods from abalone shell
powders via hydrothermal solid-state conversion without surfactants
or complex agents. The composition of the samples contained a small
amount of calcium carbonate (aragonite and calcite) and organic matter.
However, the calcium carbonate content gradually decreases as a func-
tion of the prolonged hydrothermal time. This decrease changes slightly
over a longer time. This study solves the resource waste and environmen-
tal pollution problem that is caused by abandoned abalone shells, and we
synthesized HAP for potential bone repair materials.
Acknowledgment
This research was supported by the National Natural Science Foun-
dation of China (31100677 and 31370958) and the Scientific Project of
Fujian Education Department (JA14031).
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