Materials Letters 63 (2009) 2100–2102

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Materials Letters
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m a t l e t

Utilization of biowaste eggshells to synthesize nanocrystalline

hydroxyapatite powders
K.P. Sanosh a,b, Min-Cheol Chu b, A. Balakrishnan a,b, T.N. Kim a, Seong-Jai Cho b,⁎
a
Department of Information and Electronic Materials Engineering, College of Engineering, Paichai University, Daejeon, 302-735, Republic of Korea
b
Division of Metrology for Emerging Technology, Korea Research Institute of Standards and Science, 1 Doryong-Dong, Yuseong-Gu, Daejeon 305-340, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: Nano hydroxyapatite (HA) powder was successfully synthesized from biowaste chicken eggshells. The
Received 20 May 2009 nanopowders were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM),
Accepted 27 June 2009 particle size distribution (PSD) analyzer, and Fourier transform infrared spectroscopy (FT-IR) techniques.
Available online 5 July 2009
Selected area electron diffraction (SAED) analysis during TEM showed the particles to be polycrystalline in
nature. The resulting HA powder exhibited an average size of ~35 nm with a narrowly distributed particle
Keywords:
size range from 5 to 90 nm. XRD and FT-IR analysis showed that the powders produced were of high purity.
Nanomaterials
Sol–gel preparation
The present study provides a simple sol–gel precipitation method to obtain nano HA powders of high purity
Particle distribution from biowaste chicken eggshells.
Eggshells © 2009 Elsevier B.V. All rights reserved.
Hydroxyapatite

1. Introduction
Over the years, hydroxyapatite (HA, Ca10(PO4)6(OH)2) ceramics
have gained attention because of their usage in bone grafting,
resulting from their excellent osteoconductive and bioactive proper-
ties [1]. With the ever-growing need to develop clean, non-toxic and
environmentally friendly techniques, HA powders have been
extracted using bio products like corals [2], cuttlefish shells [3],
natural gypsum [4], natural calcite [5], bovine bone [6], etc. Chemical
analysis has shown that these products which are otherwise
considered as biowaste are rich sources of calcium in the form of
carbonates and oxide. One of such biowastes is chicken eggshells.
Everyday million tons of eggshells are generated as biowaste around
the globe. The eggshell represents ~11% of the total weight of an egg
and is composed of calcium carbonate (~ 94%), calcium phosphate
(~1%) and organic matter (~4%) [7]. Besides being economically cheap
and plentiful in nature, these eggshells have shown to be biocompa-
tible in the human body during implantation, but not osteoconductive
[8]. Hence, converting these powders into HA prior to implantation is
advantageous. There are reported studies where eggshells are
converted into different Ca-precursors for deriving HA. For instance,
Nayar and Guha [9] in their study reported dissolving eggshells in
chloride solution prior to mixing with phosphate precursors. The
problem with this technique is that the removal of chloride ions is not
⁎ Corresponding author. Tel./fax: +82 42 868 5388.
E-mail addresses: sjcho@kriss.re.kr (K.P. Sanosh), the_krecian@yahoo.com (S.-J. Cho).
easy. Our experience shows that if the synthesized dried HA powder is
not washed thoroughly with hot water; the presence of Cl− in the
powder leaves a yellow discoloration and contaminates the powder. In
another study reported by Sasikumar et al. [10], egg shells are
dissolved directly in concentrated HNO3, however an additional EDTA
test is required to determine the exact molar concentration of the Ca
based solution prior to sol–gel mixing. The methodology adopted by
Riveria et al. [7] uses sealed containers to heat CaO derived from
eggshell with phosphate based precursor at very high temperatures of
1050 °C for a prolonged holding time of 3 h. Since, particle size
distribution data is not available for the above studies, considering the
calcination temperature and holding time used, we believe that the
average particle size for a powder batch is generally submicronic to
micronic. In the present study, we report a simple sol–gel precipita-
tion technique to synthesize nano HA powders using CaO derived
from chicken eggshells. Nano HA powders are highly bioactive and
osteoconductive which is attributed to their large surface energy.
Besides the simplicity, the advantage of this technique is that the
synthesized HA powder (~ 35 nm) is narrowly distributed over a size
range from 5 to 90 nm.
2. Materials and methods
Biowaste chicken egg shells were firstly cleaned in boiling water
and calcined in air using an electric furnace at 900 °C (heating rate of
10 °C/min) for 1 h. The calcined powder was ground in an alumina
mortar–pestle. The XRD analysis (Fig. 1a) of this calcined powder
revealed pure phases of CaO. This CaO powder was completely
dissolved in concentrated HNO3 (Dae-jung chemicals and metals co.,

0167-577X/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2009.06.062
 K.P. Sanosh et al. / Materials Letters 63 (2009) 2100–2102 2101

Fig. 1. XRD patterns of (a) Calcined eggshell powders showing pure CaO phases and (b) HA powders dried and calcined at different temperatures for 30 min.

Korea) and was diluted with distilled water such that 1 M calcium
nitrate (Ca (NO3)2, CN) was obtained. 0.6 M potassium dihydrogen
phosphate (KH2PO4, Dae-jung chemicals and metals co., Korea, KDP)
solution in distill water was prepared. This KDP solution was slowly
added to the above CN solution. This solution mixture was kept
constant at pH = 10 by adding ammonia. The solution was rigorously
stirred for 1 h and kept for ageing overnight at room temperature. A
bilayer solution of clear ammonia at the top and white precipitate
powder at the bottom of the beaker was obtained. The excess
ammonia solution at the top was poured out and the precipitate was
−
washed with distilled water to remove the presence of NH+ 4 and NO3
ions. This precipitate was filtered out using filter paper and allowed to
dry at 65 °C for 24 h in a dry oven. The resultant cake obtained was
calcined in air at different temperatures ranging from 150 to 700 °C
for 30 min using an electrical furnace and employing a heating rate of
10 °C/min. Transmission electron microscope (TEM) (HRTEM, Model
Tecnai-Philips F30, FEI Co., Hillsboro) was used to observe the
morphology and the particle size of calcined HA powders, while
the selected area electron diffraction (SAED) was used to study the
crystallinity of the sample. The X-ray diffraction (XRD) pattern of
the final HA nanopowder was obtained with Cu Kα radiation (λ =
1.5418 A°) on a D8 Advance (Bruker-axs, Germany) diffractometer The
particle size distribution (PSD) of the powder was carried out using a
condensation particle counter (GRIMM Aerosol Technik, Gmbh,
Germany (serial no 5400)). The Fourier transform infrared spectro-
scopy (FT-IR) was done with Nexus 6700 FT-IR (Thermo-Nicolet, Inc.)
equipped with an attenuated total reflectance (ATR) accessory (Smart
Miracle, PIKE Tech.).
particles exceeding 100 nm in size could be attributed to the particle
aggregation during calcination.
TEM micrographs of dried powders at 65 °C showed high
amorphicity (Fig. 3a), while powders calcined at 700 °C showed
prolate spheroidal morphology (Fig. 3b) with particle sizes varying
between 30 and 50 nm. SAED analysis (Fig. 3c) revealed the
polycrystalline nature of this calcined powder.
Particle formation by sol–gel is a very complex process. It involves
nucleation, growth, aggregation and agglomeration [12,13]. The
process by which HA starts to nucleate prior to growth can be given
by the following reactions:
900 -C
Y CaO + CO
CaCO3 2 ð1Þ
(Eggshells)
CaO þ 2HNO3 →CaðNO3 Þ2 þ H2 O ð2Þ
10CaðNO3 Þ2 þ 6KH2 PO4 þ 14NH4 OH →Ca10 ðPO4 Þ6 ðOHÞ2 þ 6KNO3
þ14NH4 NO3 þ 12H2 O:
ð3Þ
Fig. 4 presents the FT-IR patterns for HA calcined at 700 °C. The
spectra show a sharp and strong band at 3572 cm− 1 and a weak broad
band ranging between 3550 and 3350 cm− 1. The 3572 cm− 1 band
corresponds to the OH− group, and the broad band at 3550–3350 cm− 1,

3. Results and discussion

Fig. 1(b) shows the XRD pattern of the HA nanopowder calcined at

different temperatures for 30 min. The nanopowders were character-
ized by broad peaks with no secondary phases indicating that the
synthesized HA was pure. It was also observed that the crystallinity of
HA powders increased with temperature. The HA powders calcined at
700 °C showed well defined broad crystalline peaks. It should be noted
that this calcination temperature of 700 °C for obtaining crystalline HA
from eggshells is much lower than the previous reported works [7,10].
The crystallite size obtained from the XRD patterns using the Scherrer
equation [11] for the calcined powder at 700 °C was about 43 ± 15 nm
(calculated for four powder batches), which was in close agreement
with the PSD analysis (Fig. 2).
PSD showed a narrow skewed distribution centered at ~ 35 nm. It
was seen that more than 98% of the total amount of particles lied in
the range from 5 to 90 nm particle size. The detection of larger size Fig. 2. PSD profile of HA powders calcined at 700 °C.
2102 K.P. Sanosh et al. / Materials Letters 63 (2009) 2100–2102
Fig. 3. TEM images of HA powders (a) dried at 65 °C, (b) calcined at 700 °C, (c) SAED of HA powders calcined at 700 °C.
Fig. 4. FT-IR patterns of HA powders calcined at 700 °C.
to strongly adsorbed and/or bound H2O [14]. H2O bands were also
observed at lesser values of 1650 cm− 1. Similarly OH− was detected at
635 and 595 cm− 1. A strong band of PO3− 4 group was seen at 1037, 967
and 565 cm− 1. The bands obtained for respective phosphate and
hydroxyl groups of pure HA, were in agreement with other published
data [15,16]. A weak band of CO2− 3 was detected in the region around
1465 and 875 cm− 1. The band at 875 cm− 1 indicates n2 mode of CO3
group [14] and it suggests a minor amount of B-type carbonate
substitution i.e. small part of the PO4 (B-type) groups in the apatitic
structure was replaced by CO2−3 . The characteristic bands from inorganic
carbonate ion suggest that carbon gets dissolved in the organics from
atmosphere and does not pyrolyze completely and may instead dissolve
into the HA crystal. This dissolution could be beneficial to the
synthesized HA's bioactivity attributing to the fact that carbonates are
constituents of bone structures [17].
4. Conclusions
In this study, chicken eggshells were used to synthesize nano
hydroxyapatite powder via sol–gel method. The nano HA powder
synthesized at 700 °C by this technique showed prolate spheroidal
morphology. Average HA particle sizes evaluated from XRD, PSD and
TEM observations showed proximate values between 30 and 50 nm.
SAED analysis revealed that the synthesized HA was polycrystalline.
FT-IR studies showed all the characteristic bands of HA and presence
of CO2−
3 bands during calcination at 700 °C. The present study shows
that biowaste egg shells can be effectively utilized for synthesizing
pure nano HA powders.
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