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International Conference on Chemistry and Material Science (IC2MS) 2017 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 299 (2018) 012039 doi:10.1088/1757-899X/299/1/012039
1234567890‘’“”

Synthesis and Characterization of Hydroxyapatite Powder

by Wet Precipitation Method
S. E Cahyaningrum1, N. Herdyastuty1, B. Devina1 and D. Supangat1
1
Department of Chemistry, Faculty Mathematics and Natural Science
Universitas Negeri Surabaya

Email: [email protected]
Abstract. Hydroxyapatite is main inorganic component of the bone with formula
Ca10(PO4)6(OH)2. Hydroxyapatite can be used as substituted bone biomaterial because
biocompatible, non toxic, and osteoconductive. In this study, hydroxyapatite is synthesized
using wet precipitation method from egg shell. The product was sintered at different
temperatures of 800°C to 1000°C to improve its crystallinity. The hydroxyapatite was
characterized by X-ray analysis, Scanning Electron Microscopy (SEM) and Fourier Transform
Infrared Spectroscopy (FTIR) to reveal its phase content, morphology and types of bond
present within it. The analytical results showed hydroxyapatite had range in crystallinity from
85.527 to 98.753%. The analytical functional groups showed that presence of functional
groups such as OH, (PO4)32-, and CO32- that indicated as hydroxyapatite. The result of
characterization SEM indicated that hydroxyapatite without sintering and HAp sintering at 800
o
C were irregular shape without pore. The best hydroxyapatite with temperature sintering at
900 oC showed oval shaped with pores without agglomerated.

1. Introduction
Hidroxyapatite is one of bioceramic was used as materials making of filler bone and theet [1]. Filler
Bone of hidroxyiapatite can occupy by bone network because hidroxiapatite have looking like with
bone composition. Hidroxyapatite have high biocompatibility and also have the character of
osteoconduktive that is can stimulate growth of bone. Chemical formula of HAp is Ca10(PO4)6(OH)2
with ratio of molar Ca/P 1.67 [2]. Hydroxiapaptite has characteristic pore, bioactive, biocompatible,
and osteoconductive [3-4]. Making of HAp can use the source of natural and synthetic calcium [5].
Source of synthetic calcium which is generally used for the synthesis of HAp is CaO, Ca(NO3)2,
Ca(OH)2, CaCO3 and CaCl2 [6-7]. Source of natural calcium which used for the synthesis of HAp
generally have high calcium rate among others, coral [8], seashell [9], eggshell [10] and also limestone
[3].
At this research, source of calcium which is used in HAp synthesis is eggshell. Exploiting of egg in
society still limited for food, by exploiting its just flesh while egg shells are thrown. The waste of egg
shell can contaminate of land, water ground and air. Waste of egg shell contain of calcium compound
(CaCO3) which is high enough, that is around 53-78% from weight of crab shell dry. This calcium rate
height can be used as materials of HAp. With content of CaCO3 big, eggshell can be used as CaO
precursor by calcinated at temperature 1000oC. The aim of calcinations is to eliminate carbonate ion
able to bother process of sythesis. HAp can be synthesed with few methods, among others,
hydrothermal [11-12], sole gel [13-14], dry method [15] and wet precipitation method [5]. Sythesis
HAp with wet precipitation method have many excellence, the side product only water, and possibility
of contamination during processing is very low, so that in course of HAp yield is perity high level
enough[16], moreover expense of which released is cheap relative. Other advantage of wet
precipitation method is the reaction easy and do not contaminate environment.

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International Conference on Chemistry and Material Science (IC2MS) 2017 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 299 (2018) 012039 doi:10.1088/1757-899X/299/1/012039
1234567890‘’“”

2. Material and methods

2.1 Synthesis Hidroxiapatite
Eggshells of duck were collected and cleaned from impurities in their surface, after that the egg shells
of duck were calcinated at 900 oC to produce calcium oxide. Synthesis hidroxyapatite was done by
reacting calcium precursor and phosphate with comparison of concentration of molar Ca/P 1.67.
Solution of Ca(OH)2 0.5 M was added by phosphoric acid 0.3 M with wise drop methods later then
trap closed chemical glass to use alumunium foil to produced suspension. The suspension was added
with NaOH 1 M until pH 10. The solution was aging over night to produce HAp powder. The HAp
powder was cleaned with aquademin until neutral, and then was added with HNO3 6 M and sintering
in furnace with variation temperature are 800, 900 and 1000 oC for 2 hours. The crystal HAp was
storaged in furnace until cold and is weighed with analitycal balance until constant in mass. The HAp
crystal was characterized with some instrument. The phase composition of the HAp crystal was
studied by X-ray diffractometry. The functional group was studied with Fourier transform infrared
spectroscopy (FTIR) and scanning electron microscopy (SEM) to examined the surface of
morphological characteristics.

3. Results and Discussion

CaO was produced from calcination eggshell of duck that reacted with H2O to produce Ca(OH)2
solution as equation:
CaO (s) + H2O (l) → Ca(OH)2 (aq) …(1)
The Ca(OH)2 was added with H3PO4 solution with wise drop methods at 60 oC until pH 7. Synthesis
of HAp under 60 oC produce amorf structure, so that the synthesis of Hap must be done at 60 oC
(Wang, 2010). Hap that produce in this research was characterized with some intrumentations
Analysis crystalinity with XRD was showed in picture 1.

Figure 1. X-ray diffraction patterns of hydroxyapatite synthesized HAp-TS;

HAp 800; HAp 900 and HAp 1000

Figure 1 shows X-ray diffraction of HAp-TS, HAp-800, HAp-900, and HAp-1000. At HAp-TS
sampel have 2θ = 32.045o; 32.272o; and 33.116o. HAp-800 has highest top at 2θ= 31.810o; 32.197o;
and 32.949o; HAp-900 have highest top at 2θ= 31.792o; 32.197o; and 32.933o. HAp-1000 have highest
top at 31.811o; 32.214o; and 32.951o. Highest top of HAp-TS represent highest top of carbonate apatite

2
International Conference on Chemistry and Material Science (IC2MS) 2017 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 299 (2018) 012039 doi:10.1088/1757-899X/299/1/012039
1234567890‘’“”

matching with JCPDS no. 35-0180 that property of type carbonate apatite of A (AKA) and of JCPDS
no. 19-0272 that property of type carbonate apatite of B (AKB). Highest topat HAp-800, HAp-900,
and HAp-1000 represent highest top of HAp matching with JCPDS no. 09-0432 that property of HAp.

Table 1. Composition of HAp.

Apatite
HAp Tetracalcium ciclo Decaphospate 16
Sample carbonate
(% b/b) Hydrate (% b/b)
(% b/b)
HAp-TS 50.4 49.6 -
HAp-800 72.0 28.0 -
HAp-900 82.7 17.3 -
HAp-1000 99.1 0.9 -

Table 1 shows that increase of temperature of sintering, perity of HAP carbonate apatite
composition and excelsior smaller. Composition of HAp at HAp-TS, HAp-800, HAp-900, and HAp-
1000 are 50.4; 72.00; 82.70; and 99. 10% b/b. HAp owning highest perity that is HAp-1000, if
compared to HAp-TS show composition which look like that is with difference 0.7 %b/b. At HAp TS
there are carbonate apatite phase is bigger. According to ISO-13779:2008, HAp as implant have
minimize 50% b/b HAP fase. Pursuant to quantitative analysis of XRD, all HAp are without and with
treatment of sintering have larger one mass from 50 % w/w.

Figure 2 FTIR spectra of HAp –TS; HAp- 800; HAp- 900 and HAp-1000

The results of FTIR spectra in different sintering temperatures are shown in the Fig 2. This spectrum
(Figure 2) that informs about the hydroxyl (OH) functional group by absorption band at 600, 700, 800
and 900°C, respectively at around 3400-3571 cm-1. FTIR spectra showed that absorption from the PO4
3- on 1150 – 1000 cm–1 and known as the characteristics of bands for hydroxyapatite. The absorption
bands of functional groups are presence at around 1069, 1011, 1043, and 1016 cm-1. The phosphate
functional (PO43-) at HAp with stretching vibrasi there are at1000 - 1150 medium and at 960 cm-1 and
also bending vibrasi perceived at 560 - 610 cm-1. The identifying the existence of carbonate in crystal
perceived from FTIR spectra for the sampel of HAp and carbonate apatite.

3
International Conference on Chemistry and Material Science (IC2MS) 2017 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 299 (2018) 012039 doi:10.1088/1757-899X/299/1/012039
1234567890‘’“”

Table 2 Crystalinity of HAp

Fraction Crystalinity
Sample  (rad)
Amorf Crystal (%)
HAp-TS 0.033 2.970 19.074 86.527
HAp-8 0.022 1.760 52.800 96.774
HAp-9 0.019 1.140 57.570 98.058
HAp-10 0.017 1.020 80.750 98.753

Crystalinity HAp-TS, HAp-800, HAp-900, HAp-1000 respectively that are 86.527; 96.774;
98.058; and 98.753%. The smallest crystalinity is HAp-TS. The so small HAp-TS crystalinity for
no process sintering at sample. At HAp which was not sintering, slimmer particles are atom formation
and crystal more is not regular compared to HAp which is sintering.

(A) (B)

(C) (D)
Figure 3 SEM images of hydroxyapatite: HAp-TS (A), HAp-800 (B), HAp-900, (C), HAp-
1000 (D), 5000x.
The surface morphology of the HAp crystal was investigated by SEM. The result of characterization
SEM indicated that hydroxyapatite without sintering and HAp sintering at 800 oC were irregular shape
without pore. The best hydroxyapatite with temperature sintering at 900 oC showed oval shaped with
pores without agglomerated. Crystal size measure of HAp as implant have to span certain so that
earning application as implant. Smallest size measure of application able to reside in at scale of nano
(Chandrasekar, al et 2013). Biggest size measure according to standard of HAp-Bank Tissu RS Dokter
Sutomo, Surabaya that is size measure 1193.48 m.
4. Conclusion
The results of this research hydroxyapatite can be synthesised from eggshell of duck with wet
precipitation methods. Temperature of sintering has effect in degree and phase crytalination of HAp.

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International Conference on Chemistry and Material Science (IC2MS) 2017 IOP Publishing
IOP Conf. Series: Materials Science and Engineering 299 (2018) 012039 doi:10.1088/1757-899X/299/1/012039
1234567890‘’“”

The FTIR spectra analysis showed that HAp have some functional group there are –OH, -(PO4)32-,
dan -CO32-. Analysis with SEM morphology showed that hidroxypatite in the form of block with
spread over pore to flatten.

Acknowledgment
The researcher wish thanks to DRPM DIKTI for support this research with Hibah Penelitian Berbasis
Kompetensi Program 2017 No. Contract: 0001.88/UN38.11-P/LT/2017
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