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Materials Letters
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Producing hydroxyapatite from sh bones by heat treatment

B. Ratna Sunila, , M. Jagannathamb
a
Department of Mechanical Engineering, Rajiv Gandhi University of Knowledge Technologies (AP-IIIT), Nuzvid 521202, India
b
Department of Metallurgical and Materials Engineering, Indian Institute of Technology Madras, Chennai 600036, India

AR TIC LE I NF O A B S T R A C T

Keywords: Hydroxyapatite Biomaterials Fish bones Bioceramics Ceramics
The present work demonstrates a low cost route to produce hydroxyapatite (HA)
from sh bones (natural source) by a simple heat treatment process. The produced
HA was characterized by X-ray diraction (XRD),
scanning electron microscopy and transmission electron microscopy (TEM).
Elemental composition obtained from energy dispersive X-ray analysis conrmed
the presence of Ca, P, O and Mg. XRD analysis has clearly
shown that the produced phase as HA. The powders were heated from 600 to 1000
C and from the TEM
observations, large fused crystals (200 nm) were noticed. XRD analysis of the heat
treated powders have also not shown new phases and which is an indication of the
purity level of HA.

1. Introduction
Hydroxyapatite (HA) is a well known bioceramic material which is widely used as a
biomaterial in many biomedical applications. HA is acalcium phosphate mineral phase
that can be found in natural bone. Afew synthesizing routes have been developed to
produce HA asreported in the literature. Precipitation, microwave irradiation,
ultrasound irradiation, sol-gel, electrodeposition, hydrothermal process and spray
pyrolysis methods are a few examples. A few routes have been also reported in the
literature indeveloping HA by natural sources such as sea corals, egg shells,sh bones
and sh scales. Presence of additional ions such asmagnesium, zinc, strontium etc. is
the advantage with naturally derived HA. Producing HA from sh bones is a low-cost
process which also yields pure HA as per the earlier reports. Ozawa and Suzuki
reported the production of HA from sh bone waste (Japanese sea bream) by heating Figure 2 XRD Pattern of HA Powders after Heat Treatment at Different Temperature
(6001300 C) and observed that the powder contains hydroxyapatite phase in major
fraction. Boutinguiza et al. have successfully produced microHA and nanoHA from
sh bones (Xiphias gladius called as sword sh and Thunnus thynnus called as tuna
sh). The present work demonstrates producing HA from Sheelavati sh (known as
roho labio sh, a cheap sh widely available in south Indian rivers) by a simple heat
treatment process.

2. Experimental details
Sheelavati (roho labio) sh was obtained from Krishna river which is geographically
located at south east of India. The bones of the sh were collected and boiled at 100C
after carefully removing the skeletal esh from the bones. Then the bones were dried
in hot air oven. Fig. 1 (a) shows the photograph of the bones. The dried bones were
cut intosmall pieces and were placed in a glass container. Then heat treatment was
carried out as per the cycle shown in Fig. 1(b).The heat treatment was carried out at
dierent temperatures suchas 600, 700, 800, 900 and 1000 C. The HA powders were
collected at these temperatures and used for dierent characterizations. The powders Figure 3 SEM images and EDS Analysis of HA Powders Heat Treatment at a) 600oC,
were characterized using X-ray diraction (XRD) using CuKa radiation. Scanning b)Corresponding EDS Spectra, c)800oC and d) 1000oC
was done between 20 and 80 with 0.1 step size. Then the unit cell parameters were
calculated by using software (UnitCell, UK). Scanning electron microscopy (SEM,
Quanta 200,Netherlands, Operating voltage 30 kV) attached with energy
dispersivespectroscopy (EDS) was carried out to analyze the powders. The powders
were ultrasonically dispersed in ethanol and a drop of the HA containing ethanol was
placed on the carbon coated Cu grid and then transmission electron microscopy
(TEM, Tecnai G2) was carried out at 200 kV operated voltage. Selected area electron
diraction (SAED) patterns were also obtained for the powders.

3. Result and Discussion

Figure 4 TEM Observations of the HA Powders: a) 600oC b) Corresponding SAED

Pattern, c) 800oC, and 1000oC
4. Conclusion
Pure hydroxyapatite (HA) was produced by using Sheelavati (roho labio) sh through
a simple heat treatment process. The produced HA was stable up to 1000 C which is
a characteristic of pure HA with Ca/P ratio not less than 1.67. SEM observations
conrmed the composition of the powder along with presence of Mg ions. The size of
the HA crystal was measured as submicrometer level from TEM observations. Hence
from the results, it can be concluded that the HA can be economically produced from
Sheelavati (roho labio) sh bones by a simple heat treatment process for wide range
biomedical applications.
Figure 1 a) Photograph of the fish bones and b) Heat treatment cycle up to 600oC By: ONIL ANDIKA