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Procedia Engineering 184 (2017) 442 – 448

The Effect of Sodium Alginate on the Properties of Hydroxyapatite

NanthiniKanasan1, a, Sharifah Adzila1, b, Nor AzimahMustaffa1, Gurubaran, P2

a) nanthini.kanasan@yahoo.com
b) adzila@uthm.edu.my
1
Faculty of Mechanical and Manufacturing, Universiti Tun Hussein Onn Malaysia, Johor, Malaysia
2
School of Mechatronic Engineering, Universiti Malaysia Perlis, Pauh Putra Campus, Arau, Perlis, Malaysia,

Abstract

The aim of this research is to investigate the effect of sodium alginate on the physical, mechanical and morphology of non-sinter
of hydroxyapatite. The ceramic based materials as hydroxyapatite and natural polymer as sodium alginate composite materials
are investigated based on their application of bone implants in biomedical fields. Precipitation method was performed to prepare
HA/SA powder. The hardness and fracture toughness was identified by using Vickers Hardness Test. The density of compacted
powders was increased and attained highest density at 97/3% (HA/SA) about 1.46g/cm3.The Vickers indentation was used to
determine the fracture toughness of brittle materials by measure the crack of the sample due to the ease of sample preparation and
simplicity of this test. The morphology, particle size and distribution of microstructure surfaces were characterized by using a
Field Emission Scanning Electron Microscope (FESEM). The powder characterization is important to identify the crystalline
composition that exists in the mixed powder. Hydroxyapatite (HA)/sodium alginate (SA) are characterized through XRD. The
crystallinity of XRD powder can be identified by testing the lattice parameter that existed in the various parameter.

©©2017
2017Published
The Authors. Published
by Elsevier by Elsevier
Ltd. This is an openLtd.
access article under the CC BY-NC-ND license
Peer-review under responsibility of the organizing committee of the Advances in Material & Processing Technologies
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer review under responsibility of the organizing committee of the Advances in Materials & Processing Technologies Conference
Conference.

Keywords: Hydroxyapatite, Sodium Alginate, Precipitation, Vickers Hardness, Fracture Toughness,XRD

1. INTRODUCTION

Bone tissues engineering promote a better way in regeneration and repair of defects bones. Variety material
has been proposed for used in bone tissues engineering. One of the materials that promote success in bone tissues
engineering are the hydroxyapatite. Hydroxyapatite (HA) are the major component for tooth and bone mineral that
constituent similarity to a composition in hard tissues. The stoichiometry are represented by the formula
Ca10(PO4)6(OH) which consist of calcium and phosphorus with the ratio (Ca/P) of 1.67. Hydroxyapatite (HA) is a
bioactive group that widely used especially in biomedical field for bone implant applications due to its
biocompatibility, non-toxicity and osteoconductivity. This can be prepared as dense ceramic, ceramic coating,
powder and porous ceramic which required for specific applications (Ramli et al., 2011, Sharifah Adzila et al., 2013,

1877-7058 © 2017 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer review under responsibility of the organizing committee of the Advances in Materials & Processing Technologies Conference
doi:10.1016/j.proeng.2017.04.115
 Nanthini Kanasan et al. / Procedia Engineering 184 (2017) 442 – 448 443

Lala et al., 2016, Kantharia et al. 2014). Hydroxyapatite is an inorganic element of bone that widely used due to it
characteristic while, alginate (Alg) is a natural polymer that is synthesis from brown algae and it prefer to be used in
biomedical application due to it characteristic such as biocompatibility, low cost and low toxicity (Ilie et al., 2016).
The application of hydroxyapatite as bioceramic in the biomedical fields such as orthopedic and dental
fields are limited to a load-bearing area due to its characteristic which is brittle and low fracture toughness between
0.8-1.2MPam1/2.Vickers indentation is more prefer to be used to determine the fracture toughness test of brittle
materials such as ceramic. This is due to simplicity, quick and inexpensive of a test. The small sample of materials
can be used to test the fracture toughness and the preparation are easy due to only polished samples are needed to be
clearly seen the diamond shape (C.B.Ponton et al., 1998).
Among the bioceramic group, composites are more prefer to be used due to its characteristic which can
fulfil the mechanical properties required in the biomedical field. The development of composites materials are
important in implants application as their physical and mechanical strength is close to the strength of bone which
exhibits a high fatigue resistance of load such as corrosive resistance and fracture toughness (Orlovskii, Komlev,
and Barinov 2002).The most useful approaches are to enhance the strength and reduce the brittle of HA ceramic is
by adding or mixed with polymer materials to form a composites materials.
Based on this research, calcium phosphate based ceramic-hydroxyapatite (HA) and a natural polymer-
sodium alginate (SA) are employed. The precipitation method was used to prepare the HA and HA/SA to enhance
the densification and hardness of composite materials. Densification behavior is investigated based on the physical
and mechanical properties of composites materials. The physical and mechanical properties are investigated to
improve the composite materials and produce the high strength of bone that can be used in load bearing area for
implants applications.

2. EXPERIMENTAL METHOD

Two precursors used in the preparation of hydroxyapatite/ sodium alginate (HA/SA) were commercially
available HA nanopowder Ca10(PO4)6(OH)2 (99.5%, Emory) and sodium alginate NaC6H7O (Sigma-Aldrich). The
sample ratio were from 100/0%, 99.5/0.5%, 97/3%, 95/5%, 92/8% and 90/10% (HA/SA). The HA powder was used
to mix with distilled water under constant stirring in hot-plate for 2 hours and another 2 hours by pouring the SA
powder. After mixing process, the suspension was left overnight for 24 hours to precipitate the solution. The
precipitate solution was filtered and dried for 24 hours at 80˚C.
The phase existence in the mixed powders is analyzed by using the X-ray diffraction (XRD) (Shimadzu
XRD 6000 diffractometer) under ambient conditions using Cu-Ka (λ= 0.154056nm) as radiation source at current
40mA with voltage 40kV. The spectra of XRD are recorded at 2Ѳ= 10˚ to 80˚ at a scanning speed 1˚/min and step
size at 0.02˚. The XRD peaks that obtained were compared with standard reference Joint Committee of Powder
Diffraction Standards (JCPDS) file for HA. Morphologies of HA and HA/SA composite were observed and
characterized by using Field Emission Scanning Electron Microscope (FESEM). The sample was coated with gold
at 20 milliampere at 60s with 15kV voltage.
The prepared mixed powders were compacted into pellets by using uniaxial pressed in a steel die of 13mm
at about 2.5MPa load at 5 minutes. Density was measured based on Archimedes principle by using distilled water as
an immersion technique. By analysed varies parameter of the sample, the bulk density was measured and recorded
with using Mettler Toledo Densitometer. The surface of samples was grinded and polished before indentation is
performed on the samples at 0.2HV testing loads with an indentation time of 10s. The hardness of samples was
determined by using Vickers hardness under HMV,Shimadzu. The hardness and fracture toughness analyses of HA
and HA/SA composites were carried out by using an optical microscope. The fracture toughness (K IC) of samples
was identified the crack of each sample which has five indentations and the average was measured and recorded.
The indentation of fracture toughness was determined through the Niihara equation.
444 Nanthini Kanasan et al. / Procedia Engineering 184 (2017) 442 – 448

3. RESULTS AND DISCUSSION

3.1 X-Ray Diffraction Analyses (XRD)

The existed of hydroxyapatite (HA) and sodium alginate (SA) composition of crystalline phase are shown in Figure-
1. The peaks and the phase of HA presence in mixed powder are highlighted in Figure-1. The XRD pattern of
powder shows that the material is highly crystalline of HA crystals. All the peaks are matched with the pattern
JCPDS card NO. 9-432 for HA. The peaks of HA exhibit sharp diffraction peaks which indicate the high
crystallinity of the structure and there is no impurity phase. The XRD for all composition were almost similar and
exhibit an increase in crystallinity of HA. HA phase are appears to be stable with no secondary phase peaks
correspond to any calcium phosphate group are observed. There is also no shifted peaks are observed in XRD
analyses.

Fig. 1: XRD pattern of HA/SA powder for pure HA and HA/SA composites

3.2 Densification

Densification at the various composition ratio of pure HA and HA/SA composite samples are shown in Figure-2.
The increase in density leads to decrease in porosity due to the increase in sodium alginate (SA) ratio concentration.
The increase in density leads to increase in hardness up to 95/5% (HA/SA).The compacted powder are attained
maximum density at ratio 97/3% (HA/SA) which about 1.41g/cm3. Beyond at ratio 97/3% (HA/SA), there is the
decrease in density even though with further increase in SA. The maximum density is achieved when there has a
good compact structure between the samples which indicates that the HA has a good bonding with SA molecules.
The increase in density at 97/3% (HA/SA) leads to increase the hardness value. The density is decreased at 95/5%
(HA/SA) ratio are due to the effect of porosity of unsintered samples. The previous study by Rajkumar et al., 2011
said that the increase in density are at 97/3% (HA/SA) and the further increase in sodium alginate composition ratio
will decrease the density due to the effect of a microstructure.
 Nanthini Kanasan et al. / Procedia Engineering 184 (2017) 442 – 448 445

3.3 Micro hardness Study

Figure-3 shows the hardness of sample at various ratio concentration of pure HA and HA/SA. The increase of
hardness for hydroxyapatite (HA) and hydroxyapatite/sodium alginate (HA/SA) are due to the existence of closed
porosity and because of the increase of the particles size of each sample. The hardness of sample is linearly increase
at 100/0%, 99.5/0.5%, 97/3% and 95/5% (HA/SA) with 0.015GPa, 0.017GPa, 0.034GPa and 0.047GPa respectively.
The maximum value of hardness is attained with 95/5% (HA/SA) at about 0.047GPa and the further increase in a
composition of sodium alginate decreased the hardness of composites at 92/8% (HA/SA) with 0.044GPa. Based on
Figure-3, the hardness of HA/SA composites are higher if compared with the pure HA. The decrease of hardness at
92/8% (HA/SA) is due to lack of interfacial bonding between the samples and it is similar to Xie et al., 2010.

1.5

1.4
Relative Density (g/cm³ )

1.3

1.2

1.1

100/0 99.5/0.5 97/3 95/5 92/8 90/10

Ratio Composition (%)

Fig. 2: Density (g/cm²) versus composition ratio of HA/SA

0.05

0.04
Hardness (GPa )

0.03

0.02

0.01
100/0 99.5/0.5 97/3 95/5 92/8 90/10
Ratio Composition (%)

Fig. 3: Hardness (g/cm²) versus composition ratio of HA/SA

446 Nanthini Kanasan et al. / Procedia Engineering 184 (2017) 442 – 448

3.4 Fracture Toughness

The cracks that happen during indentation are measured as fracture toughness. Fracture toughness test was used to
identify the ability of materials to withstand the crack and resist fracture. Usually, it decreased linearly with
porosity. The fracture toughness of ceramic is poor if compared to composites. The fracture toughness of pure
hydroxyapatite (HA) is 0.120MPa.m1/2. The sample shows a maximum fracture toughness at 95/5% (HA/SA) with
0.326MPa.m1/2. There is the initial decrement in the fracture toughness values due to the influence of density and
hardness of samples. Based on Figure-4, the fracture toughness of HA does not reach the value of 1MPa.m1/2 while
the fracture toughness for human bone is 2-12MPa.m1/2. The fracture toughness of the samples are increases with the
decrease of particle size. The previous study by Xie et al., 2010 said that the fracture toughness is dependent on the
bulk density results. The decrease in fracture toughness is due to the increased in density.
Fracture Toughness (MPa.m^1/2)

0.3

0.2

0.1
100/0 99.5/0.5 97/3 95/5 92/8 90/10
Ratio Composition (%)

Fig. 4: The Fracture toughness versus composition ratio

3.5 Microstructure Analysis

Figure-5 shows the shape and particle size of the pure HA and HA/SA samples. The hydroxyapatite particle is fully
distributed in sodium alginate and form an agglomerated surface on it. The HA grains are not clear due to the porous
structure of composite materials. The alginate is porous and it promotes cell proliferation and new bone tissues
growth. The pores are decreased due to the increasing of hydroxyapatite content. The average particles size of
hydroxyapatite is increasing with the sodium alginate content. The addition of alginate in an excessive amount
resulting to particle agglomeration. The uniform mixing process of hydroxyapatite into the sodium alginate are
difficult to achieve due to the characteristic of alginate itself. Wang et al., 2009 said that the alginate content is
adhesive and should not be more than 30 percentage to avoid the agglomerated particles on the HA surface. It
indicates that the precipitation of HA should be mixed with smooth and with low alginate content. The images of
particles are not clear due to unsintered samples and it cannot be easily identified due to agglomerate and the
amorphous phase. The amorphous phase are happened due to the content of alginate in the hydroxyapatite samples.
The increase in alginate contents were resulted to more obscure areas and this tend to affect the images of particle in
FESEM. The crosslink of alginate and hydroxyapatite were happen due to the interaction of Ca 2+ with the carboxyl
groups of G units in the polymer. Lin and Yeah, 2004, said that alginate will effects the growth of hydroxyapatite by
the interaction of Ca2+ and carboxyl groups. The microstructure of FESEM shows that pure HA are exhibit loose and
discrete particle with irregular shapes and size. The composite microstructure of 97/3% and 95/5% (HA/SA) tends
to be more homogeneous and compact with
 Nanthini Kanasan et al. / Procedia Engineering 184 (2017) 442 – 448 447

the increase of sodium alginate composition if compared with the pure HA. It is similar to the Rajkumar et al., 2011,
said that the composites structure are more compact with the increase in sodium alginate composition which
resulting to increase the bonding between particles and decrease the porosity of the samples. In this experiment, the
particles aggregated irregularly for 92/8% and 90/10% due to further increase in SA ratio and it can be proved in
FESEM result. The EDS confirmed the presence of hydroxyapatite and sodium in the unsintered samples. EDS
analyses are cleared shown the existence of Ca, P and O in the HA samples while Ca,P,O and Na in HA/SA
samples. Hydroxyapatite particle cannot be identified individually due to fully covered by SA polymer surface
which resulting to complete composite structure. The composite microstructure occurs due to the interaction of Ca 2+
of HA and COO- of SA and it identified by FESEM analysis.

Fig. 5: FESEM of HA and HA/SA at various composition ratio

448 Nanthini Kanasan et al. / Procedia Engineering 184 (2017) 442 – 448

4. CONCLUSIONS

HA/SA composites powder with different composition ratio were mixed by using precipitation method. The effect
of SA on the crystallinity, microstructure, densification and mechanical properties of HA of compacted powder was
studied. XRD analysis shows that the crystallinity of composite change with the composition of hydroxyapatite.
Further characterization is studied in terms of microstructure, particle sizes, and shape by using FESEM. The
microstructure analysis shows that the HA are fully distributed into the sodium alginate and it forms the irregular
shape between each particle. The ceramic-polymer composites materials have faced some problem such as
aggregation of the ceramic particle due to lack of bonding strength. The mixing in precipitation method is very
important because it influences the physical and mechanical properties due to agglomeration of ceramic-polymer
composite materials. The agglomeration of materials happens due to difficulty in intermixing between the
hydrophilic ceramic and hydrophobic polymer suspension. The maximum density ratio of 97/3% (HA/SA) is about
1.41g/cm3 and the maximum hardness was achieved by 95/5% (HA/SA) at 0.047GPa.The interaction between the
chemical are due to bonding of Ca2+ and carboxyl group of alginate that makes the microstructure of HA/SA are
more compact. It can be concluded that the composites are more compact and it influences the increasing of sodium
alginate content in HA structure.

Acknowledgements

This study was supported under the Contract Grant Vot number U562. The authors gratefully acknowledge the
Office for Research, Innovation, Commercialization and Consultancy Management (ORICC), Universiti Tun
Hussein Onn Malaysia and Centre Graduate of Study (UTHM).

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