CHARACTERIZATION OF BIOCOMPOSITES OF

SHEEP HYDROXYAPATITE (SHA)/SHELLAC/SUGAR

AS BONE FILLER MATERIAL
Triyono, J., Yushak, R., Triyono, T.,
Mechanical Engineering Department, Faculty of Engineering, Universitas Sebelas Maret
Jl. Ir. Sutami 36A, Kentingan, Surakarta, 57126, Central Java, Indonesia
Email: jokotri5528@gmail.com

Abstract. The use of biomaterials in orthopedics is increasing. This led to growth of new innovations in the field of
medicine, one of them is development of biomaterials. Study of Sheep Hidroxyapatite (SHA)/shellac/sugar
biocomposite characterization was to determine the phase of material, porosity, hardness and compressive strength of
them. This research was conducted to develop new types of biomaterials that can be used as bone filler material.
Analysis that used in this research was dry methods. The results showed that observation of XRD (X-Ray Diffraction)
shows the pattern of diffraction 2θ: 31.6472°, 32.7753°, 32.0723°, microvickers samples SHA/shellac/sugar to a
maximum of 7:38 ± 0.1395 VHN and a minimum of 4.91 ± 0:37 VHN, testing a sample DTS SHA/ shellac/sugar to a
maximum of 5:43 ± 1.395 ± 2.62 MPa and 0162 MPa minimum. SEM observations of a sample with
SHA/shellac/sugar porosity many contained in the sample SHA/shellac/sugar 60:40 % and 70: 30 % wt.

INTRODUCTION
The use of biomaterials in the field of health especially orthopedics continues to increase along with the
increase of various cases and bone diseases (Gunawarman et al, 2010). Biomaterial is the main constituent of
inorganic component of bone (Herdianto et al, 2011). One of the constituents of biomaterials is hydroxyapatite.
Hydroxyapatite (HA, Ca10(PO4)6(OH)2) is a natural inorganic element of bone that can be utilized for bone
regeneration and reconstruct bone tissue. These biomaterials have structures similar to human bones that can be
used as substitutes for damaged human bones.
As a ceramics materials, HA has a poor mechanical properties, that it why it is used in non-load bearing
application. A pure mineral bone has been developed, removing all organic components of bovine bone and
sintering remnant mineral constitution by high-temperature heat-treatment (Triyono et al, 2014)
Biowaste, such as bovine bone in Indonesia is glutted availability and it can be used for source of
hydroxyapatite (HA) which is profoundly useful for biomedical applications, economical and eco-friendly. HA
material can be derived from natural sources that can form a strong bond with bone tissue. Components of bovine
bone are 93% hydroxyapatite. (Rahmawati et al, 2012). Application of HA-sized particles for damage bone and
teeth repairing are very promising potential.
Multiple methods have been used for preparation of hydroxyapatite powder, as reviewed in several
works. Two main methods for preparation of hydroxyapatite powders are wet methods and solid state reactions
(Pujiyanto et al, 2014)
The purpose of this research is to know the diffraction pattern of sheep hydroxyapatite (SHA) using X-
Ray Diffraction and density (XRD), hardness, compression and density of materials. Observation of
microstructure was done by Scanning Electronic Microscope (SEM).

MATERIALS AND METHODS

Sheep bone powder 45 μm was calcined at 900°C to obtain pure shellac hydroxyapatite (SHA) materials.
Furthermore, SHA was coated by shellac by means of SHA was immersed in a shellac solution and deposited for
24 hours. Shellac coated SHA then were mixed sugar with ratio of HA : sugar were 70:30, 60:40 and 50:50 (%wt).
It was used control material (shellac coated HA only without sugar). Materials were then sintered at 900°C, heating
rate 10oC/minutes and holding time for 2 hours. Each of ratio has 5 specimens, so the total of specimens were 20
pcs. Biocomposites of SHA/shellac/sugar powder were then poured into mold Ø 13mm thick 3mm and compacted
60 Bar. After those processes, specimens were conducted to XRD and SEM observation, hardness test,
compressive strength test, and density test.
Result and Discussion
a. Pattern of XRD
Fig. 1 (a and b) showed the XRD test results of SHA/shellac and SHA/shellac/sugar

Fig 1 a) XRD pattern of SHA/Shellac

Fig 1 b) XRD pattern of SHA/Shellac/sugar

The objective of X-Ray Diffraction (XRD) observation of SHA/shellac/sugar biocomposite was to

identify crystalline phase in biocomposite material by determining lattice structure parameters for particle size.
XRD observations with 40kV, 30mA, and Cu 1.54060 A. Figures 1 a) and b) show the shape of XRD diffraction
patterns. The diffraction pattern between SHA/shellac and SHA/shellac/sugar which have diffraction pattern is
almost same, so it can be said that SHA shellac and SHA/shellac/sugar have become hydroxyapatite (HA) with
value 2θ: 31.760º, 32.900º, 32.160º (Herliansyah et al, 2009).

b. Vickers Hardness Testing

The results of hardness test of SHA/shellac/sugar tablets 50:50, 60:40, 70:30, and SHA/shellac (as
control) are shown in Figure 2 below.

9
7,38
8
7
Vickers Hardness

5,32
6 4,91
(VHN)

5
4 3,1
3
2
1
0
CONTROL 50:50 60:40 70:30
Ratio of mixing shellac coated SHA/sugar
(%Wt)
Figure 2. Hardness microvickers of SHA/shellac/sugar after calcination.

Figure 2 shows the relationship between a percentage of SHA and hardness of specimen. From Figure 2
 It can be explained that the greater percentage of HA will increase the hardness of material. The hardness of
SHA/shellac/sugar sample was lowest on the SHA/shellac/sugar 50:50 mixture variation ie 4.91±0.37 VHN.
The hardness of 70:30 %wt was the highest of 7.38±0.1395 VHN. The hardness of the control specimen was
lower than the lowest one. Hardness increases with the percentage of HA. In other words, the increased
hardness was proportional to the less percentage of the amount of sugar as a porogenizer. This was in
accordance with Chen et al. (2008) which stated that the specimen hardness increases with the percentage of
HA composition.
Higher of heating temperatures affected microstructural shape, surface of the sample and cause higher
hardness (Kurniawan et al, 2014). Other factors affected hardness were composition of specimen,
compaction pressure (Amin and Irawan, 2008) and composition of porogenic materials. The porogenic
material causes density of material to increase.

c. Compressive Strength
The Diametral Tensile Strength (DTS) test was performed after calcination at 900ºC using a
Universal Testing Machine (JTM Technology Machine, 0.5T Capacity) with 50kg load and loading rate
5mm/min. The variation sample of test were 50:50, 60:40, 70:30 and SHA/shellac (as a control). Specimens
shaped tablets. The test results are shown in Figure 3 below.

8 5,43
7
Compresson Strength

6
3,38
5
(MPa)

3,10
4
3
2
0,56
1
0
Control 50/50 60/40 70/30
Shellac coated HA/sugar
(% Wt)

Figure 3. Compressive Strength of SHA/shellac/sugar after calcination.

Figure 3 shows the relationship between shellac coated SHA/sugar against the compressive strength
of the material. It could be seen in Figure 3 that the greater percentage of HA would cause increased
compressive strength. The lowest compressive strength in 50/50 ratio was 3.10±0.37 MPa. The highest
compressive strength in 70/30 ratio was 5.53±1.395 MPa. The compressive strength of the control material
was 0.56 MPa. This value was lower than the lowest compressive strength. Increasing of compressive
strength was proportional directly to the percentage of HA. In other words, increasing in compressive
strength was inversely proportional to the percentage of sugar. The less sugar amount caused the porosity
that occurs also slightly and cause the increased compressive strength. This was accordance with Chen et al
(2008) which stated that compressive strength of the specimen increases with the increasing percentage of
HA composition.

d. Density Test
Density testing was done to find out the comparison between actual density and theoretical density
(rule of mixture). Density test result was used to predict the various phenomena that occured, such as
predicting the strength of the material. Figure 4 shows the actual density value of SHA/shellac/sugar.
 1,600
1,400
1,200
1,000

Densty
0,800
0,600
0,400
0,200
0,000
Control 50/50 60/40 70/30

Actual Density Theoritically Density

Figure 4 Actual density of SHA/shellac/sugar

Figure 4 shows the actual density increase for all ratios. The actual sample density was 50:50; 60:40
and 70:30 have a mean value of 1.021 gr/cm3, 1.116 gr/cm3 and 1.202 gr/cm3 respectively. Theoretically
density values of samples were 50:50; 60:40 and 70:30 have an average value of 1.076 gr/cm3, 1.291 gr/cm3,
and 1.506 gr/cm3 respectively. The actual density of the control sample had a value of 1.304 gr/cm3. The
density value of the theoretical control was 1,423 gr/cm3. The actual density value of SHA/shellac and sugar
sample was influenced by the percentage of its constituent elements. This was accordance by research which
stated that the increasing %wt HA, the density value increases (Khalil, 2012).

e. Porosity of Sheep Hydroxyapatite (SHA)/Shellac/Sugar

Porosity testing was used to calculate the empty gap/cavity containing air or gas. Porosity value was
derived from the actual and theoretical density calculations. The porosity value of SHA/shellac/sugar was
shown in Figure 5.

1,000

0,950
Porosity

0,900

0,850

0,800

0,750

0,700
Control 50/50 60/40 70/30

Figure 5 Porosity of SHA/shellac/sugar

Figure 5 shows the relationship between variation of material mixture against porosity. The porosity
of 50:50, 60:40 and 70:30 have the average of 0.949%, 0.865% and 0.798% respectively. The less
percentage of sugar caused the resulting porosity to be less. Porosity was due to the difference in melting
temperature of each constituent material. Sugar and shellac have melting temperatures of 186°C
(Drebushchak, 2006) and 105°C (Tontowi, 2012) respectively. The melting temperature of sugar and shellac
was lower than the melting temperature of HA 1670°C. This was accordance by research which stated that
the porosity value of HA-zirconia decreases with increasing wt% zirconia, while the value of compressive
strength was increasing (Pujiyanto et al, 2015).
f. SEM observations
Figure 6-8 shows the observation of SHA/shellac/sugar material at various ratios.

porosity

aglomeration

Figure 6 Photo SEM SHA/shellac/sugar 50:50

porosity

aglomeration

Figure 7 Photo SEM SHA/shellac/sugar 60:40

porosity
s

aglomeration

Figure 8 Photo SEM SHA/shellac/sugar 70:30

Figure 6-8 shows the porosity and agglomeration that occured in specimen. Specimen with a ratio of
50:50 indicated there was regularly porosity (Figure 6). In Figures 7 and 8 it could be seen there were irregularly
porosity. The formation of porosity were caused by the particles of the filler material in the biocomposites
(Triyono et al, 2015). The results of the test were shown in Figures 6-8 were relevant to results of previous research
stated that at higher temperatures the powder particles have fused and formed larger HA agglomeration and have
a rough microstructure (Teh et al, 2014).
CONCLUSION
1. The X-Ray Diffraction (XRD) observation shows that SHA/shellac/sugar as the purity phase of
hydroxyapatite (HA). The 2θ value for the HA compound corresponds to the standard diffraction pattern.
2. The highest hardness of SHA/shellac/sugar was 7.38±0.1395 VHN (70:30). Then the hardness of SHA/
shellac/lowest sugar was 4.91±0.37 VHN (50:50).
3. The strongest value of SHA/shellac/sugar press was 5.43±1.395 MPa (70:30), then the SHA/shellac/lowest
sugar compressive strength was 2.62 ± 0.162 MPa (50:50).
4. SEM observations were made on SHA/shellac/sugar samples of 50:50, 60:40, 70:30 %Wt. In
SHA/shellac/sugar samples 50:50 %wt HA clumps were irregular, uneven, and the enlarged porous shape,
indicated by 100x magnification. At high temperatures, the powder particles have fused and formed larger
HA clumps and have a rough microstructure.
5. The amount of %wt of sugar as a porous fabric affects the value of hardness, compressive strength, and
porosity.

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