Materials Today Sustainability 17 (2022) 100100

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Materials Today Sustainability

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materials-today-sustainability

Behavior of sintered body properties of hydroxyapatite ceramics:

effect of uniaxial pressure on green body fabrication
Ade Indra a, *, Arya Buana Putra a, Nofriady Handra a, Hendriwan Fahmi a, Nurzal a,
Asfarizal a, Mastariyanto Perdana a, Anrinal a, Adi Subardi b, Jon Affi c, Gunawarman c
a
Mechanical Engineering Department, Engineering Faculty, Institut Teknologi Padang, Kp Olo 25143 Padang, West Sumatera, Indonesia
b
Mechanical Engineering Department, Institut Teknologi Nasional Yogyakarta, Sleman 55281, Daerah Istimewa, Yogyakarta, Indonesia
c
Mechanical Engineering Department, Engineering Faculty, Universitas Andalas, Limau Manis 25166 Padang, West Sumatera, Indonesia

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

Article history: Hydroxyapatite (HA) sintered bodies have been made through the pressureless sintering method. Uni-
Received 19 July 2021 axial compaction pressure was varied from 10 to 190 MPa to obtain the optimum pressure required for
Received in revised form manufacturing green bodies. Before the process of making green bodies, HA powder was added with
31 October 2021
10 wt% polyvinyl alcohol (PVA) as a binder. The preheating process was carried out at a temperature of
Accepted 20 December 2021
Available online 24 December 2021
700
C with a holding time of 1 h to remove PVA, followed by the process of sintering at a temperature of
1200
C with a holding time of 2 h in the air environment. The properties of HA sintered bodies were
studied by characterizing their microstructure and phase and determining their linear shrinkage, density,
Keywords:
Hydroxyapatite ceramics
relative density, and Vickers hardness. The results showed that tangential contact had occurred between
Pressureless sintering the particles at a uniaxial compaction pressure of 40 MPa, as evidenced by good grain bonding found in
Physical properties the sintered bodies. It was found that uniaxial pressures of 130e190 MPa generated grain bonding more
Mechanical properties perfectly and hardness values that meet the standards for HA sintered bodies. The strengthening
mechanism is modeled by illustration as imperfect tangential contact and perfect tangential contact
between the powders on the green body.
© 2021 Elsevier Ltd. All rights reserved.

1. Introduction other one's particles, resulting in a significant increase in the values

Hydroxyapatite (HA), known chemically as Ca10(PO4)6(OH)2, is
one of the non-toxic bioceramics that has biocompatibility and
similarity in composition with human bones [1e10]. Besides having
advantages, HA has poor mechanical properties such as low values
of hardness and fracture toughness and is brittle [11e16].
Many studies have been conducted to improve HA mechanical
properties, such as making HA composites with strengthening
materials. Some studies reported that HA, strengthened by ZrO2,
alumina, and bioactive glass (BG), separately, experienced an in-
crease in the values of compressive strength and hardness values
[17], relative density and hardness [18], and compressive strength
and hardness [19], respectively. A recent study on a mixture of
micron- and nano-sized HA powders showed a significant increase
in the values of relative density and compressive strength owing to
the filling of the micron-sized powder into the gaps between the
* Corresponding author.
E-mail address: adeindra@itp.ac.id (A. Indra).
of relative density and compressive strength [20].
Besides, the addition of binders when making green bodies can
improve the mechanical properties because it can create robust
tangential bonds between powders [21]. We have previously
reported that the addition of 2.5e10 wt% PVA can increase the
tangential bond between powders, as evidenced by the significant
increase in hardness value from 4.4 to 6.0 GPa with the addition of
5 wt% PVA [21].
Determining an optimum temperature of the sintering process is
also an attempt to improve HA mechanical properties. Many studies
have reported the effect of sintering temperature on titanium/
carbonated HA nano biocomposites [22], naturally derived HA [23],
the effect of sintering temperature on nano-sized HA [24], and the
effect of sintering temperature on HA-alumina composites [25].
The pressure used in making green bodies is another factor that
also influences the properties of HA sintered bodies. Some studies
reported that pellet-shaped HA was made with uniaxial pressing at
a pressure of 216 MPa [26], HA-titanium oxide biocomposites were
made in the form of pellets with the uniaxial pressing method at a

https://doi.org/10.1016/j.mtsust.2021.100100
2589-2347/© 2021 Elsevier Ltd. All rights reserved.
A. Indra, A.B. Putra, N. Handra et al.
pressure of 40 MPa [27], and HA/sodium alginate biocomposites
were made with uniaxial pressing at 19.9 MPa [28]. Another study
addressed the effect of HA and Ag, Ta2O5, or CeO2 addition on the
properties of ultrafine-grained Ti31Mo alloy at a uniaxial pressing
of 600 MPa [29]. From these studies, differences were found in the
use of uniaxial pressure values that had triggered doubts among
researchers to determine the exact value of uniaxial pressure when
making green bodies.
In this study, we made HA sintered bodies with the pressureless
sintering method. Green bodies were produced with a variation of
uniaxial pressure to determine the exact or optimum value of
uniaxial pressure.
2. Materials and method
2.1. Materials
Analytical commercial HA with a powder size of 2.5 ± 0.5 mm
(product of Sigma-Aldrich Co., USA) was used as the main material
in this study. Polyvinyl alcohol (PVA) obtained from Jaya Kimia,
Indonesia, was used as a binder. Pure water was used for the entire
experimental process (product of Brataco, Indonesia). All materials
were used directly without any preliminary treatment.
2.2. Method
2.2.1. Powder characterization
X-ray diffraction (XRD) test (XRD-PANalytical, Type PW3040/
60, the Netherlands) was carried out to characterize the crys-
talline phase of HA powder. The working conditions of XRD were
set with Cu anode at 40 kV and 30 mA and time scanning at the
step of 7.14 s. The results of the XRD test on HA powders were
then compared qualitatively with the International Center
Diffraction Data (ICDD). The form of HA powder was observed
using a scanning electron microscope (S3400N Hitachi, Japan),
and the powder size distribution was analyzed using ImageJ
software and a histogram.
2.2.2. Sample preparation
Before manufacturing green bodies, HA powder sized 2.5 mm was
mixed with 10 wt% liquid PVA homogeneously for 1 h using a rotary
mixer (PM-ME-LabITP: diameter ¼ 40 mm, length ¼ 55 mm). Green
bodies were made by using the uniaxial pressing method with a
variation of pressure of 10, 40, 70, 100, 130, 160, and 190 MPa, using a
stainless steel mold with a diameter of 8 mm. The sintering process
was done by a preheating temperature of 700
C with a holding time
of 1 h to remove PVA, continued by a sintering temperature of
1200
C with a holding time of 2 h (using Ceramic Fiber Muffle
Furnace B-ONE). The illustration of sample preparation can be seen
in Fig. 1.
Fig. 1. Illustration of sample preparation.
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Materials Today Sustainability 17 (2022) 100100
2.2.3. Characterization of the sintered body
Characterization of the properties of HA sintered bodies was
performed to determine the optimal uniaxial pressure in making
HA green bodies. It involved several tests, including linear
shrinkage test, density test, XRD, microstructural observation, and
micro-hardness. The linear shrinkage test was done by comparing
data before and after the sintering process, involving those of
diameter, weight, and thickness shrinkages. The Archimedes
method was used to determine HA actual density. The relative
density was calculated by comparing its actual density with its
theoretical density, which is 3.156 g/cm3 [30e34]. Crystalline-
phase characterization was carried out on one of the samples of
sintered bodies by the same method as described previously. Before
observing the microstructure, the sample was coated with an ion
sputter (E1045 Hitachi, Japan). A scanning electron microscope
(S3400N Hitachi, Japan) was used to observe the microstructure of
HA sintered bodies with various magnifications. The observation
was focused on the shape and distribution of the pores that
occurred in HA sintered bodies owing to differences in uniaxial
pressure when making green bodies.
3. Results and discussion
3.1. Powder characterization
The XRD testing was carried out to characterize the crystalline
phase of HA powder, and the results were then qualitatively
compared with ICDD references. Table 1 and Fig. 2 (b) show the
pattern of the main peaks at the position of 2 thetas for HA powder
sized 2.5 mm. HA powder was identified at angles of 31.74, 32.83,
and 34.06 with consecutive intensities of 100.0%, 54.4%, and 24.6%,
respectively. The XRD results obtained were also similar to those
reported by previous studies [1,35]. When compared with HA in
ICDD reference code 01-072-1243 with the chemical formula
Ca10(PO4)6(OH)2 with the position of 2 thetas of 31.74, 32.17, and
32.86, there are similarities as in Fig. 2 (c). Fig. 3 (a) shows
a scanning electron microscopy (SEM) photo of the HA powder,
where the shape of the HA powder is a microsphere which is
similar to previous research reports [36,37]. Fig. 3 (b) shows the
result of the analysis of the size distribution of HA powder using
ImageJ and histogram software. The analysis showed that the size
of the HA powder was distributed from 0.5 to 3.5 mm, with an
average particle size of 1.3 mm.
3.2. Characterization of the sintered body
3.2.1. Characterization of the sintered body phase
HA sintered bodies have been characterized, in terms of the
phase, as shown in Table 1 and Fig. 2 (a). The results of the char-
acterization were indicated by the position of the main peaks of the
A. Indra, A.B. Putra, N. Handra et al. Materials Today Sustainability 17 (2022) 100100

Table 1
Pattern of peaks of HA.

HA powder HA sintered body ICDD, ref. code 01-072-1243

Position o2q Intensity (%) Position o2q Intensity (%) Position o2 q Intensity (%)

31.74 100.00 31.76 100.00 31.74 100.00

32.83 54.40 32.91 88.90 32.17 45.30
34.06 24.60 34.11 15.50 32.86 56.40

HA, hydroxyapatite.

Fig. 2. XRD peaks pattern, (a) HA sintered body at 1200
C, (b) HA powder with a particle size of 2.5 mm, (d) HA ref. pattern 01-072-1243. XRD, X-ray diffraction; HA, hydroxyapatite.

Fig. 3. HA powder analysis (a) SEM image of HA powder, (b) histogram of HA powder size distribution. HA, hydroxyapatite; SEM, scanning electron microscopy.

2 thetas of 31.76, 32.91, and 34.11 with intensities of 100.0, 88.9, and
15.5%, respectively. These results are consistent with several studies
that have been previously reported [36,38,39]. The results of the
XRD test of HA sintered bodies have similarities to the results XRD
of HA powder in terms of the position of the main peaks, which
indicated there is no phase change after the sintering process.
Other studies reported that the phase change in HA sintered bodies
occurs at sintering temperatures of 1300
C or more [39].
3.2.2. Linear shrinkage
Fig. 4 shows the correlation of uniaxial pressure and diameter,
thickness, and weight shrinkages of sintered bodies. Diameter
shrinkage was found to decrease in line with the increase in
uniaxial pressure, namely from 20.51% at a pressure of 10 MPa to
15.48% at 190 MPa. The highest value of diameter shrinkage
occurred at the lowest uniaxial pressure owing to the low density
between the powders in the green bodies so that the sintering
process required high shrinkage to form grain bonds in the sintered
bodies. Meanwhile, the lowest shrinkage value occurred at the
highest uniaxial pressure because the density between the pow-
ders was very good in the green bodies, so the sintering process did
not require high shrinkage to form grain bonds in the sintered
bodies. Previous studies have reported that the shrinkage diameter
is 19% at a pressure of 200 MPa [40]. Thickness shrinkage, similar to

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A. Indra, A.B. Putra, N. Handra et al. Materials Today Sustainability 17 (2022) 100100

Fig. 4. Correlation between uniaxial pressure and diameter, thickness, and weight
shrinkages.

diameter shrinkage, decreased with the increase in uniaxial pres-

sure, namely from 18.92% at a pressure of 10 MPa to 13.93% at
190 MPa, owing to the same cause of the decrease in diameter
shrinkage. Weight shrinkage seemed to be constant at uniaxial
pressures of 10e70 MPa, namely about 13%. Meanwhile, under
uniaxial pressures of 100e190 MPa, the increase in shrinkage was
almost the same, namely about 15%. The change in weight
shrinkage occurred at a uniaxial pressure of 100 MPa, which was
thought to be the optimum pressure. Fig. 5 shows the correlation of
uniaxial pressure and the diameter and thickness of green bodies.
All the samples have the same diameter, which is 8.32 mm, because
they came from the same mold. The thickness decreased signifi-
cantly from 4.23 mm at 10 MPa to 3.86 mm at 40 MPa and was seen
to be constant at uniaxial pressures of 40e190 MPa. From these
data, it was alleged that the density of green bodies began to be
reached at 40 MPa.

Fig. 6. SEM image of HA sintered bodies with a variation of uniaxial pressure of (a)
10 MPa, (b) 40 MPa, (c) 70 MPa, (d) 100 MPa, (e) 130 MPa, (f) 160 MPa, and (g) 190 MPa.
HA, hydroxyapatite; SEM, scanning electron microscopy.
Fig. 5. Correlation of uniaxial pressure and green body diameter and green body
thickness.

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bond on the sintered bodies. Furthermore, Fig. 6 (b) indicates HA

sintered bodies with a uniaxial pressure of 40 MPa. There was a
very significant reduction in the number of pores compared with
Fig. 6 (a). In this condition, it was alleged that the green body
density level began to be reached, evidenced by the thickness of
green bodies which decreased significantly at 40 MPa. Fig. 6(ceg)
shows HA sintered bodies with uniaxial pressures of 70, 100, 130,
160, and 190 MPa, but there is no significant difference between
them. SEM images show that the sintering process occurred well at
uniaxial pressures ranging from 70 to 190 MPa.

3.2.4. Density and relative density

This section discusses the results of the density test and the
calculation of relative density. Fig. 7 shows the correlation of uni-
axial pressure and density and relative density. Both density and
relative density were found to increase in line with increasing
uniaxial pressure. Density increased from 3.047 g/cm3 at 10 MPa to
3.086 g/cm3 at 40 MPa and was seen to be constant from 40 to
190 MPa. Relative density also increased with increasing uniaxial
pressure from 96.6% at 10 MPa to 97.8% at 40 MPa and was seen to
Fig. 7. Correlation of uniaxial pressure and density and relative density.
be constant under uniaxial pressures of 40e190 MPa. These data
are supported by SEM images (Fig. 6a and b), where there are many
pores at 10 MPa, decreasing significantly at 40 MPa. Several
previous studies reported that at a pressure of 30 MPa, the value of
a micron-sized HA sintered body relative density is around 97%
[41], and under pressures ranging from 65 to 70 MPa, a density
obtained is 2.66 g/cm3 [42]. Fig. 8 shows the correlation of uniaxial
pressure and relative density and diameter shrinkage. Relative
density increases with increasing uniaxial pressure, whereas
diameter shrinkage decreases with increasing uniaxial pressure. To
produce grain bonding in the sintering process with low uniaxial
pressure, a high shrinkage of diameter is required. Meanwhile, to
produce grain bonding in the sintering process with high uniaxial
pressure, low shrinkage of diameter is needed. A summary of the
test results can be seen in Table 2.

Fig. 8. Correlation of uniaxial pressure and relative density and diameter shrinkage.
3.2.3. Characteristics of the microstructure
Fig. 6 shows the results of the SEM test of sintered bodies with a
variation of uniaxial pressure, whereas Fig. 6 (a) depicts the HA
sintered body with a pressure of 10 MPa. It can be seen that there
are a lot of pores, indicating the low density of HA powder at the
time of making green bodies, so it was difficult to have a good grain
3.2.5. Microhardness
This section discusses the result of testing the mechanical
properties in terms of the hardness value of the HA sintered body.
Fig. 9 shows the effect of uniaxial pressure on the Vickers hardness
value of the HA sintered body. The higher the uniaxial pressure
applied to the making of the green body, the higher the hardness
value. This correlates with the relative density of the HA sintered
body which also increases as the value of uniaxial pressure in-
creases. Fig. 9 shows that the value of hardness increases signifi-
cantly from uniaxial pressure 10 MPa to 40 MPa with each value of
3.17 GPae3.86 GPa. From the uniaxial pressure of 40 MPae100 MPa,
it looks stable and there is no significant increase in the hardness
value. At uniaxial pressure of 100 MPa with a hardness value of
4.03 GPa, it has a value that is still below the minimum hardness
requirement of the HA sintered body, as reported in previous

Table 2
Resume of the properties of HA sintered bodies.

Uniaxial Diameter Weight Thick Green body Density Relative Vickers

pressure (MPa) shrinkage (%) shrinkage (%) shrinkage (%) thick (mm) (g/cm3) density (%) hardness (GPa)

10 20.51 ± 0.14 13.464 ± 0.650 18.92 ± 0.80 4.23 ± 0.24 3.047 ± 0.008 96.6 ± 0.3 3.17 ± 0.23
40 18.96 ± 0.21 13.419 ± 0.728 18.03 ± 0.77 3.86 ± 0.05 3.086 ± 0.008 97.8 ± 0.2 3.86 ± 0.54
70 18.24 ± 0.31 13.886 ± 0.522 16.14 ± 0.98 3.90 ± 0.09 3.082 ± 0.009 97.7 ± 0.3 4.00 ± 0.61
100 17.45 ± 0.26 15.422 ± 0.569 16.04 ± 0.78 3.94 ± 0.10 3.083 ± 0.013 97.7 ± 0.4 4.03 ± 0.15
130 17.07 ± 0.40 15.172 ± 0.673 15.29 ± 0.82 3.87 ± 0.06 3.083 ± 0.008 97.7 ± 0.3 4.68 ± 0.21
160 16.29 ± 0.21 15.825 ± 0.500 15.25 ± 0.61 3.76 ± 0.05 3.090 ± 0.009 97.9 ± 0.3 4.71 ± 0.17
190 15.48 ± 0.41 15.781 ± 0.620 13.93 ± 0.75 3.75 ± 0.05 3.080 ± 0.013 97.6 ± 0.4 4.77 ± 0.48

HA, hydroxyapatite.

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A. Indra, A.B. Putra, N. Handra et al. Materials Today Sustainability 17 (2022) 100100

studies [43]. From the uniaxial pressure of 100 MPae130 MPa, there
was a significant increase in the value of hardness, from 4.03 GPa to
4.68 GPa. At uniaxial pressure from 130 MPa to 190 MPa, there is no
significant increase in the value of hardness. At 130 MPa, uniaxial
pressure with a hardness value of 4.68 GPa has met the minimum
value requirements of the hardness of the HA sintered body. From
the hardness test results, it can be concluded that uniaxial
pressure in making HA green body is recommended at a minimum
pressure of 130 MPa. Vickers hardness at uniaxial pressure of
130 MPae190 MPa, which is 4.68 GPae4.77 GPa, respectively, has
met the hardness requirements of the HA sintered body for cortical
bone applications, which is at least 4.2 GPa [43]. Fig. 10 shows an
illustration of the tangential contact model that occurs in the green
body. Fig. 10 (a) shows imperfect tangential contact where some of
the HA particles do not come into tangential contact after forming
the green body, so that it will produce large pores on the HA sin-
tered body. The illustration in Fig. 10 (a) is also reinforced by the
SEM photo in Fig. 6 (a) where the uniaxial pressure of 10 MPa
produces large pores on the HA sintered body. Fig. 10 (b) shows
perfect tangential contact where all HA particles have occurred in
Fig. 9. Correlation of uniaxial pressure and hardness.
tangential contact after forming the green body, so as to minimize
the formation of pores on the HA sintered body. This, which in turn,

Fig. 10. Illustration of the effect of uniaxial pressure, (a) low pressure, (b) high pressure.

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A. Indra, A.B. Putra, N. Handra et al. Materials Today Sustainability 17 (2022) 100100

Table 3
Comparison of the properties of sintered body HA with several other studies.

Uniaxial pressure (MPa) Materials Sintering temperature (oC/ht) Diameter shrinkage (%) Relative density (%) Vickers hardness (GPa) Ref

200 TCP/HA 1150/2 h e e 4.98 [44]

0 HAp 1100/2 h e e 0.93 [45]
5  104 e e 1.09
20 Hap (nano) 1150 e 90 e [12]
1250 e 96 e
285 HAP (nano) 1250/40 min e 95.94 ± 2.64 4.91 ± 0.06 [46]
200 HA (micron) 1250/2 h 30.8 >99 6.08 ± 0.28 [47]
25 HA (micron) 1300/2 h e 98 4.20 ± 0.1 [48]
200 HA (micron/nano) 1200/2 h 13.80 ± 0.47 96.36 ± 0.62 e [20]
1 HAcb (micron) 900/2 h e e 0.65 [49]
75 nHA/P2O5 1050/2 h e e 1.0 [50]
190 HA (micron) 1200/2 h 15.48 ± 0.41 97.6 ± 0.4 4.77 ± 0.48 Present study

HA, hydroxyapatite.; HAp, hydroxyapatite; TCP, tricalcium phosphate.

can increase the hardness value of the HA sintered body. The
illustration in Fig. 10 (b) is also reinforced by the SEM photo in
Fig. 6(eeg) where the uniaxial pressure of 130 MPae190 MPa
produces fewer pores than the others. A comparison of the prop-
erties of HA sintered body with several other studies can be seen in
Table 3.
4. Conclusion
Acknowledgment
This research was funded under the contract No. 027/LL10/GP-
PTTJ/2021 concerning grant for PTUPT, Ministry of Research and
Technology/National Research and Innovation Agency, Deputy for
Research and Development Encouragement, Indonesia. The authors
thank the Ceramics Research Group team and “KBK Material”
Department of Mechanical Engineering, Faculty of Engineering,
Institut Teknologi Padang.

Relative density increases as the uniaxial pressure increases,

and conversely, diameter shrinkage decreases as the uniaxial
pressure increases. Relative density increases under uniaxial pres-
sures ranging from 10 to 40 MPa and is constant under those
ranging from 40 to 190 MPa. SEM images prove that HA sintered
bodies under a pressure of 10 MPa have a high number of pores.
Grain bonding in HA sintered bodies begins at a uniaxial pressure of
40 MPa and occurs completely at pressures of >70 MPa. Changes in
weight shrinkage occur at 100 MPa, whereas the standard hardness
value of sintered body HA is obtained at uniaxial pressure of
130 MPa, which is thought to be the optimum uniaxial pressure.
Author contribution statements
Conceptualization: Ade Indra; Jon Affi; Gunawarman.
Data curation: Ade Indra; Arya Buana Putra; Nofriady Handra;
Hendriwan Fahmi; Asfarizal; Mastariyanto Perdana.
Formal analysis: Ade Indra; Arya Buana Putra; Nofriady
Handra; Hendriwan Fahmi; Nurzal; Asfarizal; Mastariyanto Per-
dana; Anrinal; Adi Subardi; Jon Affi; Gunawarman.
Funding acquisition: Ade Indra; Arya Buana Putra.
Investigation: Ade Indra; Jon Affi; Gunawarman.
Methodology: Ade Indra; Jon Affi; Gunawarman.
Project administration: Arya Buana Putra.
Resources: Ade Indra; Arya Buana Putra; Nofriady Handra;
Hendriwan Fahmi; Nurzal; Asfarizal; Mastariyanto Perdana; Anri-
nal; Adi Subardi; Jon Affi; Gunawarman.
Software: Ade Indra; Arya Buana Putra.
Supervision: Ade Indra; Jon Affi; Gunawarman.
Validation: Ade Indra; Asfarizal; Adi Subardi.
Writing - original draft: Ade Indra.
Writing - review and editing: Ade Indra; Nofriady Handra.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this article.
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