Available online at SciVerse ScienceDirect

J. Mater. Sci. Technol., 2013, 29(6), 573e581

Thermo-mechanical, Wear and Fracture Behavior of High-density

Polyethylene/Hydroxyapatite Nano Composite for Biomedical Applications:
Effect of Accelerated Ageing
H. Fouad1)*, R. Elleithy2), Othman Y. Alothman3)
1) Biomedical Engineering Department, Faculty of Engineering, Helwan University, P. O. Box 11792, Helwan, Egypt
2) Printpack Inc, 400 Packets Crt, Williamsburg, VA 23185, USA
3) Chemical Engineering Department, King Saud University, P. O. Box 800, Riyadh 11421, Saudi Arabia
[Manuscript received December 22, 2012, in revised form January 15, 2013, Available online 21 March 2013]

The objective of this work is to demonstrate how the viscoelastic, thermal, rheological, hardness, wear resistance
and fracture behavior of bioinert high-density polyethylene (HDPE) can be changed by the addition of
hydroxyapatite (HAP) nano particles. Also the effects of accelerated thermal ageing on the composite
properties have been investigated. Different weight fractions of HAP nano particles up to 30 wt% have been
incorporated in HDPE matrix by using melt blending in co-rotating intermeshing twin screw extruder. The
fracture toughness results showed a remarkable decrease in proportion to the HAP content. The differential
scanning calorimetry results indicated that the melting temperature and crystallinity were affected by the
addition of HAP nano particles into the matrix. The complex viscosity increased as the percentage of HAP
increased due to the restriction of the molecular mobility. The dynamic mechanical analysis results revealed
that higher storage modulus (8.3
1011 Pa) could be obtained in the developed HDPE/HAP in 30 wt%
compared to neat HDPE (5.1
1011 Pa). Finally, the hardness and wear resistance of HDPE were improved
significantly due to the addition of HAP nano particles. The changes in the HDPE and its nano composite
properties due to ageing showed that the HDPE and its nano composites crystallinity increased while the
fracture toughness, hardness, wear resistance, storage and loss modulus decreased.

KEY WORDS: High-density polyethylene (HDPE); Hydroxyapatite (HAP); Hardness; Accelerated ageing; Dynamic mechanical analysis
(DMA); Differential scanning calorimetry (DSC); Fracture

1. Introduction modulus of HDPE/HAP composite to natural bone shows

The concept of fabricating bioactive composites for bone re-
placements by reinforcing a high-density polyethylene (HDPE)
matrix with a bioactive hydroxyapatite (HAP) was introduced in
early 1980s[1]. The mechanical coupling of the reinforcement
and the matrix is resulting from the shrinkage of HDPE matrix
and HAP particles during the composite processing[2]. The HAP
increases the stiffness of the composite and provides bioactivity,
while HDPE provides toughness but bioinert. Therefore, the
mechanical and biological properties of HDPE/HAP composite
can be tailored to meet specific clinical requirements. The closer
* Corresponding author. Prof.; Tel.: þ20 25558410; Fax: þ20 25558294;
E-mail address: menhfefnew@hotmail.com (H. Fouad).
1005-0302/$ e see front matter Copyright Ó 2013, The editorial office of
Journal of Materials Science & Technology. Published by Elsevier
Limited. All rights reserved.
http://dx.doi.org/10.1016/j.jmst.2013.03.020
promise in solving the problem of bone resorption that has been
encountered with the use of implants made up of other con-
ventional materials[3e6]. The implants made of HDPE/HAP
composite encouraged bone apposition rather than the fibrous
encapsulation which was encountered with other implant mate-
rials. Tanner et al.[2] have reported successful clinical applica-
tions of this composite as orbital implants to treat problems such
as post-enucleation socket syndrome and orbital floor fractures.
Also the HDPE/HAP composite can be used successfully as
middle ear implant.
It has been reported that the elastic modulus of HAP (in the
micro scale)/polyethylene (PE) composite can reach the lower
range of human cortical bone modulus[7]. This can be attributed
to the low dissolubility and degradation of relatively large size of
HAP[8]. Recently, the nano-scale HAP has been developed and
an HDPE/HAP nano composite with acceptable properties can
be easily processed. The nano HAP particles have high surface
area and its size is similar to the mineral found in human hard
574 H. Fouad et al.: J. Mater. Sci. Technol., 2013, 29(6), 573e581
tissues[8]. Also the nano HAP takes the advantage of homoge-
nous distribution in the polymer matrix.
The mechanical and rheological properties of HDPE/HAP
composite have been extensively studied[9e14]. Wang et al.[15]
studied the effect of HAP particle size on the HDPE/HAP
composite properties. The results showed that the composites
with smaller HAP particles had higher torsional, tensile modulus
and tensile strength, but had lower fracture strain. Joseph et al.[6]
studied the effects of surface and morphology of HAP on the
rheology and processability of an injection molding grade
HDPE/HAP composite. Eniwumide et al.[16] investigated the
effects of HAP morphology and PE molecular weight on the
fracture toughness of PE/HAP composite.
It is well known that PE and its composites have a viscoelastic
behavior even under normal loading conditions. Their overall
mechanical properties change over time due to ageing either on
shelf or in vivo. The ageing of PE and its composites causes
subsurface oxidative degradation (between 1 and 2 mm) under
the polymer surface[17]. This oxidative degradation causes
embrittlement of the polymer and loss of its overall mechanical
properties. The characterization of ageing effects on the behavior
of PE and its composites that are used as bone substitutes will
help in understanding and predicting the in vivo behavior of
these composites with time. Because oxidation of PE (due to
natural ageing) takes months or years to reach an appreciable
level at ambient or body temperature, thermal ageing techniques
have been developed to accelerate the oxidation of PE with the
expectation that the material behavior after accelerated ageing
will be comparable to naturally aged ones. Based on this
assumption, accelerated thermal ageing has been widely used by
many researchers to investigate the resistance of PE to
ageing[18e21]. Using this ageing technique, from 5 to 10 years of
shelf ageing can be simulated within a time period of few weeks.
To the best of our knowledge, the effects of in vivo/in vitro
ageing on the properties of HDPE/HAP nano composite have not
been investigated. Also, it is remarked that there is a lack of data
on the viscoelastic and bioactive behavior of HAP/PE nano
composite. Therefore, the present study is a part of research
project that is intended to study the effects of accelerated ageing
on thermal, mechanical, viscoelastic and fracture behavior of
HDPE/HAP nano composites. Also, in this project, the effect of
nano HAP ratio on the nano composite bioactivity will be
investigated. The main objectives of this part of the project are:
(1) fabricating of HDPE/HAP nano composite by using melt
blending in a co-rotating intermeshing twin screw extruder, (2)
studying the effects of HAP nano particles percentage and arti-
ficial ageing on the thermal, rheological, viscoelastic, fracture
toughness, hardness and wear behavior of the HDPE nano
composite.
2. Experimental
2.1. Material
The polymer used in the present work is an injection molding
grade of HDPE which is referred as HDPE. The manufacturer
(SABIC Company SA) indicated that this HDPE has melt flow
index of about 30 g/10 min and density of about 0.94 g/cm3. The
estimated average molecular weight was about 700,000 g/mol
(calculated from the melt viscosity). The hydroxyapatite (HAP)
nano particles were obtained from Fluidinova, Engenharia de
Fluidos, SA, Portugal. According to the manufacturer data, the
typical nano-crystal size is less than 100 nm and the average
aggregate size is 2.5 mm with specific surface area of 100 m2/g.
2.2. Preparation of specimens
Weight ratios of 0, 10, 20 and 30 wt% of the HAP nano
particles were pre-mixed with neat HDPE pellets to get the
required nano composite pre-blend. The pre-blend was com-
pounded in Farrell co-rotating intermeshing twin screw extruder.
The twin screw extruder has a diameter of 26 mm and length/
diameter (L/D) ¼ 35. The screw speed was kept constant at 12 r/
min. The temperature profile used (from feed to die) was 180,
230, 235, 240, 240, 235, and 240  C. The extrudates from the
extruder were cooled in a water bath at about 12  C, air dried,
then palletized into granules. The granules were further dried and
conditioned in the lab environment for 40 h. An injection
molding machine (Asian Plastic Machinery, Double Toggle I
Machine, Super Master Series SM 120) was used to get a set of
standard ASTM D638 type-I tensile specimens[22]. Specimens
were conditioned in a standard lab environment for 40 h before
further testing. ASTM D638 standard was used as our guide.
Although the standard recommends testing of at least 5 speci-
mens, ASTM standard allows testing fewer specimens if so
mentioned in the report. In the present study all the experimental
tests were performed with 3 specimens. All the results presented
here are the median of the three measurements.
2.3. Ageing procedure
The accelerated ageing of HDPE/HAP nano composite spec-
imens is performed in saline solution at temperature of 80  C for
4 weeks that equals around 6 years of natural ageing[21]. In the
present study, it is assumed that the ageing procedures used will
result in ageing mechanism comparable to the real in vivo ageing
mechanism[23].
2.4. Characterization methods
The morphological studies of HDPE/HAP nano composites
cryo-fracture surface and single edge notched (SEN) fractured
samples were examined by scanning electron microscopy (SEM,
Joel, USA) at 15 kV. Prior to SEM examination, the nano
composite specimens were coated with a thin layer of gold to
dissipate the build-up of heat and electrical charges.
Infrared radiation (IR) was performed in the attenuated total
reflection (ATR) mode by using a Bruker Spectrum Tensor 27
system equipped with an ATR cell with a diamond reflection
element. This machine was used for measuring and scanning the
IR absorption spectra of HDPE/HAP aged and non-aged nano
composite. Samples were applied directly onto the surface of
ATR crystal. Spectra result from the accumulation of 16 scans at
4 cm1 resolution. The wavenumber range was 4000e
400 cm1.
The single edge notched (SEN) specimens for the fracture
toughness measurements were prepared by inducing a pre-crack
to one side of the ASTM tensile sample (type-III) with a sharp
thin razor blade. The pre-crack length was fixed at 10% (a/D).
Different SEN specimens were prepared as described and tested
for their fracture toughness. All of the reported measurements for
all of the tests in this research represent the median of 3 ex-
periments. The tensile tests were performed at 50 mm/s. The
fracture toughness (KI) of the neat HDPE and its nano composite
 H. Fouad et al.: J. Mater. Sci. Technol., 2013, 29(6), 573e581
specimens were calculated according to Eq. (1) by SEN speci-
mens under tension[17,24]. Eq. (2) can also be used to calculate
the fracture toughness considering the geometric correction
factor Y2[24].
pffiffiffiffiffiffiffiffi
KI ¼ s p a (1)
KI2 ¼ Y 2 ða=DÞs2 a (2)
where KI is the fracture toughness, s is the applied stress, a is the
pre-crack length and D is the width of the sample tested.
Calorimetric measurements for aged and non-aged HDPE/
HAP nano composite specimens were performed by means of
differential scanning calorimetry (DSC, Shimadzu-60). Each
sample (about 7 mg) is sealed in an aluminum pan and heated
from 20 to 150  C at a rate of 5  C/min, then cooled down to
30  C at cooling rate of 5  C/min. The DSC samples were taken
from the cross section of HAP/HDPE specimens which have
2 mm thickness. Previous results indicated that the ageing
mechanism causes subsurface degradation under the polymer
surface up to 2 mm in depth[17]. The heat of fusion is calculated
by integrating the area under the DSC endothermic peak for the
first heat. The melting temperature is registered as the maximum
point of the endothermic melting peak. The percentage crystal-
linity was calculated by normalizing the heat of melting to that of
100% crystalline PE (290 J/g), by the following equation[25e27].
DHm
Xc ¼ (3)
DHmþ
where Xc is the degree of crystallinity, DHm is the specific
enthalpy of melting, DHmþ is the specific enthalpy of melting
for 100% crystalline PE.
The rheological and viscoelastic behavior of the HDPE/HAP
nano composite were characterized by dynamic mechanical
analysis (DMA) via AR-G2 from TA, USA. The rheological
properties were measured via a plateeplate geometry that had
25 mm plate diameter, and a gap of 1.0 mm. The specimens were
heated to 190  C, stabilized at this temperature for 5 min. The
specimens were tested over a frequency range from 0.01 to
600 rad/s. The viscoelastic properties were measured under
torsional arrangement. The specimens were heated to 80  C,
stabilized at this temperature for 5 min, and then a frequency
sweep test was performed. The frequency sweep was performed
from 0.1 to 600 rad/s. The temperature sweep experiment was
also performed at a fixed strain rate.
The Rockwell hardness of HDPE and HDPE/HAP nano
composites was calculated from Leeb rebound test. Leeb test is a
typical rebound hardness test where the energy of an indenter
Fig. 1 SEM micrographs of HAP/HDPE nano composite and neat HAP powder: (a) 20 wt% HAP, (b) 30 wt% HAP, (c) HAP powder.
575
before and after an impact is calculated. Hence, the hardness of
the material could be determined.
The preliminary dry wear resistances of HDPE and HDPE/
HAP nano composites were investigated by using the Taber
abrasion tester, ASTM D4060-10. A set of two rotating abrasive
wheel CS-10 with diameter of 50 mm and thickness of 12.6 mm
was run against the HDPE and HDPE/HAP nano composite
specimens at contact load of 1000 g. The rotational speed was set
to 72 r/min for 10,000 cycles. The wear rate of the specimens
was determined by measuring the specimen weight loss.
3. Results and Discussion
3.1. Morphological examination
The surface morphologies of HAP powder and HDPE/HAP
composite specimens containing 20 and 30 wt% HAP are shown
in Fig. 1. A reasonable distribution of HAP particles was ach-
ieved in the composite. Although the used HAP particles were in
the nano scale-range according to the manufacturer data, this
micrograph shows agglomeration of some nano particles to be in
the micro scale-range (100 nm). This agglomeration could be
attributed to the tendency of HAP nano particles to decrease their
contact surface with HDPE matrix. Therefore, bigger particle
size of HAP is clearly visible in the micrograph of composite
specimens. The HAP appears as bright spots distributed in the
dark HDPE matrix.
3.2. FT-IR results
The Fourier transform infrared (FT-IR) spectra of the non-
aged HDPE and its HAP nano composites are shown in
Fig. 2(a). All the characteristic bands corresponding to HDPE are
observed. In the spectrum of non-aged HDPE, the peaks at 700
and 1473 cm1 are observed which correspond to the rocking
and bending vibrations of CeH, respectively. Two other peaks
are shown at about 2894 cm1, assigned to asymmetric CeH
stretching, while symmetric CeH stretching occurs at
2916 cm1. By comparing the spectra of HDPE/HAP specimens
with neat HDPE, it can be found that the transmittance intensity
of the HDPE/HAP specimens is reduced. This decrease may
refer to a decrease of unsaturated groups due to cross-linking.
When nano-scale HAP is added to HDPE with doping levels
10, 20 and 30 wt%, the spectra show two new peaks at about
1055 and 1105 cm1. These new peaks can be assigned to the
vibrations phosphate groups from HA. Moreover, the intensity of
these peaks was increased as doping levels of HAP increase.
Fig. 2(b) shows the FT-IR spectra of aged neat HDPE and
aged HDPE with different concentrations of nano-scale HAP.
The spectra with or without ageing effect have the same peaks
576 H. Fouad et al.: J. Mater. Sci. Technol., 2013, 29(6), 573e581
Fig. 2 FT-IR spectra of the neat (a) and aged (b) samples with nano
HAP.
with no observable difference except the small two peaks at
about 2400 and 2420 cm1. These two peaks can be assigned to
intramolecular hydrogen bonded stretching OeH band.
3.3. Fracture toughness measurements
Eq. (1) was used to calculate the fracture toughness of HDPE
and its nano composites. The fracture toughness (KI) of the nano
composites was smaller than that of the neat HDPE as seen in
Fig. 3. The nano particles acted as crack initiators or stress
raisers in the nano composite that induce failure at low stresses
and strains. Also, the presence of HAP nano particles restricted
the molecular mobility of HDPE matrix[15,28]. In other words, the
addition of nano HAP led the composites specimens toward
brittle behavior and reduced the fracture toughness[26,29]. Similar
trends for the fracture toughness of HDPE/HAP composite have
been obtained by Zhang and Tanner[30] where the fracture
toughness of the composite decreased with increasing HAP
Fig. 3 Variation of the fracture toughness (KI) with the HAP
percentage.
content. The results of Fig. 3 also indicate that the accelerated
ageing results in a remarkable reduction in the nano composite
fracture toughness. This change can be regarded due to the
reduction in polymer chain segment by molecular chain session
that would take place during accelerated ageing[23].
The microscopic investigation of the fracture surfaces of
HDPE/HAP composite specimens with a pre-crack revealed a
completely different morphologies and fracture mechanisms
compared to the cryo-fractured ones. The fracture surface of
pre-cracked specimens can be divided into 3 main zones: I,
initial pre-crack; II, slow crack propagation zone; and IV, fast
crack propagation zone. In addition, the crack propagation zone
could be further subdivided into 3 zones, namely, transition
zone III (slow-to-fast propagation zone) and two skin zones V
and VI[31].
From the fractographic investigation of fracture surface on
neat HDPE specimens (Fig. 4(a)), it is clearly visible that the
specimen fractured via both ductile and brittle fracture mode.
Characteristic parabolic crack propagation is observed in these
specimens. The characteristic parabolic crack propagation is not
fully developed in the specimens containing 10, 20 and 30 wt%
of HAP. Because of the increased formation of microvoids in the
interface during the fracture process of the HDPE/HAP com-
posite, at this case, the fibrillation becomes more difficult than
that of neat HDPE matrix. The fracture surface of HDPE/HAP
composite displays more brittle characteristics than that of the
neat HDPE which is indicated by the debonding of HAP from
HDPE matrix (Fig. 5). This results in deterioration of the fracture
toughness of the composite compared with neat HDPE. Similar
results have been obtained for the fracture toughness mechanism
of HDPE/CaCO3 micro composites[31].
3.4. Thermal properties
In the present work, the DSC thermograms of tested material
are divided into two main groups. The first is the non-aged
HDPE and HDPE/HAP nano composites. The second is the
accelerated aged HDPE and HDPE/HAP nano composites. For
the first group, the thermal properties for the melting (first heat)
of neat HDPE and HDPE/HAP nano composites with different
HAP content are shown in Fig. 6. This figure shows the DSC
results of the first heat for HDPE and HDPE/HAP nano com-
posite with 10, 20 and 30 wt% HAP nano particles. These results
indicate that the melting temperature (Tm) decreases with
increasing HAP nano particles percentage as listed in Table 1.
These data imply that the HAP filler has some influence on the
PE lamellar crystallinity.
The crystallization of HDPE/HAP nano composites was
judged via the heat of fusion DH. A blend with less crystallinity
requires less heat to be melted, i.e. lower DH. The DSC results
(Table 1) indicate that the crystallization decreases due to the
presence of HAP. The main reason that explains this phenome-
non is the formation of conglomerates of the filler. If these
conglomerates exceed the critical size, they lose their nucleating
capacity. The presence of HAP particles restricts the mobility of
the molecules, weakens the intermolecular interaction of the
HDPE chains hence the crystallinity decreases[26]. On the other
hand, it is believed that melting at lower temperature is associ-
ated with thinner lamellar in the composite. This is because the
HAP filler has higher specific heat capacity, thus making it to be
a better heat conductor. This in turn causes the cooling of HDPE/
HAP composite to be faster and results in thin lamellar formation
rather than thick crystal growth. When melting temperature
 H. Fouad et al.: J. Mater. Sci. Technol., 2013, 29(6), 573e581 577

Fig. 4 SEM micrographs of neat HDPE and HAP/HDPE single edge fracture samples: (a) neat HDPE, (b) neat HDPE: ductile to brittle transition,
(c) 10 wt% HAP, (d) 10 wt% HAP: ductile to brittle transition, (e) 20 wt% HAP, (f) 20 wt% HAP: ductile to brittle transition.

decreases, it is expected that the degree of crystallinity indicates
a lower value.
Fig. 7 shows the DSC results of the first heat for accelerated
aged HDPE and HDPE/HAP composite with 10, 20 and 30 wt%
HAP nano particles. These results indicate that the melting
temperature (Tm) decreases due to ageing while the crystallinity
increases. These results show that the crystallization of aged
composites has the same trend like the non-aged ones. The
crystallinity of accelerated aged specimens is 5%, 6.4%, 4%,
6.5% higher than that for non-aged specimens for neat HDPE,
10, 20 and 30 wt% HDPE/HAP, respectively.
The changes in the DSC results of aged HDPE and its nano
composites can be attributed to the oxidation and chain scission
of the tested material due to accelerated ageing. The tested
polymer chain scission process allows further crystal perfection
and growth to occur. Therefore, the aged HDPE has higher
degree of crystallinity compared to non-aged material. The chain
scission produces an overall decrease in tie molecules, allowing
for lamellar rapprochement and reordering which resulting in an
increase of the crystallinity as indicated in the DSC results.
Similar results have been obtained by Fouad[23] for ultra high
monocular weight polyethylene (UHMWPE) where the degree
of crystallinity increased due to ageing.
3.5. Rheological behavior of HA/HDPE nano composites
The relationship between the complex melt viscosity and the
angular frequency at 190  C of non-aged HDPE and
HDPE þ 10, 20 and 30 wt% HAP nano particles is shown in
Fig. 8. This figure shows that the viscosity of HDPE/HAP nano
composites is higher than that of the neat HDPE especially at
lower frequencies. These curves could be divided into two
578 H. Fouad et al.: J. Mater. Sci. Technol., 2013, 29(6), 573e581

Fig. 5 SEM micrographs of HAP/HDPE single edge fracture sample with 30 wt% HAP at higher magnification.

shown in Figs. 9 and 10, respectively. These experiments were

Fig. 6 Thermogram showing the melting behavior of non-aged HDPE
and its composites.
regions; (i) high shear thinning at lower frequencies, and (ii) low
shear thinning at higher frequencies. The increases in the nano
composite viscosity can be attributed to the restriction of the
molecular mobility and the reduction of the free volume that are
induced by the addition of the HAP nano particles.
Similar trends have been also obtained for the variation of
complex melt viscosity and the angular frequency for aged
HDPE and its nano composites. Only the viscosity of aged
HDPE/HAP nano composites is higher than that of the non-aged
ones. This increase in complex melt viscosity can be attributed to
increasing crystallinity of specimens due to ageing as indicated
in the DSC results.
3.6. Dynamic mechanical analysis
Plots of storage (G0 ) and loss modulus (G00 ) at different fre-
quencies for non-aged HDPE and its HAP nano composites are
carried out at frequencies ranging from 0.1 to 600 rad/s at 80  C.
The results show a strong dependence of the tested material
viscoelastic behavior on the testing frequency (strain rate). The
storage and loss modulus increase as the testing frequency in-
creases confirming that the viscoelastic behavior of HDPE and
its nano composite are strain rate dependent. Additionally, the
storage modulus of all HDPE/HAP nano composites increases
with increasing content of HAP nano particles. This increase in
the modulus of nano composites can be attributed to the increase
in the stiffness of polymeric matrix as a result of the decrease of
free volume and the mobility restriction due to the presence of
HAP nano particles[26,29].
The effects of testing temperature on the viscoelastic proper-
ties (G0 and G00 ) of non-aged HDPE and HDPE/HAP nano
composites are shown in Figs. 11 and 12 at 1 rad/s. The results
show that the G0 and G00 significantly decrease with increasing
testing temperature. The reduction in the values of G0 and G00
obtained at higher temperature can be justified by the higher
mobility of polymer chains at elevated temperature.
Compared to the non-aged HDPE and HDPE/HAP specimens,
the accelerated ageing results in remarkable decrease on the
tested material storage and loss modulus for all testing fre-
quencies as indicated in Fig. 13. For example, for pure HDPE at
0.1 rad/s, the storage modulus decreases from 5
1011 to
2.5
108 Pa due to ageing. The reduction in the mechanical
properties of aged HDPE specimens and its nano composites is
regarded to the material oxidation and its corresponding chain
scission. The chain scission process results in an increase of
polymer crystallinity (due to lamella thickening), breakage of the
polymer long chains, reduction of tie molecules, reduction in the
tested material molecular weight, increase in material brittleness,
and weakening in their properties[23].

Table 1 DSC results for aged and non-aged HDPE and HAP/HDPE composites

Non-aged specimens Aged specimens

Tm ( C) DHm (J/g) Tc ( C) Tm ( C) DHm (J/g) Tc ( C)

HDPEþ0 wt% HAP 134 162 114 131.9 170 113.6

HDPEþ10 wt% HAP 133 155.3 114 131.6 165 114
HDPEþ20 wt% HAP 132.3 146 115 130.5 152 114.3
HDPEþ30 wt% HAP 132.1 137.6 114.8 130.4 146.2 113.8
 H. Fouad et al.: J. Mater. Sci. Technol., 2013, 29(6), 573e581 579

Fig. 7 Thermogram showing the melting behavior of aged HDPE and

its composites.
Fig. 10 Variation of G00 with frequency for HDPE and HDPE nano
composites at 80  C.

to ageing. The average value of hardness decreases from 31.2 to

25.1 MPa for neat HDPE while the average value decreases from
43.3 to 35.2 MPa for HDPE þ 30 wt% HAP composite due to
ageing. The reduction of the hardness in the tested material can be
attributed to the polymer chain scission and the corresponding
reduction of tie molecules due to accelerated ageing. Similar re-
sults have been observed where the hardness of UHMWPE
increased from 23 to 30.5 MPa due to adding 30 wt% HAP nano
particles to pure polymer[28].

Fig. 8 Complex viscosity as a function of the angular frequency at

190  C.

3.7. Rockwell hardness results

The Rockwell hardness of HDPE and HDPE/HAP nano com-

posites that was calculated from Leeb rebound test is shown in
Table 2. The results show that the material gets harder as the HAP
nano particles content increases, which echoes the increase in the
viscoelastic moduli. Comparing with neat HDPE, the average
value of hardness is up to 43.3 MPa for HDPE þ 30 wt% HAP
composite, which is 39% higher than that of pure HDPE. This
increase can be regarded to the reduced mobility of the molecules
due to presence of hard HAP nano particles that have strong anti-
deformation ability. Compared to non-aged HDPE and its nano Fig. 11 Variation of G0 with temperature for HDPE and HDPE nano
composites, the hardness results show a remarkable decrease due composites at 1 rad/s.

Fig. 9 Variation of G0 with frequency for HDPE and HDPE nano Fig. 12 Variation of G00 with temperature for HDPE and HDPE nano
composites at 80  C. composites at 1 rad/s.
580 H. Fouad et al.: J. Mater. Sci. Technol., 2013, 29(6), 573e581

Fig. 13 Variation of G0 and G00 for aged and non-aged HDPE nano
composites at 1 rad/s. Fig. 14 Physical cross-linking of HAP nano particles (black) and
elongated HDPE chains.

Table 2 Rockwell hardness of HDPE and its composites As indicated earlier, the wear resistance is related to the me-
chanical properties of the tested material. Therefore, the reduc-
Rockwell hardness tion in the mechanical properties of aged HDPE specimens due
Non-aged specimens Aged specimens to oxidation and its corresponding chain scission will affect the
wear resistance. This can be shown from Table 3 where the wear
HDPEþ0 wt% HAP 31.2  1 25.1  1.8 rate of neat HDPE and 30 wt% HDPE/HAP increases by 4.5%
HDPEþ10 wt% HAP 37.1  3 29.8  2 and 10.5% due to accelerated ageing.
HDPEþ20 wt% HAP 40.2  2 33.1  3 The experimental results showed that the addition of HAP
HDPEþ30 wt% HAP 43.3  2.5 35.2  2.3
nano particles changed the mechanical properties of the HDPE.
From the microscopic examination of the nano composite frac-
ture surface, it is suggested that the HAP nano particles are
3.8. Abrasion rate results located in the amorphous region within HDPE matrix as sche-
matically depicted in Fig. 14. This interstitial placement of HAP
was suggested as well for polypropylene (PP)/nanoclay and
The wear resistance of HDPE composite is related to its me-
HDPE/GNPs (graphite nano particles) composites[27,32]. Such
chanical properties, especially its surface properties. The im-
interstitial arrangement restricts the mobility of the long chains
provements in hardness and modulus due to the addition of HAP
of the polymer molecules during the deformation of the nano
are clearly favorable to increase the wear resistance of HDPE
composites. These interstitial restrictions could act as physical
nano composites. Hard HAP nano particles have strong anti-
cross-links of polymer chains which reduced the chain mobility.
deformation ability. During motion, these hard phase particles
Also a mechanical interlocking is expected between the HAP
deform and support a significant portion of the normal applied
and polymer matrix due to the shrinkage of polymer matrix on
load. Therefore, the surrounding HDPE matrix is subjected to
the HAP during cooling after polymer processing[27]. These two
lower shear stress during the wear process. This explains the
mechanisms, interstitial restriction and mechanical interlocking,
wear results of Taber abrasion test after 10,000 cycles by using a
decreased the deformability of the molecular chains and hence
set of two CS-10 wheels at 1000 g load as listed in Table 3. As
increased the stiffness of composites as indicated from the results
the content of nano HAP increases, the weight loss of the sample
of the viscoelasticity and hardness tests.
decreases. The wear rate of 30 wt% HAP nano composite is 36%
lower than that of neat HDPE. When the hardness of HDPE
increases due to the addition of HAP nano particles, the 4. Conclusions
ploughing resistance on the composite surface increases and the
shear stress between HDPE/HAP composite and steel wheel
(1) HDPE with acceptable distribution of HAP nano particles
decreases resulting in lower wear rate. Similar trend has been
was successfully prepared by using twin screw extrusion
obtained by Wang et al.[28] where the wear resistance of
with some agglomeration of HAP nano particles.
UHMWPE increased by 50% when 30 wt% HAP was added to
(2) The melting temperature and crystallinity decreased with
pure UHMWPE.
increasing content of HAP nano particles due to the
mobility restriction of the molecules.
(3) Ageing of HDPE/HAP nano composites resulted in
Table 3 Taber abrasion weight losses of HDPE and its composites reduction of the melting temperature and increase of the
crystallinity due to expected oxidation and chain scission.
Weight loss (mg)
(4) Melt viscosity of HDPE composites increased due to the
Non-aged specimens Aged specimens addition of HAP nano particles and due to accelerated
ageing.
HDPEþ0 wt% HAP 89 93
(5) With increasing content of HAP nano particles, the storage
HDPEþ10 wt% HAP 67 75
and loss modulus of the nano composite increased while the
HDPEþ20 wt% HAP 60 70
HDPEþ30 wt% HAP 57 63 fracture toughness decreased proportional to the HAP
content
 H. Fouad et al.: J. Mater. Sci. Technol., 2013, 29(6), 573e581
(6) The hardness and wear resistance of HDPE were improved
significantly due to the addition of hard HAP nano particle
particles.
(7) Ageing of HDPE/HAP nano composites resulted in the
reduction of the storage, loss modulus, hardness, wear
resistance and the fracture toughness.
Acknowledgment
The authors extend their appreciation to the Deanship of
Scientific Research at King Saud University for funding the
work through the research group project No. RGP-VPP-133.
REFERENCES
[1] W. Bonfield, M.D. Grynpas, A.E. Tully, J. Bowman, J. Abram,
Biomaterials 2 (1981) 185e196.
[2] K.E. Tanner, R.N. Downes, W. Bonfield, Br. Ceram. Trans. 93
(1994) 104e107.
[3] A.P. Unwin, I.M. Ward, P. Ukleja, J. Weng, J. Mater. Sci. 36 (2001)
3165e3177.
[4] L. Fang, Y. Leng, P. Gao, Biomaterials 26 (2005) 3471e3478.
[5] S.M. Rea, R.A. Brooks, S.M. Best, T. Kokubo, W. Bonfield, Bio-
materials 25 (2004) 4503e4512.
[6] R. Joseph, W.J. McGregor, M.T. Martyn, K.E. Tanner, P.D. Coates,
Biomaterials 23 (2002) 4295e4302.
[7] Y. Zuo, Y.B. Li, J.D. Li, X. Zhang, H.B. Liao, Y.Y. Wang, W.H.
Yang, Mater. Sci. Eng. A 452e453 (2007) 512e517.
[8] G. He, T. Dahl, A. Veis, A. George, Nat. Mater. 2 (2003) 552e558.
[9] R.A. Sousa, R.L. Reis, A.M. Cunha, M.J. Bevis, Compos. Sci.
Technol. 63 (2003) 389e402.
[10] L. Fang, Y. Leng, P. Gao, Biomaterials 27 (2006) 3701e3707.
[11] L. Fang, P. Gao, Y. Leng, Compos. Pt. B-eng 38 (2007) 345e351.
[12] C. Albano, L. Cataño, L. Figuera, R. Perera, A. Karam, G. Gon-
zález, K. Noris, Polym. Bull. (2009) 45e55.
581
[13] M. Younesi, M.E. Bahrololoom, Mater. Des. 30 (2009) 4253e
4259.
[14] C. Albano, R. Perera, L. Cataño, A. Karam, G. González, J. Mech.
Behav. Biomed. Mater. 4 (2011) 467e475.
[15] M. Wang, R. Joseph, W. Bonfield, Biomaterials 19 (1998) 2357e
2366.
[16] J.O. Eniwumide, R. Joseph, K.E. Tanner, J. Mater. Sci. Mater. Med.
15 (2004) 1147e1152.
[17] M. Flannery, T. Mcgloughlin, E. Jones, C. Birkinshaw, Wear 265
(2008) 999e1008.
[18] A. Greco, A. Maffezzoli, Polym. Test. 27 (2008) 61e74.
[19] S.M. Kurtz, O.K. Muratoglu, M. Evans, A.A. Edidin, Biomaterials
20 (1999) 1659e1688.
[20] F. Medel, E. Gomez-Barrena, F. Garcia-Alvarez, R. Rios, L. Gracia-
Villa, J.A. Puertolas, Biomaterials 25 (2004) 9e21.
[21] V. Premnath, A. Bellare, E.W. Merrill, M. Jasty, W.H. Harris,
Polymer 40 (1999) 2215e2229.
[22] ASTM D638-98, Standard Test Method for Tensile Properties of
Plastics, Annual Book of ASTM Standards, vol. 08.01, PA,
USA, 1999.
[23] H. Fouad, J. Appl. Polym. Sci. 118 (2010) 17e24.
[24] J.G. Williams, Fracture Mechanics of Polymers, Ellis Horwood,
UK, 1987.
[25] A.H.I. Mourad, H. Fouad, R. Elleithy, Mater. Des. 30 (2009) 4112e
4119.
[26] H. Fouad, R. Elleithy, J. Mech. Behav. Biomed. Mater. 7 (2011)
1376e1383.
[27] C. Parra, G. González, C. Albano, Macromol. Symp. 286 (2009)
60e69.
[28] Q. Wang, J. Liu, S. Ge, J. Bionic. Eng. 6 (2009) 378e386.
[29] H. Fouad, R. Elleithy, S.M. Al-Zahrani, A.M. Al-haj, Mater. Des.
32 (2011) 1974e1980.
[30] Y. Zhang, K.E. Tanner, J. Mater. Sci. Mater. Med. 14 (2003)
63e68.
[31] I. Ali, R. Elleithy, J. Appl. Polym. Sci. 122 (2011) 3303e3315.
[32] A. Chafidz, A.M. Al-haj, R. Elleithy, J. Mater. Sci. 46 (2011)
6075e6086.