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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


promise in solving the problem of bone resorption that has been
The concept of fabricating bioactive composites for bone re- encountered with the use of implants made up of other con-
placements by reinforcing a high-density polyethylene (HDPE) ventional materials[3e6]. The implants made of HDPE/HAP
matrix with a bioactive hydroxyapatite (HAP) was introduced in composite encouraged bone apposition rather than the fibrous
early 1980s[1]. The mechanical coupling of the reinforcement encapsulation which was encountered with other implant mate-
and the matrix is resulting from the shrinkage of HDPE matrix rials. Tanner et al.[2] have reported successful clinical applica-
and HAP particles during the composite processing[2]. The HAP tions of this composite as orbital implants to treat problems such
increases the stiffness of the composite and provides bioactivity, as post-enucleation socket syndrome and orbital floor fractures.
while HDPE provides toughness but bioinert. Therefore, the Also the HDPE/HAP composite can be used successfully as
mechanical and biological properties of HDPE/HAP composite middle ear implant.
can be tailored to meet specific clinical requirements. The closer 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
* Corresponding author. Prof.; Tel.: þ20 25558410; Fax: þ20 25558294;
E-mail address: menhfefnew@hotmail.com (H. Fouad).
to the low dissolubility and degradation of relatively large size of
1005-0302/$ e see front matter Copyright Ó 2013, The editorial office of HAP[8]. Recently, the nano-scale HAP has been developed and
Journal of Materials Science & Technology. Published by Elsevier an HDPE/HAP nano composite with acceptable properties can
Limited. All rights reserved. be easily processed. The nano HAP particles have high surface
http://dx.doi.org/10.1016/j.jmst.2013.03.020 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- typical nano-crystal size is less than 100 nm and the average
nous distribution in the polymer matrix. aggregate size is 2.5 mm with specific surface area of 100 m2/g.
The mechanical and rheological properties of HDPE/HAP
composite have been extensively studied[9e14]. Wang et al.[15] 2.2. Preparation of specimens
studied the effect of HAP particle size on the HDPE/HAP
composite properties. The results showed that the composites Weight ratios of 0, 10, 20 and 30 wt% of the HAP nano
with smaller HAP particles had higher torsional, tensile modulus particles were pre-mixed with neat HDPE pellets to get the
and tensile strength, but had lower fracture strain. Joseph et al.[6] required nano composite pre-blend. The pre-blend was com-
studied the effects of surface and morphology of HAP on the pounded in Farrell co-rotating intermeshing twin screw extruder.
rheology and processability of an injection molding grade The twin screw extruder has a diameter of 26 mm and length/
HDPE/HAP composite. Eniwumide et al.[16] investigated the diameter (L/D) ¼ 35. The screw speed was kept constant at 12 r/
effects of HAP morphology and PE molecular weight on the min. The temperature profile used (from feed to die) was 180,
fracture toughness of PE/HAP composite. 230, 235, 240, 240, 235, and 240  C. The extrudates from the
It is well known that PE and its composites have a viscoelastic extruder were cooled in a water bath at about 12  C, air dried,
behavior even under normal loading conditions. Their overall then palletized into granules. The granules were further dried and
mechanical properties change over time due to ageing either on conditioned in the lab environment for 40 h. An injection
shelf or in vivo. The ageing of PE and its composites causes molding machine (Asian Plastic Machinery, Double Toggle I
subsurface oxidative degradation (between 1 and 2 mm) under Machine, Super Master Series SM 120) was used to get a set of
the polymer surface[17]. This oxidative degradation causes standard ASTM D638 type-I tensile specimens[22]. Specimens
embrittlement of the polymer and loss of its overall mechanical were conditioned in a standard lab environment for 40 h before
properties. The characterization of ageing effects on the behavior further testing. ASTM D638 standard was used as our guide.
of PE and its composites that are used as bone substitutes will Although the standard recommends testing of at least 5 speci-
help in understanding and predicting the in vivo behavior of mens, ASTM standard allows testing fewer specimens if so
these composites with time. Because oxidation of PE (due to mentioned in the report. In the present study all the experimental
natural ageing) takes months or years to reach an appreciable tests were performed with 3 specimens. All the results presented
level at ambient or body temperature, thermal ageing techniques here are the median of the three measurements.
have been developed to accelerate the oxidation of PE with the
expectation that the material behavior after accelerated ageing 2.3. Ageing procedure
will be comparable to naturally aged ones. Based on this
assumption, accelerated thermal ageing has been widely used by The accelerated ageing of HDPE/HAP nano composite spec-
many researchers to investigate the resistance of PE to imens is performed in saline solution at temperature of 80  C for
ageing[18e21]. Using this ageing technique, from 5 to 10 years of 4 weeks that equals around 6 years of natural ageing[21]. In the
shelf ageing can be simulated within a time period of few weeks. present study, it is assumed that the ageing procedures used will
To the best of our knowledge, the effects of in vivo/in vitro result in ageing mechanism comparable to the real in vivo ageing
ageing on the properties of HDPE/HAP nano composite have not mechanism[23].
been investigated. Also, it is remarked that there is a lack of data
on the viscoelastic and bioactive behavior of HAP/PE nano
2.4. Characterization methods
composite. Therefore, the present study is a part of research
project that is intended to study the effects of accelerated ageing
The morphological studies of HDPE/HAP nano composites
on thermal, mechanical, viscoelastic and fracture behavior of
cryo-fracture surface and single edge notched (SEN) fractured
HDPE/HAP nano composites. Also, in this project, the effect of
samples were examined by scanning electron microscopy (SEM,
nano HAP ratio on the nano composite bioactivity will be
Joel, USA) at 15 kV. Prior to SEM examination, the nano
investigated. The main objectives of this part of the project are:
composite specimens were coated with a thin layer of gold to
(1) fabricating of HDPE/HAP nano composite by using melt
dissipate the build-up of heat and electrical charges.
blending in a co-rotating intermeshing twin screw extruder, (2)
Infrared radiation (IR) was performed in the attenuated total
studying the effects of HAP nano particles percentage and arti-
reflection (ATR) mode by using a Bruker Spectrum Tensor 27
ficial ageing on the thermal, rheological, viscoelastic, fracture
system equipped with an ATR cell with a diamond reflection
toughness, hardness and wear behavior of the HDPE nano
element. This machine was used for measuring and scanning the
composite.
IR absorption spectra of HDPE/HAP aged and non-aged nano
composite. Samples were applied directly onto the surface of
2. Experimental
ATR crystal. Spectra result from the accumulation of 16 scans at
4 cm1 resolution. The wavenumber range was 4000e
2.1. Material 400 cm1.
The single edge notched (SEN) specimens for the fracture
The polymer used in the present work is an injection molding toughness measurements were prepared by inducing a pre-crack
grade of HDPE which is referred as HDPE. The manufacturer to one side of the ASTM tensile sample (type-III) with a sharp
(SABIC Company SA) indicated that this HDPE has melt flow thin razor blade. The pre-crack length was fixed at 10% (a/D).
index of about 30 g/10 min and density of about 0.94 g/cm3. The Different SEN specimens were prepared as described and tested
estimated average molecular weight was about 700,000 g/mol for their fracture toughness. All of the reported measurements for
(calculated from the melt viscosity). The hydroxyapatite (HAP) all of the tests in this research represent the median of 3 ex-
nano particles were obtained from Fluidinova, Engenharia de periments. The tensile tests were performed at 50 mm/s. The
Fluidos, SA, Portugal. According to the manufacturer data, the fracture toughness (KI) of the neat HDPE and its nano composite
H. Fouad et al.: J. Mater. Sci. Technol., 2013, 29(6), 573e581 575

specimens were calculated according to Eq. (1) by SEN speci- before and after an impact is calculated. Hence, the hardness of
mens under tension[17,24]. Eq. (2) can also be used to calculate the material could be determined.
the fracture toughness considering the geometric correction The preliminary dry wear resistances of HDPE and HDPE/
factor Y2[24]. HAP nano composites were investigated by using the Taber
abrasion tester, ASTM D4060-10. A set of two rotating abrasive
pffiffiffiffiffiffiffiffi
KI ¼ s p a (1) 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
KI2 ¼ Y 2 ða=DÞs2 a (2) to 72 r/min for 10,000 cycles. The wear rate of the specimens
was determined by measuring the specimen weight loss.
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. 3. Results and Discussion
Calorimetric measurements for aged and non-aged HDPE/
HAP nano composite specimens were performed by means of 3.1. Morphological examination
differential scanning calorimetry (DSC, Shimadzu-60). Each
sample (about 7 mg) is sealed in an aluminum pan and heated The surface morphologies of HAP powder and HDPE/HAP
from 20 to 150  C at a rate of 5  C/min, then cooled down to composite specimens containing 20 and 30 wt% HAP are shown
30  C at cooling rate of 5  C/min. The DSC samples were taken in Fig. 1. A reasonable distribution of HAP particles was ach-
from the cross section of HAP/HDPE specimens which have ieved in the composite. Although the used HAP particles were in
2 mm thickness. Previous results indicated that the ageing the nano scale-range according to the manufacturer data, this
mechanism causes subsurface degradation under the polymer micrograph shows agglomeration of some nano particles to be in
surface up to 2 mm in depth[17]. The heat of fusion is calculated the micro scale-range (100 nm). This agglomeration could be
by integrating the area under the DSC endothermic peak for the attributed to the tendency of HAP nano particles to decrease their
first heat. The melting temperature is registered as the maximum contact surface with HDPE matrix. Therefore, bigger particle
point of the endothermic melting peak. The percentage crystal- size of HAP is clearly visible in the micrograph of composite
linity was calculated by normalizing the heat of melting to that of specimens. The HAP appears as bright spots distributed in the
100% crystalline PE (290 J/g), by the following equation[25e27]. dark HDPE matrix.

DHm 3.2. FT-IR results


Xc ¼ (3)
DHmþ
The Fourier transform infrared (FT-IR) spectra of the non-
where Xc is the degree of crystallinity, DHm is the specific aged HDPE and its HAP nano composites are shown in
enthalpy of melting, DHmþ is the specific enthalpy of melting Fig. 2(a). All the characteristic bands corresponding to HDPE are
for 100% crystalline PE. observed. In the spectrum of non-aged HDPE, the peaks at 700
The rheological and viscoelastic behavior of the HDPE/HAP and 1473 cm1 are observed which correspond to the rocking
nano composite were characterized by dynamic mechanical and bending vibrations of CeH, respectively. Two other peaks
analysis (DMA) via AR-G2 from TA, USA. The rheological are shown at about 2894 cm1, assigned to asymmetric CeH
properties were measured via a plateeplate geometry that had stretching, while symmetric CeH stretching occurs at
25 mm plate diameter, and a gap of 1.0 mm. The specimens were 2916 cm1. By comparing the spectra of HDPE/HAP specimens
heated to 190  C, stabilized at this temperature for 5 min. The with neat HDPE, it can be found that the transmittance intensity
specimens were tested over a frequency range from 0.01 to of the HDPE/HAP specimens is reduced. This decrease may
600 rad/s. The viscoelastic properties were measured under refer to a decrease of unsaturated groups due to cross-linking.
torsional arrangement. The specimens were heated to 80  C, When nano-scale HAP is added to HDPE with doping levels
stabilized at this temperature for 5 min, and then a frequency 10, 20 and 30 wt%, the spectra show two new peaks at about
sweep test was performed. The frequency sweep was performed 1055 and 1105 cm1. These new peaks can be assigned to the
from 0.1 to 600 rad/s. The temperature sweep experiment was vibrations phosphate groups from HA. Moreover, the intensity of
also performed at a fixed strain rate. these peaks was increased as doping levels of HAP increase.
The Rockwell hardness of HDPE and HDPE/HAP nano Fig. 2(b) shows the FT-IR spectra of aged neat HDPE and
composites was calculated from Leeb rebound test. Leeb test is a aged HDPE with different concentrations of nano-scale HAP.
typical rebound hardness test where the energy of an indenter The spectra with or without ageing effect have the same peaks

Fig. 1 SEM micrographs of HAP/HDPE nano composite and neat HAP powder: (a) 20 wt% HAP, (b) 30 wt% HAP, (c) HAP powder.
576 H. Fouad et al.: J. Mater. Sci. Technol., 2013, 29(6), 573e581

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
Fig. 2 FT-IR spectra of the neat (a) and aged (b) samples with nano composite displays more brittle characteristics than that of the
HAP. 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
with no observable difference except the small two peaks at results have been obtained for the fracture toughness mechanism
about 2400 and 2420 cm1. These two peaks can be assigned to of HDPE/CaCO3 micro composites[31].
intramolecular hydrogen bonded stretching OeH band.
3.4. Thermal properties
3.3. Fracture toughness measurements
In the present work, the DSC thermograms of tested material
Eq. (1) was used to calculate the fracture toughness of HDPE are divided into two main groups. The first is the non-aged
and its nano composites. The fracture toughness (KI) of the nano HDPE and HDPE/HAP nano composites. The second is the
composites was smaller than that of the neat HDPE as seen in accelerated aged HDPE and HDPE/HAP nano composites. For
Fig. 3. The nano particles acted as crack initiators or stress the first group, the thermal properties for the melting (first heat)
raisers in the nano composite that induce failure at low stresses of neat HDPE and HDPE/HAP nano composites with different
and strains. Also, the presence of HAP nano particles restricted HAP content are shown in Fig. 6. This figure shows the DSC
the molecular mobility of HDPE matrix[15,28]. In other words, the results of the first heat for HDPE and HDPE/HAP nano com-
addition of nano HAP led the composites specimens toward posite with 10, 20 and 30 wt% HAP nano particles. These results
brittle behavior and reduced the fracture toughness[26,29]. Similar indicate that the melting temperature (Tm) decreases with
trends for the fracture toughness of HDPE/HAP composite have increasing HAP nano particles percentage as listed in Table 1.
been obtained by Zhang and Tanner[30] where the fracture These data imply that the HAP filler has some influence on the
toughness of the composite decreased with increasing HAP 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/
Fig. 3 Variation of the fracture toughness (KI) with the HAP HAP composite to be faster and results in thin lamellar formation
percentage. 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 degree of crystallinity compared to non-aged material. The chain
a lower value. scission produces an overall decrease in tie molecules, allowing
Fig. 7 shows the DSC results of the first heat for accelerated for lamellar rapprochement and reordering which resulting in an
aged HDPE and HDPE/HAP composite with 10, 20 and 30 wt% increase of the crystallinity as indicated in the DSC results.
HAP nano particles. These results indicate that the melting Similar results have been obtained by Fouad[23] for ultra high
temperature (Tm) decreases due to ageing while the crystallinity monocular weight polyethylene (UHMWPE) where the degree
increases. These results show that the crystallization of aged of crystallinity increased due to ageing.
composites has the same trend like the non-aged ones. The
crystallinity of accelerated aged specimens is 5%, 6.4%, 4%, 3.5. Rheological behavior of HA/HDPE nano composites
6.5% higher than that for non-aged specimens for neat HDPE,
10, 20 and 30 wt% HDPE/HAP, respectively. The relationship between the complex melt viscosity and the
The changes in the DSC results of aged HDPE and its nano angular frequency at 190  C of non-aged HDPE and
composites can be attributed to the oxidation and chain scission HDPE þ 10, 20 and 30 wt% HAP nano particles is shown in
of the tested material due to accelerated ageing. The tested Fig. 8. This figure shows that the viscosity of HDPE/HAP nano
polymer chain scission process allows further crystal perfection composites is higher than that of the neat HDPE especially at
and growth to occur. Therefore, the aged HDPE has higher 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


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].
Fig. 6 Thermogram showing the melting behavior of non-aged HDPE The effects of testing temperature on the viscoelastic proper-
and its composites. 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
regions; (i) high shear thinning at lower frequencies, and (ii) low show that the G0 and G00 significantly decrease with increasing
shear thinning at higher frequencies. The increases in the nano testing temperature. The reduction in the values of G0 and G00
composite viscosity can be attributed to the restriction of the obtained at higher temperature can be justified by the higher
molecular mobility and the reduction of the free volume that are mobility of polymer chains at elevated temperature.
induced by the addition of the HAP nano particles. Compared to the non-aged HDPE and HDPE/HAP specimens,
Similar trends have been also obtained for the variation of the accelerated ageing results in remarkable decrease on the
complex melt viscosity and the angular frequency for aged tested material storage and loss modulus for all testing fre-
HDPE and its nano composites. Only the viscosity of aged quencies as indicated in Fig. 13. For example, for pure HDPE at
HDPE/HAP nano composites is higher than that of the non-aged 0.1 rad/s, the storage modulus decreases from 5  1011 to
ones. This increase in complex melt viscosity can be attributed to 2.5  108 Pa due to ageing. The reduction in the mechanical
increasing crystallinity of specimens due to ageing as indicated properties of aged HDPE specimens and its nano composites is
in the DSC results. regarded to the material oxidation and its corresponding chain
scission. The chain scission process results in an increase of
3.6. Dynamic mechanical analysis polymer crystallinity (due to lamella thickening), breakage of the
polymer long chains, reduction of tie molecules, reduction in the
Plots of storage (G0 ) and loss modulus (G00 ) at different fre- tested material molecular weight, increase in material brittleness,
quencies for non-aged HDPE and its HAP nano composites are 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 581

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