Processing and Mechanical Properties of Ultra-high Molecular Weight Polyethylene Reinforced by Silver Nanoparticles

Processing and Mechanical Properties of Ultra-high Molecular Weight

Polyethylene Reinforced by Silver Nanoparticles
Xueqin Kang*, Chi Yao, Lei Qiao, Gaofeng Ge, and Peizhong Feng
China University of Mining and Technology, Xuzhou, Jiangsu 221116, China
Received: 29 December 2014, Accepted: 31 January 2017

SUMMARY
The present study was designed to investigate the mechanical performance of ultra high molecular weight
polyethylene (UHMWPE) reinforced by silver nanoparticles. The Ag/UHMWPE nanocomposites were prepared
by a plate vulcanizing machine and tested with a contact angle micrometer, UMT friction tester, electronic
universal testing machine and MicroXAM three-dimensional profilometer to characterise the wettability, ball
indentation hardness, creep resistance, compression properties, and friction and wear performance. A scanning
electron microscope (SEM) was employed to describe the morphology of the Ag/UHMWPE nanocomposites
surfaces following the friction and wear tests. These results demonstrate that the compressive yield strength, ball
indentation hardness and creep resistance increased with an increase in the content of silver nanoparticles. The
contact angle of the Ag/UHMWPE nanocomposites with bovine calf serum decreases with an increase in the
content of silver nanoparticles and this change increases the wettability of the Ag/UHMWPE nanocomposites.
Therefore, the friction coefficient decreases, but the wear mechanism changes from scratch and furrow to fatigue
flakes when the mass fraction of silver nanoparticles exceeds 0.3%. The composite with a silver nanoparticles
mass fraction of 0.3% exhibits a low friction coefficient and good wear resistance.

Keywords: UHMWPE, Silver nanoparticles, Friction and wear, Composite material

1. INTRODUCTION
Ultra-high molecular weight
polyethylene (UHMWPE) is
a distinctive polymer with the
highest wear resistance, better
bio-compatibility1, lower friction2,
better chemical inertness and higher
impact resistance3 compared to any
other polymers. It has been used as
a bio-medical material for artificial
joint replacement 4 , engineering
bearing 5, valves and automotive
components. Despite the suitability
of UHMWPE for artificial joints,
there are challenges regarding
the wear properties of UHMWPE
components 6. To overcome these
problems, UHMWPE composites
were fabricated by adding reinforced
particles and fibre fillers. Carbon
*Corresponding author. Tel,: +86 13775984956, E-mail: cumtkxq@cumt.edu.cn (X. Kang)
©
Smithers Information Ltd., 2017
fibres7,8, kaolin5, natural coral particles9,
zirconium particles7, TiO210, Al2O311,
carbon nanotubes12-15, graphene16-18,
hydroxyapatite19-21, etc. were used
to improve the wear behaviour of
UHMWPE artificial joints. The
studies of UHMWPE composites in
abrasive wear conditions have been
investigated extensively by many
researchers. Chang 22 researched
UHMWPE filled with micro- and
nano-ZnO particles friction and wear
performance under dry sliding wear.
Senatov23 studied the fractographic
character of UHMWPE reinforced
by aluminium oxide, zinc oxide and
bronze powder. The mechanical and
abrasive wear resistance of UHMWPE
was improved by these additives;
however, the wear debris produced
in the process of friction and wear
became smaller. Livermore found
a positive correlation between the
amount of resorption of the proximal
part of the femur and the degree of
wear, and tests in vitro demonstrated
that the macrophage response to
particulate wear debris is dependent
on the number and size of added
particles24. Cells are more reactive
to small phagocytosible particles
and irregularly shaped particles than
to larger and more regularly shaped
particles. This induces artificial joint
infection25. To avoid artificial joint
infection, antiseptic materials can be
added into the UHMWPE artificial
joint. Silver ions have inhibitory
and antibacterial properties against
a broad spectrum of bacterial strains.
Owing to its unique properties,
silver nanoparticles have been used
recently for infection treatment. The
nanoscale features and the rapid
release of several silver species of
silver nanoparticles improve the
treatment efficiency26.

Polymers & Polymer Composites, Vol. 25, No. 9, 2017 683

 Xueqin Kang, Chi Yao, Lei Qiao, Gaofeng Ge, and Peizhong Feng
In this work, Ag/UHMWPE
nanocomposites were prepared by
using plate vulcanizing machine. The
effects of silver nanoparticles on the
UHMWPE mechanical properties were
studied. Compression performance,
contact angle, ball indentation hardness,
creep resistance, and friction and
wear performance of Ag/UHMWPE
nanocomposites were determined
using an electronic universal testing
machine, contact angle micrometer and
UMT friction tester. The worn surface
and wear volume were observed by
using a SEM and a three-dimensional
profilometer to investigate the friction
and wear mechanisms.
2. EXPERIMENTAL
2.1 Materials
Silver nanoparticles with an average
diameter of 25 nm and specific
surface area of 10~20 m2/g were
provided by Beijing DK S&T Ltd.,
China. UHMWPE powder GUR 4150
(molecular weight 9 000 000 g/mol) was
supplied by SCM Industrial Chemical
Co. Ltd., China. A silane coupling agent
(γ-aminopropyl triethoxysilane, trade
name: KH550) was purchased from
Shanghai Wenhua Chemical Pigment
Co. Ltd., China and used to introduce
reactive functional groups on the
surface of the silver nanoparticles.
2.2 Surface Modification of
Silver Nanoparticles
The silane coupling agent was dissolved
in an aqueous ethanol solution
containing 140 ml of ethanol and 10
ml of deionised water. The solution
was stirred for half an hour and then
silver nanoparticles were added. The
mixture was dispersed in an ultrasonic
cleaner for 3 min, and then stirred for
4 h by means of mechanical stirring
at 353K. The pH of the mixture was
adjusted to 9-10 by the addition of
sodium hydroxide solution. The
precipitate was collected and washed
with ethanol to remove the by-products,
and then dried at 373K under vacuum
conditions for 24 h.
684
2.3 Specimen Preparation
Firstly 0.1, 0.3, 0.7 and 1.0 wt%
of silver nanoparticles were mixed
homogeneously with UHMWPE
using a dry mechanical ball mill. The
mixing process took 4 h to complete:
2 h each for both the clockwise and
anticlockwise direction. After mixing,
the UHMWPE or Ag/UHMWPE
samples were preheated and hot
pressed at a temperature of 473K for
2 h at a test pressure of 15 MPa. The
final product with different dimensions
according to the standard was obtained
after cooling with the equipment to
room temperature. The roughness of
the sample surface was measured with
a contact-type roughness measuring
instrument (JB-4C) and the value was
a maximum of 0.08 μm.
2.4 Compression Performance
Test
The stress of wear-resistant material in
actual use was commonly compressive
stress.TheDinENISO604-2003standard
was used as the reference standard for
the compression experiment. The
sample size was 10 m×10 mm×5 mm,
the test instrument was a WDW-20
electronic universal testing machine
and the test speed was 1 mm/min. The
stress and strain were calculated using
the following equations:
σ = P/A0 (1)
where σ is the stress, in MPa, P the
experimental load, in N, and A0 the
original sectional area, in m2.
ε = (L0-L)/L0 (2)
Figure 1. Liquids on solid polymer at the different contact angle
Polymers & Polymer Composites, Vol. 25, No. 9, 2017
where ε is the strain, L the length of the
sample after deformation, in mm, and
L0 the original length of the sample,
in mm27.
2.5 Contact Angle Test
Contact angle measurements were
conducted according to the sessile
drop technique and the readings were
taken by a contact angle micrometer
(JC2000B).
To measure the contact angle, a
0.05 ml drop of bovine calf serum at
room temperature was deposited on
the UHMWPE and Ag/UHMWPE
nanocomposites surfaces. The bovine
calf serum drop was deposited on
the sample surface accurately with
a micro-syringe. Each sample was
tested ten times and the results were
then averaged. The contact angle θ is
illustrated in Figure 1.
As is well-known, the contact angle, θ,
for the non-wetting and wetting cases
are﹥π/2 and﹤π/2, recpectively28.
Bovine calf serum is commonly used
as a lubricant in wear measurements to
simulate the body fluid environment29.
2.6 Ball Indentation Hardness
Test
To properly obtain the hardness of
the UHMWPE and Ag/UHMWPE
nanocomposites, the experiment
tested the ball indentation hardness
of these samples. The UMT friction
tester (CETR, USA) was used to
test the hardness using the standard
of ISO 2039-1: 2003 standard as a
reference. The indenter comprised a
zirconia ceramic ball with a diameter
 Processing and Mechanical Properties of Ultra-high Molecular Weight Polyethylene Reinforced by Silver Nanoparticles
of 5 mm. The initial load was 9.8 N
and the test load was 49 N. Each
sample was tested ten times and
the results were averaged. The ball
indentation hardness is calculated using
the following equation, based on the
measured depths of the impression:
(3)
where Pmax is the test load, in N, on the
indenter, D is the diameter of the ball
indenter, in mm, and hmax is the reduced
depth of the impression, in mm.
2.7 Indentation Creep Property
Test
Viscoelasticity is a characteristic
property of UHMWPE and its
composites that produce creep
deformation under the action of force.
Serious creep deformation affects the
precision of UHMWPE artificial joint
and causes joint replacement failure.
The creep behaviour of materials,
to some extent, can be reflected by
the indentation creep30,31. Thus, the
experiment tested the indentation
creep resistance of the UHMPWE and
Ag/UHMWPE nanocomposites. The
indenter comprised a zirconia ceramic
ball with a diameter of 5 mm. The
constant load applied to the sample
was 49 N for a period of 1 800 s. In
the process of ball indentation, when
the load was increased to 49 N, the
indentation depth was set as zero and
the depth was noted20. Each sample
was tested seven times and the results
were then averaged
2.8 Friction and Wear Test
The friction and wear test was carried
on a UMT friction tester using a
zirconia ceramic ball sliding on
the UHMWPE and Ag/UHMWPE
nanocomposites with a reciprocating
amplitude of 10 mm and a velocity
of 2 mm/s. The zirconia ceramic ball
with a diameter of 5 mm and a surface
roughness of 0.01~0.03 μm was
mounted on the holder connected to
a three-dimensional force sensor. The
Polymers & Polymer Composites, Vol. 25, No. 9, 2017
applied normal load was 19.8 N. The
wear test was run under lubrication
conditions, in a bovine calf serum
diluted fluid, for a duration of 3 600 s.
The bovine diluted fluid was composed
of 25% (volume percent) bovine calf
serum and 75% (volume percent)
deionised water. The temperature of
the lubricant was 310±1K. Before and
after the wear test, each specimen was
cleaned in an acetone-filled ultrasonic
bath and dried. The wear volume
was taken as the wear parameter
in this study to eliminate the fluid
absorption effect. This was calculated
by a MicroXAM three-dimensional
profilometer. Each sample was tested
seven times and the results were then
averaged. The worn surfaces of Ag/
UHMWPE nanocomposites were
observed with a SEM.
2.9 Scanning Electron
Microscopy
To study mechanisms of wear, the worn
surfaces were examined in a scanning
electron microscope (SEM, FEI Quanta
TM 250). A typical image was chosen
for each material. The UHMWPE
surface was sputter-coated with gold
to increase conductivity to facilitate
Figure 2. Compressive stress-strain curve of Ag/UHMWPE nanocomposites
examination, and the sample chamber
was drawn to a low-vacuum with an
acceleration voltage of 20.0 kV.
3 EXPERIMENTAL RESULTS
AND DISSCUSSION
3.1 Compression Properties
Figure 2 shows the stress-strain curve
of the Ag/UHMWPE nanocomposites
at room temperature. According to
this curve, the compressive yield
stress was 16.82, 18.00, 18.76, 20.53
and 21.5 MPa for silver nanoparticle
contents of 0%, 0.1%, 0.3%, 0.7% and
1.0% at room temperature, respectively.
At these points the sample underwent
significant deformation, whereby
the height decreased, and the middle
part presented a cydariform shape.
As the stress gradually increased, the
samples continued deforming, and
finally the stress increased rapidly
while the compressive strain varied
little. Therefore, the compressive stress
of the Ag/UHMWPE nanocomposites
exhibited an increasing tendency when
the silver nanoparticle content increased
from 0% to 1.0%. Silver nanoparticles
restricted the chain movement of
UHMWPE during the compression
685
 Xueqin Kang, Chi Yao, Lei Qiao, Gaofeng Ge, and Peizhong Feng

process, increasing the compressive and then increased slowly. The final The change in ball indentation hardness
yield stress. The plasticity of the sample indentation depth decreased with an and creep properties can be attributed
was lost gradually, while its stiffness increase in silver nanoparticle content. to the following factors: first, the
increased. However, the Ag/UHMWPE hardness and creep properties of silver
nanocomposite samples did not reach Figure 3. Image from a microscope nanoparticles are better than UHMWPE;
failure after compressive yield, and of contact angle of Ag/UHMWPE second, silver nanoparticles dispersed
thus the compression performance nanocomposites and bovine calf serum in UHMWPE matrix impede the
of the samples with different silver movement of the UHMWPE molecular
nanoparticle content also showed good chain. The deformation produced
performance. by the UHMWPE matrix is smaller
under the same stress, and thus the
ball indentation hardness and creep
3.2 Wetting Properties
resistance increase with an increase
Figure 3 shows an image taken from in silver nanoparticle content.
a microscope picture of the contact
angle of bovine calf serum on an Ag/
UHMWE nanocomposite surface. Figure 4. Contact angle as a function of filling content for silver nanoparticles
Figure 4 shows the contact angles under
different silver nanoparticle contents at
room temperature. The contact angle
decreased with increasing silver
nanoparticle in the UHMWPE, and it
appeared a decline when the content
of silver nanoparticles increased.
According to the change in contact
angle, it can be seen that the wettability
of the Ag/UHMWPE nanocomposites
increased with an increase in the silver
nanoparticle content, mainly because
of the difference wettability of the
UHMWPE and the silver nanoparticles
with calf serum.

3.3 Hardness and Creep

Resistance
Figure 5 shows the ball indentation Figure 5. Ball indentation hardness as a function of filling content for silver
nanoparticles
hardness of Ag/UHMWPE
nanocomposites under different
silver nanoparticle content. The ball
indentation hardness of UHMWPE was
14.87 MPa, and this value increased
when silver nanoparticles were added.
The ball indentation hardness of Ag/
UHMWPE nanocomposites was 17.40,
18.63, 21.71 and 22.23 MPa at room
temperature when the content of silver
nanoparticles was 0.1%, 0.3%, 0.7%
and 1.0%, respectively.

Figure 6 shows the creep resistance of

the Ag/UHMWPE nanocomposites. It
can be seen that the indentation depth
of these nanocomposites increased
drastically in the first 200 s of the test,

686 Polymers & Polymer Composites, Vol. 25, No. 9, 2017

 Processing and Mechanical Properties of Ultra-high Molecular Weight Polyethylene Reinforced by Silver Nanoparticles

Figure 6. Indentation depth of Ag/UHMWPE nanocomposites as function of time 3.4 Friction and Wear
Performance
Figure 7 shows the friction coefficient
and wear volume of Ag/UHMWPE
nanocomposites under different silver
nanoparticle content at 310±1 K. It can
be seen from figure that the friction
coefficient decreased with an increase
in silver nanoparticle content, but the
overall change was low. During the
friction and wear process, an UHMWPE
transfer film formed on the surface
of the zirconia ceramic ball, leading
UHMWPE on UHMWPE wear.
The friction coefficient was mainly
determined by the wettability of the
Ag/UHMWPE nanocomposites. This
wettability improved with the addition
Figure 7. Friction coefficient and wear volume of UHMWPE at different silver
nanoparticle content of silver nanoparticles. This contributed
to the formation of a lubricating film
on the surface of the Ag/UHMWPE
nanocomposites and then caused a
decrease in friction coefficient.

The wear volume initially decreased

with an increase in silver nanoparticle
content, but increased when the content
increased from 0.3% to 1.0%. The
wear volume reduction below 0.3%
was mainly caused by two factors.
First, the ball indentation hardness,
creep resistance and compressive yield
strength are enhanced by the silver
nanoparticles, and the deformation of
the Ag/UHMWPE nanocomposites
decreases under the same load. Thus,
Figure 8. Wear morphology of (a) UHMWPE and UHMWPE samples reinforced
the wear volume is reduced. Second, the
with (b) 0.1%, (c) 0.3% and (d) 1.0% silver nanoparticles
wettability of UHMWPE is improved
by the silver nanoparticles and this
enhances the wear resistance of the Ag/
UHMWPE nanoparticles. Figure 8
shows the wear morphology of the Ag/
UHMWPE nanocomposites. It can be
seen from the figure that the friction
and wear mechanism is scratch and
furrow in UHMWPE andAg/UHMWPE
nanocomposites samples. Fatigue flakes
form when the silver nanoparticle content
is greater than 0.3%, and an increasing
number of fatigue flakes are produced
with increasing silver nanoparticle
content. Thus, the wear volume increases
when the silver nanoparticle content is
greater than 0.3%.

Polymers & Polymer Composites, Vol. 25, No. 9, 2017 687

 Xueqin Kang, Chi Yao, Lei Qiao, Gaofeng Ge, and Peizhong Feng
4. CONCLUSIONS
The following conclusions can be
drawn from this study:
1. The compressive yield strength of
the UHMWPE sample was 16.82
MPa, compared to 21.5 MPa with
a silver nanoparticle content of
1.0%. Therefore, the compressive
yield strength of UHMWPE
increased with an increase in silver
nanoparticle content.
2. The contact angle of the UHMWPE
with the bovine calf serum
decreased with an increase in silver
nanoparticle content, and thus the
wettability increased.
3. The ball indentation hardness
and the final indentation depth of
the UHMWPE sample was 14.87
MPa and 90.8 μm, respectively,
compared to 22.23 MPa and 68.7
μm with a silver nanoparticle
content of 1.0%. Therefore, the
ball indentation hardness and
creep resistance increased with
an increase in silver nanoparticle
content.
4. The trend of the friction coefficient
change is similar to the change in
contact angle at different silver
nanoparticle content. According
to the wear volume and wear
morphology, the composite with
the silver nanoparticles mass
fraction of 0.3% exhibited a low
friction coefficient and good wear
resistance.
In the future, significant efforts are
required to study the antibacterial activity
of Ag/UHMWPE nanocomposites in
joint implants.
688
ACKNOWLEDGEMENTS
This work was financially supported
by China Scholarship Council
(201606425077), the Fundamental
Research Funds for the Central
Universities (2015XKZD01),
the Priority Academic Program
Development of Jiangsu Higher
Education Institutions, and the National
Natural Science Foundation of China
(51275514).
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