Biocompatible polymer composites based on ultrahigh molecular weight

polyethylene perspective for cartilage defects replacement

F.S. Senatov
a
, M.V. Gorshenkov
a,
, S.D. Kaloshkin
a
, V.V. Tcherdyntsev
a
, N.Yu. Anisimova
b
,
A.N. Kopylov
b
, M.V. Kiselevsky
b
a
National University of Science and Technology MISIS, Moscow, Russian Federation
b
N.N. Blokhin Russian Cancer Research Center of RAMS, Moscow, Russian Federation
a r t i c l e i n f o
Article history:
Available online 22 October 2012
Keywords:
UHMWPE
Composite
Biomaterial
Wear
Mechanical activation
a b s t r a c t
The purpose of this study was to evaluate mechanical properties, microstructure and biocompatibility of
nano-compounds obtained by mechanical activation of UHMWPE powder and several types of particulate
llers in a planetary ball mill. The effect of particle shape and concentration of Al
2
O
3
on properties of the
composite was investigated. The effectiveness of reinforcing a polyethylene matrix by mechanoactivated
alumina in the form of nanopowder or microspheres was shown. Reinforcing of the polymer by nanopar-
ticles signicantly improves wear-resistance. No signs of blood serum brin deposition on the surface of
the samples were observed. Also no signs of pathological changes in physiology or anatomy were noticed
on the animals with implanted samples. UHMWPE-based composites obtained by mechanical activation
and hot pressing and lled with ceramic particles can be used as a biocompatible material for the replace-
ment of cartilage.
2012 Elsevier B.V. All rights reserved.
1. Introduction
The development of synthetic implantates to replace cartilage
defects, for example, the replacement of joints, is an actual prob-
lem of modern medicine. Modern biocompatible materials, used
for joint implantates, must have high impact strength, wear-resis-
tance and corrosion resistance. Ultrahigh molecular weight poly-
ethylene (UHMWPE) is used in joint replacement prostheses
because of its excellent properties of bio-compatibility, chemical
stability, and low friction coefcient. To improve the functional
characteristics, such as strength, polymers may be reinforced with
hard inorganic llers [1]. Ultrane llers, including nanosized par-
ticles, are of particular interest. It was shown [2] that the use of
nanosized powders as llers for polymer matrices can signicantly
enhance the mechanical, tribological and other functional charac-
teristics of polymer composites.
Currently, for obtaining composite polymeric materials
mechanical activation of polymer and ller is widely used for
pre-processing of raw materials. Mechanical activation increases
the adhesion of the ller to the matrix [3,4]. Mechanical activation
also helps to reduce the particle size of polymers and in some
cases, may be accompanied by rupture of polymer chains, the
transformation of the crystalline and amorphous structures, the
appearance of oriented amorphous regions [59]. As noted in
[10], brous form of UHMWPE particles increases the contact area
of the particles during compaction and gets a denser structure than
in the case of spherical particles. Therefore in this paper, we pro-
pose to make a preliminary mechanical treatment of UHMWPE
powder and several types of particulate llers in a planetary ball
mill and evaluate microstructure and biocompatibility of obtained
nano-compounds.
2. Materials and experiment
UHMWPE powder Polinit-2 (OJSC Kazanorgsintez, Russia) with molecular
weight 2
.
10
6
g/mol was used as the polymer matrix, Al
2
O
3
was used as a strength-
ening phase in the form of nanopowder with 50 nm particles (JSC Siberian Chem-
ical Combine, obtained by plasma method) or microspheres with size 1000 nm
(National University of Science and Technology MISIS, obtained by pyrolysis of
ultrasonic aerosols). The rst stage of the process of polymer composite obtaining
was mechanical activation of UHMWPE powder and alumina with various ratios
in a planetary ball mill Fritsch Pulverisette 5 (Germany), equipped with agate grind-
ing bowl (500 ml) and alumina grinding balls (10 mm). The grinding bowl lling
with grinding bodies was 45 vol.%. Based on changes of morphology of the particles
of UHMWPE during mechanical activation the optimal duration was chosen. Hot
pressing of the mechanoactivated mixture was performed using a hydraulic thermo
press MEGA KSC-10A (Spain) on the following mode: compression load 76 MPa
with heating for 1.5 h from 20 C to 160 C, holding at this temperature for
30 min, followed by hot pressing with a load of 80 MPa and subsequent cooling un-
der pressure.
Study of the shape and size of the powder particles after the mechanical activa-
tions was performed with a scanning electron microscope JEOL JSM-6610LV (accel-
erating voltage 20 kV). For studying of non-conductive polymeric samples, the
surface of polymer composite samples was covered with a layer of platinum (10
20 nm) by Auto Fine Coater JFC-1600 (Jeol, USA).
0925-8388/$ - see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jallcom.2012.10.014

Corresponding author. Tel.: +7 9262810334.

E-mail address: mvg@misis.ru (M.V. Gorshenkov).
Journal of Alloys and Compounds 586 (2014) S544S547
Contents lists available at SciVerse ScienceDirect
Journal of Alloys and Compounds
j our nal homepage: www. el sevi er . com/ l ocat e/ j al com
To study the effect of particle shape and concentration of Al
2
O
3
on properties of
the composite microindentation, the determination of tensile strength and impact
strength were used. Microhardness measurements were performed using microind-
enter CSM Micro Indentation (CSM Instruments SA, Switzerland) with a load of
100 mN (the maximum depth of 200 microns, the depth resolution 0.3 nm). Mea-
surement of tensile strength, yield strength, elongation and Youngs modulus of
the specimen in tension was carried out according to Russian measurement stan-
dards (GOST11262-80) on Instron 150LX (USA) with the strain-rate 10 mm/min
using a rectangular sample measuring 60 10 2 mm. Toughness was determined
on samples of size 80 10 4 mm with a V-notch Charpy method in accordance
with Russian measurement standards (GOST 4647-80) on POE Instron 2000 (USA)
with a reserve of the pendulum energy 50 J.
Tribological tests were carried out in the regime of friction in distilled water by
pin-on-disk method on CETR-UMT-3 (Bruker AXS, Switzerland). Form of the test
sample: pin with a diameter of 6.3 mm and a length of 10 mm; counter-body: steel
45; sliding velocity 200 rpm, normal load 5 MPa, the test time 4 h, the length of fric-
tion 4 km, temperature 27 C. These parameters were similar to standard parame-
ters of cartilage friction tests in some other works [1113].
Biocompatibility of the samples (Al
2
O
3
/UHMWPE-0.50.5) was researched
in vitro and in vivo. Samples were sterilized in the 96% ethanol during 24 h and then
were dried in sterile conditions. We made our research on mouse bone-marrow
derived MSC (mesenchymal stem cells) and human broblasts. We took C57/BlackB
mouse bone marrow as a source of MSC. Cell concentration was 440 10
5
cell/ml.
MSC were placed on the surface of a sample, and cultivated in cultural medium
(RPMI-1640 (Sigma, USA) containing 10% heat-inactivated (56 C, 30 min) fetal bo-
vine serum (Hyclone Laboratories, Logan, UK), 2 mM L-glutamine and antibiotics
(100 lg/ml penicillin sodium salt and 100 lg/ml streptomycin sulfate (Sigma,
USA)) in 37 C, 5% CO
2
during 30 days xed by May Grunwald giemsa and staining
by hematoxylineosin [14].
For evaluation of brin dropping we took citrated healthy donor blood serum
and extracted plasma on the surface of the sample. After moistening of the samples,
we incubated them in blood serum during ve days, in 37 C and 5% CO
2
.
In vivo we researched sample toxicity in six mice C57/Black, they were narco-
tized by ether, skin on their back was dissected and 0.6 0.6 samples were im-
planted subcutaneously into 1 1 area. After 60 days mice were euthanized and
samples were taken out. Also connective tissue surrounding the sample was taken
out too. Samples were xed and stained.
Biocompatibility features were evaluated with light reecting microscopy, with
AxioScop 40 microscope (Zeiss, Germany).
3. Results and discussion
It was shown [15] that due to the high melt viscosity UHMWPE
particles can retain the shape of the initial particles after thermo
pressing. Owing to this fact the microstructure of UHMWPE can
be regarded as a polycrystalline structure in metals, where grains
are the particles of UHMWPE. An example of the UHMWPE struc-
ture is shown at the Fig. 1. Mechanical activation in certain modes
can contribute to obtaining a more dense structure of the compos-
ite by changing the shape of the original UHMWPE particles. The
hard reinforcing particles at a rate much smaller than the size of
the original polymer particles are distributed on the surface of
UHMWPE only. Therefore, the hard particles reinforce only the
grains boundary and do not reinforce the body of the UHMWPE
particle as it shown at Figs. 2 and 3.
The homogeneous tension composite without necking associ-
ated with high molecular weight of UHMWPE, while stretching
the compacted samples containing different amounts of micro-
spheres and ultrane alumina powder, is observed, and it conrms
the results of [16]. Both strength and Youngs modulus increase
was determined after addition of a ller in UHMWPE. According
to [17], reinforcing of the material by mechanically activated dis-
persed llers due to the retention of oxide particles in a polymer
matrix by van der Waals forces and hydrogen bonds with the
molecular chains of UHMWPE.
In accordance with previous study [18], the optimal polymer
lling was 3 wt.% of ceramic particles. Increasing of ultimate stress
limit by 38% and Youngs modulus in 2.85 times was achieved by
lling UHMWPE with alumina particles (Table 1). There is less
yield strength in the case of lling the polymer matrix by micro-
spheres. This fact can be explained by a smaller surface area
(12 m
2
/g) and spherical shape of particles, which can leave the ma-
trix under the load. Nanoparticles also have a greater surface area
(55 m
2
/g) and irregular shape, which increases the contact area
with the polymer matrix and improves the adhesion. Such behav-
ior of mechanical properties of polymeric composites is conven-
tional, reinforcing of polymer matrix with hard particles
(including nanosized powders) results in an increase of elasticity
modules and yield stress [19]. Very often this gain in elasticity
Fig. 1. SEM micrograph of quasibrittle fracture surface of UHMWPE-based
composite.
Fig. 2. Grain boundary of UHMWPE-based composite reinforced by Al
2
O
3
microspheres.
Fig. 3. Grain boundary of UHMWPE-based composite reinforced by Al
2
O
3
nanoparticles.
F.S. Senatov et al. / Journal of Alloys and Compounds 586 (2014) S544S547 S545
modulus and yield stress is desirable, because in most cases these
properties dene the stress limit of material under loading and it
does not undergo plastic deformation.
The destruction of UHMWPE, as other amorphouscrystalline
polymers, carried out by spreading of microcracks. Hard ceramic
particles inhibit the spreading of cracks that leads to an increase
of elongation. As a consequence, there was a signicant increase
in the impact strength of the composite. Positive effect on the im-
pact strength of the composite states in the case of lling by micro-
spheres is higher than in the case of lling by nanopowders,
because microspheres behave like closed pores.
The ratio of the elastic modulus of the nanocomposite to the
elastic modulus of bone tissue is 1:13 and 1:14 versus 1:21 in
the case of unlled UHMWPE, which is especially important be-
cause a large difference of the elastic modulus can lead to micro-
strain on the border of the prosthesis-bone and lead to
degradation of the implantate.
The friction coefcient has decreased in 2.5 times after 4 h of
friction in case of composite with microspheres in comparison
with pure UHMWPE, but increased in 1.4 times in the case of com-
posite with nanoparticles as it is shown in Fig. 4. But wear-resis-
tance has decreased in case of lling polymer matrix with
microspheres (Fig. 5). This can be attributed to the larger size of
microparticles compared with the nanoparticles and, most impor-
tantly, their spherical shape. Consequently, the ceramic particles
more active crumble from the polymer matrix during the loading,
leading to intensive wear of the composite body and counter-body.
Based on the tribological properties composites with nanoparticles
are preferred, because of higher wear-resistance. This fact is very
important for using this material in joint replacement operations.
We did not observed signs of blood serum brin deposition on
the surface of the samples. That is a good feature of material for
cartilage defects replacement, because brin dropping with follow-
ing calcication can cause decreasing of the smoothness of the
joint surface, pain and loss of function. Studying the surface of
samples showed absence of MSC monolayer on the surface, we no-
ticed only single adhered cells (04 cells/sm
2
) on the surface of the
tested samples after cocultivation with human broblasts (Fig. 6).
No signs of pathological changes in physiology or anatomy were
noticed on the animals with implanted samples. Studying the
microstructure showed absence of signs of colonization by recipi-
ent cells on the surface. The implantate for replacement cartilage
defects must not adhere cells of recipient tissues on its surface be-
cause this will result in decreasing its quality and characteristics.
So that characterizes Al
2
O
3
/UHMWPE composite as a very perspec-
tive for using as a implantate.
4. Conclusions
As a result of the investigation it was shown that UHMWPE-
based composites lled by ceramic particles with better
physicalmechanical properties can be obtained by mechanical
activation and hot pressing, and can be used as a biocompatible
material for the replacement of cartilage.
Table 1
Comparison of the values of various parameters for the pure UHMWPE and the composite material with 3 wt.% Al
2
O
3
of different types.
Ultimate
strength (MPa)
Youngs
modulus (MPa)
E
material
/E
bone
Yield strength
(MPa)
Elongation
(%)
Hardness
(MPa)
Impact elasticity
(kJ/m
2
)
UHMWPE 31.9 0.97 1:21 22.0 120 50 50
Composite with nanoparticles 40.0 1.53 1:13 26.5 160 109 63
Composite with microspheres 36.0 1.4 1:14 24.5 150 100 73
Fig. 4. Friction coefcients of UHMWPE and UHMWPE-based composites.
Fig. 6. UHMWPE-based composite surface with single adhered cells (04 cells/sm
2
)
after cocultivation with human broblasts.
Fig. 5. Wear of UHMWPE and UHMWPE-based composites.
S546 F.S. Senatov et al. / Journal of Alloys and Compounds 586 (2014) S544S547
According to the study of the complex mechanical properties of
composite materials based on UHMWPE, the effectiveness of rein-
forcing a polyethylene matrix by mechanoactivated alumina in the
form of nanopowder or microspheres was shown. Effect of micro-
spheres on the mechanical properties of the composite is compara-
ble to the effect of nanopowder, but the reinforcing of the polymer
matrix occurs to a much lesser extent, due to the smaller surface
area because of the spherical shape and smaller surface area. Be-
cause of this fact wear of samples with microspheres is much more
intensive. Therefore, the composites with nanoparticles are prefer-
able to use as implantates for replacement cartilage defects.
References
[1] N.N. Mallikarjuna, A. Venkataraman, T.M. Aminabhavi, J. Appl. Polym. Sci. 94
(6) (2004) 25512554.
[2] Mahfuz Hassan, S. Islam Muhammad, K. Rangari Vijaya, et al., Composites 35
(68) (2004) 543550.
[3] G. Wang, Y. Chen, Q. Wang, J. Polym. Sci. B 46 (8) (2008) 807817.
[4] H. Huang, J. Appl. Polym. Sci. 74 (6) (1999) 14591464.
[5] H. Huang, J. Appl. Polym. Sci. 78 (11) (2000) 20162024.
[6] M. Stranz, U. Koster, F. Katzenberg, J. Metastab. Nanocryst. Mater. 2425
(2005) 463466.
[7] J. Fonta, J. Muntasell, E. Cesari, Mater. Res. Bull. 36 (2001) 16651673.
[8] D. Esterly, B. Love, J. Polym. Sci. B 42 (1) (2004) 9197.
[9] M. Stranz, U. Koster, J. Alloys Comp. 434435 (2007) 447450.
[10] K.S. Han, J.F. Wallace, R.W. Truss, P.H. Geil, J. Macromol. Sci. Phys. B 19 (3)
(1981) 313349.
[11] J. Katta, Z. Jin, E. Ingham, J. Fisher, Osteoarthr. Cartilage 17 (2009) 662668.
[12] L. McCann, E. Ingham, Z. Jin, J. Fisher, Osteoarthr. Cartilage 17 (2009) 995
1000.
[13] Ines M. Basalo, Nadeen O. Chahine, Michael Kaplun, Faye H. Chen, Clark T.
Hung, Gerard A. Ateshian, J. Biomech. 40 (2007) 18471854.
[14] Hematoxylin and Eosin Staining of Tissue and Cell SectionsCold Spring Harb
Protoc, 2008. http://dx.doi.org/10.1101/pdb.prot4986.
[15] C.W.M. Bastiaansen, H.E.H. Meyer, P.J. Lemstra, Polymer 31 (1990) 1435
1440.
[16] S.L. Bazhenov, Fillers: Their Effect on the Failure Modes of Plastics, Plastics
Additives, Chapmen and Hall, London, New York, Madras, 1998. p. 252.
[17] D.S. Xiong, J.M. Lin, D.L. Fan, Biomed. Mater. 1 (3) (2006) 175179.
[18] F.S. Senatov, S.D. Kaloshkin, V.V. Tcherdyntsev, D.V. Kuznetsov, Russ Metall
(Metally) 4 (2012) 344349.
[19] S.-Y. Fu, X.-Q. Feng, B. Lauke, Y.-W. Mai, Composites: Part B 39 (2008) 933
961.
F.S. Senatov et al. / Journal of Alloys and Compounds 586 (2014) S544S547 S547