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QPIC), and CoCr and alumina ceramic femoral heads (K-MAX
HHA) were obtained from Japan Medical Materials Co. (Osaka, Japan). For PMPC
grafting, PE and CLPE liners after coating with benzophenone as photosentisizer
were placed in the MPC aqueous solution (0.5 mol/L) and photoinduced polymeri-
Fig. 1. Contact angles of a water drop on PE plates with or without cross-linking and
PMPC grafting. Data are expressed as means (bars) standard errors (error bars) for 10
plates/group. *p < 0.01, signicant effects of PMPC grafting.
from 23 to 95%, depending on which conventional PE was used as
a control [14]. Another strategy for reduction of the wear particles is
the change of the femoral head material from metal to ceramics to
reduce the friction against the PE liner. Among them, alumina
ceramic is prevalent wi th substantially lower PE wear rates than
conventional metal heads [1517].
Considering that the healthy human joint cartilage surface is
covered wi th a nanometer-scaled phospholipid layer [18], grafting
a phospholipid-like layer on the liner surface may realize an ideal
lubricity resembling the physiological joint surface. We found that
the 2-methacryloyloxyethyl phosphorylcholine (MPC) polymers
are biocompatible and hydrophilic due to phospholipid polar
groups in the side chain [19,20]. The MPC polymers can suppress
biological reactions even when they are in contact wi th living
organisms [2125]. Medical devices such as intravascular stents,
soft contact lenses and the articial lung are used clinically using
the MPC polymers [2628]. Aiming at the elimination of peri-
prosthetic osteolysis, we have developed a novel hip CLPE liner
wi th poly(MPC) (PMPC) grafting on its surface, and found that the
graft dramatically decreased the production of wear particles
during 3 10
6
cycles in the hip joint wear simulator using the Co
Cr alloy femoral head [2931]. We also showed that the polymer
particles grafted wi th PMPC were biologically inert and did not
cause the subsequent bone resorptive responses [31]. For clinical
zation on the liner surface was carried out using an ultra-high pressure mercury
lamp (UVL-400HA, Riko-Kagaku Sangyo, Funabashi, Japan), as previously reported
Fig. 2. Dynamic coefcients of friction for the various types of PE plates against CoCr
alloy and alumina ceramic balls. Data are expressed as means (bars) standard errors
(error bars) for 5 plates/group. *p < 0.01, signicant effects of PMPC grafting.
Fig. 3. Wear amount of PE liners with or without cross-linking and PMPC grafting in
the hip joint simulator. (A) Time course of wear amount generated from PE, CLPE,
PMPCPE, and PMPCCLPE liners during 5 10
6
cycles of loading against CoCr alloy
femoral heads in the hip joint simulator. At intervals of 5 10
5
cycles the liners were
removed from the simulator, and the weight loss was determined as the wear amount.
(B) Water absorption of the liners which was only loaded axially to the femoral heads
without rotational motion to determine the water weight absorbed by the liners
during soak in the lubricant. Data are expressed as means (symbols) standard errors
(error bars) for 8, 10, 5 and 10 liners for PE, CLPE, PMPCPE, and PMPCCLPE liners,
respectively.
Please cite this article in press as: Moro T et al., Wear resistance of articial hip joints with poly(2-methacryloyloxyethyl..., Biomaterials (2009),
doi:10.1016/j.biomaterials.2009.02.020
ARTI CLE IN PRESS
T. Moro et al. / Biomaterials xxx (2009) 17 3
[30,31,34,35]. The wavelength of photopolymerization was selected by a glass color
l ter as 350 50 nm.
2.2. Surface analyses
The surface elemental conditions of the PE and CLPE liners or plates with and
without PMPC grafting were analyzed using highly sensitive X-ray photoelectron
spectroscopy (XPS AXIS-HSi165, Kratos/Shimadzu, Kyoto, Japan) equipped with
a 15-kV Mg-Ka radiation source at the anode. The functional group vibrations of the
surfaces were examined by Fourier-transform infrared (FT-IR) spectroscopy with
attenuated total reection (ATR) equipment. The FT-IR/ATR spectra were obtained
using an FT-IR analyzer (FT/IR615, JASCO, Tokyo, Japan) for 32 scans (1.2 s/scans)
over the range of 8002000 cm
1
at a resolution of 4.0 cm
1
. Hydrophilicity was
evaluated by the static water contact angles on the surfaces using the sessile drop
method with an optical bench-type contact angle goniometer (Model DM300,
Kyowa Interface Science, Saitama, Japan). Drops of puried water (1.0 mL) were
deposited on the liner surface, and the contact angles were directly measured with
a microscope 60 s after dropping, according to the International Organization for
Standardization (ISO) 15989 standard. At least ten contact angles were measured
and averaged.
2.3. Dynamic coefcient of friction
The dynamic coefcients of friction between the plates and the CoCr alloy
and alumina ceramic balls were measured using a ball-on-plate machine (Tri-
bostation 32; Shinto Scientic, Tokyo, Japan) as a preliminar y test for tribo-
logical properties [36]. A CoCr alloy and alumina ceramic ball wi th a diameter
of 9.0 mm was prepared. The surface roughness of the ball was about 0.010 mm,
which was comparable to that of the femoral head products. Each of the
untreated CLPE and PMPC grafted CLPE surfaces were used to prepare ve
sample pieces. The friction tests were performed at room temperature wi th
a load of 0. 98 N, sliding distance of 25 mm, and frequency of 1 Hz. Pure water
was used as the lubricant medium.
2.4. Hip joint simulator
A hip joint wear simulator test was performed under the conditions recom-
mended by the ISO standard [37]. A 12-station hip simulator apparatus (MTS, MTS
Systems, Minneapolis, MN, USA) with PE and CLPE liners with or without PMPC
grafting in 46 mm acetabular cups that were coupled to 26 mm CoCr alloy or
alumina ceramic femoral head were mounted on the rotating blocks to produce
a biaxial or orbital motion. A Paul-type loading prol e which is a physiological
walking simulation with continuous cyclic motion and loading was applied
(maximum force; 2744 N, frequency; 1 Hz) [38]. A diluted bovine calf serum
(25 vol%) in distilled water was used as the lubricant. Sodium azide (10 mg/L) and
EDTA (20 mM) were added to prevent microbial contamination and minimize
calcium phosphate formation on the implant surface. The simulator was run up to
5 10
6
cycles for 3 months. At intervals of 5 10
5
cycles the liners were removed
from the simulator and weighed on a microbalance (Sartorius GENIUS ME215S,
Sartorius AG, Gottingen, Germany) to determine the wear amount. The lubricant was
collected and stored at 20 C for further analysis. Since the liners are known to
absorb water during their soak in the lubricant, therefore we also measured the
weight gain of the liners which were cyclically axial-loaded to the femoral heads
without rotational motion (i.e., load-soak control) every 5 10
5
cycles to determine
the amount of wear sustained.
After the total loading, morphological change of the liner surface was measured
by a 3-dimensional coordinate measuring machine (XYZAX GS800B, Tokyo Seimitsu,
Tokyo, Japan). To evaluate the actual removal of material caused by wear, melt-
recovery experiments were performed and the liner surface was analyzed with
a confocal scanning laser microscope (OLS1200, Olympus, Tokyo, Japan) as previ-
ously reported [39]. For the femoral head surface, in addition to el d emission
scanning electron microscopy (SEM, JSM-6330F, JEOL DATUM, Tokyo, Japan) evalu-
ation, the surface roughness value Ra was measured using a roughness measuring
instrument (SURFTEST-501, Mitutoyo, Yokohama, Japan) with a 5 mm diameter
contact probe.
For isolation of wear particles, the lubricant after the loading was incubated
wi th 5.0 N NaOH solution in order to digest adhesive proteins that were
degraded and precipitated; the particles were then collected and under went
sequential l trati ons (0.1 mm of minimum pore size), as previously reported
[40]. Particle size was dened using the maxi mum dimensions determined by
the SEM analysis.
2.5. Statistical analysis
The results derived from each measurement in the static water contact angle
measurement and friction test were expressed as mean values and standard devi-
ation. Standard analysis of variance (ANOVA) was applied to the data of the existed
among those groups, in this study. Two combinations (e.g., PE and PMPCPE in the
static water contact angle measurement) were especially made with Students t-test
(p < 0.05).
Fig. 4. Optical ndings of the surfaces of the four liners and corresponding femoral heads in the hip joint simulator. (A) Three-dimensional morphometric analysis and (B) confocal
scanning laser microscopic analysis of PE, PMPCPE, CLPE, and PMPCCLPE liners surfaces before (pre) and after 5 10
6
cycles of loading in the hip joint simulator. Scale bars
200 mm. (C) SEM images of the CoCr femoral head surfaces before (pre) and after 5 10
6
cycles of loading. Scale bars 5 mm.
Please cite this article in press as: Moro T et al., Wear resistance of articial hip joints with poly(2-methacryloyloxyethyl..., Biomaterials (2009),
doi:10.1016/j.biomaterials.2009.02.020
4
ARTI CLE IN PRESS
T. Moro et al. / Biomaterials xxx (2009) 17
Fig. 5. SEM images of the wear particles isolated from lubricants of the simulators with four kinds of liners. Low (top; 5000) and high (bottom; 30,000) magnications of SEM
images of the wear particles isolated from lubricants of the simulators with four kinds of liners. Scale bars 1.0 and 0.1 mm, respectively.
3. Results
3.1. Surface analyses of PE plates with or without cross-linking
and PMPC grafting
Successful photoinduced graft polymerization of tMPC on both
PE and CLPE plates was conrmed by XPS and FT-IR/ATR spectros-
copy. The XPS for nitrogen (N1s) and phosphorus (P2p) atoms showed
the respective peaks at 403 eV and 133 eV only on the plates wi th
PMPC grafting (PMPCPE &PMPCCLPE), but not on those without it
(PE & CLPE). These peaks were characteristic of the phosphoryl-
choline present in the MPC units, since they were assigned to the
N