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Tribological characteristics of polyvinylpyrrolidone (PVP) as a lubrication

additive for artificial knee joint

Article in Tribology International · January 2016

DOI: 10.1016/j.triboint.2015.08.043

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 Tribology International 93 (2016) 214–219

Contents lists available at ScienceDirect

Tribology International
journal homepage: www.elsevier.com/locate/triboint

Short communication

Tribological characteristics of polyvinylpyrrolidone (PVP)

as a lubrication additive for artificial knee joint
Yang Guo a, Zhixiu Hao a,b,n, Chao Wan c,nn
a
Department of Mechanical Engineering, Tsinghua University, Beijing 100084, PR China
b
State Key Laboratory of Tribology, Tsinghua University, Beijing 100084, PR China
c
Department of Engineering Mechanics, Tsinghua University, Beijing 100084, PR China

art ic l e i nf o a b s t r a c t

Article history: The effect of polyvinylpyrrolidone (PVP) on tribological properties of joint prostheses is still unclear
Received 11 June 2015 despite its good lubricity and biocompatibility. PVP solutions with five concentrations were prepared
Received in revised form with two different solvents. The viscosity, surface tension, and static contact angle of the solutions were
26 August 2015
measured as well as the friction coefficient and wear volume of artificial joint pairs. With PVP con-
Accepted 28 August 2015
centration increasing, the friction coefficient firstly decreased significantly but subsequently tapered off
Available online 7 September 2015
after a high level. The inclusion of PVP also improved the wear resistance of the pair. It implies that PVP
Keywords: could be a promising lubrication additive for artificial joints.
Polyvinylpyrrolidone & 2015 Elsevier Ltd. All rights reserved.
Lubrication
Artificial knee joint
Tribological properties

1. Introduction behaviours, such as charged polymer brushes-grafted hollow silica

Total knee arthroplasty (TKA) is a usual clinical treatment for
knee osteoarthritis. However, the number of TKA revision is
increasing greatly every year all over the world because of the
longer survival of TKA patients as well as their raising activity
intensity [1]. It was reported that the TKA revision rate increased
to 16%, 26%, and 31% for five, ten, and fifteen years after the pri-
mary TKA, respectively [2]. Aseptic loosening, one of the major
reasons for the revisions, is caused by wear debris. Nowadays
some improvements of the tribological property of artificial joints
have been attempted by pretreating the titanium alloy using
thermal oxidation [3], modifying surface using hexadecylpho-
sphonic acid films [4], and adding lubricants into the artificial
joints [5–8]. Compared to the first two methodologies, adding
lubricants is more convenient and easier for achieving great tri-
bological properties in the artificial joints (f.i., lower friction
coefficient). Polyethylene glycol (PEG) was considered into syno-
vial fluid for increasing the wear resistance of UHMWPE in artifi-
cial knee joint but no significant great result was achieved [5].
Some other lubricants were also used for improving tribological
n
Corresponding author at: State Key Laboratory of Tribology, Tsinghua Uni-
versity, Beijing 100084, PR China
nn
Corresponding author.
E-mail addresses: haozx@tsinghua.edu.cn (Z. Hao),
chaowan@tsinghua.edu.cn (C. Wan).
nanoparticles [7], and poly(3-sulfopropyl methacrylate potassium
salt) brushes grafted poly(N-isopropylacrylamide) microgels [8].
Although low friction coefficient was obtained by these lubricants,
the conditions of the friction pair (i.e., steel-to-steel and PDMS-to-
Si in the studies) were greatly different from that in the artificial
joints (i.e., Ti6Al4V-to-UHMWPE). In a research of fabricating
artificial cartilage, mixing 15 wt% polyvinylpyrrolidone (PVP) in
polyvinylalcohol (PVA) hydrogel was found to decrease the friction
coefficient by about 30% [6]. However, it is still unclear whether
some lubricants could improve the tribological properties of the
Ti6Al4V–UHMWPE friction pair.
PVP is one of biocompatible water-soluble polymers and has
been used as blood plasma substitutes as well as in articular car-
tilages [9–11]. Besides its good biocompatibility, PVP aqueous
solution also has good lubricating properties. The friction coeffi-
cient, wear scar diameter, and seizure load of PVP aqueous solu-
tions were measured under the four-ball tribotester condition and
good lubricating properties of water were achieved by adding a
lower concentration of PVP [12]. However, the four-ball tribotester
condition is totally different with articular knee joints that consist
of Ti6Al4V balls and ultra-high molecular-weight polyethylene
(UHMWPE) liner. In addition, only a lower range of the PVP con-
centration (i.e., from 0 to 5 wt%) was analyzed in their study.
Therefore, whether PVP is a promising lubricating additive in
artificial joints is still unclear and needs to be determined. In this
paper five different PVP concentrations from 0 to 20 wt% were

http://dx.doi.org/10.1016/j.triboint.2015.08.043
0301-679X/& 2015 Elsevier Ltd. All rights reserved.
 Y. Guo et al. / Tribology International 93 (2016) 214–219 215

tested as well as two different solvents (i.e., deionized water and

25% bovine serum solution). The test condition was designed to be
similar as the physiological conditions of the artificial joints, i.e.,
Ti6Al4V balls, UHMWPE disc, and at body temperature. The visc-
osity, surface tension, static contact angle, friction coefficient and
wear volume for the PVP solutions with different concentrations
were measured and compared. We hypothesised that PVP could be
a potential effective lubricant for artificial knee joint and the
change of the PVP concentration would have a significant influ-
ence in the lubricating properties of the PVP solutions.

2. Materials and methods

2.1. Materials

Medical grade PVP K30 (Jiaozuo Zhongwei Special Products

Pharmaceutical Inc., Henan province, China) was dissolved in
deionized water and bovine serum aqueous solution. The mole-
cular mass of PVP K30 is 40,000 g/mol [9]. The bovine serum
aqueous solution (with 25% bovine serum concentration) was
prepared by diluting bovine serum (Thermo Fisher Scientific Inc.,
MA, USA) with deionized water. In order to study the effect of PVP
on the lubricating properties of knee joint prosthesis, five PVP
concentrations were selected for the above two solvents, corre-
sponding to 0, 5, 10, 15, and 20 wt% of PVP in the deionized water
as well as in the bovine serum aqueous solution. These five PVP
concentrations were selected according to some previous studies
about manufacturing artificial cartilages with PVP and poly(vinyl
alcohol) (PVA) [6,13]. All the preparations of the PVP solutions
were carried out at room temperature.
Both Ti6Al4V balls (surface roughness of around 60 nm) and
UHMWPE discs (surface roughness of around 110 nm) were cho-
sen as the two components of the friction pair for simulating the
practical interface in the artificial knee joints. The Ti6Al4V balls
(about 8 mm diameter) were purchased from Changda Inc.
(Guangdong province, China) and UHMWPE discs were provided
by Röchling Engineering Plastics KG (Haren, Germany).
2.2. Tribological characterisation of PVP solutions
The viscosities of the PVP solutions were obtained at 37 °C
using Anton Paar Physica MCR301 (Anton Paar GmbH, Graz, Aus-
tria) with shear rate from 1 to 3000/s. According to the high
evaporation rate of the droplet at 37 °C, the static contact angles of
the PVP solutions on the UHMWPE discs were measured at room
temperature by Dataphysics OCA20 (DataPhysics Instruments
GmbH, Filderstadt, Germany). The surface tensions of the solutions
were also tested at room temperature using Dataphysics DCAT21
(DataPhysics Instruments GmbH, Filderstadt, Germany) by the
Wilhelmy plate method, where the plate was made from platinum
which ensured complete wetting in the liquid. The viscosity, sur-
face tension and static contact angle for each PVP concentration
were measured 6–8 times using the corresponding PVP solution
for eliminating measuring errors.
In order to analyze the lubricating effect of the PVP solutions on
the knee joint prosthesis, the friction coefficients of all the 10 PVP
solution groups (i.e., five different concentrations of PVP in two
different solvents) were tested using a universal ball-on-disc
machine UMT-3 (Center for Tribology Inc., California, USA). Both
the Ti6Al4V ball and the UHMWPE disc were ultrasonic cleaned
firstly, and were mounted in the UMT-3 with the friction surface
immersed in the PVP solution (shown in Fig. 1). According to the
standard test method for total joint prostheses (i.e., ASTM F732), a
compression load of 2.94 N was exerted (yielding a maximum
Hertzian pressure of 29.7 MPa on the contacting surface) and a
Fig. 1. Schematic of the experiments for the PVP solutions with five different
concentrations as well as two solvents. Ti6Al4V balls (A) were loaded on the
UHMWPE discs (B), and a reciprocating stroke was performed under the PVP
solutions (C).
reciprocating sliding with 15 mm stroke was performed at the
speed of 30 mm/s. It was found that the results of the friction
coefficient became stable after a long duration (shown in Fig. 2).
Therefore, the reciprocating stroke was maintained for 5 min and
the friction coefficient of each PVP solution was determined by
averaging the friction coefficient measurements in the last one
minute. The friction coefficient measuring test was performed six
times for each PVP solution.
Further, two PVP concentrations with the two solvents (i.e.,
0 and 15 wt% in the deionized water and the bovine serum solu-
tion) were compared in the wear test of the Ti6Al4V–UHMWPE
pair. Higher compression load (5.29 N), longer stroke length
(18.5 mm), higher frequency (2 Hz), and longer test period (4 h)
were selected from the ASTM F732 test standard to accelerate the
wear of the samples. Then both three-dimensional morphology
and volume of the wear tracks on the UHMWPE discs were mea-
sured by a three-dimensional confocal microscope phase shift
MicroXAM-3D (KLA-Tencor Corporation, California, USA). The
volume of the wear tracks was calculated by multiplying the
average cross sectional area of the wear tracks and the stroke
length. The temperature during the whole friction and wear tests
was controlled at 37 ± 1 °C for simulating the in vivo temperature
of the joint prosthesis. The wear test was performed three times
for each PVP solution.
2.3. Statistical analysis
Two-way analysis of variance (two-way ANOVA) was used to
identify any significant difference in the friction coefficient values
of the PVP solutions with different concentrations as well as sol-
vents. A Bonferroni adjustment was chosen for all the multiple
comparisons. The viscosity, surface tension and static contact
angle from the different groups were also compared using two-
way ANOVA, respectively. Student's t-test (t-test) was used to
analyze the difference in wear volume between the PVP solutions
with different concentrations. Significance for all the tests was
defined as P o0.05.
216 Y. Guo et al. / Tribology International 93 (2016) 214–219

Fig. 2. Typical curves of friction coefficient vs. time for different PVP solutions with Ti6Al4V balls sliding on UHMWPE discs. (a) The PVP deionized water solutions; (b) the
PVP bovine serum solutions.

3. Results aqueous solution decreased with the PVP concentration increas-

3.1. Viscosity
The viscosity values of the PVP solutions with different con-
centrations are shown in Fig. 3(a). Regardless of the solvent, the
viscosity became higher with the PVP concentration increasing. The
viscosity of the PVP bovine serum solution was similar to that of the
PVP deionized water solution under the concentration of 0 and 5 wt%,
but became significantly higher when the concentration was beyond
5 wt%. Compared with the deionized water (i.e., 0 wt% PVP), the 5 wt%
PVP aqueous solution had a viscosity with about two-fold value. Each
5% increase of the PVP concentration led to about one time increase of
the solution viscosity. Similar trend was found in the variation of the
bovine serum solution viscosity with the PVP concentration varying.
3.2. Surface tension
Fig. 3(b) shows the surface tensions of the PVP solutions with
the different concentrations. The surface tension of the PVP
ing, whereas that in the PVP bovine serum solution increased
greatly. The largest decrease of the surface tension in the PVP
aqueous solutions was found between 0 and 5 wt% concentrations
(71.970.0712 mN/m vs. 67.770.0414 mN/m). On the contrary, the
surface tension of the PVP bovine serum solution increased sig-
nificantly during the PVP concentration increasing from 0 to
20 wt%.
3.3. Wettability
The static contact angles of the different PVP solutions on the
UHMWPE disc are shown in Fig. 3(c). The static contact angle of
the PVP deionized water solution on UHMWPE was significantly
lower than that of the PVP bovine serum solution when the con-
centration was 0 wt% (P o0.05). With the PVP concentration
becoming higher, the contact angle of the PVP deionized water
solution had some increase while that of the PVP bovine serum
solution decreased a little. But no significance was found between
the two solutions with the concentration being 5, 10, and 15 wt%.

Fig. 3. Comparisons of the tribological characteristics of different PVP solutions in the friction pair of Ti6Al4V balls and UHMWPE discs. (a) Viscosity; (b) surface tension;
(c) static contact angle; (d) friction coefficient.
 Y. Guo et al. / Tribology International 93 (2016) 214–219 217

When the concentration was 20 wt%, the contact angle of the PVP 0.060 for the bovine serum solution. The wear resistance of the
deionized water solution was significantly higher than that of the UHMWPE disc was also improved significantly under the 15 wt%
PVP bovine serum solution (P o0.05). PVP solutions compared to that under the 0 wt% PVP solutions
(Fig. 5). These measurements signify PVP contribute to the lubri-
3.4. Lubricating properties cating properties of the artificial knee joint pairs. According to
both its low toxicity [14] and good lubricating properties, moder-
Fig. 3(d) shows the friction coefficient of the PVP solutions with ate PVP concentrations (i.e., 10 wt% or 15 wt%) might be appro-
different concentrations under the Ti6Al4V ball-UHMWPE disc priate to be used as a promising lubricating additive in the artifi-
friction pair. About 50% reduction of the friction coefficient was cial knee joints.
found during the increase of the PVP concentration. The friction Further analysis of the lubrication regime in the Ti6Al4V–
coefficient of the PVP deionized water solutions changed from UHMWPE pair was developed as follows. First, the friction coef-
about 0.090 to about 0.042 and that of the PVP bovine serum
ficient is demonstrated to be higher with the viscosity increasing
solutions decreased from about 0.12 to about 0.060. However, no
under hydrodynamic lubrication regime according to the Stribeck
significant decrease was measured in the friction coefficient when
curve. But the friction coefficient in our study was found to
the PVP concentration reached up to some levels, i.e., 15 wt% for the
decrease with the increase of the solution viscosity (shown in
deionized water solution and 10 wt% for the bovine serum solution.
Fig. 6). It indicates that hydrodynamic lubrication is not formed in
the Ti6Al4V–UHMWPE pair. For determining the lubrication
3.5. Wear volume
regime, the ratio result (λ) representing relative film thickness was
The three-dimensional morphology of the wear tracks on the
UHMWPE discs is shown in Fig. 4. It was found that the wear
tracks were all obvious regardless of the solvent and PVP con-
centration. However, the comparison of the volume of the wear
tracks indicated that the wear volume under the 15 wt% PVP
concentration reduced significantly by 20% and 36% compared to
that under the 0 wt% PVP concentration with deionized water and
bovine serum solution, respectively (shown in Fig. 5).

4. Discussion

In our study both the friction coefficient and wear resistance in

the Ti6Al4V–UHMWPE friction pair were measured under PVP
solutions with different concentrations. The friction coefficient Fig. 5. Volume of the wear tracks on the UHMWPE discs after 4-h wear test.
was reduced significantly (about 50%) by increasing PVP, from (a) 0 wt% PVP in deionized water; (b) 15 wt% PVP in deionized water; (c) 0 wt% PVP
0.090 to 0.042 for the deionized water solution and from 0.12 to in bovine serum solution; (d) 15 wt% PVP in bovine serum solution. *Po 0.05.

Fig. 4. The three-dimensional morphology of the wear tracks on the UHMWPE discs after 4-h wear test. (a) 0 wt% PVP in deionized water; (b) 15 wt% PVP in deionized
water; (c) 0 wt% PVP in bovine serum solution; (d) 15 wt% PVP in bovine serum solution.
218 Y. Guo et al. / Tribology International 93 (2016) 214–219
Fig. 6. Friction coefficient vs. viscosity of PVP solution with different kinds of
solvent.
further calculated [15], which was defined as
Hmin
λ=
R a2ball + R a2disc
where Hmin is the minimal lubrication film thickness, Raball is the
surface roughness of the Ti6Al4V ball, and Radisc is that of the
UHMWPE disc. Hmin is determined from the previous paper [16] as
⎛ η μ ⎞0.65 ⎛ F ⎞−0.21
Hmin = 7.43 1 − 0.85e−0.31 R ⎜ 0 ⎟
( ) ⎜ ⎟
⎝ E‵R ⎠ ⎝ E‵R2 ⎠
where R is the radius of the Ti6Al4V ball, η0 is dynamic viscosity of the
PVP solution, μ is mean surface velocity μ = ( μball + μdisc )/2 = 15 mm/ s ),
2
2 1 − v ball
and F is the load. The parameter E‵ is defined as ( +
E ball
where Eball , vball and vdisc , are the Young's modulus and Poisson's
ratio of the Ti6Al4V ball and UHMWPE disc, respectively. It is con-
cluded that the ratio λ is less than 1, between 1 and 3, and more
than 3 when the pair is under boundary lubrication, mixed lubri-
cation and fluid film lubrication, respectively [15]. The λ values were
calculated to be less than 1 for all the PVP solutions in this study,
indicating the similar conclusion that boundary lubrication regime
is formed in the friction pairs.
As it formed boundary lubrication, it is suggested that mole-
cules adhered to the friction surface might be the main factor for
reducing the friction coefficient. The variation of the friction
coefficient with the PVP solutions changing could support the
hypothesis of the lubrication mechanism. First, the friction coef-
ficient would remain constant since the PVP concentration reaches
up to a high level. The concentration level of the PVP bovine serum
solution was also found to be lower than that of the PVP deionized
water solution for attaining the stabilisation of friction coefficient
(i.e., 10 wt% vs. 15 wt%). These could be resulted from the amount
of the PVP molecules adhered to the friction surfaces. The amount
of the PVP molecules on the surfaces, i.e., the friction properties,
would not be influenced by the change of the PVP concentration
since the PVP molecules on the surfaces reached saturation. In
addition, the friction coefficient of the bovine serum solution
levelled off more early than that of the deionized water solution
when the PVP concentration increased. This could be explained by
the adhesion of some proteins of the bovine serum solution on the
surfaces of the friction pair. The adhesion of the proteins would
induce less available space for PVP molecules on the surfaces of
the joint prostheses, which manifested that the friction coefficient
of the PVP bovine serum solutions attained stabilisation at a lower
concentration. The adhesion of the proteins of the bovine serum
solutions also accounted for that higher friction coefficient was
obtained from the PVP bovine serum solutions than the PVP
deionized water solutions (shown in Fig. 3(d)).
However, there are still some limitations in our study. First, the
sliding movement used in the friction and wear test was not the
same as the real movement in the artificial joints although the
selected movement has met the test standard of total joint pros-
theses (i.e., ASTM F732). Some friction tests of the PVP solutions
will be performed under the physiological loading conditions of
sliding and rolling in the future. Second, whether high PVP con-
centrations have serious toxicity for the tissues around artificial
joints should be justified. The PVP solutions with different con-
centrations might have different osmotic pressure, and its effect
needs to be analyzed. Third, the time of the wear test in the paper
is a few short compared to the service life of artificial joints in
human body. The wear test with longer time would be developed
where the morphology of wear debris should be characterized as
well as its biological influence.
5. Conclusions
It is known that PVP is a good lubricant with outstanding
biocompatibility. However, whether PVP provides a lubricating
role in artificial joints is still unclear. In this paper we investigated
the viscosity, surface tension, and static contact angle of different
PVP solutions with five concentrations and two solvents. Both the
friction coefficient and wear volume of the friction pair were
measured in the friction/wear tests where the physiological con-
ditions were simulated by Ti6Al4V balls, UHMWPE disc, and body
temperature. It was found that the friction coefficient decreased
significantly with PVP concentration increasing, but subsequently
tapered off after a high concentration (i.e., 10 wt% for the PVP
1 − v2
disc )
bovine serum solution and 15 wt% for the PVP deionized water
Edisc
solution). The wear resistance of the UHMWPE disc was also
improved significantly by the inclusion of PVP. According to the
good lubricating property and biocompatibility of the PVP in the
artificial joint pairs, it seems that PVP could be considered as a
potential lubricating additive for the artificial joints in the future.
Acknowledgement
Financial supports from the project of National Natural Science
Foundation of China (51275267) are gratefully acknowledged.
References
[1] Kurtz S, Ong K, Lau E, Mowat F, Halpern M. Projections of primary and revision
hip and knee arthroplasty in the United States from 2005 to 2030. J Bone Jt
Surg Am Vol 2007;89A:780–5.
[2] Carr AJ, Robertsson O, Graves S, Price AJ, Arden NK, Judge A, et al. Knee
replacement. Lancet 2012;379:1331–40.
[3] Wang S, Liu YH, Zhang CX, Liao ZH, Liu WQ. The improvement of wettability,
biotribological behavior and corrosion resistance of titanium alloy pretreated
by thermal oxidation. Tribol Int 2014;79:174–82.
[4] Zhang CX, Liu YH, Wen SZ. Excellent tribological behavior of hexadecylpho-
sphonic acid films formed on titanium alloy. Sci China Technol Sci
2014;57:1816–23.
[5] Kobayashi M, Koide T, Hyon SH. Tribological characteristics of polyethylene
glycol (PEG) as a lubricant for wear resistance of ultra-high-molecular-weight
polyethylene (UHMWPE) in artificial knee join. J Mech Behav Biomed Mater
2014;38:33–8.
[6] Ma RY, Xiong DS, Miao F, Zhang JF, Peng Y. Friction properties of novel PVP/
PVA blend hydrogels as artificial cartilage. J Biomed Mater Res A
2010;93A:1016–9.
[7] Liu GQ, Cai MR, Zhou F, Liu WM. Charged polymer brushes-grafted hollow
silica nanoparticles as a novel promising material for simultaneous joint
lubrication and treatment. J Phys Chem B 2014;118:4920–31.
[8] Liu GQ, Liu ZL, Li N, Wang XL, Zhou F, Liu WM. Hairy polyelectrolyte brushes-
grafted thermosensitive microgels as artificial synovial fluid for simultaneous
biomimetic lubrication and arthritis treatment. ACS Appl Mater Interfaces
2014;6:20452–63.
[9] Haaf F, Sanner A, Straub F. Polymers of n-vinylpyrrolidone-synthesis, char-
acterization and uses. Polym J 1985;17:143–52.
 Y. Guo et al. / Tribology International 93 (2016) 214–219
[10] Fischer F, Bauer S. Polyvinylpyrrolidon. Ein Tausendsassa in der Chemie. Chem
unserer Zeit 2009;43:376–83.
[11] Shi Y, Xiong DS, Zhang JF. Effect of irradiation dose on mechanical and bio-
tribological properties of PVA/PVP hydrogels as articular cartilage. Tribol Int
2014;78:60–7.
[12] Sulek MW, Sas W, Wasilewski T, Bak-Sowinska A, Piotrowska U. Polymers
(polyvinylpyrrolidones) as active additives modifying the lubricating proper-
ties of water. Ind Eng Chem Res 2012;51:14700–7.
[13] Zheng YD, Huang XS, Wang YJ, Xi TF, Chen XF, Xu H. The surface lubricative
properties of PVA/PVP hydrogels treated with radiation used as artificial car-
tilage. Appl Surf Sci 2008;255:568–70.
View publication stats
219
[14] Bergfeld WF, Belsito DV, Carlton WW, Klaassen CD, Schroeter AL, Shank RC,
et al. Final report on the safety assessment of polyvinylpyrrolidone (PVP). Int J
Toxicol 1998;17:95–130.
[15] Jin ZM, Stone M, Ingham E, Fisher J. Biotribology. Curr Orthop 2006;20:32–40.
[16] Hamrock BJ, Dowson D. Elastohydrodynamic lubrication of elliptical contacts
for materials of low elastic modulus. I. Fully flooded conjunction. J Lubr
Technol 1978;100:236–45.