Applied Surface Science 255 (2008) 568–570

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

The surface lubricative properties of PVA/PVP hydrogels treated with radiation

used as artificial cartilage
Yudong Zheng a,*, Xiaoshan Huang a, Yingjun Wang b, Tingfei Xi a, Xiaofeng Chen b, Hong Xu b
a
College of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China
b
College of Materials Science and Engineering, South China University of Technology, Guangzhou 510641, China

A R T I C L E I N F O A B S T R A C T

Article history: In this work, poly(vinyl alcohol)/polyvinylpyrrolidone (PVA/PVP) hydrogels were prepared by cycled
Available online 1 July 2008 freezing and thawing process, and subsequently with irradiation crosslink processing. The exterior micro-
structure and frictional coefficients of compound hydrogels with and without radiation treatment were
PACS: compared. The changes of surface lubricative properties were observed in physiological condition in vitro.
61.80. x Without radiation treatment, the friction coefficient of PVA/PVP hydrogels increased rapidly in water
68.37. d because of the solubility and exudation of PVP, which could induce the decline of their lubricative action.
61.25.hp While after radiation treatment, the surface lubricative properties of PVA/PVP hydrogels in water were
87.85.J
improved and stable due to the crosslink between PVA and PVP.
Keywords: ß 2008 Elsevier B.V. All rights reserved.
Irradiation
Surface lubrication
Hydrogels
Artificial cartilage

1. Introduction dressing [8,9], was compounded with PVA hydrogels artificial

Artificial cartilage replacements have been one of the most
challenging and attractive themes in the fields of surgical clinical
and biomaterial research because a natural articular cartilage lacks
the capability of self-recovery [1,2]. The physiological functions of
articular cartilage serve as a soft conjoin cushion between bones in
human arthrosis, which could transfer and distribute the laden
stress equally, and reduce friction and abrasion [3]. Surface
lubricative and biomechanical properties are important to
articular cartilages in order to reduce and transfer stress and
abrasion in human arthrosis [4,5].
Poly(vinyl alcohol) (PVA) hydrogels prepared through freezing
and thawing methods with high-water contents show good
biocompatibility, high-mechanical strength, and good chemical
stability, and have been examined for use as promising artificial
cartilage materials [6,7]. Nevertheless PVA hydrogels are not of
sufficient lubrication due to the strong action of the hydrogen bond
formed in inner molecules. In order to improve the surface
lubrication, polyvinylpyrrolidone (PVP), which is a water-soluble
polymers with excellent biocompatibility and surface activity, and
can be used as a lubricant and temporary skin cover or wound
* Corresponding author. Tel.: +86 10 62330802; fax: +86 10 62332336.
E-mail address: mcyzheng@vip.sina.com (Y. Zheng).
cartilage. The irradiation processing would be performed after a
freezing and thawing process, because the rigid chain of PVP
macromolecules interfere with the crystallization of PVA mole-
cules and gel formation, which results in the decrease of
mechanical properties of the hydrogels. Furthermore PVP mole-
cules in the compound hydrogels without chemical crosslink tend
to dissolve in water in a physiological environment gradually,
leading to deterioration of the performance of the hydrogels.
In this work, PVA/PVP hydrogels were prepared by a cycled
freezing and thawing process, and subsequently processed with a
cobalt 60 irradiation crosslink. The surface micro-morphologies of
compound hydrogels with various PVP contents and irradiated
conditions were compared using scanning electron microscope.
The surface frictional coefficients of compound hydrogels with and
without radiation treatment were measured. The changes of the
surface lubricative properties in water were observed.
2. Experiments
The homogeneous solutions of PVA (molecular average weight
was 79 000, the degree of alcoholysis was 99%, Guizhou chemical
agent factory) and PVP (K30, Beijing Yili Chemical Co.), which were
prepared in advance, were mixed and stirred continuously under
an ultrasonic dispersive instrument at 85 8C for 30–60 min. Then
the air bubbles were removed from the solution. The concentra-

0169-4332/$ – see front matter ß 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2008.06.144
 Y. Zheng et al. / Applied Surface Science 255 (2008) 568–570 569

Fig. 1. SEM photographs of the hydrogels (a) PVA, (b) PVA/PVP (20%) and (c) PVA/PVP (40%).

Fig. 2. SEM photographs of the hydrogels (a) PVA/PVP (40%) 20 kGy and (b) PVA/PVP (40%) (50 kGy).

tions of PVP were between 10 and 40 wt.%. The compound
hydrogels were obtained by casting the mixed solution into the
special mould and processing as reference [7]. Then PVA/PVP
hydrogels were exposed to 60Co-rays at ambient temperature with
different irradiative times and doses.
The surface micro-morphology of PVA/PVP hydrogels was
observed using a scanning electron microscope (SEM) (Philips-xl
30ESEMX, Germany). The samples were sprayed with gold in
advance. The surface frictional coefficient of PVA/PVP hydrogels
were measure by the UMT-2 micromechanical instrument (Center
of Tribology, USA).
3. Results and discussion
Fig. 1 shows the SEM photographs of PVA and PVA/PVP
hydrogels. The surface of PVA hydrogels is not glazed, and there are
a lot of ringed striation and micro-hole in size of 2–10 mm. It is
considered that the pattern was formed due to the tropistic
arrangement of PVA long molecular chain and volatilization of
water in hydrogels (see Fig. 1a). When increasing the PVP
concentration, the surface of the PVA/PVP hydrogels became
smooth and slick (Fig. 1b). When the concentration of PVP was
raised to 40%, a majority of the hole in the hydrogels became
shallow and even invisible (and Fig. 1c). It is verified that the
modified PVA hydrogels with PVP molecular could make the
surface less scraggly and become smoother. Fig. 2 is the SEM
photographs of PVA/PVP hydrogels after treated with 60Co-
radiation. Compared to Fig. 1c, the surface of the compound
hydrogels seems compact, which might relate to the intercross-
reaction and accumulation of PVA and PVP molecular under

Fig. 3. Frictional curves of PVA and PVA/PVP hydrogels. Fig. 4. Frictional coefficient vs. PVP contents with and without radiation treatment.
570 Y. Zheng et al. / Applied Surface Science 255 (2008) 568–570
Fig. 5. Changes of friction coefficient of PVA/PVP hydrogels in water with and
without irradiation treatment.
irradiated condition. The irradiation also contributed to the surface
of hydrogels becoming less slippery. But there were no obvious
changes in the surface morphology for PVA/PVP hydrogels when
processing with different irradiation doses (see Fig. 2a and b).
There are many factors affecting the lubricative properties of
PVA/PVP compound hydrogels, such as water and PVP content, the
crosslink degree and hydrogen bond. The inner hydrogen bonding
and stable structure with hexahydric ring formed between
polyvinyl alcohol molecules could lead to the limitation of
lubrication action for PVA hydrogels [10]. Fig. 3 is the frictional
curves of PVA and PVA/PVP hydrogels, which show the changes of
average micro-friction between hydrogels and testing plate. The
lubricative properties of PVA/PVP were improved greatly in
comparison to that of PVA. Fig. 4 shows the changes of frictional
coefficient of compound hydrogels with the increase of PVP
content before and after radiation treatment. It could be seen that
the friction coefficient declined continuously with the increase of
PVP contents. The radiation treatment would reduce the lubrica-
tive action from the comparison of curves A and B in Fig. 4.
Without radiation treatment, the friction coefficient of PVA/PVP
hydrogels increased rapidly when immersed in water, due to the
solubility and exudation of PVP in water, which could induce the
decline of their lubricative action (see curve A in Fig. 5). After
radiation treatment, there is a crosslink between PVA and PVP, thus
the solubility and exudation of PVP were prevented or reduced.
Therefore, the friction coefficient PVA/PVP hydrogels with radia-
tion treatment were not changed even in water until after 18 days
(see curve B in Fig. 5).
4. Conclusion
Adding PVP molecules to PVA hydrogels made the surface of
compound hydrogels less scraggly and become smoother. The
friction coefficient of PVA/PVP hydrogels declined continuously
with the increase of PVP contents. Without radiation treatment,
the friction coefficient of PVA/PVP hydrogels increased rapidly in
water. After radiation, there was a crosslink between PVA and PVP.
Therefore, the solubility and exudation of PVP from hydrogels
could be prevented, and the lubricative properties of PVA/PVP
hydrogels in water were improved.
Acknowledgement
Authors acknowledge the financial support for this study
through the National Natural Science Foundation of China Grant
50773004.
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