Journal of Bionic Engineering 7 (2010) 235–243

Effect of Preparation Methods on Mechanical Properties of

PVA/HA Composite Hydrogel

Dekun Zhang1, Junjie Duan1, Dagang Wang2, Shirong Ge2

1. School of Materials Science and Engineering, China University of Mining and Technology, Xuzhou 221116, P. R. China
2. School of Mechanical and Electrical Engineering, China University of Mining and Technology, Xuzhou 221116, P. R. China

Abstract
Poly(vinyl alcohol) (PVA) / hydroxyapatite (HA) composite hydrogel specimens were prepared with 15% PVA and 1%,
2%, 3%, 4% and 5% HA by repeated freezing-thawing. The tests of static and dynamic mechanical properties were carried out to
discuss the influence of different contents of HA and freezing-thawing cycles on the mechanical properties of PVA/HA com-
posite hydrogel. The results of static mechanical tests showed that the PVA/HA composite hydrogel with 3% HA and nine
freezing-thawing cycles had excellent stress relaxation properties, higher relaxation ratio, lower stress equilibrium value and
presented better properties of creep and recovery. The results of dynamic mechanical test showed that the PVA/HA composite
hydrogel with nine freezing-thawing cycles had higher storage modulus and loss modulus, so was the PVA/HA composite
hydrogel with 3% HA.
Keywords: composite hydrogel, HA contents, freezing-thawing cycles, static properties, dynamic properties
Copyright © 2010, Jilin University. Published by Elsevier Limited and Science Press. All rights reserved.
doi: 10.1016/S1672-6529(10)60246-6

tensile strength of PVA/HA composite hydrogel first

1 Introduction
Nowadays, Poly(vinyl alcohol) (PVA) hydrogel
has been recognized as a substitute material for the arti-
ficial articular cartilage due to its hydrophilicity and
microporous structure[1], high elasticity[2,3], mechanical
properties of absorption and exudation of body fluid[4].
These properties of PVA hydrogel are closer to human
body cartilage tissue than those of other artificial mate-
rials[5,6]. However, PVA hydrogel presents poor strength
and bioactivities. The shortcomings are overcome by
adding hydroxyapatite (HA) as the reinforced phase to
PVA composite hydrogel. PVA/HA composite hydrogel
has been extensively studied as a cartilage substitute
material[7,8]. At present, researches on the mechanical
properties of PVA/HA composite hydrogel are concen-
trated on static and quasi-static aspects. Zheng et al.[9]
showed that the tensile strength and modulus of
PVA/HA composite hydrogel both increase with HA
content. The viscosity of composite hydrogel was en-
hanced and its stress relaxation performance was more
similar to natural cartilage. Li et al.[10] found that the
increases and then decreases with the increase in HA
content. The tensile strength reaches to the maximum
value when HA concentration is 7.5%. As HA content
further increases the tensile strength decreases.
PVA/HA composite hydrogel, as a substitute ma-
terial for the cartilage, needs to bear dynamic loading in
the joint movement besides the static load of joint con-
tact. For example, dynamic loading happens when
walking and running. Large load will be applied to in-
dividual muscles of the joint and cartilage by body
muscles even without movement. The effects of muscle
relaxations and contractions to the joints around are
equivalent to alternate functions of loading and
unloading at certain frequency. Recent researches
demonstrate that the properties of PVA/HA composite
hydrogel are easily influenced by the PVA content, re-
inforced phase content, preparation conditions and ex-
perimental parameters (temperature, frequency, strain
rate, preloading, amplitude and etc). However, the in-
fluence of those factors on dynamic mechanical
properties of hydrogel materials is not clear. Therefore,

Corresponding author: Dekun Zhang

E-mail: dkzhang@cumt.edu.cn
 236 Journal of Bionic Engineering (2010) Vol.7 No.3
it is of great significance to carry out dynamic
mechanical experiments of PVA/HA composite
hydrogel.
Jeon et al.[11]studied the effect of cross-link density
on mechanical properties of hyaluronic acid hydrogels
and found that its elastic modulus increases first, and
then decreases with theoretical cross-link density of HA
hydrogel. The elastic modulus reaches to the maximum
value at the cross-link density of 20%. Stammen et al.[12]
focused on the compressive properties of PVA hydrogel
with the water contents of 75% and 80%, respectively. It
was discovered that the compressive modulus increases
from 1 MPa to 18 MPa when the strain increases from
10% to 60%, which is similar to that of articular cartilage.
Hernández et al.[13] found that the storage modulus of
PVA hydrogel increases with PVA content. Zainuddin et
al.[14] reported that the magnitudes of dynamic moduli
G'(Ȧ) and G"(Ȧ) of PVA/PVP composite hydrogel in-
crease with absorbed Ȗ-radiation doses. Krumova et al.[15]
found that the loss factor of PVA hydrogel increases with
cross-link density. Zheng et al.[16] demonstrated that the
higher the SiO2 content, the larger the storage modulus
of PVA/SiO2 nanocomposites, and the smaller the elas-
ticity. However, there are few reports on mechanical
properties of PVA/HA composite hydrogel.
PVA/HA composite hydrogels were prepared by
physical crosslinking method in this study.
Dynamic compressive fatigue tests of PVA/HA
composite hydrogels were performed to obtain
dynamic mechanical data of material storage modulus
and loss modulus. Finally, the changing laws of me-
chanical properties of PVA/HA composite hydrogels
with the HA content and freezing-thawing cycles were
investigated.
2 Experimental details
2.1 Preparation of specimens
PVA with the type of 20-99, polymerization degree
of 2050±70 and alcoholysis degree of 99.9% was chosen
as the raw material. The average diameter of nanometer
HA was less than 20 nm. PVA aqueous solution with
different concentration was prepared by dissolving
weighed PVA in deionized water and then heating it at
90ÛC for 4 h to 6 h in the incubator. The nanometer HA
powder was mixed in the PVA solution and agitated
intensively until homogeneously mixed. Afterwards,
PVA/HA composite solution was laid in the air to
deaerate, then poured into the mold and frozen at í20ÛC
for 6 h to 12 h in a low temperature freezer. The speci-
mens were taken out and thawed for 2 h to 4 h at room
temperature (25ÛC) for the next freezing process. The
above freezing-thawing process was repeated for seven,
nine, eleven times to obtain different PVA/HA compos-
ite hydrogel specimens, respectively. PVA/HA compos-
ite hydrogel specimens with different mixture ratios
were obtained by varying the mass of PVA, nanometer
HA and deionized water. In this experiment, PVA/HA
composite hydrogel specimens were prepared with the
PVA content of 15% and HA contents of 1.0%, 2.0%,
3.0%, 4.0% and 5.0% respectively. PVA/HA composite
hydrogel specimens were cut to cuboids of 5 mm × 5
mm × 1 mm and dried naturally at room temperature for
about 1 h. Then the micro-morphologies were obtained
using XL30 ESEM.
2.2 Stress relaxation properties
The stress relaxation tests of PVA/HA composite
hydrogel were performed on UMT-2 micro-tribometer
according to China standard GB1685-85. The initial
thickness of PVA/HA composite hydrogel specimen was
4 mm and the flat-head cylinder indenter was used. The
specimen was compressed to 2.5 mm with the speed of
5 mm·miní1. Then the load was kept constant for 15 min
and changing compression stress values were recorded
with sampling interval of 0.02 s. Each test was repeated
three times to obtain the average value.
2.3 Creep and reversion properties
The creep and reversion properties were measured
using the WDW biological mechanical testing rig.
PVA/HA composite hydrogel specimen swelled in de-
ionized water for 30 min to saturation. Then the speci-
men was fixed at the center of lower platen before being
filled with deionized water. The upper pressure head was
controlled by means of the WDW Electronic Universal
Testing Machine to contact with the PVA/HA composite
hydrogel specimen. Afterwards, the specimen was
loaded in the load control mode to 985 N with the speed
of 50 N·sí1. The pressure of 1.6 MPa (equivalent to 985
N) was maintained for 15 min. Finally, the specimen was
unloaded with the speed of 2 mm·sí1 and the time for
reverting was 15 min. The changing curves of com-
pression strain with time were recorded by LK-G series
laser displacement sensor.
 Zhang et al.: Effect of Preparation Methods on Mechanical Properties of PVA/HA Composite Hydrogel 237
2.4 Dynamic mechanical properties The maximum stress ımax and strain İmax in each
The mechanical loss behavior under the dynamic cycle can be calculated from the stress-strain curve and
loading is a mechanical relaxation behavior of defor- the ratio of the maximum stress to maximum strain is the
mation energy loss caused by the asynchronous response complex modulus E* of PVA/HA composite hydrogel
between strain and stress under alternate external peri- specimen
odic force. Dynamic mechanical properties of PVA/HA
E* V max / H max . (1)
composite hydrogels were studied by means of the
WDW biological fatigue testing machine. The hydrogel The loss of mechanical work of the material in a
specimen swelled in deionized water for 30 min first, compression-restoration cycle can be calculated from
and then the thickness was measured. The specimen was the imaginary parts of stress and strain:
fixed at the center of cylindrical mold before deionized
water was poured in. The upper pressure head was 'W v³ V sin(Zt  G )d(H sinZt )
0 0

Z
23 /
moved downward and contacted with PVA/HA com-
posite hydrogel specimen, when the position was re-
³ V H Z sin(Zt  G ) cos Ztdt
0 0 0

corded as “0” position. Then the testing machine started 3V 0H 0 sin G 3 H 02 E cc. (2)
and applied the default load to the specimen. Finally, the The loss of mechanical work of the material in the
specimen was dynamically loaded with the displacement dynamic compression process is proportional to the
mode. square of deformation amplitude and loss modulus E".
Fig. 1 shows the test schematic diagram of dynamic The storage modulus Ec can be obtained by the arithme-
mechanical properties of PVA/HA composite hydrogel tic square root of complex modulus and loss modulus.
specimen. Lu is the specimen thickness before deforma- The loss factor is calculated from the ratio of loss
tion. S is the specimen deformation amount and it modulus to storage modulus.
reaches the equilibrium position at the preset load value.
The alternate load is applied to the specimen with the Ec E *2  E cc2 , (3)
amplitude of A and frequency of f. The specimen de- tanG E cc / E c. (4)
formation amount changes between La (thickness at the
maximum compression) and Li (thickness at the mini- 3 Results and discussions
mum compression). The changing curves of load and 3.1 Microstructure of PVA/HA composite hydrogel
displacement with time are recorded during the dynamic Fig. 2 shows the ESEM photos of PVA/HA com-
loading process. The diameter of the composite hydrogel posite hydrogel specimens with nine freezing-thawing
specimen is 48 mm and thickness is 5 mm. The preset cycles and different HA contents. It is seen from Fig. 2a
load value is 2000 N with the initial loading rate of
0.1 mm·sí1 and frequency of 1.5 Hz. The amplitude is
10% of the specimen thickness with 2000 experimental
cycles.

Non-deformation specimen Upper pressure head

Minimum
compression

Maximum
compression

(a) 3% HA
Fig. 1 Dynamic compression model of PVA/HA composite hy- Fig. 2 ESEM morphologies of PVA/HA composite hydrogel
drogel specimen. specimens with different HA contents.
 238 Journal of Bionic Engineering (2010) Vol.7 No.3
Acc.V Magn Det WD 100 ȝm
20.0kV 400x GSE 9.2 0.9 Torr
(b) 4% HA
Fig. 2 Continued.
that PVA/HA composite hydrogel with 3% HA contains
lot of micro holes and the HA powder particles are uni-
formly distributed in the PVA matrix and well packed by
the hydrogel. However, many micro holes minimize and
even close because of the lower water content. For
PVA/HA composite hydrogel with 4% HA, Fig. 2b
shows that the HA particles are not uniformly distributed
in the hydrogel matrix, and there exist some HA particle
agglomerates.
3.2 Influence of freezing-thawing cycles on the stress
relaxation of PVA/HA composite hydrogel
Fig. 3 shows the stress relaxation curves of
PVA/HA composite hydrogel specimens prepared with
different freezing-thawing cycles. The results demon-
strate that the rate of stress relaxation changes with the
freezing-thawing cycles. PVA/HA composite hydrogel
specimens prepared with seven and nine freez-
ing-thawing cycles show better stress relaxation per-
formances, which present stronger dissipation against
external impact. However, the PVA/HA composite hy-
drogel specimen with eleven freezing-thawing cycles
exhibits worse relaxation performance due to the low
relaxation rate. Therefore, the stress relaxation of
PVA/HA composite hydrogel does not increase linearly
with freezing-thawing cycles. The microstructures of
PVA/HA composite hydrogel are adjusted in the freez-
ing-thawing process. But PVA/HA composite hydrogel
specimens get harder and produce lower elasticity with
more freezing-thawing cycles.
1.1
7 cycles
1.0 9 cycles
0.9 11 cycles
0.8
0.7
0.6
0.5
0.4
0.3
0 200 400 600 800 1000
T (s)
Fig. 3 Stress relaxation curves of PVA/HA composite hydrogels
with different freezing-thawing cycles.
Fig. 4 presents the histogram of stress relaxation
ratio of PVA/HA composite hydrogel specimens with
different freezing-thawing cycles. The results demon-
strate that relaxation ratios of PVA/HA composite hy-
drogel are greatly affected by freezing-thawing cycles.
The stress relaxation ratios of PVA/HA composite hy-
drogel specimens with seven and nine freezing-thawing
cycles are similar and both over 65% compared with the
stress relaxation ratio of 45.87% for composite hy-
drogels with eleven freezing-thawing cycles. With the
increase in physical cross-linking treatment cycles, the
cross-linking degree between molecular chains of hy-
drogel increases, the cross-linking network structure of
the internal hydrogel is improved and PVA molecular
chains are more closely integrated. Meanwhile, the
stress shrinkage happens to the hydrogel resulting in the
hardening of hydrogel and decrease in stress dissipation.
Stress relaxation ratio (%)
Fig. 4 Histogram of stress relaxation ratio of PVA/HA composite
hydrogels with different freezing-thawing cycles.
 Zhang et al.: Effect of Preparation Methods on Mechanical Properties of PVA/HA Composite Hydrogel
3.3 Influence of HA content on stress relaxation
performances of PVA/HA composite hydrogel
Fig. 5 shows stress relaxation curves of PVA/HA
composite hydrogel specimens with different HA con-
tents. It is demonstrated that the stress relaxation prop-
erty of PVA/HA composite hydrogel specimen with nine
freezing-thawing cycles and HA content of 3% is better,
which could easily meet the requirements of reducing
the stress and impact. For the PVA/HA composite hy-
drogel as a substitute material for cartilage, the dissipa-
tion of impact can be reflected by the stress relaxation
when bearing the external impact. The higher the rate of
stress relaxation formation is, the larger the stress decay
rate is. Therefore, PVA/HA composite hydrogels possess
higher ability of impact dissipation which could protect
the joint[17].
Fig. 6 presents the histogram of stress relaxation
ratios of PVA/HA composite hydrogel specimens with
different HA contents. The results show that HA content
1.1
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0 200 400
T (s)
Fig. 5 Stress relaxation curves of PVA/HA composite hydrogels
with different HA contents.
Stress relaxation ratio (%)
Fig. 6 Stress relaxation ratios of PVA/HA composite hydrogels
with different HA contents.
239
greatly affects the stress relaxation ratio of PVA/HA
composite hydrogel. The stress relaxation ratio of
PVA/HA composite hydrogel with HA content of 3% is
nearly 18% a 37% higher than those of the composite
hydrogel with other HA contents. It is concluded that a
certain content of HA particles added to the composite
hydrogel can improve the stress relaxation performance,
while excessive HA particles can not be well-distributed,
which will reduce the stress relaxation performance.
3.4 Influence of freezing-thawing cycles on creep and
recovery of PVA/HA composite hydrogel
Fig. 7 illustrates the creep and recovery curves of
PVA/HA composite hydrogel specimens with different
freezing-thawing cycles. It is demonstrated that the
creep and recovery curves of PVA/HA composite hy-
drogel are similar to those of polymer materials. The
curves can also be divided into three stages of instanta-
neous deformation, creep and viscous flow. Freez-
ing-thawing cycles have great influence on creep and
recovery properties of PVA/HA composite hydrogel.
1% HA
2% HA The elastic deformation and creep deformation during
3% HA the 15 min pressure maintaining are both small for
4% HA
PVA/HA composite hydrogel specimens with nine
freezing-thawing cycles under the same load. Recovery
curves show PVA/HA composite hydrogel with nine
freezing-thawing cycles possesses better restitution
ability with the plastic deformation ratio of only 5% than
those with seven and eleven freezing-thawing cycles
with plastic deformation ratios of respective 8.2% and
600 800 1000 13.6%. The freezing-thawing treatment changes the
internal cross-linking degree of PVA/HA composite
0.65 7 cycles
0.60 9 cycles
0.55 11 cycles
0.50
0.45
0.40
0.35
0.30
0.25
0.20
0.15
0.10
0.05
0.00
0 200 400 600 800 1000 1200 1400 1600 1800
T (s)
Fig. 7 Creep and recovery curves of PVA/HA composite hy-
drogels with different freezing-thawing cycles.
 240 Journal of Bionic Engineering (2010) Vol.7 No.3

hydrogel, therefore, different freezing-thawing cycles
affect the creep and recovery properties of PVA/HA
composite hydrogel. The higher the cross-linking degree
is, the weaker the viscous flow is, and the larger the
plastic deformation is.
The dimensional stability could be well character-
ized by material creep resistance. When a large impact
load is applied to the joint and maintained for certain
time, the creep resistance and dimensional stability are
very important for articular cartilage substitute materials.
The treatment of freezing-thawing can improve the
crosslinking degree of PVA/HA composite hydrogel, i.e.
the ability to resist deformation or dimensional stability.
However, the creep-resistance effect of PVA/HA com-
posite hydrogel does not increase linearly with freez-
ing-thawing cycles and decreases after certain freez-
ing-thawing cycles.
It is concluded that the PVA/HA composite hy-
drogel with HA content of 3% and nine freezing-thawing
cycles presents smaller plastic deformation induced by
the creep and recovery process under certain load, better
dimensional stability and lower creep rate than PVA/HA
and smaller creep deformation as the load was main-
tained for 15 min compared with those with respective
HA contents of 1% and 4%. It is shown that the PVA/HA
composite hydrogel with HA content of 3% has better
restitution with only the plastic deformation ratio of 3%
compared with those with HA contents of 1% and 4%,
respectively. Plastic deformation ratios of PVA/HA
composite hydrogels with HA contents of 1% and 4%
are 11.85% and 8.65%, respectively. It is thought that
HA agglomerations result in the decrease in creep re-
covery properties of PVA/HA composite hydrogel.
3.6 Influence of freezing-thawing cycles on dynamic
mechanical properties of PVA/HA composite
hydrogel
Fig. 9 shows the change curves of the storage
modulus and loss modulus of PVA/HA composite hy-
drogel specimens with different freezing-thawing cycles.
Fig. 9a indicates that storage modulus of PVA/HA
composite hydrogel decrease gradually with loading
5.2

composite hydrogels with seven and eleven freez- 4.8 7 cycles

9 cycles
4.4
ing-thawing cycles, respectively. 11 cycles
4.0
E (MPa)

3.6
3.5 Influence of HA content on creep and recovery
3.2
properties of PVA/HA composite hydrogel
2.8
Fig. 8 shows the creep and recovery curves of
2.4
PVA/HA composite hydrogel specimens with different 2.0
HA contents. It is shown that the PVA/HA composite 1.6
hydrogel with HA content of 3% produces smaller elas-
1 10 100 1000
tic deformation under the same load compared with N
those with respective HA contents of 1%, 2% and 4% (a) Storage modulus

0.22
7 cycles
0.20 9 cycles
0.18 11 cycles

0.16
E (MPa)

0.14
0.12
0.10
0.08
0.06
0.04
1 10 100 1000
N
(b) Loss modulus
Fig. 8 Creep and recovery curves of PVA/HA composite hy- Fig. 9 Curves of dynamic mechanical properties of PVA/HA
drogels with different HA contents. composite hydrogels with different freezing-thawing cycles.
 Zhang et al.: Effect of Preparation Methods on Mechanical Properties of PVA/HA Composite Hydrogel
cycles. The storage modulus of PVA/HA composite
hydrogel with nine freezing-thawing cycles declines
from 4.65 MPa to 2.4 MPa. The PVA/HA composite
hydrogel with nine freezing-thawing cycles has the
largest storage modulus and its initial value is 4.65 MPa
compared with 3.36 MPa and 2.42 MPa for the storage
modulus of PVA/HA composite hydrogels with freez-
ing-thawing cycles of seven and eleven, respectively,
which is resulted from dehydration and strengthening
processes. The storage modulus of PVA/HA composite
hydrogels can be improved by freezing-thawing treat-
ment. However, the improvement is limited. Fig. 9b
shows that the loss modulus of PVA/HA composite hy-
drogel declines gradually with load cycles and freez-
ing-thawing cycles, and the initial loss modulus of
PVA/HA composite hydrogel with freezing-thawing
cycles of seven, nine and eleven are 0.19 MPa, 0.136
MPa and 0.12 MPa, respectively. This is because re-
peated freezing-thawing processes can enhance the
viscosity of PVA/HA composite hydrogel and respond to
high energy shocks in dynamic compression tests.
241
hydrogel decreases gradually with increase in testing
cycles. The loss modulus declines fast in the first ten
cycles and then tends to be equilibrium. The initial and
equilibrium loss modulus values of PVA/HA composite
hydrogel specimens with 3% HA are the largest which
are 0.59 MPa and 0.325 MPa, respectively. A large
number of micro-interface structures form in PVA hy-
drogel matrix due to the addition of HA particles which
can eliminate external shocks effectively. HA and PVA
hydrogel matrix as well as the transitional phases con-
sumes the frictional energy as a result of interface in-
teractions under the external force. However, the inter-
face interactions will not increase infinitely with the
filler content because of easy coacervate with excessive
HA particles. In addition, the loss modulus is propor-
tional to the consumed energy of PVA/HA composite
hydrogel as heat in each cycle[19]. Therefore, PVA/HA

3.7 Influence of HA content on dynamic mechanical

E (MPa)

properties of PVA/HA composite hydrogel

Fig. 10a shows the change curves of the storage
modulus of PVA/HA composite hydrogel specimens
with different HA contents and testing cycles. It is
demonstrated that the storage modulus of PVA/HA
composite hydrogel decreases gradually with the in-
crease in testing cycle. The storage modulus declines
fast in the initial period and then tends to be equilibrium. (a) Storage modulus
The equilibrium value of storage modulus of PVA/HA
composite hydrogel with HA content of 3% reaches to
the highest value of 2.33 MPa. The reason is that Ca2+
from n-HA and PVA molecules interact and more
stronger recombination action between molecules re-
E (MPa)

places intermolecular hydrogen bonds of the PVA with

the increase in HA content[18]. Therefore, the binding
role of the filler surface to the matrix molecular chain
enhances and the elastic modulus (i.e. resistance ability
of material deformation) improves. However, excessive
HA will make storage modulus decrease because of
coacervation contrarily.
Fig. 10b presents the change curves of the loss
modulus of PVA/HA composite hydrogel specimens (b) Loss modulus

with different HA contents and testing cycles. It is Fig. 10 Curves of dynamic mechanical properties of PVA/HA
shown that the loss modulus of PVA/HA composite composite hydrogels with different HA contents.
 242 Journal of Bionic Engineering (2010) Vol.7 No.3
composite hydrogel with 3% HA has greater storage
modulus and stronger resilience, that is, its restitution
ability after deformation is stronger. Its energy con-
sumption role caused by the internal friction of mi-
cro-interface structure is also stronger, which presents
stronger damping ability, shock resistance capability and
buffering capability.
4 Conclusion
PVA/HA composite hydrogels with seven and nine
freezing-thawing cycles present better stress relaxation
properties, larger relaxation rate and lower equilibrium
value of stress compared with that with eleven freez-
ing-thawing cycles. PVA/HA composite hydrogel with
nine freezing-thawing cycles and HA content of 3%
presents better stress relaxation properties. PVA/HA
composite hydrogel with nine freezing-thawing cycles
presents better creep and recovery properties. Mean-
while, the creep resistance of PVA/HA composite hy-
drogel with nine freezing-thawing cycles and HA con-
tent of 3% is better. The storage modulus of PVA/HA
composite hydrogel with nine freezing-thawing cycles
are higher than those with seven and eleven freez-
ing-thawing cycles, respectively. PVA/HA composite
hydrogel with HA content of 3% has the largest storage
modulus and loss modulus, which reflects its better res-
titution ability after deformation and good damping
ability. It also shows better impact resistance capacity
and good buffering capacity.
Acknowledgements
This research is supported by National Natural
Science Foundation of China (Grant No. 50875252),
Program for New Century Excellent Talents in Univer-
sity (Grant No. NCET-06-0479), and Natural Science
Foundation of Jiangsu Province (Grant No.
BK2008005).
References
[1] Kobayashi M, Toguchida J, Oka M. Preliminary study of
polyvinyl alcohol/hydrogel (PVA-H) artificial meniscus.
Biomaterials, 2003, 24, 639–647.
[2] ĝwiĊszkowski W, Ku D N, Bersee H E N, Kurzydlowski K J.
An elastic material for cartilage replacement in an arthritic
shoulder joint. Biomaterials, 2006, 27, 1534–1541.
[3] Stammen J A, Williams S, Ku D N, Guldberg R E. Me-
chanical properties of a novel PVA hydrogel in shear and
unconfined compression. Biomaterials, 2001, 22, 799–806.
[4] Spiller K L, Laurencin S J, Charlton D, Maher S A, Lowman
A M. Superporous hydrogels for cartilage repair: Evaluation
of the morphological and mechanical properties. Acta
Biomaterialia, 2008, 4, 17–25.
[5] Suciu A N, Iwatsubo T, Matsuda M, Nishino T. A study
upon durability of the artificial knee joint with PVA hy-
drogel cartilage. JSME International Journal: Series C,
2004, 47, 199–208.
[6] Pan Y S, Xiong D S. Recent development on biotribology of
poly (vinyl alcoho1) hydrogel. Tribology, 2006, 26,
188–192. (in Chinese)
[7] Chou L, Marek B, Wagner W R. Effects of hydroxylapatite
coating crystallinity on biosolubility, cell attachment effi-
ciency and proliferation in vitro. Biomaterials, 1999, 20,
977–985.
[8] Mano J F, Vaz C M, Mendes S C, Reis R L, Cunha A M.
Dynamic mechanical properties of hydroxyapatite-
reinforced and porous starch-based degradable biomaterials.
Journal of Materials Science: Materials in Medicine, 1999,
10, 857–862.
[9] Zheng Y, Wang Y, Chen X, Liu Q, Lu Y. Studies of
poly(vinyl alcohol)/hydroxylapatite hydrogels compounds
for cartilage implantation. Journal of Biomedical Engi-
neering, 2003, 20, 401–403. (in Chinese)
[10] Li H D, Xiao J, Cheng F M, Chen X X. Preparation and
properties of hydroxyapatite/polyvinyl alcohol compound
hydrogels. Journal of Changchun University of Technology
(Natural Science Edition), 2007, 28, 338–340. (in Chinese)
[11] Jeon O, Song S J, Lee K J, Park M H, Lee S H, Hahn S K,
Kim S, Kim B S. Mechanical properties and degradation
behaviors of hyaluronic acid hydrogels cross-linked at
various cross-linking densities. Carbohydrate Polymers,
2007, 70, 251–257.
[12] Stammen J A, Williams S, Ku D N, Guldberg R E. Me-
chanical properties of a novel PVA hydrogel in shear and
unconfined compression. Biomaterials, 2001, 22, 799–806.
[13] Hernández R, Sarafian A, López D, Mijangos C. Viscoelas-
tic properties of poly (vinyl alcohol) hydrogels and ferrogels
obtained through freezing-thawing cycles. Polymer, 2004,
45, 5543–5549.
[14] Zainuddin, Cooper-White J J, Hill D J. Viscoelastieity of
radiation-formed PVA/PVP hydrogel. Journal of Biomate-
rials Science-polymer Edition, 2002, 13, 1007–1020.
[15] Krumova M, López D, Benavente R, Mijangos C, Pereña J
M. Effect of crosslinking on the mechanical and thermal
properties of poly(vinyl alcohol). Polymer, 2000, 41,
9265–9272.
 Zhang et al.: Effect of Preparation Methods on Mechanical Properties of PVA/HA Composite Hydrogel 243

[16] Zheng P, Ling X K, Si D L. Dynamic mechanical analysis of [18] Xu F L, Li Y B, Wang X J, Zuo Y, Han J. Preparation and
polyvinylalcohol/silica nanocomposite. Synthetic Metals, characterization of nano-hydroxyapatite/polyvinyl alcohol
2005, 152, 25–28. biocomposites. Functional Materials, 2004, 35, 509–511.
[17] Ji B, Gao J, Ma Y Z, Gu Z Q, Liu G Q, Xue H B. Manu- (in Chinese)
facture of prosthetic nucleus and analysis of [19] Wu Q H, Feng Y. Introduction to Polymeric Materials,
stress-relaxation properties. Journal of University of Science Machinery Industry Press, Beijing, China, 2004. (in
and Technology Beijing, 2005, 27, 589–592. (in Chinese) Chinese)