Progress in Organic Coatings 45 (2002) 3342

The change of the properties of acrylic-based polyurethane

via addition of nano-silica
Shuxue Zhou a , Limin Wu a, , Jian Sun a,b , Weidian Shen b
a

Department of Materials Science, The Advanced Coating Research Center of China Educational Ministry,
Fudan University, Shanghai 200433, PR China
b Department of Physics and Astronomy, Eastern Michigan University, Ypsilanti, MI 48197, USA
Accepted 24 May 2002

Abstract
Acrylic-based polyurethane coatings with nano-silica particles embedded were prepared. The compositions at the surfaces and at the
interfaces with substrates were investigated by X-ray photoelectron spectrometer (XPS). The mechanical and optical properties of the
coatings were studied intensively by using pendulum hardness tester, Nano-Indenter XP, Instron testing machine, dynamic mechanical
analyzer (DMA), transmission electron micrograph (TEM), and UVVis spectrophotometer. The coatings with fumed silica and micro-silica
embedded were also investigated for comparison with the coatings containing nano-silica. The results showed that silica element neither
existed at the surfaces nor existed at the interfaces of the coatings with nano-silica or micro-silica embedded, and the silicon atoms intend to
reside inside the coatings. The macro-hardness, micro-hardness, abrasion resistance, and scratch resistance were apparently improved via
addition of nano-silica. The tensile strength and Youngs modulus were also enhanced with the increasing content of nano-silica. However,
the elongation at break decreased as nano-silica content increased. The UV absorbance in the wavelength of 290400 nm increased as
nano-SiO2 content increased. In contrast, for the polyurethane coatings with fumed silica or micro-silica embedded, only hardness and
abrasion resistance showed some increase.
2002 Elsevier Science B.V. All rights reserved.
Keywords: Acrylic-based polyurethane; Nanocomposite coating; Property

1. Introduction
In the past decade, material scientists showed great
interest in organicinorganic nanocomposites since their
application has dramatically improved material properties
in engineering plastics, enhanced rubber, coatings, and adhesives [13]. The attractive improvement includes heat
resistance, radiation resistance, mechanical and electrical
properties, which are usually resulted from the synergistic
effect between organic and inorganic components. Effects
of different nanoparticles on the properties of polymers
vary a lot. To achieve the expected improvement by adding
nanocomposites, understanding how these nanoparticles
influence the organic matrix is important.
Organicinorganic nanocomposites can be prepared by directly blending with nanoparticles and organic compounds
or a solgel process with a metal alkoxide. The most commonly used inorganic nanoparticles are SiO2 , TiO2 , ZnO,
Corresponding author.
E-mail address: lxw@fudan.ac.cn (L. Wu).

CaCO3 , etc., of them, nano-silica is the first nanoparticle

produced and has been studied in a lot of polymer systems.
For example, Kaddami et al. [4] and Hajji et al. [5] had
combined it with poly(HEMA), and Chang et al. [6] filled it
into poly(methyl methacrylate). Nano-silica could also improve scratch resistance of a coating and keep the coating
clear at the same time [7]. Petrovic et al. [8] found that
nanoparticle could enhance tensile strength and elongation
of polyurethane elastomer.
In this project, nano-silica was embedded in the
acrylic-based polyurethane, composition of the coatings at
the surface and at the interface, hardness, abrasion resistance, static and dynamic mechanical properties, scratch
resistance, and optical properties of the coatings were intensively investigated by X-ray photoelectron spectrometer
(XPS), pendulum hardness tester, Nano-Indenter XP, Instron
testing machine, dynamic mechanical analyzer (DMA),
transmission electron micrograph (TEM), and UVVis
spectrophotometer. For the sake of comparison, the effects
of fumed silica and micro-silica on polyurethane properties
were also studied.

0300-9440/02/$ see front matter 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 0 - 9 4 4 0 ( 0 2 ) 0 0 0 8 5 - 1

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S. Zhou et al. / Progress in Organic Coatings 45 (2002) 3342

2. Experimental
2.1. Materials
Nano-SiO2 (P640) with mean size of 20 nm and specific
area of 640 m2 g1 was purchased from Shanghai BONA
WEILAI New Material Co., Ltd. of China. Micro-silica was
the product of Huzhou HUANENG Fine Silica Powder Co.,
Ltd. of China and fumed silica (Aerosil R972) came from
Degussa Company of Germany.
Monomers butyl acrylate (BA, 96%), styrene (St, 97%),
methyl methacrylate (MMA, 97%) and 2-hydroxyethyl
methacrylate (HEMA, 98%) were purchased from Shanghai Gaoqiao Petrochemical Company and used as supplied.
Butyl acetate (98%) and 2-mercaptoethanol were purchased
from Shanghai Chemical Reagent Company, and act as the
solvent and chain transfer agent, respectively.
Catalyst dibutyltin dilaureate (98%) and cross-linking
agents: 1,6-hexamethylene diisocyanate homopolymer
(HDI, Desmodur N 3300) were obtained from Bayer Company and used as received. t-Butyl peroxy 2-ethyl hexanoate
(TBPH) was supplied by Aztec Chemical Company (USA)
and used as received. Coupling agent: methacryloylpropyltrimethoxysilane (KH570) was the product of Nanjing
SHUGUANG Chemical Factory of China.
2.2. Synthesis of acrylic polyol resins
A 500 ml round-bottom flask equipped with mechanical stirrer, thermometer with a temperature controller, N2
inlet and a Graham condenser was charged with half of
the total amount of butyl acetate to be used and heated to
105 C. A solution of mixture of MMA, St, BA, HEMA,
2-mercaptoethanol, TBPH and butyl acetate with/without
nano-silica was added over some period of time under a slow
stream of N2 . During the process of addition of monomer
mixture, the temperature was maintained at 105 22 C.
When addition was complete, another 10 wt.% TBPH of the
initial used TBPH weight was added, and refluxing was continued for another 1 h. The resin solution is 70 wt.%.
2.3. Preparation of nanocomposite films
Two methods were adopted for preparation of nanocomposite coatings. One was that modified or unmodified
nano-SiO2 particles was directly mixed with acrylic resins
at 60 C for about an hour under vigorous stirring, another
is using in situ polymerization in which nano-silica was
firstly dispersed in monomer mixture by ultrasonic irradiation for half an hour then polymerized according to the
method described in the preceding part. The nanocomposite
acrylic resin without any further dilution was mixed with
HDI based on 1/1 weight ratio of resin to HDI at room
temperature. Just before application, dibutyltin dilaurate
(0.05 wt.% of the total weight of the resin and polyiso-

cyanate on total solids) was mixed thoroughly into the

coating. Polyurethane coats with different thickness were
prepared by casting the above solution on Sn-coated ferrous panels using a drawdown rod and dried at 120 C for
30 min or on glass substrates dried at room temperature.
2.4. XPS analysis
A Microlab 310F (VG SCIENTIFIC, UK) multifunctional
XPS was used to determine the composition of typical elements at the surface and interface of the films with Sn-coated
ferrous panels. K radiation of Al was used as the excitation
source with a pass energy of 40 eV.
2.5. Macro-hardness
Macro-hardness was determined using pendulum hardness tester according to national standard of China
GB/T1730-93. The coating films were prepared on glass
boards and dried at room temperature. The time swinging
from 5 to 2 for the pendulum on the glass with and without films were named as t and t0 , respectively, the ratio of
t/t0 is regarded as macro-hardness.
2.6. Abrasion resistance
Abrasion resistance was determined on a round glass
board according to GB1768-79. 120# rubber abrasive wheel
was used. The film was first rubbed flat for about 100 cycles
then recorded the initial weight. For every 200 cycles rubbing, the abrasive wheel was renewed and the weight loss
was recorded, which can be used to judge the abrasion resistance.
2.7. Static mechanical property
Tensile properties were acquired by an Instron model
DXLL 100020 000 testing machine (Shanghai, China). The
specimens for tensile test were dumbbell (according to Die
C of ASTM-D412) cut from the films that were prepared on
glass substrates and had a thickness of about 7090 m, and
carried out at a crosshead speed of 200 mm/min. A 20 mm
benchmark and the original cross-sectional area were utilized to calculate their tensile properties. The ultimate tensile strength and elongation were automatically calculated
by the computer connected to Instron. The average of at
least five measurements for each sample was reported, the
experimental error is 10%.
2.8. Micro-hardness and scratch test
Micro-hardness and scratch test were carried out by
Nano-Indenter XP made by MTS, Inc. in USA. The
coatings were deposited on Sn-coated ferrous panels. A
Berkovich diamond tip (3-faced pyramid) was used in the

S. Zhou et al. / Progress in Organic Coatings 45 (2002) 3342

tests. Micro-hardness and scratch resistance were measured under a normal load ranging from 200 N to 50 mN.
The micro-hardness was calculated by dividing the normal force used in the indentation by the projected area of
indent at the surface. The scratch resistance was defined
as the normal force applied during the scratching divided
by the cross-section of the trough after scratching. The
Youngs modulus was calculated from the slope of the
load (P)penetration (h) curves at the turning point of the
unloading. The details of the experiment methods and calculations of hardness and Youngs modulus measurements
have been described in the Ref. [9].
2.9. Dynamic mechanical property
Dynamic mechanical properties of polyurethane films
were measured using DMA 242 (Netzsch, German) starting
from 150 and 200 C with heating rate of 5 C/min at the
frequency of 10 Hz.
2.10. TEM observe
Transmission electron micrographs of the nanocomposite
films were obtained by a Hitachi H-600 apparatus (Hitachi
Corporation, Japan). Samples were prepared by ultramicrotomy at room temperature, giving sections of nearly 100 nm
in thickness. No further staining was used to improve contrast.
2.11. UVVis spectra
An UVVis spectrophotometer (Hitachi UV-3000) was
used to measure the absorbance and transmittance spectra
of the films in the range 200700 nm wavelength light.

3. Results and discussion

3.1. Composition of the surface and interface
The composition of the surface and interface of
polyurethane films containing 5 wt.% nano-silica or microsilica were determined by XPS. The results are listed in
Table 1. There is no Si element detected at the surfaces and
Table 1
The composition of the surface and interface of polyurethane coats containing nano- or micro-silica (at.%)
Element

C
O
N
Si

Surface

Interface

Nano-silica

Micro-silica

Nano-silica

Micro-silica

69.1
30.9
0
0

70.9
29.1
0
0

56.3
40.1
3.6
0

46.1
38.7
15.2
0

35

interfaces of the films, no matter nano-silica or micro-silica

particles are contained in the films, suggesting that silica are
not like organic silanizing compounds in which Si segments
prefer to orient at the surface, silica like to immigrate into
the bulk. The interfaces contain N element while the surfaces have no N element, indicating that urethane segments
intend to orientate at interfaces while acrylic segments
like to cover the surface since the former have higher free
surface energy than the latter [10]. The N content at the interface of the film containing nano-silica is lower than that
of micro-silica, this is possibly because nano-silica have
considerably greater specific area than micro-silica, and the
OH groups on the surfaces of nano-silica can react with
NCO groups from HDI, resulting in more NCO groups
absorbed on the surfaces of nano-silica, which like to hide
into the bulk.
3.2. Hardness
3.2.1. Macro-hardness
A series of polyurethane films containing silica were prepared and the pendulum hardness were determined as shown
in Table 2. Sample nos. 17 were prepared by an acrylic
resin A with HDI, sample nos. 822 were prepared from
another acrylic resin B with HDI. Sample nos. 2 and 3
were obtained by in situ polymerization using unmodified
nano-silica and modified nano-silica with silane coupling
agent, respectively, other samples were obtained by directly
mixing acrylic resin with silica then cured by HDI. The data
in Table 2 display that addition of nano-silica can increase
the macro-hardness of the films no matter which preparation
method was used (see sample nos. 15). The data from two
acrylic resins (see sample nos. 1, 57 and 1215), different thickness of film (see sample nos. 811 and 1215), and
different drying time, show that macro-hardness increases
with the content of nano-silica. For sake of comparison, the
effects of fumed silica and micro-silica on macro-hardness
were also investigated. Table 2 tells us that all silica studied here can enhance the hardness of films (see sample nos.
10, 17, 22), but excessive micro-silica led to decrease in
macro-hardness.
3.2.2. Micro-hardness
Micro-hardness of the coatings with different concentration of nano-silica under different normal load is shown in
Fig. 1. The data points used in the plot is the average value
of three individual measurements performed at different
spots on the surface. The large fluctuation in the plot may
be attributable to the small size of measurement, m2 ,
roughness of the surface, and inhomogeneity of the coating. However, the tendency is clear that the micro-hardness
increases with the increasing concentration of nano-silica,
which is consistent with macro-hardness measurement.
Fig. 2 shows the change of the coatings with different types
of silica embedded in their micro-hardness. Overall, it can
be seen that the order of micro-hardness from large to

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S. Zhou et al. / Progress in Organic Coatings 45 (2002) 3342

Table 2
Macro-hardness of polyurethane films containing silica prepared at different conditions
Sample no.
1
2b
3b
4
5
6
7

Componenta resin solution/silica/HDI

Drying time (day)

Thickness (m)

Macro-hardness

Type of silica

100/0/100
99/1/100
99/1/100c
99/1/100c
99/1/100
95/5/100
90/10/100

1
1
1
1
1
1
1

79
74
78
71
74
70
73

0.57
0.60
0.62
0.61
0.61
0.75
0.77

Nano-silica

8
9
10
11

100/0/100
99/1/100
95/5/100
90/10/100

19
19
19
19

51
58
47
50

0.53
0.59
0.62
0.69

Nano-silica

12
13
14
15

100/0/100
99/1/100
95/5/100
90/10/100

5
5
5
5

88
75
81
78

0.28
0.40
0.54
0.75

Nano-silica

16
17
18

99/1/100
95/5/100
90/10/100

7
7
7

54
52
53

0.49
0.58
0.49

Micro-silica

19
20
21

99/1/100
95/5/100
90/10/100

7
7
7

68
62
76

0.45
0.58
0.46

Micro-silica

95/5/100

55

0.63

Fumed silica

22
a

Sample nos. 17 were obtained from acrylic resin A with HDI and sample nos. 822 from acrylic resin B with different monomer composition
from A, resin solid content for A and B are 70 wt.%.
b Nano-silica is combined with acrylic resin by in situ polymerization method.
c Nano-silica is treated with KH570 coupling agent.

small is nano-silica, fumed silica, and micro-silica. Fig. 3

further shows the effect of concentration of micro-silica
on the micro-hardness of the coatings. In contrast to the
nano-silica case, the micro-hardness of the coatings with
different concentration of micro-silica are about the same
under the normal force less than 10 mN. Therefore, the
addition of nano-silica to coatings can more efficiently enhance the hardness since they have considerably greater
specific surface area than micro-silica.

3.3. Abrasion resistance

Fig. 1. The change in micro-hardness of the films with different nano-silica

content with peak load.

Fig. 2. The change in micro-hardness of the films with different types of

silica and peak load.

The weight loss of the polyurethane films with different

nano-silica content at different abrasion cycle is shown in
Fig. 4. The weight loss gradually decreases as nano-silica
content increases, indicating that nano-silica can improve the
abrasion resistance of the coating film. Figs. 5 and 6 manifest
the effect of the types of silica and micro-silica content on
the weight loss of film, respectively. It was seen from Fig. 5

S. Zhou et al. / Progress in Organic Coatings 45 (2002) 3342

Fig. 3. The change in micro-hardness of the films with different

micro-silica content and peak load.

37

Fig. 6. The weight loss of the polyurethane films containing different

micro-silica content.

that the abrasion resistance of the films containing different

types of silica are nearly the same except for the fumed
silica. Fig. 6 shows that the weight loss does not change if
only a small amount of micro-silica (e.g. 1 wt.%) is added,
but the abrasion resistance increases as micro-silica content
increases.
3.4. Static mechanical property

Fig. 4. The weight loss of the polyurethane films containing different

nano-silica content.

The static mechanical properties of polyurethane films

containing different nano-silica or micro-silica contents determined on Instron testing machine, the effect of silica content on strength and elongation are plotted in Fig. 7. The film
strength considerably increases and elongation at break obviously decreases with increasing nano-silica content. This
is likely due to the reaction of isocyanate with hydroxyl
groups on the surfaces of nano-silica, which leads to a higher
cross-linking degree of the film. On the other hand, the small
specific area of micro-silica particles cannot change the tensile property of the film greatly.
3.5. Youngs modulus

Fig. 5. The weight loss of the polyurethane films containing different

types of silica.

Fig. 8 shows the Youngs modulus of the polyurethane

coatings with different concentration of nano-silica, which
was measured by Nano-indenter XP under different normal load. Again, the large fluctuation may be due to the
small size of measurement, m2 , roughness of the surface, and inhomogeneity of the coating, as mentioned above.
The tendency that the modulus increases with the increasing
nano-silica concentration is clear. Fig. 9 is the Youngs modulus of the coatings containing different types of silica under different normal load. The Youngs modulus of coating
with nano-silica and the Youngs modulus of coating with
fumed silica are about the same, while the Youngs modulus
of coating with micro-silica is distinguishably smaller than
them. Again, this is probably because some reaction of isocyanate with hydroxyl groups on the surfaces of nano-silica

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S. Zhou et al. / Progress in Organic Coatings 45 (2002) 3342

Fig. 7. Tensile properties of polyurethane films with different silica content.

Fig. 8. The Youngs modulus of polyurethane films containing different

nano-silica content.

Fig. 10. The Youngs modulus of polyurethane films containing different

micro-silica content.

had happened, resulting in a higher cross-linking degree

for nano-silica embedded film than for micro-silica contained film. Another reason is there should be greater interaction strength between nano-silica and organic matrix than
micro-silica and organic matrix since the former has greater
specific surface area than the latter. Fumed silica has to some
extent similar particle characteristic to nano-silica. As concentration of micro-silica increases to 10 wt.%, the Youngs
modulus of the coating showed an apparent increase, especially under the high normal loads, as indicated in Fig. 10.
3.6. Dynamic mechanical property

Fig. 9. The Youngs modulus of polyurethane films containing different

types of silica.

Storage modulus and loss tan as functions of temperature for the polyurethane films without or with 5 wt.% silica are presented in Figs. 11 and 12, respectively. Both
nano-silica and micro-silica can enhance storage modulus
of the polyurethane film, but nano-silica seems to be more

S. Zhou et al. / Progress in Organic Coatings 45 (2002) 3342

Fig. 11. The storage modulus of polyurethane films with or without silica
determined by DMA.

efficient for increasing modulus than micro-silica since the

former has larger surface interaction with polyurethane matrix than the latter. Fig. 12 shows that glass transition temperature (Tg ) and dissipation peak decrease after application
of silica, and the larger the particle size of silica is, the lower
the Tg is. This is probably because Tg is related to free volume in composites, addition of silica can increase the free
volume in composites, and the composite with larger particles has higher free volume fraction, which results in lower
Tg . The same phenomenon in nano-silica/PMMA system
was also found by Ou et al. [11].
3.7. Scratch resistance

39

Fig. 13. Comparison of scratch resistance of acrylic-based polyurethane

film before and after nano-silica filled.

Fig. 14. The scratch resistance of coatings containing different types of silica vs. the normal load and the scratch resistance of coatings with different concentration of micro-silica
vs. the normal load are shown in Figs. 15 and 16, respectively. The polyurethane film containing nano-silica shows
the best scratch resistance, while the coating containing
micro-silica performs the worst, as shown in Fig. 15. The
coating with a 10 wt.% micro-silica shows a superior scratch
resistance over the coatings with a 1 wt.% and a 5 wt.%
micro-silica under low normal loads. As the normal load increases beyond 1 mN, different concentration makes no difference in the scratch resistance, as indicated in Fig. 16.

The scratch resistance of polyurethane coatings with and

without nano-silica particles embedded under different normal load was measured by Nano-indenter XP and plotted in
Fig. 13. The addition of small amount of nano-silica (e.g.
1 wt.%) to the coating can dramatically improve its scratch
resistance. Increasing the concentration of nano-silica can
improve the scratch resistance furthermore, as indicated in

3.8. Optical property

Fig. 12. The dissipation peak of polyurethane films with or without silica
by DMA.

Fig. 14. Variation of the scratch resistance of coating films from resin A
with nano-silica concentration.

3.8.1. Appearance
The appearance of acrylic resin is waterwhite. However,
after nano-silica was added, there are some changes in
appearance, as indicated in Table 3. The resin with low
nano-silica concentration is still clear but becomes opaque

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S. Zhou et al. / Progress in Organic Coatings 45 (2002) 3342

Fig. 15. The scratch resistance of coating films from resin B containing
different kinds of silica.

Fig. 17. TEM micrograph of nano-SiO2 /acrylic-based polyurethane film.

Fig. 16. Dependence of the scratch resistance of coating films from resin
B on micro-silica concentration.

when the concentration increases. Theoretically, the size of

nanoparticle is small than the wavelength of visible light,
no scattering and reflecting occurs in the visible light range,
so the nanocomposite should be transparent. But nanoparticles tend to aggregate due to its high surface energy. The
Table 3
Appearance of acrylic resins and polyurethane films
No.

Silica
Types

Appearance
Concentration
(wt.%)

Acrylic resin
solution

Films

Transparent

Transparent

No silica

2
3
4

Nano-silica

1
5
10

Transparent
Slight cloudy
Slight cloudy

Transparent
Semi-transparent
Semi-transparent

5
6
7

Micro-silica

1
5
10

Cloudy
White
White

Transparent
Transparent
Transparent

Fumed silica

Transparent

Transparent

nano-silica particles used here are hydrophilic and have a

lot of OH groups at the surface. Thus, acrylic polyol has
better miscibility with nano-silica, but the solvent, butyl
acetate, is not miscible with nano-silica, causing acrylic
resin solution and the corresponding film opaque. Fig. 17
shows the TEM photograph of nano-silica dispersed in the
polyurethane film. It was seen that part of the nanoparticles
have reached nanometer scale, although some aggregates
are observed. When nano-silica content increases, the content of aggregates larger than nanometer size also increases.
For the fumed silica, both the acrylic resin solution and its
film are transparent. The appearance of the acrylic resin
solution containing micro-silica is completely opaque due
to its larger particle size, but the corresponding film become clear, which is possibly because the refractive index
of micro-silica is close to that of the polyurethane matrix.
3.8.2. UVVis spectra
The UVVis absorbance and transmittance spectra of the
films containing nano-silica are seen in Figs. 18 and 19, respectively. Fig. 18 indicates that the absorbance in the range
290400 nm wavelength increases as nano-silica content increases. Because of absorbance and reflection, the transmittance of light reduces especially in the UV range. The reduction of transmittance in the visible light range indicates
that the film become opaque, which is consistent with the
change in appearance of the film observed. Comparison of
transmittance of the film containing nano-silica with other
silica is shown in Fig. 20. There is very small absorbance for
fumed silica and no absorbance at all for micro-silica, even

S. Zhou et al. / Progress in Organic Coatings 45 (2002) 3342

Fig. 18. Absorbance spectra of polyurethane film containing different

nano-silica content.

41

Fig. 21. Absorbance spectra of polyurethane film containing different

micro-silica content.

Fig. 22. Transmittance spectra of polyurethane film containing different

micro-silica content.
Fig. 19. Transmittance spectra of polyurethane film containing different
nano-silica content.

at higher micro-silica concentration, just as seen in Figs. 21

and 22. This means that nano-silica can more efficiently enhance exterior durability of coatings or polymer films than
other silica.

4. Conclusions

Fig. 20. Transmittance spectra of polyurethane film containing different

types of silica.

Effect of nano-silica on the surface and interface, mechanical and optical properties of acrylic-based polyurethane
films was investigated. Silicon element was not detected
at surface and interface of polymer film. Addition of
nano-silica can improve the hardness, abrasion resistance,
scratch resistance, tensile strength, modulus and weatherability of the polymer film, while fumed silica or micro-silica
can only increase the hardness and abrasion resistance.
Moreover, dependences of the properties of the films on
silica content were completely different from various types
of silica.

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S. Zhou et al. / Progress in Organic Coatings 45 (2002) 3342

Acknowledgements
We would thank Shanghai Nano-Special Foundation, Key
Project of China Educational Ministry, Doctoral Foundation
of China Educational Ministry, Shanghai Shuguang Foundation and National Science Foundation of China for the
financial support for this research.
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