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J. Mater. Sci. Technol., Vol.25 No.

2, 2009

247

Electrical and Mechanical Properties of PMMA/nano-ATO


Composites
Wei Pan , Huiqin Zhang and Yan Chen
Institute of Materials and Chemical Engineering, Zhongyuan University of Technology, Zhengzhou 450007, China
[Manuscript received December 24, 2007, in revised form July 1, 2008]

Conducting nanocomposites of poly (methyl methacrylate) (PMMA) and antimony doped tin oxide (ATO)
were prepared by solution blending. The influences of ATO content on the electrical conductivity, thermal
stability, and mechanical properties of the nanocomposites were investigated. A homogeneous dispersion
of silane coupling agent modified ATO was achieved in PMMA matrix as evidenced by scanning electron
microscopy. The resultant PMMA/silane-ATO nanocomposites were electrically conductive with significant
conductivity enhancement at 4 wt pct. It was found that the composition at 4 wt pct ATO gave the higher
tensile strength. Furthermore, it gave the largest elongation at break value among all the compositions.
Thermal stability of the nanocomposites was remarkably enhanced by the incorporation of silane-ATO.
KEY WORDS: Antimony doped tin oxide; PMMA; Nanocomposites; Structure and properties

1. Introduction
Polymers can be compounded with a variety of
common and special fillers, reinforcements, and modifiers to yield specific properties in a wide range of
applications[1,2] . Among these, additives that are
electrically and thermally conductive can provide protection against static accumulation, electrostatic discharge and molding cycle reduction. Various fillers,
some of metallic, are used to improve the conductive properties of the neat polymer. However, high
concentrations of filler (e.g. 30% carbon black), can
take a toll on physical and esthetical properties of the
polymer: selection of conductive material has often
involved compromises[3,4] . The preparation of polymer composites by dispersion of small loadings of
nanosized fillers in a polymeric matrix has lately attracted much attention in the academia and the industry for its potential in improving the performance of
macromolecular materials. Nanoparticles may make
the matrix0 s physical-mechanical properties much improved with respect to traditional micro-sized fillers,
due mainly to maximization of the polymer-filler interfacial region[57] .
Particularly interesting conductive filler is antimony doped tin oxide (ATO) as it possesses good
electrical conductivity with optical transparency[810] .
When used as antistatic agent, ATO shows better performance than currently used carbon blacks, metallic pigment and organic polymer binders[11] . ATO
has been used to increase the electrical conductivity
of polyvinyl acetate-acrylate copolymer coatings[12] ,
gelatine and acrylate films[13] , and urethane and polyester coatings[14] . For different matrices, the minimum amount of ATO to obtain the aimed increase in
conductivity varied roughly from 5 to 20 vol. pct.
PMMA is an important commercial plastic, which
has extensive application in many sectors such as
in aircraft glazing, signs, lighting, architecture,
transportation and merchandising. However, the
low conductivity, less than 1014 S/cm and the
Corresponding author. Assoc. Prof., Ph.D.;
E-mail address: panwei@zzti.edu.cn (W. Pan).

static problem restrict its further applications.


PMMA/ATO conducting system has not yet been
explored but it is a competitive system for making conducting polymer. In our study, PMMA/ATO
nanocomposites were prepared by a solution-mixing
method. The relationship between the electrical properties and the morphology of the composites was studied. The effects of mixing fillers on thermal properties
of the nanocomposites were also investigated.
2. Experimental
2.1 Materials
The PMMA (LX-025) employed in this study was
purchased from Shanghai Petroleum Chemical Co.,
Ltd. (Shanghai, China). The untreated nano-ATO
particles (specific surface area: 80 m2 /g, antimony
doping level: 15%, average particles size: 40 nm) were
purchased from Shanghai Huzheng Technology Co.,
Ltd. (Shanghai, China). The silane coupling agent
(KH570, commercial grades) supplied by Shanghai
Yaohua Chemical Plant (Shanghai, China), was used
to treat the nano-ATO particles. Other agents and
process assistants (commercial grades) were obtained
from the market.
2.2 Nano-ATO particle surface treatment
Silane coupling agent (0.1 g) was mixed with 5.0 g
distilled water and 95.0 g absolute ethanol. Then
10.0 g ATO powder was added into the solvent mixture. The suspension was dispersed in an ultrasonicator for 1 h, and then was refluxed at 120 C for
24 h. After surface treatment, the ATO particles were
washed with ethanol three times in order to remove
any unreacted silane coupling agent.
2.3 Composites preparation
The silane-ATO or untreated-ATO was dispersed
in THF (tetrahydrofuran) to prepare a suspending
dispersion with certain nano-ATO content. The
PMMA was dissolved in THF by heating to a back-

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J. Mater. Sci. Technol., Vol.25 No.2, 2009

Fig. 1 SEM micrographs of freeze fractured surfaces of PMMA/ATO nanocomposites: (a) 4 wt pct untreatedATO, (b) 4 wt pct silane-ATO, (c) 8 wt pct untreated-ATO, (d) 8 wt pct silane-ATO

flow temperature of THF (about 80 C). The ATO


suspending dispersion was added drop by drop into
the PMMA solution at the backflow state, keeping
the total concentration of the ATO and the PMMA
as 20 wt pct mass ratio. The mixture solutions were
cast and left to dry in vacuum at 60 C for 48 h.
2.4 Testing methods
Morphological studies were performed by SEM
(scanning electron microscopy). Microphotographs
were taken of the surface made by fracturing the specimen in liquid nitrogen and then sputtered with gold.
A JSM5600LV scanning electron microscope was used
for morphological observation. Electrical conductivity of the composites was measured by four-probe
method. Five measurements in three different samples of each composition were carried out, and the
standard deviation was always less than 1%. Wide
angle X-ray diffraction (XRD) was carried out using a BRUKER-AXC08 X-ray diffractmeter and filtered CuK radiation. The diffraction patterns of
the composite powder of the ATO and PMMA were
obtained by scanning the samples in an interval of
2=5 60 . Thermogravimetric analyses (TGA) of
pure PMMA and PMMA/ATO nanocomposites were
performed with a TA Instruments Du Pont l090 at
10 C/min in nitrogen atmosphere. Room temperature tensile testing of the composites was conducted
on an Instron1122 testing machine at a crosshead
speed of 50 mm/min. Five samples were tested for
each case.
3. Results and Discussion
3.1 Morphology observation
The cross-section SEM micrographs of the

PMMA/untreated-ATO and PMMA/silane-ATO


nanocomposites containing 4 and 8 wt pct ATO are
shown in Fig. 1. The dark regions are PMMA phase
while the bright regions are conductive ATO phase.
Figure 1(a) and 1(c) show the poor particle dispersion in PMMA matrix. Raw ATO is agglomerated
into large size. On the other hand, the silane-ATO
particles are homogeneously dispersed in the PMMA
matrix (Fig. 1(b) and (d)). This is because the presence of the silane group on the ATO surface is likely
to give the strong interfacial interaction between the
polymer matrix and the ATO in polymer composites.
3.2 Electrical conductivity
The electrical conductivity of the PMMA/ATO
nanocomposite as a function of ATO content is shown
in Fig. 2. Figure 2 shows that the conductivity of
the PMMA/silane-ATO composites increased with increasing the ATO content. The sharp increase in the
conductivity for ATO up to 4 wt pct suggested that
the percolation threshold in the conductivity of the
nanocomposites is around 4 wt pct content. When
the ATO content was increased further, the electric
conductivity increased slowly. This demonstrates a
very low percolation threshold value for a conducting nanocomposite prepared with silane-ATO, which
is much smaller than that of conventional conducting
macro-composites. The augmentation of the electrical conductivity can be ascribed to the uniform dispersion of silane-ATO within the polymer matrix and
the formation of conducting network at very low filler
loading. With very low inorganic filler content, the
resulted nanocomposites can remain the superior inherent mechanical strength of polymeric matrix. The
nanocomposites exhibit high polymeric performance
and electrical conductivity.
Figure 2 also shows that the electrical conductivity

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J. Mater. Sci. Technol., Vol.25 No.2, 2009

-6

10

-10

10

60

2.0

50
1.5

Elongation to break / %

Tensile strength / MPa

-1

cm
Conductivity / S

2.5

70

-2

10

40

PMMA/untreated-ATO
PMMA/silane-ATO

1.0
0

10

15

20

-14

10

10

15

Silane-ATO content / %

20

Content of ATO / %

Fig. 2 Electrical conductivity of PMMA/ATO composite vs ATO content

Fig. 4 Effect of silane-ATO content on tensile strength


and elongation to break of composites

20

Weight / %

PMMA
ATO
8 wt pct ATO
12 wt pct ATO
4 wt pct

60

30

40

417 C
o

100

200

300
Temp. /

50

40

60

20

ATO
20

20

40

10

Derivativa / % min

80

100

60

/ deg.

Fig. 3 X-ray diffractrograms of PMMA, silane-ATO and


PMMA/silane-ATO

of the PMMA/untreated-ATO composites was lower


than that of the silane-ATO composites at identical
ATO content. As a result, the electrical current of
the composites filled with the well dispersed ATO was
higher than that of composites filled with the poorly
dispersed ATO. It was easier for the well dispersed
ATO to form electrical paths due to their relatively
homogeneous dispersion of nanoparticles than for the
poor dispersion ATO.
3.3 Wide-angle X-ray diffraction
It is known that the crystal structure of the
matrix has a key role in determining the properties of polymer-based composites[15,16] . The XRD
patterns of silane-ATO, the pure PMMA and the
PMMA/silane-ATO nanocomposites with 4, 8 and
12 wt pct of nano-ATO content are shown in Fig. 3.
The XRD patterns of the nano-ATO display five peaks
at 2=26.5 , 33.7 , 37.7 , 51.7 and 54.7 corresponding to the diffraction from (110), (101), (200), (220)
and (211) plane, respectively[17] . PMMA showed a
broad diffraction peak at 2=14 , which indicated
that PMMA is amorphous.
The XRD patterns of the PMMA/ATO nanocomposites showed that combine peaks appeared in the
ATO and pure PMMA. Moreover, the intensity of
the peaks assigned to the ATO in the composite increased with increasing the content of ATO. However,

400
o

500

600

Fig. 5 TGA curves of PMMA/ATO (12 wt pct)

the position of the peaks corresponding to the two


constituents of the nanocomposite was the same as
the individual of PMMA and nano-ATO, which illustrated that either the orientation of the PMMA chains
or the structure of ATO was not influenced each other
during the process of preparation.
3.4 Tensile measurement
The tensile strength and elongation at break of the
PMMA/silane-ATO composites with different ATO
contents are shown in Fig. 4. The tensile strength of
PMMA/silane-ATO nanocomposites increased with
increasing silane-ATO content up to 4 wt pct and then
decreases at higher loading. The elongation at break
behaves in a similar way. With slightly adding of
silane-ATO, the filler is uniformly dispersed in PMMA
matrix. The filler has high aspect ratio, which tends
to improve interfacial bonding and form filler-polymer
interaction because of high specific surface area of the
filler[18,19] . The lower tensile strength of nanocomposites at a higher silane-ATO loading may be due to the
inevitable aggregation of ATO nanoparticles. These
aggregates are the weakest point in the composite,
which leads to earlier tensile break.
3.5 Thermal analysis
The thermal stability of the pure PMMA and
PMMA/silane-ATO nanocomposites with 12 wt pct
nano-ATO content was characterized by TGA. The
weight loss curves as a function of temperature is
shown in Figs. 5 and 6. In the present study, 50%
of the total weight loss was considered as the thermal

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J. Mater. Sci. Technol., Vol.25 No.2, 2009

100

0
1
-

60

20

40

40
20
0

Derivativa / % min

Weight / %

80

392 C
o

100

200

300

Temp. /

400
o

500

600

Fig. 6 TGA curves of pure PMMA

decomposition temperature of the system, which usually coincides with the peak of the derivative curves.
It is observed that the thermal decomposition temperature of PMMA/ATO is around 417 C, whereas
that of pure PMMA is only 392 C. This clearly
demonstrates that the PMMA/silane-ATO system is
thermally more stable than the corresponding neat
PMMA system. The existence of inorganic materials
in polymer matrix, generally, enhances the thermal
stability of the composite[20] . The thermal stability
also increases due to the presence of the inorganic
phase and its interaction with the polymer.
4. Conclusion
PMMA/silane-ATO and PMMA/ATO composites
and the morphology were prepared by solution blending. Electrical properties and mechanical properties
of the composites and the morphology were characterized by SEM, XRD and TGA. The results showed
that the silane coupling agent onto the ATO surface
improved the dispersion of ATO in PMMA along with
much enhanced electrical property of composites compared to those containing ATO without treated. It
was found that the 4 wt pct silane-ATO sample gave
the highest tensile strength and elongation at break

value amongst all the ATO compositions from 0 to


20 wt pct. Thermal stability of the nanocomposites was remarkably enhanced by the incorporation
of silane-ATO.
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