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SAE TECHNICAL
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2003-01-2914

Challenges in Fabrication of Polymer


Nanocomposites (PNCs)
M.-T. Ton-That, J. Denault and K. C. Cole
National Research Council Canada, Industrial Materials Institute

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2003-01-2914

Challenges in Fabrication of Polymer Nanocomposites (PNCs)


M.-T. Ton-That, J. Denault and K. C. Cole
National Research Council Canada, Industrial Materials Institute
Copyright 2003 SAE International

ABSTRACT
As is the case for conventional composites, the key to
the performance of polymer nanocomposites is the
quality of dispersion of the nano-reinforcement and the
interfacial interaction between the matrix and the
reinforcement phase. Optimization of these properties
requires various special and complicated treatments,
which are not always easy to determine. The aim of this
paper is to give some examples of the application of
different approaches to both thermoset and thermoplastic polymer nanocomposites, fabricated by different
means, such as solution, melt-processing, and in-situ
polymerization.

INTRODUCTION
PNCs have recently been receiving very much attention
due to their improved properties with modest density
gain, which constitutes their main advantage over
conventional composites [1,2]. However, their performance is controlled by the level of dispersion of nanoreinforcement and the interfacial interaction between the
matrix and reinforcement phase, which are not easy to
control in most cases. Due to the atomic scale of nanoreinforcements, their interaction with the matrix becomes
much greater than for the case of macro- and microreinforcements.
As a result, dispersion of nanoreinforcement in a polymer matrix is quite difficult and
thus often requires special and complicated treatments.
In addition, with respect to the issue of the reinforcing
effect, differences in chemistry and/or structure between
nano-reinforcements and polymers have a negative
impact on the interfacial interaction between the two
phases. Various treatments and modifications, focusing
either on the chemistry or the physics or the processing
procedure, have been proposed to solve such problems
but they all have notable disadvantages, such as
increased processing costs and/or complexity, or the
loss of different properties like impact, toughness, and
ductility. Such problems still remain unsolved in various
polymer systems [3-9]. In short, fabrication of nanocomposites faces various challenges.
This paper will discuss different issues involved in the
development of thermoplastic and thermoset nanocomposites by means of different processing techniques,

such as solution, melt-processing, and in-situ polymerization, within the scope of the strategic research
program on PNCs at the NRC-IMI. Different approaches
in terms of chemistry, physics and mechanics, which
have been developed and examined during the course
of this research program, will be presented.

MATERIALS AND EXPERIMENTAL


MATERIALS
The epoxy resin selected for this study was Vantico
Araldite PY-307. Two different types of hardeners were
used, namely polyamine-based Shell Epicure 3046 and
Aldrich Maleic Anhydride (MA).
Polypropylene (PP)
6100 SM from Montell and Poly(ethylene-terephthalate)
(PET) Eastapak 9921 from Eastman were used. Three
types of nanoclay Cloisite -15A, -10A, and -30B were
kindly supplied by Southern Clay Products, Inc. and one
type of nanoclay Nanomer I30E was obtained from
Nanocor, Inc. For the preparation of PP nanocomposites, the coupling agent Polybond 3150 based on
maleic-anhydride-grafted polypropylene (MAgPP) was
obtained from Uniroyal Chemicals.
PNC FABRICATION
Thermoset epoxy nanocomposites
Two different processes were used to prepare the
nanocomposites, namely a solvent process and a direct
mixing process. In the solvent process, the nanoclay
was dispersed in methylethylketone (at a concentration
less than 5 wt%) at 40-50C for 1 h, then subjected to
ultrasonication at the same temperature for 30 min using
three different ultrasonic power levels of 175, 300 and
600 W. Finally epoxy was introduced into the mixture at
room temperature followed by ultrasonication for 30 min
also at room temperature. The sample was dried in a
vacuum oven at 40C to remove solvent. Low temperatures were used for the later steps in order to avoid
chemical reaction of the epoxy group with the organonanoclay. In the direct mixing process, the nanoclay
was dispersed directly into the epoxy matrix through
mixing at various temperatures between 70 and 180C
for a period of 1 h.

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Different mixtures of polymer, nanoclay, and coupling


agent (for the case of PP) were prepared by melt
processing in a twin-screw extruder using the same
processing conditions for all experiments. The screw
configuration was designed to obtain a sufficiently high
shear rate for achieving a good dispersion as shown in
Figure 1. The concentration of nanoclay varied between
0 and 4 wt %. For PP, coupling agent was used to
obtain a good interface, and the weight ratio between
nanoclay and coupling agent was kept constant at 1.
Some samples were passed through the extruder more
than once in order to study the effect of residence time
without modifying other parameters of the extrusion.
Test specimens were prepared by injection molding.

Figure 1. Screw configuration for nanocomposite


fabrication.
SAMPLE CHARACTERIZATION
The samples were analyzed by Fourier transform
infrared (FT-IR) spectroscopy and differential scanning
calorimetry (DSC). The FT-IR spectra were acquired on
a Nicolet Magna 860 instrument with a resolution of 4
cm-1 by means of the attenuated total reflection (ATR)
technique. The DSC curves were measured on a
Perkin-Elmer DSC7 instrument under a nitrogen atmosphere. To evaluate the dispersion of the nanoclays in
the polymer matrix, X-ray diffraction patterns were
obtained from the surface of the samples with a Scintag
X2 Powder X-ray Diffractometer with CuK radiation.
Tensile, flexural, and notched Izod impact properties
were determined according to the ASTM test methods
D638, D790 and D256, respectively, using an Instron
5500R.

RESULTS AND DISCUSSION

amine. As seen in the DSC curves for the I30E-epoxy


system in the absence of curing agent in Figure 2, a
strong exothermic peak (520-560 Jg-1) appeared in the
range between 170 and 230C at a scan rate of 5C/min
for the three clay loading levels. From this graph, Tonset,
the temperature at which the chemical or physical
phenomenon became significant, decreased with the
increase of nanoclay loading. In the second scan, a new
glass transition step appeared between Tg = 102 and
106C and also increased with the nanoclay loading. In
order to verify the nature of the reaction, these samples
were analyzed by FT-IR. On comparing the spectra of
the uncured material and the product from the first DSC
scan, the most significant change is the disappearance
of the epoxide ring band at 915 cm-1, indicative of curing.
This is accompanied by the growth of a broad band
around 1170960 cm-1 that can be assigned to stretching
of the COC ether linkages formed by reaction of the
epoxide rings. The spectrum thus indicates that the
exothermic peak in the DSC curve of the first scan can
be assigned to the homopolymerization of the epoxy
groups initiated by the onium ion of the organo-nanoclay.
Based on the chemistry of the onium ions in the two
clays, it can be concluded that the primary amine used in
I30E can play a catalyst role for the homopolymerization
of epoxy, while the quaternary amine used in 30B is
inactive. Similar behavior was observed for Shell Epon
828 systems [10].
3.5

Heat flow Endo (W/g)

Thermoplastic PP and PET nanocomposites

3
2.5

1 wt% clay
2 wt% clay
4 wt% clay

2
1.5
1
0.5
140

160

180

200

220

240

Figure 2. DSC curves of the epoxy mixtures with I30E.


THERMOSET NANOCOMPOSITES
In the direct mixing process, the Nanomer I30E and
Cloisite 30B were mixed directly into the epoxy matrix.
Temperature plays an important role because it helps to
reduce the epoxy viscosity so as to achieve a better
dispersion while at the same time it can accelerate the
diffusion of epoxy molecules into the nanoclay galleries
to achieve intercalation and exfoliation.
However,
chemical reaction between the intercalant and the epoxy
matrix may occur during mixing, and the reaction level
will depend on the temperature and the intercalant
chemistry. No chemical reaction was observed for the
case of Cloisite 30B, which is based on quaternary
amine, while a homopolymerization of the epoxy group
initiated by the intercalant was clearly observed for the
case of Nanomer I30E, which is based on primary

Because of this problem and the degradation problem of


organo-nanoclays, the maximum mixing temperature
was set at 140C for the I30E systems and 180C for the
30B systems. Temperature has a great influence on the
quality of dispersion of the nanoclays in the nanocomposites. X-ray diffraction analysis has indicated that
preparation of the nanocomposites with Nanomer I30E
at the high temperature of 140C has accelerated the
diffusion of the polymer into the clay galleries, resulting
in full exfoliation, while for the ones prepared at lower
temperatures the nanoclays are well intercalated but not
exfoliated. As shown in Figure 3, for the one prepared at
140C no peak can be observed while for the ones
prepared at lower temperature the clay peak seen in
Nanomer I30E remained present but shifted to the left,
indicating the increase of the gallery distance to 3.2 and

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3.6 nm (for 70 and 120C, respectively). It is also


observed in Figure 3 that the nanocomposite prepared
with Cloisite 30B was fully exfoliated.

mechanism, further chemical analysis experiments


would need to be conducted.
3.2

2000

Intensity

1500

Heat flow endo (W/g)

30B, 180 C
I30E, 140 C
I30E, 120 C
I30E, 70 C
Nanomer I30E

1000

500

3
2.8
2.6

4 wt% clay
No clay

2.4
2.2

50

6
2 (o)

10

80

110
140
Temperature ( C)

12

In contrast with the amine-cured system, Figure 5 shows


that the presence of Nanomer I30E complicates the
curing reaction of the epoxy system cured with maleic
anhydride, as reflected in the DSC curve with 2 distinct
peaks. It seems that the Nanomer has inhibited the
curing reaction and changed the reaction mechanism.
Different possible reasons include the poisoning of
catalyst by the organo-nanoclay, reaction between the
organo-nanoclay and hardener, etc. However, in order
to understand the change of the curing reaction

Heat flow endo (W/g)

3.1

3
4 wt% clay
No clay

2.9

2.8

2.7
60

80

100
120
140
Temperature ( C)

160

180

b
Figure 4. DSC curves of the epoxy and epoxy nanocomposites cured with amine: a) the first scan and b) the
second scan.

2.2
2
Heat flow endo (W/g)

It was also observed that, depending on the hardener


chemistry, the presence of Nanomer I30E had some
effect on the curing reaction of the epoxy system, but
this was not so for Cloisite 30B. Figure 4a demonstrates
a neglible impact of the presence of Nanomer I30E on
the curing kinetics of the epoxy system cured with
polyamine, even at the high clay loading level of 4 wt%.
However, the presence of the organo-nanoclay reduced
the glass transition temperature of the crosslinked epoxy
matrix (Fig. 4b). It can be understood that the presence
of crowded intercalant molecules on the organonanoclay surface results in significant plastification of the
epoxy matrix. In experiments conducted with untreated
nanoclays, no reduction of the glass transition
temperature was observed. This confirms the negative
impact of the intercalant on the glass transition of the
epoxy matrix.

200

Figure 3. X-ray diffraction curves of the epoxy


nanocomposites.
In the solvent process, dispersion was studied for
nanocomposites containing 2 wt% of organo-nanoclay
30B. The ultrasonic power level significantly affected the
dispersion level. Exfoliation was obtained at ultrasonic
power levels of 300 W and above. Lower ultrasonic
power levels led to intercalated nanocomposites rather
than exfoliated. Other factors that need to be further
considered include the uniformity of the ultrasound, the
ultrasonic frequence, and localized effects of ultrasound.

170

1.8
1.6
1.4

No clay
4 wt% clay

1.2
1
0.8
50

90

130
170
Temperature ( C)

210

250

Figure 5. DSC curves of the epoxy and epoxy nanocomposites cured with anhydride.

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THERMOPLASTIC NANOCOMPOSITES

via van der Waals and/or hydrogen bonding, while at the


same time its PP backbone is fully compatible with the
PP matrix.

3.1
Strength
Modulus

2.9
95
2.7
90
2.5

85

Flexural modulus (GPa)

Flexural strength (MPa)

100

2.3
PET
pure

1%30B 1%10A 2%30B 2%10A 4%30B 4%10A

Figure 6. Flexural properties of the PET nanocomposites


Effect of coupling agent
Unlike the case for PET nanocomposites, the formation
of PP nanocomposites must involve the incorporation of
a coupling agent due to the incompatibility between the
hydrophobic PP and the hydrophilic nanoclay. As seen
in Figure 7, the presence of the coupling agent greatly
improved the mechanical properties of the nanocomposites. In addition, the increase of organo-nanoclay
loading significantly increases the flexural strength and
modulus of the nanocomposites in the presence of
coupling agent but not in the absence of coupling agent.
This can be explained by the fact that the presence of
coupling agent can improve the interaction at the
interface between the nanoclay surface and the polymer
matrix, as well as the dispersion of nanoclay into the PP
matrix, since the functional MA group of the coupling
agent is believed to interact with the nanoclay surface

65

2.2
Strength

With coupling agent

Modulus

60

2
1.8

55

No coupling agent

1.6
50

1.4

45

Flexural modulus (GPa)

The flexural properties of the PET nanocomposites


prepared with different concentrations of two different
types of organo-nanoclays, Cloisite 10A and 30B, are
shown in Figure 6. The results indicate that as the clay
concentration increases, the PNC modulus increases
significantly regardless of the type of organo-nanoclay.
However, in term of stress, the Cloisite 30B shows itself
to be superior in reinforcing the PET matrix in comparison with the Cloisite 10A. The Cloisite 10A contains a
phenyl ring in the onium portion, which is believed to
have good affinity and thus good compatibility with the
PET, but the Cloisite 30B contains a hydroxyl group,
which may react with acid end-groups of the PET or can
form a strong hydrogen bond with the ester groups of the
PET backbone. Chemical and hydrogen bonds are
stronger than van der Waals bonds, so a stronger
interaction is expected between PET matrix and Cloisite
30B than between PET and Cloisite 10A. Consequently,
further experiments were conducted on Cloisite 30B.

Flexural strength (MPa)

Effect of intercalant

1.2
PP pure 1% 15A 2% 15A 4% 15A 1% 15A 2% 15A 4% 15A

Figure 7. Flexural properties of the PP nanocomposites

CONCLUSION
The fabrication of PNCs is a very complicated issue,
which involves the utilization of various principles based
on fundamental chemistry, physics, thermodynamics,
and mechanics. In addition, it is very difficult to apply
general rules to PNC fabrication; instead each individual
case must be specifically reagrded.

ACKNOWLEDGMENTS
The authors acknowledge Mr. Y. Simard and Ms. M.
Plourde for the preparation and characterization of the
samples.

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