Polypropylene-Organoclay Nanocomposites: Formulation,

Microstructure and Performance

J. Denault
,
M.N. Bureau, T. Ton-That, L.A. Utracki, F. Perrin, and K. Cole
Industrial Materials Institute, National Research Council Canada
75, de Mortagne, Boucherville (Quebec) Canada J4B 6Y4
Tel : (450) 641-5149 Fax : (450) 641-5105
e-mail : johanne.denault@cnrc-nrc.gc.ca

ABSTRACT
Polymer nanocomposites (PNC) are emerging as a new class of industrially important
materials that offer improvements over conventional composite systems. The high aspect
ratio of the nano particles leads to higher reinforcement efficiency and therefore higher
specific modulus, strength and HDT. The low nanoparticle content (< 5% by weight) also
guarantees good processabilty as well as higher recyclability potential. In this work,
nanoclay-reinforced polypropylene nanocomposites have been prepared by means of melt
processing technology. Different formulations and processing conditions have been
investigated in order to optimize the chemical and the physicochemical interaction
between the polymer matrix and the inorganic nanoparticle phases as well as their
dispersion. The processing ability and various properties such as the physicochemical,
the mechanical and thermal stability, have been evaluated. The relationship between the
formulation, processing conditions, micro/nanostructure and performance were discussed.
Specifically, the fracture toughness, using the essential work of fracture method, were
obtained for clay nanocomposites. Improvements in fracture properties were observed,
which were related to the level of dispersion of clay particles, both at the nano- and the
micro-scale. Clay micro-particles acted as void nucleation sites within the PP matrix. The
highest tensile properties and highest fracture toughness were obtained for the PNCs
showing high particle density with good particle-matrix adhesion, which led to
intermediate void nucleation but extensive fibrillation.
Keywords: Polypropylene nancomposites, processing, microstructure, mechanical
properties.
Johanne Denault, Industrial Materials Institute, National Research Council Canada
INTRODUCTION
Polymer nanocomposites (PNCs) are a new kind of composite materials in which the
reinforcement has at least one nanometric dimension. Among the range of nano-
reinforcements used in PNCs, icluding nanofibers, wiskers, carbon nanotubes, clays have
been widely studied because of their potential to exfoliate in the polymer matrix as single
nanometric platelets leading to markedly superior mechanical properties, thermal
resistance, improved flammability resistance and barrier properties at very low cost [1].
PNCs are now recognized like a kind of perfect low weight material; with only few
percent of clay (2-5 wt%)or event less for carbon nanotubes (0.1-2wt%) the materials
show overwhelming properties without significant increase of density. This new class of
material is now finding a lot of applications in different domains like ground
transportation, aerospace, biomedical and packaging mainly for food sector. In fact in
any application where performance and weight are critical.
PNCs are currently prepared by different methods, namely in-situ polymerization, solvent
process and melt compounding. PNCs are also made using a large variety of
thermosetting and thermoplastic polymers [2]. From an industrial point of view,
preparation of thermoplastic PNCs by melt blending using conventional plastic
compounding tools remains the solution of choice, specially in commodity resins like
polypropylene (PP), which is of great interest for the automotive and the packaging
industries. However, melt blending of PP-based nanocomposites remains an important
challenge since complete exfoliation, i.e. the dispersion of clay in single platelets, has not
yet been successfully achieved. Most of the developed formulations have shown a
relatively limited degree of intercalation; the distancing of clay platelets still forming
aggregate. The use of conventional coupling agents mainly based on MA-grafted PP has
been shown to significantly improve clay intercalation depending on their characteristics
as molecular weight and grafting content [3 - 5] and on the coupling agent-to-clay ratio
[3, 6, 7]. Intercalation was also shown to be affected by the type and content of clay [8 -
10] and the type of clay intercalant (i.e. clay organic modification) [11]. In general,
improved intercalation is obtained at relatively low clay content and high coupling agent-
to-clay ratio.
Johanne Denault, Industrial Materials Institute, National Research Council Canada
It is also known that in semi-crystalline PP-based nanocomposites the addition of
coupling agent can greatly affect the matrix morphology and usually leads to good clay
intercalation instead of exfoliation. In such a case, the microstructural characterization in
terms of matrix morphology and clay dispersion at both the micro- and nano-level
becomes crucial to understand the effect of the formulation on the resulting properties of
PNCs.
The first objective of this presentation is to give you an overview of the potential of
PNCs material mainly for automotive, construction and packaging applications.
Secondly, challenges encountered for the development of polypropylene PNCs will be
discussed.
EXPERIMENTAL
In this work, polypropylene 6100 SM from Montell was used. Different types of
nanoclay, Cloisite-15A, -20A, and Na were obtained from Southern Clay Products Inc.
Various coupling agent grades based on maleic anhydride- and acrylic acid-grafted
polyproylene have obtained from Easman Kodak (Epolene-43, 3015 and 3003) and
Uniroyal Chemicals (Polybond 3150 and 1001).
Amine-terminated (NH
2
-t-)coupling agent has also been prepared in our
laboratory by reactive extrusion using Polybond 3150 and 4 wt.% of Jeffamine 403
(Hunstman). Then (NH
2
-t-)coupling agent was transferred to the cation form (NH
3
+
) by
immersing the NH
2
powder into HCl solution 20 wt.% at 80
o
C for 24 h. GMAgPP
(designated as GMA) was prepared as described elsewhere (12). The amounts of grafted
GMA and styrene were 0.43 and 0.27 wt%, respectively. Table 1 provides necessary
information of the used materials.
Different blends of PP, grafted PP, and nanoclays (2 and 4wt%)were prepared by
melt process using a twin-screw extruder following the same processing conditions.
Screw configuration followed the recommendation published in the website of Nanocor,
Inc. Concentration of coupling agent was chosen to have a ratio of nanoclay and
coupling agent constant at 2. Test specimens were prepared by injection moulding at
different temperatures of 180, 200 and 220
o
C.

Johanne Denault, Industrial Materials Institute, National Research Council Canada
Table 1. Characteristics of polymer materials
Material Commercial
name
Functional group Technical information
PP PP 6100SM
-
Injection molding grade
E43 (MA1) Epolene-43 MA (MA1) AN = 45; M
w
= 9,100
E3015 Epolene-3015 MA AN = 15; M
w
= 47,000
E3003 Epolene-3003 MA AN = 8; M
w
= 52,000
3150 (MA2) Polybond 3150 MA AN = 22; ~0.5wt% of MA; MFR =
40g/10min (230
o
C, 2.16 kg)
1001 Polybond 1001 AA ~6wt% of AA; MFR = 50g/10min (230
o
C,
2.16 kg)
NH
2
(Prepared) Amine
NH
3
+
(Prepared) Onium ion
GMAgPP (Prepared) Epoxy

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. The experiments were conducted on samples
prepared by injection moulding. However, the sample surface was re-moulded on a
cleaned glass slide in order to optimize the accuracy for the comparison of the X-ray
results.
A JEOL JSM-6100 scanning electronic microscope (SEM) and a Leitz Dialux 20
optical polarised microscope (OM) combined with a hot stage were used to observe the
morphologies and crystalline structure of the materials. Some samples were chemically
etched with potassium permanganate acid solution to reveal the crystalline phase.
For the characterization of the crystallization behavior, samples were heated to
200C under nitrogen atmosphere in a Perkin-Elmer DSC-7 instrument and kept at this
temperature for 5 min before cooling down to room temperature at different cooling rates
ranging from 1 to 40C/min.
Tensile, flexural and notched Izod impact properties were determined according
to the ASTM test methods D638, D790 and D256, respectively, using an Instron 5500R.
All tests were performed at room temperature with minimum of 5 samples for each test.

Johanne Denault, Industrial Materials Institute, National Research Council Canada
RESULTS AND DISCUSSION
The X-ray curves of the Cloisite 15A and the nanocomposites with 2 wt.% of
Cloisite 15A made with different types of coupling agent are shown in Figure 1. For
comparison purposes, nanocomposite samples were also prepared without coupling
agent. The clay Closite 15A has three distinctive X-ray peaks at 2.9, 4.8 and 7.3
o
. In all
nancomposite samples, the intensity of the peaks reduced due to the drop in nanoclay
concentration, however, the position of the peaks has changed depending on the type of
coupling agent used. Without coupling agent, the second peak moved to the left and
overlapped with the first peak, resulting in a broader peak. This indicates some further
intercalation happening during extrusion. Figure 1 also illustrates that the presence of
coupling agent has eliminated the second peak for all samples, except for the E-43, and
has shifted the first peak at 2.9
o
to left at the same time. This shows a positive effect of
coupling agent on the improvement in intercalation, although the level of effect is slightly
different from each other due to their chemistry differences. However, no completed
exfoliation has been observed for these samples.

0
5000
10000
15000
20000
25000
1 2 3 4 5 6 7 8 9 10
2 (
o
)
C
P
S
0
E43
E3015
E3003
3150
1001
15A

Figure 1. Effect of coupling agent on the X-ray results

TEM observation has also showed the presence of small clusters with few large
clusters in all samples. A great distinction of the nanocomposites with coupling agent
from the one without coupling agent is the presence of some single, double and triple
layers of the nanoclay (Fig.3) beside the clusters; this a good indication of better
exfoliation.
Johanne Denault, Industrial Materials Institute, National Research Council Canada


Figure 3. TEM observation of the nanocomposite 3150
Moreover, at high concentration of organo-nanoclay and coupling agent, 4 and 8
wt.%, respectively, the intensity of the X-ray peaks in the sample without coupling agent
increased more than two folds. Contradictory, this in the nanocomposites with coupling
agent reduced dramatically. This again reconfirms the effective role of coupling agent on
the intercalation of the organo-nanoclays.
There is no significant difference of clay dispersion between the MA- and AA-g-
PP and the NH
2
-t- and NH
3
+
-t-PP. The result may be due to the saturation of the negative
sites of the nanoclays by the intercalant (onium ion), thus no more active sites for the
interaction with the NH
2
and the NH
3
+
.
At the heating rate of 10
o
C/min, DSC results confirmed the nucleating effect of
the organo-nanoclay and the coupling agent as well. The crystallization temperature (T
c
)
and the degree of crystallinity increased significantly in the presence of organo-nanoclays
and coupling agent (see Figs. 4 and 5). This was observed for all samples except forthe
E-43 sample for which degradation has been detected by FTIR analysis. This results in
lower T
c
and degree of crystallinity.
Johanne Denault, Industrial Materials Institute, National Research Council Canada
114
118
122
126
130
P
P 0
E
4
3
E
3
1
0
5
E
3
0
0
3
3
1
5
0
1
0
0
1
T
c

(
o
C
)

Figure 4. Crystalline temperature of the nanocomposites (2 wt.% of clay)

57
59
61
63
65
P
P 0
E
4
3
E
3
1
0
5
E
3
0
0
3
3
1
5
0
1
0
0
1
D
e
g
r
e
e

o
f

c
r
y
s
t
a
l
l
i
n
i
t
y

(
%
)

Figure 5. Crystallinity of the nanocomposites (2 wt.% of clay)

Figures 6 and 7 show that the presence of coupling agent significantly increases
the mechanical properties of the nanocomposites. This can be explained by the fact that
the coupling agent has improved the dispersion of the nanoclays as discussed earlier, at
the same time it also improve the interface interaction between the hydrophobic PP
matrix and the hydrophilic nanoclay surface. Among them, the 3150 and 1001 show the
greatest improvement. On the other hand, E43 exhibits a poor impact on the
nanocomposite properties. This can be due to the poor dispersion and poor thermal
stability of this sample. In addition, Figures 6 and 7 show that if the moulding
Johanne Denault, Industrial Materials Institute, National Research Council Canada
temperature increased from 200 to 220
o
C, the mechanical properties of the E43 sample is
reduced dramatically.
28
30
32
34
P
P 0
E
4
3
-
2
2
0
o
C
E
4
3
-
2
0
0
o
C
E
3
0
1
5
E
3
0
0
3
E
4
3
-
E
3
0
0
3
E
4
3
-
3
0
1
5
3
1
5
0
1
0
0
1
T
e
n
s
i
l
e

s
t
r
e
n
g
t
h

(
M
P
a
)
1500
1700
1900
2100
2300
T
e
n
s
i
l
e

m
o
d
u
l

(
M
P
a
)
Strength
Modulus

Figure 6. Tensile properties of the PP nanocomposites (2 wt.% of clay)

42
46
50
54
58
P
P 0
E
4
3
-
2
2
0
o
C
E
4
3
-
2
0
0
o
C
E
3
0
1
5
E
3
0
0
3
E
4
3
-
E
3
0
0
3
E
4
3
-
3
0
1
5
3
1
5
0
1
0
0
1
F
l
e
x
u
r
a
l

s
t
r
e
n
g
t
h

(
M
P
a
)
1300
1500
1700
1900
F
l
e
x
u
r
a
l

m
o
d
u
l

(
M
P
a
)
Strength
Modulus

Figure7. Flexural properties of the PP nanocomposites (2 wt.% of clay)

During the tensile and flexural test, rupture did not occurred for the samples
containing 2 wt.% of nanoclay but happens drastically in tensile test for all samples
containing 4 wt.% of clay (Fig.8). As expected, the ductility of the polymer matrix
reduced with the presence of organo-nanoclay and coupling agent. The largest negative
effect was obtained for the E-43 sample; the loss of ductility can be explained by the
matrix degradation.

Johanne Denault, Industrial Materials Institute, National Research Council Canada
0
100
200
300
400
500
0 E43 E3150 E1001
E
l
o
n
g
a
t
i
o
n

a
t

b
r
e
a
k

(
%
)
0
50
100
150
200
E
n
e
r
g
y

t
o

b
r
e
a
k

(
J
)
Elongation
Energy

Figure 8. Tensile properties of the nanocomposites (4 wt.% of clay)

During the tensile and flexural test, rupture did not occurred for the samples
containing 2 wt.% of nanoclay but happens drastically in tensile test for all samples
containing 4 wt.% of clay (Fig.8). As expected, the ductility of the polymer matrix
reduced with the presence of organo-nanoclay and coupling agent. The largest negative
effect was obtained for the E-43 sample; the loss of ductility can be explained by the
matrix degradation.
The tensile and fracture properties of the nanocomposites containing 4wt% of clay are
presented in Figures 9 to 11. In the absence of coupling agent, the clays are poorly
dispersed and remain in large aggregates. As a result, the clay reinforcing effect is very
limited. Owing to much better dispersion and probably a better interface, the MA1 and
MA2 significantly improve the tensile strength and stiffness of the nanocomposites.
However, the GMA leads to even better performance. The modulus improvement should
relate directly to the better dispersion, while the strength improvement should be due to a
better clay-matrix interface in this sample. In addition, its distinctive crystalline
morphology may also contribute to this exceptional improvement. For example, the fine
crystals in this sample are likely to have a negligible impact on the clay orientation
during crystallization. This means that the clay can better retain the preferred orientation
generated by injection molding. Furthermore, its fine crystalline structure should benefit
from a low level of imperfection, which has a significant impact on the material strength.
Another advantage of GMA was also observed in terms of ductility and toughness. The
typical stress-strain curves shown in Figure 10 for MA1-15A and GMA-15A indicate a
Johanne Denault, Industrial Materials Institute, National Research Council Canada
very large difference in elongation at break; GMA-15A was found to show very high
ductility in comparison to both MA1-15A and MA2-15A. This resulted in stable necking
extension to the complete specimen for GMA-15A instead of the rapid break after yield
seen for MA1-15A and MA2-15A. This behavior was confirmed by the fracture
toughness measurements reported in Figure 11.
32
33
34
35
36
0 4%15A MA-
4%15A
MA2-
4%15A
GMA-
4%15A
T
e
n
s
i
l
e

s
t
r
e
s
s

(
M
P
a
)
1600
1900
2200
2500
2800
T
e
n
s
i
l
e

m
o
d
u
l
u
s

(
M
P
a
)
Stress
Modulus

Figure 9. Tensile properties of the PP and its nanocomposites.
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
0 50 100 150 200 250 300 350
Elongation (mm)
F
o
r
c
e

(
K
N
)
GMA-15A
MA1-15A

Figure 10. Stress-strain curves for MA1-15A and GMA-15A

0
5
10
15
20
25
30
35
40
0.00 5.00 10.00 15.00 20.00 25.00
Ligament Length (mm)
W
o
r
k

o
f

F
r
a
c
t
u
r
e

(
k
J
/
m
2
)
PP
15A
MA1-15A
MA2-15A
GMA-15A

Figure 11. Work of fracture as a function of ligament length for PP and its
nanocomposites.

Johanne Denault, Industrial Materials Institute, National Research Council Canada
CONCLUSION

Preparation of PP nanocomposites is strongly influenceD by different parameters:
mixing temperature, mixing time, chemistry of the organo-nanoclay, chemistry and
concentration of the coupling agent, etc. GMAgPP provides much better dispersion and
interfacial interaction compared to MAgPP. In addition it modifies the crystallization
morphology of PP to form a very fine crystalline structure. As a result, the nanocom-
posites based on GMAgPP possess superior strength, stiffness, ductility and fracture
toughness. Each parameter has different impact on the characteristics of the obtained
nanocomposites and the interaction between these parameters has to be fully considered
in order to obtain the optimum performance.

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Johanne Denault, Industrial Materials Institute, National Research Council Canada