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Centre for Polymer Science and Engineering, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110016, India
a r t i c l e i n f o
Article history:
Received 7 June 2013
Accepted 18 August 2013
Available online 29 August 2013
Keywords:
Polypropylene
Multi wall carbon nanotubes
Tacticity
Toughness
Fracture
Crack propagation
a b s t r a c t
A remarkable toughness enhancement (>330%) of multi wall carbon nanotubes (MWCNT) lled stereo-
complex polypropylene (PP) matrix i.e. blend of isotactic-PP and syndiotactic-PP (70:30) with differences
in stereo-regularity has been observed. The enhancement has been correlated to quantiable morpholog-
ical parameters such as free-space lengths concerning dispersion and relatively greater reduction in crys-
tallite size/lamellar thickness. Systematic analysis of glass transition data and estimation of multi wall
carbon nanotubes induced reduction in interfacial polymer chain immobilization reiterates susceptibility
of polymer segments to ready-mobility. The extent of toughening has quantitatively been analyzed by
fracture-energy partitioning, essential work of fracture (EWF), approach enabling the detection of a
semi-ductile-to-tough-to-quasi-brittle transition in the MWCNT lled stereo-complex polypropylene.
Real-time fracture kinetics analysis revealed toughening mechanism to be primarily blunting-assisted;
an aspect also corroborated by extensive plastic ow without much energy dissipation in the inner frac-
ture process zone. Thus the study establishes a new pathway of tacticity-dened matrix modication to
toughen nanocomposites.
2013 Elsevier Ltd. All rights reserved.
1. Introduction
Difference in stereo-regularity (tacticity) induced matrix modi-
cation enabling the manipulation of the polymer nanocomposites
structure favorably towards enhanced energy dissipation (tough-
ening mode) is a theme not so outrightly attempted. This is be-
cause molecular level interaction involving topological
constraints, van der Waals forces, Lennard-Jones potential and Lon-
don dispersion forces may be very complex to explain the precise
nature of adhesive/cohesive interactions in understanding tough-
ening mechanisms. The topological attributes to the mechanism
of toughening has the signicance in the sense that the conformal
proximity of the zig-zag arrangements and the wrapping-up phe-
nomenon via the helical conformation of the polymer chain cong-
urations facilitate in effectively enhancing the stress transfer
mechanism by increasing the interfacial interaction. The size scale
advantage in this sense plays a crucial role since smaller dimension
of the hollow cylinders extend a larger amount of interfacial area
for molecular level interactions. This is because the effective vol-
ume fraction of the polymer chains that potentially can be ad-
sorbed per unit surface area of the reinforcing second phase is
much lower and hence may lead to promoting efcient polymer-
nanotube interaction. Such interactions involving less of loosely
entangled polymer chains renders greater extent of chain immobi-
lization enabling the interfacial polymer-nanotube network to act
as a composite phase and hence larger energy dissipation and
toughness [13]. The pioneering work of Lordi and Yao [4] postu-
lating the role of helical conformations in increasing the effective
binding of the polymer-nanotube interface and subsequently the
counter approach view point in evolving the theory of a strong
polymer-nanotube interface for enhanced toughening by Jiang
and Penn [5] reiterates the above understanding pertaining to
nanoscale reinforcement especially that of carbon nanotubes.
Wong et al. [6] have reported the determining role of polymer-
nanotube interfacial characteristics using molecular mechanics
simulations and elasticity calculations. Relatively higher interfacial
shear stresses in case of nanotubes than their micron sized coun-
terparts have reportedly been attributed to intimate solid phase
contact between polymer and nanotube at the molecular level.
Lee et al. in another fundamental work concerning the role of dis-
persion and exfoliation of single wall carbon nanotubes (SWCNT)
and multi wall carbon nanotubes (MWCNT) in polypropylene
(PP) matrix have postulated on the temperature dependence of
interfacial strength across polymer/nanotube interface and the
building-up of a three dimensional percolation network [7,8]. Cole-
mann et al. [9] in their pioneering work emphasized the role of an
0261-3069/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.matdes.2013.08.067
w
1
T
g1
w
2
T
g2
9
where T
g
, T
g1
and T
g2
correspond to the glass transition temperature
of the nanocomposites, matrix without MWCNT, reduced T
g
-equiv-
alent due to incorporated MWCNT respectively, w
1
and w
2
are the
weight fraction of the matrix and nanotube respectively.
However, in the later approach the immobilized volume frac-
tion (
T
) may be estimated from Kerners equation [41]. The
T
may be construed as responsible for storage modulus (E
0
) enhance-
ment. The
T
is taken into account in order to quantify approxi-
mately the interfacial polymer chain immobilization inuence on
the overall T
g
of the nanocomposites. The rearranged Kerners
equation for composite to estimate the immobilized volume frac-
tion of polymer chains (
T
) may be given as below.
/
T
E
c
T E
m
T
E
m
T aE
c
T
10
where E
m
(T) and E
c
(T) are the storage moduli of the matrix (IPNC-0
and ISPNC-0 matrices) and their nanocomposites respectively at a
reference temperature (i.e. at T = 25 C) and
a
24 5t
m
7 5t
m
11
where m
m
is Poissons ratio of the composites and is taken as 0.30 in
the present case. For the estimation of T
g
of the immobilized phase
in IPNC-0.5 and IPNC-1.0, IPNC-0 has been taken as the matrix,
whereas for the same compositions of ISPNC series ISPNC-0 has
been taken as the matrix. Since theoretically the unaffected T
g
in
a nanocomposite system indicates the unaffected bulk relaxation
phenomenon of the polymer chains, hence the nanocomposites
with T
g
identical to that of the unlled matrix, may be assumed
to be the system with virtual absence of any immobilization/mobi-
lization effects. The T
g
estimates obtained by adhering to the above
two approaches are given in Table.5. It could be clearly observed
that the T
g
of the immobilized PP phase in IPNC in the composition
range of IPNC-0.5 to IPNC-1.0 remained at 10 C. Such observa-
tions indicated the formation of an ordered interphase that is
dynamically (unaltered) resembling i-PP chains. In contrast in
ISPNC the T
g
of the immobilized phase remained in the range of
12 C to +4.7 C. These indicate that the incorporation of
MWCNT into ISPNC matrix readily enhances the segmental mobil-
ity. This fundamentally reiterates the possibility of MWCNT induced
nano-structural reorganization facilitating an increase in the overall
amorphous free volume space (fraction); which in turn, microme-
chanically, may lead to corresponding ductile toughening effects.
Table 5
Nanotube induced immobilized volume fraction at the interface, thermal property and crystalline morphological properties.
T
@ 25 C
T
g
(C) T
g
#
(C) T
g
##
(C) TGA Crystallite size
$
(nm) Crystallinity from
WAXD (%)
Crystallinity from
DSC (%)
L
lamellar
(nm)
T
onset
(C) (040)
i-PP
IPNC-0 0 23 443.6 3.85 55.10 53.78 1.997
IPNC-0.5 0.103 25 2 10 449.7 3.80 56.03 54.06 1.983
IPNC-1.0 0.076 21 2 10 451.5 3.83 56.84 55.52 1.991
IPNC-1.5 0.056 23 450.8 3.70 56.83 55.21 1.993
IPNC-2.0 0.102 23 449.6 3.79 56.94 56.63 1.994
IPNC-3.0 0.166 23 450.3 3.77 58.46 58.02 1.990
ISPNC-0 0 24 416.1 3.66 35.10 30.67 1.987
ISPNC-0.5 0.026 26 2 12 440.9 3.47 34.61 25.57 1.927
ISPNC-1.0 0.049 20 1 5 443.5 3.12 34.64 30.20 1.930
ISPNC-1.5 0.053 22 3 9 425.2 3.49 35.83 29.20 1.933
ISPNC-2.0 0.071 24 422.2 4.25 35.94 29.61 1.924
ISPNC-3.0 0.113 23 10 17 422.2 3.90 35.46 31.10 1.925
T
= Volume fraction of immobilized polymer chains at 25 C; T
g
= glass transition temperature of the composites, T
g
#
= Reduced equivalent glass transition temperature due
to incorporation of MWCNT; T
g
##
= glass transition temperature of immobilized volume fraction of polymer chain (immobilized volume fraction of polymer are converted to
corresponding weight fraction of the polymer to apply Fox equation), $ = crystallite size estimated from Scherrers equation, L
lamellar
= lamellar thickness deduced from the
Thomson Gibbs equation.
718 D. Das, B.K. Satapathy / Materials and Design 54 (2014) 712726
3.5. Fracture behavior of the nanocomposites
3.5.1. Load displacement diagram and the validity of the EWF
approach
The loaddisplacement diagram of i-PP, IPNC-0 (i-PP/PP-g-MA),
ISPNC-0 (i-PP/s-PP/PP-g-MA) and its MWCNT lled nanocompos-
ites are shown in Fig. 7. All the composites viz. IPNC and ISPNC
and their neat components have not only shown thermoplastic
behavior but also have shown self-similar nature of the force
displacement diagrams, indicating pre-conditional validity of
EWF approach. It is also clear from the loaddisplacement diagram
that displacement becomes higher in case of i-PP/PP-g-MA as
compared to i-PP although maximum load required for the stable
crack propagation remain almost unaffected. In case of IPNC-0.5
(i-PP/PP-g-MA/0.5 wt.% MWCNT) the displacement is higher as
compared to the neat component, but further addition of
MWCNT affect the displacement as well as the maximum load
for the stable crack propagation. Interestingly, in the stereo-com-
plex matrix system, ISPNC-0 the displacement becomes nearly
double as compared to its neat counterpart (i.e. IPNC-0) and re-
mains unaffected up to ISPNC-1.5. The plane stress criteria for
the applicability of post-yield fracture mechanics (PYFM) concept
is ensured by the Hills analysis [42] as shown in Fig. 8. The anal-
ysis revealed that the net section stress (r
n
) remained indepen-
dent of the ligament length (l). The full yielding of the entire
ligament length region in the DENT specimens occurred at max-
imum load (F
max
) and prior to the resumption of crack propaga-
tion, which is visually ensured. The total works of fractures (W)
for various nanocomposites were obtained by integration of the
total area under the loaddisplacement diagrams. After normali-
Fig. 4. Light optical micrographs of (a) i-PP, (b) s-PP (c) IPNC-0, (d) ISPNC-0, (e) IPNC-0.5, (f) ISPNC-0.5, (g) IPNC-1.0, (h) ISPNC-1.0.
D. Das, B.K. Satapathy / Materials and Design 54 (2014) 712726 719
zation by ligament area (B. l) the specic work of fracture (w) is
obtained.
3.5.2. Work of fracture-composition relationship and transition in
fracture modes
The specic work of fracture as a function of ligament length (l)
for i-PP, IPNC and ISPNC are shown in Fig. 9. The linear t of the
data points across the valid range of l leads to the determination
of slope as non-essential work of fracture (N-EWF; bw
p
) and inter-
cept as essential work of fracture (EWF; w
e
) for each composition.
The variation of w
e
and bw
p
as a function of MWCNT content is
shown in Fig. 10. It has been observed that with the incorporation
of 5 wt.% PP-g-MA into i-PP as the matrix, i.e. in IPNC-0, w
e
in-
creased by 125% with respect to i-PP which is followed by a sharp
drop of 70% in w
e
value in the nanocomposites containing
0.5 wt.% MWCNT (IPNC-0.5). On further addition MWCNT into
the nanocomposites, w
e
values are found to remain broadly unaf-
fected till 1.5 wt.% of MWCNT followed by a linear increase till
IPNC-3. In contrast blending of i-PP matrix with 30 wt.% of s-PP
(ISPNC-0) lead to an enhancement in w
e
by 135%, whereas on
incorporation of MWCNT into ISPNC as the matrix till ISPNC-1.5
a consistent reduction in w
e
could be observed. However, despite
the reduction in w
e
of ISPNC the gross magnitude of the same re-
mained well above their corresponding IPNC counterparts. These
inevitably indicate an intrinsic enhancement in the resistance to
crack initiation of the nanocomposites based on stereo-complex
PP-matrix, i.e. ISPNC when compared to i-PP based IPNC systems.
Mechanistically, these observations indicate the non-linear depen-
dency of the crack growth prior to failure. The resistance to crack
propagation (bw
p
) increased by 9% and 77% for IPNC-0 and
IPNC-0.5 respectively, when compared to i-PP matrix (Fig. 10b).
Such a remarkable toughening may be attributed to an improved
state of dispersion of MWCNT in the polymer as evident from the
TEM micrographs (Fig. 1). These ndings are in striking contrast
to the earlier reports where an increase in bw
p
by 15% was re-
ported in case of i-PP/MWCNT nanocomposites in the absence of
PP-g-MA [13]. The role of PP-g-MA in improving the dispersion
of MWCNT in polymer matrix was reported independently by Pra-
santha et al. [43] and Yang et al. [44] while investigating the
mechanical and toughness properties of nylon and PP nanocom-
posites. However upon further increasing the amount of MWCNT
up to 1.5 wt.% as in IPNC-1.5, the bw
p
decreases by 57% compared
to IPNC-0.5. Following such a reduction, upon further addition of
MWCNT the magnitude of bw
p
remained nearly unaffected.
Interestingly in ISPNC-0.5 and ISPNC-1.0 the bw
p
increased by
123% and 339% respectively when compared to the ISPNC-0
matrix. The maxima in bw
p
in ISPNC-1.0 indicate the composition
with maximum resistance to crack propagation that essentially ac-
counts for the energy dissipation in the outer-plastic deformation
zone (OPDZ). However, on further increasing the MWCNT content
to ISPNC-1.5 and ISPNC-2.0 a sharp reduction in bw
p
by 60% was
observed. The magnitude of w
e
showed a nearly linear decrease
with the increase in MWCNT content from ISPNC-0.5 to ISPNC-
1.5 indicating a systematic decrease in the resistance to crack ini-
tiation of the nanocomposites. Theoretically resistance to crack ini-
tiation has a qualitative correspondence to the energy dissipated in
80 90 100 110 120 130 140 150 160 170 180
IPNC-3.0
IPNC-2.0
IPNC-1.5
IPNC-1.0
IPNC-0.5
IPNC-0
i-PP
Temperature ( C)
H
e
a
t
f
l
o
w
(
e
n
d
o
)
[
H
(
J
/
g
)
]
110 120 130 140 150 160 170
Temperature (
C)
Helical form I
melting of s-PP
Shift of T
m
a- ISPNC-0
b- ISPNC-0.5
c- ISPNC-1.0
d- ISPNC-1.5
e- ISPNC-2.0
f- ISPNC-3.0
a
b
c
d
e
f
H
e
a
t
f
l
o
w
(
e
n
d
o
)
[
H
(
J
/
g
)
]
(a) (b)
Fig. 5. Differential scanning calorimetry (DSC) heat scans for the nanocomposites (a) IPNC (b) ISPNC.
-25 0 25 50 75 100 125 150
0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.14
0.16
0.18
Temperature ( C) Temperature ( C)
i-PP
IPNC-0
IPNC-0.5
IPNC-1.0
IPNC-1.5
IPNC-2.0
IPNC-3.0
t
a
n
ISPNC-0
ISPNC-0.5
ISPNC-1.0
ISPNC-1.5
ISPNC-2.0
ISPNC-3.0
(a) (b)
Fig. 6. Variation of loss tangent (tand) with temperature (T) of the nanocomposites (a) IPNC (b) ISPNC.
720 D. Das, B.K. Satapathy / Materials and Design 54 (2014) 712726
0
0
50
100
150
200
250
300
350
400
450
500
550
600
650
700
750
L
O
A
D
(
N
)
DISPLACEMENT (mm)
3.89 mm
4.67 mm
6.49 mm
7.46 mm
9.56 mm
i-PP
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 0 1 2 3 4 5 6 7 8 9
0
50
100
150
200
250
300
350
400
450
500
550
600
650
700
DISPLACEMENT (mm)
L
O
A
D
(
N
)
3.65 mm
4.28 mm
5.91 mm
6.74 mm
7.78 mm
9.39 mm
IPNC-0
1 2 3 4 5 6 7 8 9 10 11
0
100
200
300
400
500
600
DISPLACEMENT (mm)
L
O
A
D
(
N
)
3.81 mm
4.86 mm
5.74 mm
6.79 mm
7.32 mm
9.48 mm
IPNC-0.5
0 1 2 3 4 5 6
0
75
150
225
300
375
450
525
600
675
L
O
A
D
(
N
)
DISPLACEMENT (mm)
3.89 mm
4.99 mm
5.98 mm
7.34 mm
9.69 mm
IPNC-3.0
0 4 8 12 16 20 24
0
75
150
225
300
375
450
DISPLACEMENT (mm)
L
O
A
D
(
N
)
1.87 mm
3.66 mm
4.67 mm
5.94 mm
6.61 mm
7.38 mm
ISPNC-0
0 2 4 6 8 10 12 14 16 18 20
0
50
100
150
200
250
300
350
400
450
500
550
L
o
a
d
(
N
)
Displacement (mm)
2.35 mm
3.87 mm
4.83 mm
6.65 mm
8.34 mm
ISPNC-1.0
Fig. 7. Self-similarity of loaddisplacement diagrams.
0
20
40
60
80
100
i-PP
IPNC-0
IPNC-0
IPNC-1.0
IPNC-1.5
IPNC-2.0
IPNC-3.0
N
e
t
s
e
c
t
i
o
n
s
t
r
e
s
s
(
N
/
m
m
2
)
Ligament length (mm)
(a)
3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10 11
0
10
20
30
40
50
60
70
80
90
100
Ligament length (mm)
N
e
t
s
e
c
t
i
o
n
s
t
r
e
s
s
(
N
/
m
m
2
)
ISPNC-0
ISPNC-0.5
ISPNC-1.0
ISPNC-1.5
ISPNC-2.0
ISPNC-3.0
(b)
5 .
Fig. 8. Hills analysis plot: variation of net section stress (r
n
) with ligament length (l) (a) IPNC (b) ISPNC.
D. Das, B.K. Satapathy / Materials and Design 54 (2014) 712726 721
the inner fracture process zone (IFPZ). On a critical look into the
data, it was observed that ISPNC-0 and ISPNC-2.0 showed w
e
-max-
ima and w
e
-minima respectively. In contrast, ISPNC-1.0 showed an
intermediate value of w
e
that is 60% lower than that of ISPNC-0.5
and 40% higher than that of ISPNC-1.5. These observations imper-
atively indicate the existence of a semi-ductile-to-tough-to-quasi-
brittle transition in ISPNC in the composition range of 0.5
1.5 wt.% of MWCNT, unlike the failure transition involving defor-
mation with plastic-ow to deformation without plastic-ow in
IPNC. The semi-ductile, tough and quasi-brittle natures of the
respective ISPNC compositions are characterized by the high-w
e
/
low-bw
p
, high-w
e
/high-bw
p
and low-w
e
/low-bw
p
combina-
tions of the fracture mechanics parameters. Comprehensively such
a nature of the failure transition in ISPNC underlines the role of tac-
ticity-dened modication of the polymer matrix on the fracture
toughness of MWCNT lled polymer nanocomposites. Furthermore
the fracture surface morphology of these compositions by SEM
have revealed a systematic transition in the nature of their failure
characteristics and are discussed in a subsequent section.
3.6. Morphology and fracture toughness correlation
The observed signicant and moderate enhancements in tough-
ness due to tacticity differences in the stereo-complex PP matrix
(ISPNC) and in the conventional (single form crystalline matrix)
i-PP (IPNC) may be correlated to morphological parameters; qual-
itatively with extent of dispersion and quantitatively with the
lamellar thickness (L
lamellar
) of the PP chains. Several authors have
attributed toughness and stiffness enhancements to dispersion and
distribution uniformity of nanotubes [32,45,46]. The length-scale
(radius of gyration of polymer chains and nanotube dimensions)
and time-scale (segmental relaxation of polymer and mobility of
nanotube within the framework of entangled polymer chains) cor-
respondences in nanocomposites are theoretically well demon-
strated and was reported that a fundamentally different
toughening mechanism operates in these class of nano-structured
materials where the singular mobility of the nano-inclusion in the
polymer matrix under deformation denes the energy dissipation
capability of the material [47]. Interestingly the preceding argu-
ment seems to be in agreement to the fact that the singular mobil-
ity of MWCNT may get accentuated by the increase in the overall
amorphous nature of the matrix. This is well in agreement to our
observations manifested in the form of signicant reduction in T
g
and reduction in crystallite size (as obtained from Scherrers equa-
tion) upon blending of s-PP, i.e. upon rendering the nature of ma-
trix-polymer stereo-complex. To further correlate the
morphological parameters, composition specic lamellar thick-
nesses (L
lamellar
) was estimated following the ThomsonGibbs
equation and was analyzed vis--vis the fracture parameters w
e
and bw
p
values. The ThomsonGibbs equation may be given as,
L
lamellar
2rT
0
m
DH
m
T
0
m
T
m
12
where r is lamellar surface free energy (0.122 J m
2
), DH
v
is melt-
ing enthalpy of lamellar with innite thickness (192.28 10
6
-
J m
3
), T
0
m
is equilibrium melting temperature [48,49]. The
calculated lamellar thickness for the investigated IPNC and ISPNC
3 4 5 6 7 8 9 10
25
50
75
100
125
150
175
200
225
250
275
300
i-PP
IPNC-0
IPNC-0.5
IPNC-1.0
IPNC-1.5
IPNC-2.0
IPNC-3.0
S
p
e
c
i
f
i
c
w
o
r
k
o
f
f
r
a
c
t
u
r
e
Ligament length (mm)
(a)
1 2 3 4 5 6 7 8 9 10
50
100
150
200
250
300
350
400
450
500
550
600
650
Ligament length (mm)
S
p
e
c
i
f
i
c
w
o
r
k
o
f
f
r
a
c
t
u
r
e
(
N
/
m
m
)
ISPNC-0
ISPNC-0.5
ISPNC-1.0
ISPNC-1.5
ISPNC-2.0
ISPNC-3.0
(b)
(
N
/
m
m
)
Fig. 9. Variation of specic work of fracture (w) with ligament length for (a) IPNC (b) ISPNC.
Fig. 10. Variation of plane stress fracture parameters with MWCNT content (a) essential work of fracture (EWF; w
e
) and (b). non-essential work of fracture (N-EWF; bw
p
).
722 D. Das, B.K. Satapathy / Materials and Design 54 (2014) 712726
compositions are shown in Table 5. It could be clearly observed that
the w
e
-essential work of fracture has a direct correspondence to
lamellar thickness indicating that the resistance to stable crack ini-
tiation has a direct correlation to lamellar thickness and crystallite
arrangement [50]. However, the inverse correlation to bw
p
may the-
oretically be construed as lamellar break-up/destruction phenome-
non leading to an increase in resistance to stable crack propagation.
The scenario may be simplistically explained as the availability of
more of random polymer chains segments in the larger frame of
the material architecture facilitating energy dissipation mechanism
by promoting the singular mobility of the embedded MWCNT in the
entangled polymer chain networks with substantially lesser
hindrance.
3.7. Kinetics of crack propagation
The investigated nanocomposites showed ductile yielding,
though the nature of the ductile response remained dependent
on MWCNT content and therefore this observation encouraged
the authors to probe into the nature of such transitions in failure
dynamics in real-time framework following the kinetics of crack
growth approach. In both type of nanocomposites the matrix-dom-
inant ductile-yielding behavior has been observed to get altered
with the state of dispersion/distribution of nanoscopic inclusions
and hence with their consequent effects on morphological changes.
The determination of kinetics parameters of crack growth has been
done by using an optical video monitoring system in combination
with digital image correlation (DIC) techniques. The real-time
crack growth has further been monitored with periodic recording
of crack extension (Da), crack tip opening displacement (CTOD,
d) and CTOD rate (dd/dt) data at various deformation stages as
shown in Fig. 11. The systems i-PP (IPNC-0) and IPNC-2.0/IPNC-
3.0 have undergone much faster crack extension than the other
IPNC systems while the slowest crack extension was registered
for IPNC-0.5. In contrast a drastic retardation (>5-fold) of the crack
extension could be observed in ISPNC when compared to i-PP
(IPNC-0), an observation solely attributed to tacticity induced ste-
reo-complexity of the matrix. On incorporation of MWCNT to
ISPNC-0 matrix the crack extension rates have been observed to
get further retarded, especially at larger time scales, with ISPNC-
0.5 exhibiting the slowest crack extension rate. Interestingly
ISPNC-2.0/ISPNC-3.0 has also been observed to undergo failure at
much faster rate than ISPNC-0 matrix, an observation resembling
IPNC-2.0/IPNC-3.0. These observations corroborate the intrinsic
correspondence between poor dispersion and faster crack exten-
sion leading to catastrophic failure. The CTOD data, indicating the
inherent blunting efciency of material, of IPNC revealed a similar
trend to that of Da showing the lowest CTOD-rate of IPNC-0.5. In
contrast the CTOD-rate of ISPNC showed nearly identical values
irrespective of the extent of MWCNT incorporation. Since isolated
analysis of the kinetic parameters may lead to discrepancies quan-
titatively, the analysis of the fracture parameters has been carried
out in a cooperative fashion by analyzing the plots of dd/dt versus
Da.
The variations of CTOD-rate (dd/dt) with crack extension (Da)
for IPNC and ISPNC are shown in Fig. 11. It has been observed that
barring i-PP and IPNC-0 all the investigated nanocomposites failed
within Da 2.0 mm, i.e. at one third of the ligament length
l 6 mm. Interestingly such a range of Da when compared to the
displacement measured in the loaddisplacement diagrams for
l 6 mm remains well beyond the load-maxima in the failure of
DENT specimens. However, the maximum crack extension for i-
PP and IPNC-0 exceeds the generally observed extent of Da to fail-
ure for the nanocomposites irrespective of tacticity modication
i.e. stereo-complexity. Further the dd/dt has been observed to be
leveled off within dd/dt 0.04 mm/s. It must be mentioned that
the leveling off limit of dd/dt is little (1.5 times) higher than the
strain rate (e
9
= 0.033 mm/s) at which the fracture experiments
have been conducted. Based on these observations, the kinetically
dened failure map of the nanocomposites may be divided into
four failure-regimes as indicated in Fig. 11. The four macro-failure
regimes and their associated deformation attributes may be sum-
marized as given in Table 6.
It was observed that in IPNC and ISPNC systems the failure map
remained mostly conned in regime-II indicating the possibility of
MWCNT induced toughening, though the extent of toughening and
their underlying mechanistic attributes may not be easy to quan-
tify. However, from the plots it is amply evident that in ISPNC,
the CTOD-rate has been found to be more uniform as compared
to IPNC systems. Additionally the nature of clustering of the mea-
sured data points in regime-II essentially indicates the inherent
dependence of the macroscopic kinetic parameters on the morpho-
logical attributes of the systems. For ISPNC the less random clus-
tering of the data points may imply a better state of dispersion
unlike their IPNC counterparts. A more comprehensive analysis
based on qualitative estimation of J-integral and tear modulus re-
sponses may lead to further details of the inuence of stereo-com-
plexity (tacticity-dened blending) of matrix on fracture toughness
response of these nanocomposites, an aspect which will be fol-
lowed up in future.
3.8. Fracture surface morphology by SEM
The fracture surface morphology responsible for the associated
micro-deformation and crack propagation mechanisms of the i-PP
and the stereo-complex PP blend (i-PP/s-PP: 70/30) i.e. ISPNC-0 as
the matrices and their MWCNT lled nanocomposites have been
evaluated by scanning electron microscopy and is shown in
0.00
0.02
0.04
0.06
0.08
0.10
0.12
Regime-I
Regime-IV
Regime-III Regime-II
Steady state d/dt for i-PP/ PP-g-MA
Steady state d/dt for nanocomposites
C
T
O
D
r
a
t
e
d
/
d
t
[
m
m
/
s
]
Crack extension a (mm)
i-PP
IPNC-0
IPNC-0.5
IPNC-1.0
IPNC-1.5
IPNC-2.0
IPNC-3.0
Steady state d/dt for i-PP
0 1 2 3 4 5 6 0 1 2 3 4 5 6
0.00
0.02
0.04
0.06
0.08
0.10
0.12
Regime-I
Regime-IV
Regime-III
Regime-II
Steady state d/dt for
nanocomposites
Steady state d/dt for i-PP/ PP-g-MA
C
T
O
D
r
a
t
e
d
/
d
t
[
m
m
/
s
]
Crack extensiona (mm)
IPNC-0
ISPNC-0
ISPNC-0.5
ISPNC-1.0
ISPNC-1.5
ISPNC-2.0
ISPNC-3.0
(a) (b)
Fig. 11. Kinetics of crack propagation of the nanocomposites crack tip opening displacement (CTOD) rate dependence on crack growth (a) IPNC nanocomposites (b) ISPNC
nanocomposites.
D. Das, B.K. Satapathy / Materials and Design 54 (2014) 712726 723
Fig. 10. It was clearly observed that IPNC-0 showed a homogeneous
surfacemorphologywhereas IPNC-0.5showeddistinct signs of peel-
ing-off tendencies of fracture surface layers indicating the fracture
resistance tobe controlledmore bycrackpropagatingalong the frac-
tureplane. The observationis alsocorroboratedbythe fact that there
is a small decrease in the w
e
(essential work of fracture process) of
IPNC-0.5 as compared to IPNC-0 as shown in Fig. 12. Interestingly
the failure surface morphology of the stereo-complex blend matrix
i.e., ISPNC-0, the surface showed signs of alternately patterned
peeled-off strips indicating the presence of a quasi-co-continuous
morphologydue to asymmetric stereocomplexity. Onincorporating
0.5 wt.% of MWCNT i.e., the nanocomposite ISPNC-0.5 revealed
intensive brillation process involving thin brils and briler strips
to be involved in the course of fracture under uni-axial tension. On
further increasing the MWCNT content to 1.0 wt.% i.e., in ISPNC-
1.0, the nanocomposite showed relatively distinct and dense popu-
lationof brillatedstructures spanningacross the crackalsoreferred
as crack-bridging, highly stretched brils (0.10.3 lm) indicating
strong interfacial interaction between PP and MWCNT due to ste-
reo-complexity and very long brillar strips (210 lm) undergo-
ing fragmentation to lead to smaller strips (24 lm) and
brils(0.81.0 lm) at their tips prior to failure. On increasing the
MWCNT content to 3.0 wt.%, as in ISPNC-3.0, the fracture surface re-
vealed i-PP/MWCNT (80:20) masterbatch rich domains as the re-
gions responsible for failure initiation. Such a failure mechanism
may be attributed to highly localized morphology with improper
dispersion and distribution since the MWCNT rich region does not
get inltrated effectively by the excessively added i-PP or s-PP so
as to lead to a state of real dilution. Hence the fracture surface in
these regions showed the relative absence of any signs of plastic-
deformation/shear-yielding prior to failure causing quasi-brittle/
ductility-arrested failure characteristics.
Table 6
The macro-failure regimes and their associated deformation.
Regimes dd/dt Da Deformation attributes
Regime-I High (>0.04 mm/s) Low (<2.0 mm) Ductile yielding/plastic ow
Regime-II Low (<0.04 mm/s) Low (<2.0 mm) Tough
Regime-III Low (<0.04 mm/s) High (>2.0 mm) Resistant to crack propagation
Regime-IV High (>0.04 mm/s) High (>2.0 mm) Catastrophic failure
Fig. 12. SEM investigation fracture surfaces of nanocomposites (a) IPNC 0.0, (b) IPNC 0.5, (c) ISPNC 0.0, (d) ISPNC 0.5, (e) ISPNC 1.0, (f) ISPNC 3.0.
724 D. Das, B.K. Satapathy / Materials and Design 54 (2014) 712726
4. Conclusions
A new phenomenon of matrix stereo-complexity enhancing the
fracture toughness by >330% and improvement of the extent of dis-
persion of MWCNT in polypropylene has been observed. Dispersion
morphology was quantitatively explained in terms of the ratio of
free space length to inltrated free space lengths. Such morpholog-
ical consequences leading to a decrease in T
g
of MWCNT lled ste-
reo-complex or tacticity modied blends of polypropylene relative
to the nanocomposites based on isotactic-only matrix by 28 C
has been observed. The fracture toughness performances of these
nanocomposites have been observed to be signicantly affected
as estimated by essential work of fracture approach. A semi-duc-
tile-to-tough-to-quasi-brittle transition in ISPNC in the composi-
tion range of 0.51.5 wt.% of MWCNT has been observed that
was primarily attributed to a corresponding transition in the nat-
ure of deformation occurring with (in ISPNC) and without (in IPNC)
plastic ows respectively. A set of distinctly evolved and novel cri-
teria for the semi-ductile, tough and quasi-brittle natures ISPNC
compositions have emerged that are characterized by high-w
e
/
low-bw
p
, high-w
e
/high-bw
p
and low-w
e
/low-bw
p
combina-
tions of the fracture mechanics parameters respectively. A vefold
retardation of the crack extension in tacticity modied relative to
the unmodied virgin isotactic PP matrix could be observed. The
enhanced dispersion in stereocomplex PP matrix based nanocom-
posite have shown a direct bearing on the CTOD rate as reected
in the blunting response. Fracture surface morphology revealed
signicant crack-bridging, brils stretching across a growing crack
accompanied by extensive brillation and formation of microstrips
getting terminally fragmented into micro-brils as the possible
toughening mechanism in stereocomplex PP matrix based MWCNT
lled nanocomposites.
Our study demonstrates a new pathway for toughening of car-
bon nanotube based thermoplastic polymer nanocomposites by
blending of two different stereo-regular forms of the chemically
identical polymer matrix. The conceptual validation has success-
fully been established with regard to PP/MWCNT nanocomposites,
where remarkable toughness enhancement has been corroborated
by signicant (nearly vefold) retardation of the crack-growth
phenomenon assisted by efcient crack-blunting mechanism.
Acknowledgements
This paper is dedicated to late Prof. Roland Weidisch. Authors
gratefully acknowledge the nancial support, vide Grant No.SR/
S3/ME/0010/2008 by Department of Science and Technology New
Delhi, India.
References
[1] Jancar J, Douglas JF, Starr FW, Kumar SK, Cassagnau P, Lesser AJ, et al. Current
issues in research on structureproperty relationships in polymer
nanocomposites. Polymer 2010;51:332143.
[2] Zerda AS, Lesser AJ. Intercalated clay nanocomposites: morphology,
mechanics, and fracture behavior. J Polym Sci Part B: Polym Phys
2001;39:113746.
[3] Andrews R, Weisenberger MC. Carbon nanotube polymer composites. Curr
Opin Solid State Mater Sci 2004;8:317.
[4] Lordi V, Yao N. Molecular mechanics of binding in carbon-nanotubepolymer
composites. J Mater Res 2000;15:27709.
[5] Jiang KR, Penn LS. Improved analysis and experimental evaluation of the single
lament pull-out test. Compos Sci Technol 1992;45:89103.
[6] Wong M, Paramsothy M, Xu XJ, Ren Y, Li S, Liao K. Physical interactions at
carbon nanotube-polymer interface. Polymer 2003;44:775764.
[7] Lee G-W, Jagannathan S, Chae HG, Minus ML, Kumar S. Carbon nanotube
dispersion and exfoliation in polypropylene and structure and properties of the
resulting composites. Polymer 2008;49:183140.
[8] Lee SH, Cho E, Jeon SH, Youn JR. Rheological and electrical properties of
polypropylene composites containing functionalized multi-walled carbon
nanotubes and compatibilizers. Carbon 2007;45:281022.
[9] Coleman JN, Cadek M, Ryan KP, Fonseca A, Nagy JB, Blau WJ, et al.
Reinforcement of polymers with carbon nanotubes. The role of an
ordered polymer interfacial region. Experiment and modeling. Polymer
2006;47:855661.
[10] Schaefer DW, Justice RS. How Nano Are Nanocomposites? Macromolecules
2007;40:850117.
[11] Smith Jr JG, Connell JW, Delozier DM, Lillehei PT, Watson KA, Lin Y, et al. Space
durable polymer/carbon nanotube lms for electrostatic charge mitigation.
Polymer 2004;45:82536.
[12] Mu M, Winey KI. Improved load transfer in nanotube/polymer composites
with increased polymer molecular weight. J Phys Chem C 2007;111:179237.
[13] Satapathy BK, Gan M, Weidisch R, Ptschke P, Jehnichen D, Keller T, et al.
Ductile-to-semiductile transition in PP-MWNT nanocomposites. Macromol
Rapid Commun 2007;28:83441.
[14] Gan M, Satapathy BK, Thunga M, Weidisch R, Ptschke P, Jehnichen D.
Structural interpretations of deformation and fracture behavior of
polypropylene/multi-walled carbon nanotube composites. Acta Mater
2008;56:224761.
[15] Gan M, Satapathy BK, Thunga M, Weidisch R, Ptschke P, Janke A.
Temperature dependence of creep behavior of PPMWNT nanocomposites.
Macromol Rapid Commun 2007;28:162433.
[16] Bao SP, Tjong SC. Mechanical behaviors of polypropylene/carbon nanotube
nanocomposites: the effects of loading rate and temperature. Mater Sci Eng A
2008;485:50816.
[17] Bhuiyan MA, Pucha RV, Worthy J, Karevan M, Kalaitzidou K. Dening the lower
and upper limit of the effective modulus of CNT/polypropylene composites
through integration of modeling and experiments. Compos Struct
2013;95:807.
[18] Wichmann MHG, Schulte K, Wagner HD. On nanocomposite toughness.
Compos Sci Technol 2008;68:32931.
[19] Prashantha K, Soulestin J, Lacrampe MF, Krawczak P, Dupin G, Claes M.
Masterbatch-based multi-walled carbon nanotube lled polypropylene
nanocomposites: assessment of rheological and mechanical properties.
Compos Sci Technol 2009;69:175663.
[20] Coleman JN, Khan U, Blau WJ, Gunko YK. Small but strong: a review of the
mechanical properties of carbon nanotubepolymer composites. Carbon
2006;44:162452.
[21] Du J-H, Bai J, Cheng H-M. The present status and key problems of carbon
nanotube based polymer composites. eXPRESS Polym Lett 2007;1(5):
25373.
[22] Desai AV, Haque MA. Mechanics of the interface for carbon nanotubepolymer
composites. Thin-Wall Struct 2005;43:1787803.
[23] Kovalchuk AA, Shevchenko VG, Shchegolikhin AN, Nedorezova PM, Klyamkina
AN, Aladyshev AM. Effect of carbon nanotube functionalization on the
structural and mechanical properties of polypropylene/MWCNT composites.
Macromolecules 2008;41:753642.
[24] Zhang X, Zhao Y, Wang Z, Zheng C, Dong X, Su Z, et al. Morphology and
mechanical behavior of isotactic polypropylene (iPP)/syndiotactic
polypropylene (sPP) blends and bers. Polymer 2005;46:595665.
[25] Yang L, Zhang Z, Wang X, Chen J, Li H. Effect of ultrasonic irradiation on the
microstructure and the electric property of PP/CPP/MWNT composites. J Appl
Polym Sci 2013;128:151020.
[26] Brny T, Czigny T, Karger-Kocsis J. Application of the essential work of
fracture (EWF) concept for polymers, related blends and composites: a review.
Prog Polym Sci 2010;35:125787.
[27] Clutton EQ. ESIS TC4 experience with the essential work of fracture method.
ESIS Publ 2000;27:18799.
[28] Benkhenafou F, Chemingui M, Fayolle B, Verdu J, Ferouani AK, Lefebvre JM.
Fracture behaviour of a polypropylene lm. Mater Des 2011;32:15159.
[29] Khare HS, Burris DL. A quantitative method for measuring nanocomposite
dispersion. Polymer 2010;51:71929.
[30] Clancy TC, Ptz M, Weinhold JD, Curro JG, Mattice WL. Mixing of isotactic and
syndiotactic polypropylenes in the melt. Macromolecules 2000;33:945263.
[31] Vukovic R, Bogdanic G, Karasz FE, MacKnight WJ. Phase behavior and
miscibility in binary blends containing polymers and copolymers of styrene,
of 2,6-dimethyl-1,4-phenylene oxide, and of their derivatives. J Phys Chem Ref
Data 1999;28:85168.
[32] Lippow SM, Qiu X, Ediger MD. Effect of tacticity on the segmental dynamics of
polypropylene melts investigated by 13C-nuclear magnetic resonance. J Chem
Phys 2001;115:49615.
[33] Logakis E, Pollatos E, Pandis C, Peoglos V, Zuburtikudis I, Delides CG, et al.
Structure-property relationships in isotactic polypropylene/multi-walled
carbon nanotubes nanocomposites. Compos Sci Technol 2010;70:32835.
[34] Ma L-F, Wang W-K, Bao R-Y, Yang W, Xie B-H, Yang M-B. Toughening of
polypropylene with b-nucleated thermoplastic vulcanizates based on
polypropylene/ethylenepropylenediene rubber blends. Mater Des 2013;51:
53643.
[35] Gregoriou VG, Kandilioti G, Bollas ST. Chain conformational transformations in
syndiotactic polypropylene/layered silicate nanocomposites during
mechanical elongation and thermal treatment. Polymer 2005;46:1134050.
[36] Lovinger AJ, Lotz B, Davis DD. Interchain packing and unit cell of syndiotactic
polypropylene. Polymer 1990;31:22539.
[37] Gatos KG, Kandilioti G, Galiotis C, Gregoriou VG. Mechanically and thermally
induced chain conformational transformations between helical form I and
trans-planar form III in syndiotactic polypropylene using FT-IR and Raman
spectroscopic techniques. Polymer 2004;45:445364.
D. Das, B.K. Satapathy / Materials and Design 54 (2014) 712726 725
[38] Fereidoon A, Ahangari MG, Saedodin S. Thermal and structural behaviors of
polypropylene nanocomposites reinforced with single-walled carbon nanotubes
by melt processing method. J Macromol Sci Part B 2008;48:196211.
[39] Ptschke P, Bhattacharyya AR, Janke A, Goering H. Melt mixing of
polycarbonate/multi-wall carbon nanotube composites. Compos Interfaces
2003;10:389404.
[40] Rocco AM, Pereira RP, Felisberti MI. Miscibility, crystallinity and
morphological behavior of binary blends of poly(ethylene oxide) and
poly(methyl vinyl ethermaleic acid). Polymer 2001;42:5199205.
[41] Puknszky B. Interfaces and interphases in multicomponent materials: past,
present, future. Eur Polymer J 2005;41:64562.
[42] Hill R. On discontinuous plastic states, with special reference to localized
necking in thin sheets. J Mech Phys Solids 1952;1:1930.
[43] Prashantha K, Soulestin J, Lacrampe MF, Claes M, Dupin G, Krawczak P. Multi-
walled carbon nanotube lled polypropylene nanocomposites based on
masterbatch route: Improvement of dispersion and mechanical properties
through PP-g-MA addition. eXPRESS Polym Lett 2008;2:73545.
[44] Yang B-X, Shi J-H, Pramoda KP, Goh SH. Enhancement of the mechanical
properties of polypropylene using polypropylene-grafted multiwalled carbon
nanotubes. Compos Sci Technol 2008;68:24907.
[45] Alig I, Ptschke P, Lellinger D, Skipa T, Pegel S, Kasaliwal GR, et al.
Establishment, morphology and properties of carbon nanotube networks in
polymer melts. Polymer 2012;53:428.
[46] Kutvonen A, Rossi G, Puisto SR, Rostedt NKJ, Ala-Nissila T. Inuence of
nanoparticle size, loading, and shape on the mechanical properties of polymer
nanocomposites. J Chem Phys 2012;137. 214901/1-/8.
[47] Gersappe D. Molecular mechanisms of failure in polymer nanocomposites.
Phys Rev Lett 2002;89:058301.
[48] Sun X, Shen H, Xie B, Yang W, Yang M. Fracture behavior of bimodal
polyethylene: effect of molecular weight distribution characteristics. Polymer
2011;52:56470.
[49] Viana JC, Cunha AM, Billon N. The thermomechanical environment and the
microstructure of an injection moulded polypropylene copolymer. Polymer
2002;43:418596.
[50] Lach R, Grellmann W. Time-and temperature-dependent fracture mechanics of
polymers: general aspects at monotonic quasi-static and impact loading
conditions. Macromol Mater Eng 2008;293:55567.
726 D. Das, B.K. Satapathy / Materials and Design 54 (2014) 712726