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Article history:
Received 15 September 2009
Received in revised form 27 January 2010
Accepted 2 February 2010
Available online 6 February 2010
Keywords:
A. Carbon nanotubes
C. Laminate
A. Nanocomposites
A. Polymermatrix composites (PMCs)
C. Delamination
B. Fatigue
B. Fracture
a b s t r a c t
We show that the addition of small volume fractions of multi-walled carbon nanotubes (CNTs) to the
matrix of glassber composites reduces cyclic delamination crack propagation rates signicantly. In
addition, both critical and sub-critical inter-laminar fracture toughness values are increased. These
results corroborate recent experimental evidence that the incorporation of CNTs improve fatigue life
by a factor of two to three in in-plane cyclic loading. We show that in both the critical and sub-critical
cases, the degree of delamination suppression is most pronounced at lower levels of applied cyclic strain
energy release rate, DG. High-resolution scanning electron microscopy of the fracture surfaces suggests
that the presence of the CNTs at the delamination crack front slows the propagation of the crack due
to crack bridging, nanotube fracture, and nanotube pull-out. Further examination of the sub-critical fracture surfaces shows that the relative proportion of CNT pull-out to CNT fracture is dependent on the
applied cyclic strain energy, with pull-out dominating as DG is reduced. The conditions for crack propagation via matrix cracking and nanotube pull-out and fracture are studied analytically using fracture
mechanics theory and the results compared with data from the experiments. It is believed that the shift
in the fracture behavior of the CNTs is responsible for the associated increase in the inter-laminar fracture
resistance that is observed at lower levels of DG relative to composites not containing CNTs.
2010 Elsevier Ltd. All rights reserved.
1. Introduction
The formation and propagation of inter-laminar cracks in
composite materials leads to a signicant reduction in laminate
strength and stiffness, ultimately resulting in failure. The conditions
that favor delamination can range from out-of-plane tensile loads to
in-plane compressive loads, with crack initiation occurring at structural discontinuities such as edges, notches or voids. Delamination
can also be initiated by local transverse low-velocity impact, a
serious concern since the damage is sub-surface and difcult to
detect. Such defects can propagate under fatigue loading applied
transverse to the delamination plane resulting in cyclic delamination crack propagation leading to fast fracture and failure. Suppression of delamination is therefore of interest, particularly in primary
structures.
In this work, the effect of introducing CNTs into the matrix of
conventional ber-reinforced composites subjected to delamination
propagation under fatigue loading is studied. These hybrid composites were subjected to cyclic out-of-plane loading and both the critical and sub-critical strain energy release rates were measured and
compared to those measured in conventional composites. High-res* Corresponding author. Tel.: +1 510 642 4933; fax: +1 510 643 5599.
E-mail address: dharan@me.berkeley.edu (C.K.H. Dharan).
0266-3538/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compscitech.2010.02.001
902
C.S. Grimmer, C.K.H. Dharan / Composites Science and Technology 70 (2010) 901908
poor mechanical behavior of bulk polymers [410] have had varying success with the best-case examples managing to increase
properties such as stiffness and strength by a factor of two or so.
However, when these CNT-inltrated polymers are used as the matrix in conventional ber-reinforced composites, the overall
improvements in strength and stiffness are negligible [11]. While
integration of CNTs into the bulk matrix polymer of a laminate
has shown signicant improvement in inter-laminar shear
strength [12], the use of CNTs locally in the inter-laminar regions
of a laminate has shown limited [13,14] to no [15] improvement
in shear strength at the cost of added processing steps.
Micro-bers, or whiskers, such as silicon carbide have been grown
directly on the surface of continuous ber reinforcements with interlaminar mechanical properties improving signicantly, but at the expense of reduced in-plane properties due to weakening of the macroscale ber itself by the whisker growth [16]. More recently, CNTs
have been grown on the surface of continuous carbon ber; improvements in load transfer at the ber/matrix interface [17], inter-laminar shear strength [18,19], and delamination fracture toughness
[20] were obtained. Further efforts have also been directed at transfer-printing forests of aligned CNTs to the surface of prepreg [21].
While very different in their methods and results, these previous
efforts appear to be constrained by the trade-off mentioned between
the quality of the nano-scale reinforcement and manufacturability.
In the end, properties such as composite (monotonic) strength and
stiffness are almost completely dominated by the choice of the
macro-scale ber reinforcement. Furthermore, to obtain high volume fractions or a high degree of alignment in CNTs results in prohibitive manufacturing complications. Our efforts are instead
focused on evaluating the suppression of high-cycle fatigue damage
in conventional composite materials when small quantities of CNTs
are dispersed evenly in the matrix polymer using a simple and scalable manufacturing process.
Closed-form solutions and numerical models of classical delamination have been developed by several investigators [22,23]. Additionally, models of delamination in both random short ber
composites [24,25] and oriented through-thickness reinforced
composites [26] have been proposed. However, there have been
no models that take into consideration cyclic loading effects or
how nano-scale reinforcements affect cyclic delamination crack
growth. In this work, we demonstrate the effects that low volume
fraction randomly dispersed CNTs have on the propagation of inter-laminar fatigue cracks, and present an energy model to describe the behavior observed.
As discussed elsewhere [27], we have developed a simple manufacturing process that is scalable for use in industry, and yet is
able to achieve signicant improvements in the fatigue performance of the hybrid composite. By examining the behavior of
CNThybrid composites subjected to high-cycle fatigue loading,
we have brought to light an area where we believe nano-reinforcement can be of most use. While the macro-scale mechanical properties such as strength and stiffness are almost completely
dominated by the choice of ber and ber volume fraction used,
it is the micro- and nano-scale properties and failure mechanisms
that can be inuenced by nano-scale secondary reinforcements.
H
GIC
Pdd
wDa
903
C.S. Grimmer, C.K.H. Dharan / Composites Science and Technology 70 (2010) 901908
Fig. 1. Cyclic mode I delamination crack propagation data for glass ber-epoxy
laminates with and without the addition of 1% by weight of CNTs. Values shown are
the constants C, m in the equation: da/dN = C(DG)m.
Fig. 2. Cyclic delamination fracture surface at low DG (220 J/m2). Note the
preponderance of pulled-out CNTs relative to the number of fractured CNTs.
da
CDGm
dN
da is the incremental crack advancement corresponding to an incremental load cycle, dN, at an applied cyclic strain energy release rate
of DG. For the TWDCB specimens, DG is given by [33]:
2
DG
12k
E1 h
P2MAX P2MIN
Fig. 3. CNT fracture behavior at high DG (830 J/m2). A much smaller number of
pulled-out CNTs than fractured CNTs are present at the fracture surface at high DG
values.
223
430
830
0.56
0.39
0.26
904
C.S. Grimmer, C.K.H. Dharan / Composites Science and Technology 70 (2010) 901908
Fig. 4. Three states of a conventional and hybrid composite (adapted from Budiansky et al., 1986).
905
C.S. Grimmer, C.K.H. Dharan / Composites Science and Technology 70 (2010) 901908
~
Similarly, for the case of the hybrid composite matrix, State (0)
~
~
corresponds to a free body of volume V and surface ST , not subjected
to any external loads, exhibiting no displacements or strains, con~ corresponds
~ 0 . State (1)
taining some internal stress distribution r
~ which result in a stress
to the same body, with applied tractions T,
~ 1 , and corresponding strains ~e1 .
~ 1 , displacements u
distribution r
~ has undergone
~ State (2)
With no change in the surface tractions T,
some internal cracking resulting in new crack surface ~
SC , frictional
sliding due to pull-out at the new CNT/matrix interfacial surface
~
SF , and new values of
SP , fracture of CNTs creating new CNT surface ~
~ 2 , displacements u
~ 2 , and strains ~e2 .
stress distribution r
The constitutive relations relating stress to strain in the two
cases are
e Mr r0
~ r
~e M
~ r
~ 0
~ are the
for the CNT/glassber hybrid composite, where M and M
elastic compliances for the two cases.
For the case of the conventional composite, the potential energy
in each of the three states respectively is described by [39]:
Z
1
2 V
Z
1
2 V
Z
1
2 V
p0
r0 : Mr0 dV
p1
r1 : Mr1 dV
p2
6
Z
T u1 dV
r2 : Mr2 dV
T u2 dV
1
2
r1 r2 : Mr1 r2 dV
ST
T u1 u2 dS
r2 : Mr1 r2 dV
10
From 4, 9, and 10 the general form for potential energy loss due to
matrix cracking, in going from State (1) to State (2) is
1
2
r1 r2 : e1 e2 dV
11
1
p~ 1 p~ 2
2
Z
~
V
~ r
~
~1 r
~ 2 : M
~1 r
~ 2 dV
r
Z
~S
T
~1 u
~2 d~S
T~ u
~S
P
~S
F
sP dP d~S
Wdd~S
15
where W is dened as the cohesive traction corresponding to the inter-atomic forces binding two halves of a nanotube together per unit
nanotube cross-sectional area, is the distance between the two
halves, and 0 is the equilibrium carboncarbon bond length. Writing
Eq. (10) with accented notation and adding the terms found in (14)
and (15) gives the new virtual work equation for the hybrid composite
Z
~S
T
~1 u
~ 2 d~S
T~ u
Z
V~
~ r
~1 r
~ 2 dV~ sP
r~ 2 : M
Z
Z
~S
F
13
dd~S
~S
P
Wdd~S
16
Combining Eqs. (5), (12), and (16) gives the nal form for the potential energy loss in an elastic body due to matrix cracking, frictional
sliding and fracture of the nanotubes:
1
2
Z
~
V
~1 r
~ 2
r
Z
~S
P
dd~S
Z
~S
F
Wdd~S
17
The next step is to develop a means for making a direct comparison of the two potential energy loss equations previously developed, or more specically to make a direct comparison of the
~ While
potential energy difference between State (2) and State (2).
the two relations, Eq. (11) for the case of the conventional composite, and Eq. (17) for the case of the hybrid composite, have a similar
form, they are derived for two different materials and as such,
steps need to be taken before a direct comparison is valid. This crucial necessary step is to recognize that while the two materials are
in fact different, the outward, macro-scale mechanical behavior of
the two materials is argued here to be equivalent. As we have
shown earlier [27], the difference in the elastic modulus and the
yield strength of the CNT and non-CNT epoxy samples are small
and are well within the statistical variability and measurement
uncertainties that are to be expected in such tests. In light of this
established symmetry in material properties one can equate the
macro-scale compliances of the two matrix materials:
~
MM
18
p~ 2 p~ 2 sP
12
~ sP
: ~e1 ~e2 dV
ST
14
ST
T u1 u2 dS
p1 p2
dd~S
~S
P
Equating the external virtual work of the traction T over the displacement u1 u2 to the internal virtual work corresponding to
the internal stress, r2 over the strain M(r1 r2),
p~ 1 p~ 2
where for each state, the volume integral describes the stored elastic energy and the surface integral describes the work done at the
surface of the body by the applied tractions. Taking the compliance
to be a constant, r1 : Mr2 r2 : Mr1 ; the change in potential
energy of the body due to the internal cracking is
p1 p2
sP
ST
Z
~S
P
dP d~S
Z
~S
F
Wdd~S
19
Eq. (19) represents the difference in lost potential energy between the
~ The right
two bodies required to reach the damaged States (2) and (2).
hand side of Eq. (19) is the amount of strain energy that is absorbed by
the two damage processes unique to the hybrid composite, during the
formation of a unit area of matrix crack. It is this absorption of strain
energy in a way that does not promote the growth and coalescence of
matrix microcracks that has been proposed here as the means by
which the hybrid composites are able to signicantly outperform
conventional composites in high-cycle fatigue.
906
C.S. Grimmer, C.K.H. Dharan / Composites Science and Technology 70 (2010) 901908
mf
Vf
0:009
mf 1 mf qf =qm
20
NR
Z p=2
Vf
Vf
cos u sin u du
pr2
2p r 2
0
21
where u is the angle between the normal to the fracture plane and
the axis of the nanotube as shown in Fig. 5. Substituting the pertinent values into Eq. (21)
N0R NR /
22
1 EGIC
rp
2p S2y
!
23
where E is the Youngs modulus and Sy the yield strength whose values are 2 GPa and 40 MPa, respectively [27].
NCC nCC
Z
~S
F
WddS
24
sP
rut do
4dt
2 !
di
1
do
25
Symbol
Value
sp
dt
~P
S
5701700 MPa
250 nm
15,700 nm2
Number of CC bonds
CC bond energy
NCC
nCC
2330
348 kJ/mol
C.S. Grimmer, C.K.H. Dharan / Composites Science and Technology 70 (2010) 901908
"
~2 P
~2
EP
!
f
#
NCC nCC 1 f N0R
26
~ 2 are p2 and p
~ 2 normalized per unit area of crack
where P2 and P
surface, respectively, the sum inside the square brackets corresponds to the potential energy loss through each of the two mechanisms, pull-out or fracture, scaled by the frequency by which each
mechanism occurs, and N 0R is the number of CNTs involved in the
fracture process per unit area of crack surface created, with / from
Eq. (23) conservatively estimated to be 2.
E, the differential energy release rate, is the difference in the rate
of potential energy dissipated by CNT pull-out and CNT fracture per
unit area of new crack surface created in a CNT/glassber hybrid
composite when compared to an equivalent delamination crack in
a conventional glassber composite. Eq. (26) allows one to estimate
the differential increase in energy dissipation resulting from the
incorporation of CNTs in glassber composites. Shifting the delamination response of the conventional composite (without CNTs) to
the right by E corresponds to the response of the composite containing CNTs. This was done using the experimentally measured values
of the pull-out fraction, f, as a function of DG (given in Table 1) for
the estimated range of values for sp discussed earlier. The resulting
range is depicted as a shaded zone in Fig. 6 and shows good correlation with the cyclic data. As DG increases, the effect of the CNTs in
delaying delamination crack propagation decreases due to a
decreasing fraction of pull-out relative to fracture. In other words,
the CNTs act to slow crack propagation when the applied DG is small,
i.e., in the high-cycle regime, when a larger fraction of them are being
pulled-out. At faster crack propagation rates corresponding to higher values of DG, the CNTs tend to fracture rather than pull-out making them ineffective in slowing crack propagation.
5. Summary
The delamination crack propagation behavior in the two composite types (glassber composites with and without the addition
of CNTs), both under critical and sub-critical levels of applied strain
energy, can be readily understood through examination of Fig. 1.
The critical strain energy release rate, GIC, in the conventional
glassber composites is found to be consistent with values reported elsewhere [1,44], with the corresponding value for the hybrid composites only slightly higher, in agreement with previous
studies [12]. The convergence of the response at increasing levels
907
908
C.S. Grimmer, C.K.H. Dharan / Composites Science and Technology 70 (2010) 901908
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