JOURNAL OF MATERIALS SCIENCE LETTERS 4 (1985) 1276-1279

Micromechanisms of crack propagation in hybrid-particulate

composites
A. J. K I N L O C H
Department of Mechanical Engineering, Imperial College of Science and Technology,
Exhibition Rd, London SW7 2BX, UK

D. M A X W E L L , R. J. Y O U N G
Departmen t of Materials, Queen Mary College, Mile End Rd, London, E1 4NS, UK

Unmodified epoxies are relatively brittle poly-
mers with poor resistance to crack propagation,
as is illustrated by the fracture energies of such
materials typically being only of the order of
100Jm 2. To increase the crack resistance, but
without seriously impairing other important
properties, there are two methods that have been
reported [1] based upon attaining a dispersion of
a particulate second phase in the epoxy. In one
method the second phase is rubbery in character,
whereas in the other it consists of rigid brittle
particles, such as alumina, silica or glass spheres.
In an effort to attain the optimum properties
from toughened epoxy polymers we have been
investigating the structure-property relation-
ships of hybrid-particulate composites. These
novel materials contain both rubbery and rigid
dispersed phases and a previous letter [2] des-
cribed the initial results, which indicated that
such materials could possess extremely high
fracture energies. The purpose of the present
letter is to outline the micromechanisms of crack
propagation in hybrid-particulate composites.
The epoxy resin used were derived from the
reaction of bisphenol A and epichlorhydrin and
was largely composed of the diglycidyl ether of
bisphenol A, but small quantities of higher
molar-mass polymers were present. The curing
agent was piperidine which was used at a con-
centration of 5 parts per hundred of resin by
weight (phr). The rubber used was a carboxyl-
terminated random copolymer of butadiene and
acrylonitrile, CTBN (carboxyl content, 2.37
w t % ; acrylonitrile content, 18wt%; molar
mass, 3500 g mol-'), used at a concentration of
15phr. The rigid particulate filler was glass
beads with a distribution of particle diameters
from about 10 to 100/~m and an average dia-
1 276 0261-8028/85 $03.00 + .12 © 1985 Chapman and Hall Ltd.
meter of 50.3#m. In some instances the glass
beads were coated with a silane-based bonding
agent to improve the intrinsic adhesion at the
epoxy-glass interface. The bonding agent was
7-glycidoxypropyl-trimethoxysilane which was
applied by immersing the glass beads for 30 min
in a 1 vol % solution of ethanol : water (95 : 5 by
volume) and then drying the glass beads. In the
present studies the glass beads were added at a
concentration of 35 phr, giving a volume frac-
tion of glass of 0.12. This was checked by burn-
ing off the resin and weighing the residues. The
details of the preparation and testing of the
epoxy polymers will be described in detail else-
where [3, 4]. Essentially, sheets of the material
were prepared by coating in a metal mould
which was then heated for 16 h at 120°C to effect
cure of the epoxy. The modulus and yield stress
were determined from uniaxial compression
tests and the stress-intensity factor at the onset
of crack growth was ascertained using the
double-torsion test specimen. The fracture
energy, G~o,was calculated from a knowledge of
the modulus and stress-intensity factor [1]. How-
ever, for some experiments small and relatively
thin single-edge notched (SEN) specimens were
prepared and the surfaces of the specimen
polished. The specimen was then stressed in a
loading jig mounted on the table of an optical
microscope and the propagation of the crack
observed using reflected light. Finally, the frac-
ture surfaces and the polished surfaces of the
SEN specimens (i.e. the surfaces normal to the
fracture plane) were examined using both opti-
cal and scanning electron microscopy. Before
observation in the scanning electron microscope
the specimens were sputter-coated with a thin
layer (,-~ 20 nm) of platinum to make the surface
T A B L E I Typical material properties
Composition - 70° C 20°C
E ayc Glc E O'yc
(GPa) (MPa) (kJ m z) (GPa)
Unmodified epoxy: 4.1 176 0.15 3.3
Epoxy/rubber 3.3 158 0.60 2.8
Hybrid* 4.2 160 0.90 3.0
Hybrid (using
silane-coated glass
particles)* 4.4 159 0.80 3.0
*vf(glass) = 0.12; rubber = 15phr.
conductive and reduce charging. However, note
that in our experiments the SEN specimens were
deformed and fractured prior to coating. This is
in contrast with when the specimens are first
coated and then fractured in situ in a scanning
electron microscope. In the latter case, artefacts
may arise owing to the presence of the coating.
Obviously, the optical microscope has a lower
resolution, but subsequent observation in the
electron microscope compensates for this dis-
advantage.
Values of the modulus, E, true uniaxial-
compressive yield-stress, ayo, and fracture
energy, G~c,are shown as a function of test tem-
perature in Table I. These results will be dis-
cussed in detail in subsequent papers [3, 4], but
there are several interesting points to note here.
Firstly, comparing the rubber-modified epoxy to
the simple unmodified epoxy, the former material
is considerably tougher but has a somewhat
lower modulus and yield strength. Secondly, the
hybrid-particulate composites possess even
higher values of Gic , and the presence of the rigid
glass particles has led to the increase in tough-
ness not being accompanied by a significant loss
of stiffness, although the yield strength is
unaffected by the presence of the glass particles.
Thirdly, it may be seen that the use of a silane
bonding agent to improve the intrinsic adhesion
at the epoxy-glass interface only appears to have
a significant effect at the highest test tem-
perature, and even then only upon the value of
G~c which is increased.
As stated above, the purpose of the present
letter is to outline the micromechanisms of crack
propagation and two basic toughening mechan-
isms have been identified: (i) crack pinning and
(ii) localized plastic shear-yielding.
The crack-pinning mechanism basically
assumes that a propagating crack can be
50°C
alc E Oye alc
(MPa) (kJm z) (GPa) (MPa) (kJm 2)
90 0.16 2.8 71 0.50
72 1.8 2.2 53 3.3
72 2.8 2.6 54 4.5
72 2.9 2.6 54 5.7
impeded by rigid impenetrable well-bonded
particles [5]. This arises because when a crack
meets an array of such obstacles it becomes
pinned and tends to bow out between the parti-
cles forming secondary cracks. Thus, a new frac-
ture surface is formed and the length of the crack
front is increased because of its change of shape
between the pinning positions. Now energy is
not only required to create the new fracture
surface, but, by analogy with the theory of dis-
locations, energy must also be supplied to the
newly formed non-linear crack front, which is
assumed to possess a line energy. This latter
factor, particularly, is suggested to lead to the
enhanced crack resistance often observed when
impenetrable particles are well-bonded into a
brittle matrix. The fractographic studies provide
strong evidence that crack pinning is an opera-
tive mechanism in the composites. Fig. 1 clearly
shows crack bowing between glass particles.
Further, when such secondary cracks do even-
tually break away from the pinning positions
then this frequently leads to characteristic tails
or steps on the fracture surface at the rear of the
inclusions, owing to the meeting of the two arms
Figure 1 Optical micrograph of glass-filled epoxy showing
the pinned crack front bowing between glass particles.
(Arrow indicates direction of crack propagation).
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Figure 2 Scanning electron micrograph of fracture surface of
hybrid-particulate composite (containing silane-coated glass
particles) tested at - 7 0 ° C. (Arrow indicates direction of
crack propagation).
of the crack front from different fracture planes.
The scanning electron micrograph shown in Fig.
2 illustrates this feature. In this micrograph the
dispersed rubber particles, having a diameter of
about 1 to 3 #m, may be clearly distinguished
and these rubbery particles induce more local-
ized plastic deformations around the propagat-
ing crack tip (see below), leading to a somewhat
rougher fracture surface. However, the presence
of tails or steps behind the glass particles may
still be discerned.
The second main mechanism is that of local-
ized plastic shear-yielding occurring in the
vicinity of the propagating crack tip. Such plas-
tic deformation is clearly visible in the scanning
electron micrograph of a fracture surface of a
hybrid-particulate composite, shown in Fig. 3.
Indeed, the plastic deformation has resulted in
the glass particles becoming debonded from the
epoxy matrix and the rubbery particles have
cavitated and seem to lie in somewhat enlarged
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Figure 3 Scanning electron micrograph of fracture surface of
hybrid-particulate composite tested at 30° C.
"holes". (It is the cavitation of the rubbery parti-
cles that gives rise to the stress-whitening that
often accompanies crack propagation, especially
at the highest test temperatures. In these
materials it is not indicative of crazing, which
would involve cavitation in the matrix.) The
localized plastic deformations occur to a greater
extent in the epoxy polymers containing dis-
persed rubbery particles, compared to the simple
epoxy polymer, owing to interactions between
the stress fields ahead of the crack and the rub-
ber particles [6, 7]. Also, they occur to a greater
extent at higher test temperatures since the yield
stress decreases as the temperature is increased,
(cf. Figs. 2 and 3).
Further insight into the micromechanism
involving localized plastic shear-yielding comes
from the in-situ observation of crack propa-
gation through the hybrid-particulate com-
posites. Fig. 4 is a reflection optical micrograph
showing the specimen's surface, normal to the
advancing crack plane. The large dark holes are
where glass particles have been removed during
Figure 4 Optical reflection
micrograph of crack growth
in a hybrid-particulate com-
posite tested at 20 ° C.
Figure 5 Scanning electron micrograph of the surface, normal to the crack plane, of the hybrid-particulate composite shown
in Fig. 4. The surfaces were tilted at about 30 ° to the horizontal.
polishing of the specimen. The light circular
regions are glass particles, but some show dark
areas at the poles where debonding has appar-
ently occurred ahead of the crack tip. The rub-
bery particles appear as very small dark parti-
cles. It may be seen that many fine black lines
connect the rubbery particles in the vicinity of
the crack and tend to lie at an angle of about 45 °
to the maximum principal tensile stress (which
is, of course, perpendicular to the crack direc-
tion) and therefore are indicative of plastic shear
bands. That they are indeed shear bands, rather
than surface microcracks, was confirmed by
examination of the fractured specimens in the
scanning electron microscope. The plastic shear
bands develop under constant volume defor-
mation which gives rise to furrows in the surface.
Such furrows may be clearly seen in Figs. 5a and
b and there are no signs at all of any microcracks
in the matrix. It was found that contrast from
the furrows was rather weak when the surface
was viewed normal to the electron beam. How-
ever, the contrast was significantly improved by
tilting the specimens by up to 30 ° from the hori-
zontal. In the optical microscope, using reflected
light normal to the surface, these furrows scatter
the light and the shear bands therefore appear as
dark lines. Now the dark lines seem to be not
only associated with the rubbery particles, but
also, to some extent, with the glass particles.
Thus, the local stress concentrations introduced
by the glass particles seem to assist in initiating
shear deformations in the matrix. Hence, the
glass particles may increase the toughness by this
micromechanism as well as via the crack-pinning
mechanism. The former mechanism would be
expected to be more significant at higher test
temperatures, when the yield stress of the matrix
is relatively low.
The detailed effects of material composition
and test conditions on the mechanical properties
and micromechanisms will be discussed in forth-
coming publications [3, 4].
References
1. A. J. K I N L O C H and R. J. Y O U N G , "Fracture
Behaviour of Polymers" (Applied Science, London,
1983).
2. D. M A X W E L L , R. J. Y O U N G and A. J. K I N -
L O C H , J. Mater. Sci. Lett. 3 (1984) 9.
3. R. J. Y O U N G , D. M A X W E L L and A. J. K I N -
LOCH, J. Mater. Sci., in press.
4. A. J. K I N L O C H , D. M A X W E L L and R.J.
Y O U N G , ibid. in press.
5. F. F. L A N G E , Phil. Mag. 22 (1970) 983.
6. A. J. K I N L O C H , S. J. SHAW, D. A. T O D and
D. L. H U N S T O N , Polymer 24 (1983) 1341.
7. A. J. K I N L O C H , S. J. SHAW and D. L. H U N -
STON, ibid. 24 (1983) 1355.
Received 7 February
and accepted 12 March 1985
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