Materials Science and Engineering A 384 (2004) 284–298

Some aspects of surface deformation and fracture of 5–20% calcium

carbonate-reinforced polyethylene composites
R.D.K. Misraa,∗ , P. Nerikara , K. Bertrandb , D. Murphyb
a Material Science and Engineering Group, Department of Chemical Engineering, University of Louisiana at Lafayette,
P.O. Box 44130, Lafayette LA 70504-4130, USA
b Westlake Polymers Corporation, P.O. Box 3608, Sulphur LA 70664, USA

Received 12 April 2004

Abstract

The paper describes the surface deformation and fracture process during tensile straining of 5–20% calcium carbonate-reinforced polyethy-
lene composites and compares the behavior with unreinforced neat polyethylene as a function of strain rate of tensile test. Calcium carbonate-
reinforced polyethylene composites exhibit increased tensile modulus in comparison to neat polyethylene, while the influence on yield
strength is not clearly discernible. Calcium carbonate reinforcement reduces the extent of cold drawing of the polymer matrix. The primary
surface deformation process of crazing-tearing and fibrillation in unreinforced neat polyethylene is altered to ridge/wedge tearing in calcium
carbonate-reinforced polyethylene composites. The mode of fracture in neat polyethylene is crazing-tearing and fibrillation, while in calcium
carbonate-reinforced composites, the mode of fracture is fibrillation. However, the nature of fibrillation (layered or non-layered) depends on
percent reinforcement and strain rate of tensile test. High strain rate and high percent reinforcement favors predominantly layered fibrillation
in calcium carbonate-reinforced polyethylene composites.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Polyethylene; Composites; Deformation; Fracture

1. Introduction judicious choice of reinforcement, particle size and shape,

There is currently a renewed interest in thermoplas-
tics polymeric materials such as polyethylene (PE) and
polypropylene (PP) in view of their relative low cost and recy-
clability [1–5]. Among the different thermoplastic materials,
polyethylene is increasingly versatile in its applications and
efforts are being made to synthesize polyethylene with long
chain branching. The current efforts are aimed at improving
the physical and mechanical properties of thermoplastics
such as modulus, strength, heat distortion temperature, and
shrinkage during molding by reinforcement with minerals.
In recent years, the incorporation of mineral fillers in ther-
moplastics is being adopted to enhance mechanical proper-
ties. The degree of improvement, however, depends on the
∗ Corresponding author. Tel.: +1-337-482-6430; fax: +1-337-482-1220.
E-mail address: dmisra@louisiana.edu (R.D.K. Misra).
volume fraction, and the surface treatment that promotes in-
teraction between the polymer matrix and filler [6,7]. The
common fillers used in thermoplastics are carbon black [8,9],
titanium dioxide [10,11], calcium carbonate [7,12–14], and
calcium sulphate anhydride fibers [11]. Among these, cal-
cium carbonate is a preferred commodity mineral, roughly
spherical in shape, and can be obtained with a high whiteness.
The reinforcement of thermoplastics with fillers gener-
ally enhances modulus, yield strength, and impact strength.
The modulus increases with increase in volume fraction of
the reinforcement filler [7,13–19] restricting the mobility and
deformability of the matrix by introducing a mechanical re-
straint, the degree of which depends on the particulate spacing
and the properties of the particle and the matrix [17]. Particle
size and dispersability are important factors that determine
yield and tensile strength. The fracture resistance of rein-
forced polymers is far from understood. This is because of

0921-5093/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2004.06.047
 R.D.K. Misra et al. / Materials Science and Engineering A 384 (2004) 284–298
the presence of local inhomogeneity in polymeric composite
materials. The failure mode depends on interfacial strength,
dewetting, stress concentration at the interface, and relative
brittle or ductile nature of the filler and the matrix material
[20].
In recent years, the deterioration of impact resistance in
reinforced polymers [15–17,21] has been attributed to micro-
weakness in the structure of these two phase systems caused
by stress concentration or discontinuity in stress transfer at the
polymer-filler interface. In another study, the use of smaller
CaCO3 particles of size less than ∼2 ␮m in the polyolefin
blends improved dispersion and resulted in increase in impact
resistance [22]. In isotactic polypropylene, impact strength
increased with the volume fraction of filler (φ) content up
to φ = 0.04 and then decreased such that 35 vol.% filler ex-
hibited impact strength lower than that of unfilled isotactic
polypropylene [17,23]. The increase in impact strength at
low φ was believed to be due to nucleation of small size crys-
tallites [24] and to the ability of the material to absorb more
energy because of increased amorphous content. A further in-
crease in φ, reduced the deformability of isotactic polypropy-
lene, reducing the ductility in the skin area so that the com-
posite tends to form a weak structure.
Polyethylene and polypropylene are polymeric materials
with weak intermolecular interaction forces. The polymer
chains, however, accommodate into the crystal structure. It
is this crystallinity that imparts mechanical strength to the
polymer. The presence of fillers, blending polymers or addi-
tives interferes with the polyolefin molecules fitting into the
crystal structure [17] and strength properties may decrease.
However, if the loss in crystallinity is compensated by en-
hanced interaction of the polymer matrix with reinforcement
filler, then the yield strength is retained or may increase. Thus,
the polymer matrix-filler reinforcement interface plays a de-
cisive role in obtaining the ultimate yield strength in filled
polymer composites [17,25].
The crystallization temperature of the polymeric compo-
nents is believed to depend on the network density or specific
surface area of the filler. Mitsuishi et al. [26] observed that
the crystallization temperature for filler with needle shape
was higher than that of spherical or cubic shape for same
weight percent of reinforcement filler. This difference in crys-
tallization behavior was attributed to surface topography of
the filler, chemical properties of the filler surface, and resid-
ual stress around the filler. Kowalewski et al. [27] investigated
the relationship of crystallization behavior with the structure,
surface topography, and state of coagulation of the filler using
chalk as a crystal-nucleating agent. They identified that the
surface topography of the filler was an important factor influ-
encing the crystallization behavior and the nucleating ability
depends on the crystal structure. On the other hand, Mauritz
et al. [28] reported from the viewpoint of chemical properties
of fillers that the alternative rows of plus and minus induced
epitaxial crystallization of polyethylene.
It is now well recognized that plastic deformation of crys-
talline and amorphous components of a semi-crystalline poly-
285
mer involves a number of mechanisms of plastic deforma-
tion. The mechanical deformation processes identified in lin-
ear low-density polyethylene include kinking, surface shear
yielding, surface cracking, sub-surface yielding, and ductile
ploughing [2,3,29]. At the fine scale, the X-ray scattering re-
sults supported by light and electron microscopy suggested
that tensile deformation of semi-crystalline polymers, in gen-
eral, first involves elongation of amorphous tie chains fol-
lowed by slip and tilting of crystalline lamellar chains and ori-
entation of blocks of crystals along the tensile axis [30]. More
recently, it was proposed from wide-angle X-ray scattering
measurements that amorphous component has similar de-
grees of freedom and kinematic constraints as the crystalline
constituent [31]. However, resistance to plastic deformation
of the crystalline part is greater than that of the amorphous
constituent. The early stage of tensile deformation is first
confined to amorphous layers as inner lamellar shear, which
in turn produces relatively large localized strains. Continued
plastic deformation produces long range coherence, when the
extent of orientation of molecular chains in the amorphous
and crystalline constituents of polymer come close to each
other [31].
In the effort to develop polymeric materials characterized
by high resistance to surface and bulk deformation, exami-
nation of surface deformation and how it relates to bulk de-
formation and fracture assumes particular significance. Re-
cent electron microscopy studies on long and short chain
polypropylenes indicated that domains of elastic, yielding,
and cold drawing were similar, but the micromechanisms
of deformation processes were different [32–34]. The mi-
cromechanisms of deformation define the response of the
material in terms of material condition, rate of deformation,
geometry of the damaging implement, strain and temperature.
Also, micromechanisms of deformation may vary in size and
importance.
In the present paper, tensile deformation behavior and
concurrent microstructural evolution in calcium carbonate-
reinforced polyethylene micrometric composites is investi-
gated and compared with un-reinforced neat polyethylene.
2. Experimental procedure
Standard (ASTM D368) tensile bars of neat and calcium
carbonate (5, 10, and 20%) reinforced polyethylene were cast
by the injection molding process. The direction of molding
corresponded with the longitudinal axis of the specimen. The
nominal melt flow index was 20 g/10 min at 230/2.16 (i.e. at
230 ◦ C and 2.16 kg piston force).
The tensile tests were conducted at 20 ◦ C (293 K) using a
computerized MTS 210 tensile testing machine at displace-
ment rates in the range of 50–380 mm/min (strain rate ∼
0.017–0.125 s−1 ). Two types of tests were performed. In the
first type of tests, the samples were tested to failure, while
the second type of tests involved tensile loading at a constant
displacement rate to pre-determined strains at different points
286 R.D.K. Misra et al. / Materials Science and Engineering A 384 (2004) 284–298

on the engineering stress–strain plots. Subsequently, the two
types of test samples were examined by field emission scan-
ning electron microscopy to study the micromechanism and
stages of plastic deformation leading to fracture.
Differential scanning calorimetry (DSC) was employed to
determine the heat of fusion and percent crystallinity of neat
polyethylene and its micrometric composites. Sections cut
from the samples were heated from 20 to 180 ◦ C at a rate
of 10 ◦ C/min, held at that temperature for 1 min, then cooled
to −20 ◦ C at a rate of 10 ◦ C/min, held at −20 ◦ C for 1 min
and heated to 20 ◦ C at 10 ◦ C/min. This temperature range
enabled the samples to go through a cycle of melting and
crystallization.
and crystallization temperatures is summarized in Table 1.
The percent crystallinity was estimated using a value of heat
of fusion for 100% crystalline polyethylene of 292 J/g. Fig. 1
and Table 1 show that starting crystallization temperature ap-
pears to have increased by ∼3 ◦ C on reinforcement of neat
polyethylene with calcium carbonate. This behavior was con-
sistently observed on repeated experimentation, suggesting
that crystallization is enhanced to a small extent in the pres-
ence of reinforcement. The increase in bulk crystallinity on
reinforcement with calcium carbonate is significant and is
expected to influence the mechanical behavior.
3.2. Tensile deformation behavior

The engineering stress–strain plots for neat polyethylene,

3. Results and discussion
3.1. Crystallization
Differential scanning calorimetry plots for exothermic and
endothermic experiments are presented in Fig. 1. The data ob-
tained from Fig. 1 in terms of percent crystallinity, melting
5, 10, and 20% calcium carbonate-reinforced polyethylene
at selected displacement rates of 50–380 mm/min (strain rate
0.017–0.125 s−1 ) exhibiting elastic and plastic deformation
regions are presented in Fig. 2. The regions of significance
are elastic region, yielding, cold drawing, and fracture. At
the displacement rate of 50 mm/min (strain rate ∼ 0.017 s−1 )
(Fig. 2), neat polyethylene, 5 and 10% calcium carbonate-

Fig. 1. Differential scanning calorimetry (DSC) plots for exothermic and endothermic experiments for neat and calcium carbonate-reinforced high-density neat
polyethylene composites.

Table 1
Physical and mechanical properties of calcium carbonate-reinforced polyethylene composites
Materia Heat of fusion for Crystallinity Crystallization Melting Modulus at Yield stress (MPa)
neat polyethylene (%) temperature temperature 50 mm/min
(J/g) (◦ C) (◦ C) (MPa) 50 mm/ 125 mm/ 250 mm/ 380 mm/
min min min min
Neat PE 125 43 113.9 133.3 1050 24 25 26 25
5% CaCO3 –PE 156 53 116.8 137.4 1190 26 27 29 28
composite
10% CaCO3 –PE 166 57 116.7 136.1 1365 27 28 29 29
composite
20% CaCO3 –PE 197 67 115.5 137.9 1695 24 25 28 29
composite
 R.D.K. Misra et al. / Materials Science and Engineering A 384 (2004) 284–298 287

reinforced polyethylene did not fracture until a strain of
∼1000% (maximum allowable strain in the MTS tensile test-
ing equipment), while the 20% calcium carbonate-reinforced
polyethylene failed at a strain of ∼800%. The influence of
calcium carbonate reinforcement was more apparent from en-
gineering stress–strain plots obtained at displacement rates
of 250 mm/min and greater (Fig. 2b–d) because at these
displacement rates, fracture occurred for all the materials.
Fig. 2 shows that reinforcement of neat polyethylene with
calcium carbonate decreases fracture strain. It is expected
that at a constant displacement rate or strain rate of tensile
test, the fracture strain would decrease with increase in per-
cent reinforcement. The matrix-particle interface provides a
potential site for crack nucleation and the failure initiates
when the particles are debonded from the matrix such that
the fracture strain has a value that is intermediate between
the mineral and the polymer matrix. Two aspects may be
noted from Fig. 2a–d. First, with increase in percent rein-
forcement, the region of cold drawing was reduced. Sec-
ond, for a particular percent reinforcement, the increase in
displacement rate of tensile test decreased the cold drawing
region.

Fig. 2. Engineering stress–strain plots for neat and 5, 10, and 20% calcium carbonate-reinforced high-density polyethylene at varying displacement rates and
at 20 ◦ C (293 K): (a) 50 mm/min (strain rate ∼ 0.017 s−1 ); (b) 125 mm/min (strain rate ∼ 0.04 s−1 ); (c) 250 mm/min (strain rate ∼ 0.083 s−1 ); (d) 380 mm/min
(strain rate ∼ 0.125 s−1 ). The inset figure shows the events of tensile deformation.
288 R.D.K. Misra et al. / Materials Science and Engineering A 384 (2004) 284–298

Fig. 2. (Continued ).

3.2.1. Tensile modulus and yield strength
The tensile modulus of calcium carbonate-reinforced
polyethylene composites consistently increased with increase
in percent reinforcement (Table 1) implying increase in
rigidity and stiffness on the addition of calcium carbon-
ate. The consistent increase of tensile modulus with per-
cent calcium carbonate suggests interaction of the reinforce-
ment with polymer matrix as recently proposed by Misra
and co-workers [35] using atomic force microscopy. Atomic
force microscopy indicated higher crystallinity at the matrix-
particle interface compared to regions away from the inter-
face. Thus, while one may attribute the increase in modulus to
the effective reinforcement of polyethylene by calcium car-
bonate mineral particles that act in concert, it is important
to emphasize that any theoretical treatment of modulus in
polymer composites involves three phases, viz. matrix, par-
ticle, and matrix-particle interface and is discussed in detail
elsewhere [35–37].
In regard to the yield strength, there appears to be ∼2 MPa
increase on the addition of 5 and 10% calcium carbonate rein-
forcement to the polymer matrix, while for 20% calcium car-
bonate reinforcement, the yield stress is similar to that of neat
polyethylene. The small difference may very well be within
the experimental range for neat polyethylene. It is difficult
 R.D.K. Misra et al. / Materials Science and Engineering A 384 (2004) 284–298 289

to conclude from Table 1 that calcium carbonate had a clear

discernible influence on the yield stress of neat polyethylene.
A similar behavior was observed for wollastonite- and talc-
reinforced polypropylenes and ethylene–propylene copoly-
mers [35,38–41]. The reinforcement of polypropylene in-
creased the modulus, but yield strength remained unaffected.

3.3. Micromechanism of tensile straining

To study the deformation processes taking place during

tensile straining, samples were unloaded at pre-determined
strains on the engineering stress–strain plots of the type pre-
sented in Fig. 2a–d. These include: (a) end of elastic limit; (b)
progress in yielding and cold drawing, and; (c) fracture. The
unloaded samples were studied using high resolution field
emission SEM to identify the micro-scale response of neat
and reinforced polyethylene composites, tensile deformed to
different strains and at varying displacement rates.

3.3.1. Microstructural evolution in neat polyethylene

At a low displacement rate of ∼50 mm/min (strain rate ∼
0.017 s−1 ) and a nominal strain of ∼1.0, wedge shaped fea-
tures (Fig. 3a; strain rate ∼ 0.017 s−1 indicated with arrows)
nucleated parallel to the tensile axis. The density of these
wedges was greater in the mid-width region of the tensile bar
compared to regions away from it. In addition to wedging,
numerous small and parallel wrinkles, referred here as ridges
formed in the matrix perpendicular to the tensile direction
(Fig. 3a). These ridges are a consequence of stress relaxation
[35,36].
With increase in strain, the wedges grew in size and den-
sity, and separated (pulled away) from the surrounding con-
straint matrix (Fig. 3b and c). The areas associated with
wedges initially appeared translucent and then opaque as the
stress whitening set in. The nucleated surface wedges grew
inwards into the material and were confirmed by interrupting
the tensile tests and performing freeze fracture experiments.
It was recently shown by electron microscopy studies that
in ductile polymeric materials such as ethylene–propylene
diblock copolymers, wedging is the dominant mode of sur-
face and bulk deformation, and fracture is characterized by
severely deformed fibrils. This type of deformation was de-
fined as fibrillated deformation. Wedge mode of deforma-
Fig. 3. SEM micrographs of tensile deformed high-density neat polyethy-
tion has recently been documented by Misra and co-workers lene at a displacement rate of 50 mm/min (strain rate ∼ 0.017 s−1 ) showing:
[42]. We believe that wedge mode of deformation occurs (a) wedge formation (indicated with arrows) at a strain of ∼ 1; (b) and (c)
at low strain rates in relatively high strength thermoplastics, ridges and extensive stretching and drawing of lamellae leading to the sepa-
while majority of the previous studies were conducted at high ration and pulling away of wedges from the constrained matrix at strains of
∼2 and 4.
strain rates on notched samples, and in environments where
crazing dominated. The necessary experimental conditions
to observe wedge mode of deformation in high strength ther- follows. During yielding (e.g. low strain of ∼0.5, displace-
moplastics are low strain and strain rate. Absence of either ment rate of ∼100 mm/min; strain rate ∼ 0.034 s−1 ), surface
of these conditions may prevent wedge mode of deformation features resembling deformation bands (Fig. 4a) were formed
to occur. normal to the tensile axis. Deformation bands are localized
At displacement rates greater than 50 mm/min (strain rate regions of intense plastic flow. The local strain in the deforma-
∼ 0.017 s−1 ), crazing also developed together with wedging tion bands is expected to be many orders of magnitude greater
and ridges. The sequence of developments of crazes was as than the surrounding less deformed regions. With increase in
290 R.D.K. Misra et al. / Materials Science and Engineering A 384 (2004) 284–298
Fig. 4. SEM micrographs of tensile deformed high-density neat polyethy-
lene showing the sequence of development of crazing: (a) formation
of surface features resembling deformation bands (displacement rate ∼
100 mm/min, strain rate ∼ 0.034 s−1 , strain ∼ 0.5); (b) development of defor-
mation bands into distinct array of crazes (displacement rate ∼ 100 mm/min,
strain rate ∼ 0.034 s−1 , strain ∼ 1.2); (c) secondary crazes (displacement
rate of 125 mm/min, strain rate ∼ 0.04 s−1 , strain ∼ 0.8).
strain, the deformation bands developed into distinct array of
crazes (Fig. 4b). The crazes formed normal to the tensile axis
and are opaque planes in the tensile strained stress-whitened
material. With subsequent growth of crack zone, a crack nu-
cleates through an array of crazes (indicated with an arrow in
Fig. 4b). The presence of crack within the craze zone modi-
fies the stress field in the neighborhood of the crack and has
components that are not parallel to the applied stress, such
that subsequent crazing (secondary crazes) occurs at an an-
gle with respect to primary craze. The secondary crazes act
as barriers to other crazes (Fig. 4c) and run at an angle with
respect to primary crazes. Also, crazing increased with strain
and displacement rate. It may be noted that at displacement
rates of less than ∼100 mm/min (strain rate ∼ 0.034 s−1 ),
only wedge mode of deformation was observed, and at dis-
placement rates of 100 mm/min (strain rate ∼ 0.034 s−1 ) and
greater, crazing was the dominant mode of deformation.
Wedging, deformation bands, and crazing are inhomo-
geneous modes of deformation in polyethylene. Inhomoge-
neous mode of deformation was suggested earlier for the
low-density polyethylene [30,43]. However, in the previ-
ous studies, the localized deformation was attributed to re-
duction in radial banding, if the spherulite originally con-
tained radial banding. In the present case of injection-molded
neat polyethylene, radial banding was absent. Another mode
of plastic deformation previously identified in low-density
polyethylene was kink bands, where one part of the crystal
shears relative to the material on either side of it [29]. It was
stated that crystalline regularity was necessary for kinking,
and will generally be observed in pure shear banding, com-
pressive banding, or when a drawn specimen is compressed
along the drawn direction (along the chain axis). Kink is sim-
ilar to the twin modes of plastic deformation in HCP metals.
The fact that kink bands were not observed in high-density
polyethylene suggests that the plastic deformation of lamellae
constituting the spherulites must involve unfolding and slip-
page of molecular chains producing wedge and craze modes
of deformation.
Crazes are crack-like defects [44] and are believed to ini-
tiate at flaws present on the surface of a polymeric material.
Although, crazes appear to be cracks, Steger and Nielser [45]
and Peterlin [46] recognized crazing to be normal stress yield-
ing, which involves dilational deformation accompanied by
localized micro-void formation with no lateral contraction.
Additionally, because of the presence of micro-voids within
the craze, the density of the crazed region is less than the un-
crazed region, resulting in the reduction of the overall strength
of the craze.
At higher displacement rates (e.g. 380 mm/min; strain rate
∼0.125 s−1 ), wedge, ridge, and crazing occurred in a manner
similar to low displacement rates. A region containing exten-
sive wedging and torn wedges is presented in Fig. 5a. It may
be noted from Fig. 5b that separation of wedges from the ma-
trix was obstructed by the partially relaxed ridges such that
the deformed fibrils had the tendency to fold at the ridges.
This behavior was more apparent in 20% calcium carbonate-
reinforced polyethylene composite (please see Section 3.3.2).
This can be envisaged as follows: at higher displacement
rates, the ridges have inadequate time to relax, and the par-
tially relaxed ridges prevent plastic deformation and separa-
tion of wedges from the matrix leading to layered fibrillation
as compared to unlayered fibrillation observed at low dis-
placement rates (Fig. 3c).
 R.D.K. Misra et al. / Materials Science and Engineering A 384 (2004) 284–298 291

Fig. 5. SEM micrographs of tensile deformed high-density neat polyethylene showing commencement of layered fibrillation.

The final fracture surface of neat polyethylene tensile
tested at low displacement rates of 50–100 mm/min (strain
rate ∼ 0.017–0.034 s−1 ) was 100% ductile in nature, referred
here as fibrillated structure (fibrillated structure is character-
ized by severely deformed lamellae with enhanced plastic
flow). SEM micrograph of the fracture surface at a displace-
ment rate of 125 mm/min is presented in Fig. 6. Consider-
ing that wedging was the dominant mode of deformation
at displacement rates of less than 100 mm/min (strain rate
∼ 0.034 s−1 ), and wedges grew inwards from the material,
the final fracture through fibrillation (Fig. 6) involved wedge
growth, multiplication, and severe deformation.
At displacement rates greater than 125 mm/min (strain rate
∼ 0.042 s−1 ), two types of fracture morphologies, fibrillation

Fig. 6. SEM micrographs of the fracture surface of high-density neat polyethylene tensile tested at a displacement rate of 125 mm/min (strain rate ∼ 0.04 s−1 )
showing fibrillation.
292 R.D.K. Misra et al. / Materials Science and Engineering A 384 (2004) 284–298

Fig. 7. SEM micrographs of the fracture surface of high-density neat polyethylene tensile tested at a displacement rate of 300 mm/min (strain rate ∼ 0.1 s−1 )
showing fibrillated fracture in the mid-thickness and crazing-tearing away from the mid-thickness region of the fracture surface.

and crazing-tearing characterized neat polyethylene. Fig. 7
shows SEM micrographs of one-half of the fracture surface
at a displacement rate of 300 mm/min (strain rate ∼ 0.1 s−1 )
with fibrillation in the mid-thickness and crazing/tearing in
the remaining surrounding region. This mixed-mode of de-
formation can be described as follows. As stated above, neat
polyethylene deformed at lower displacement rates indicated
that the wedge density was maximum in the mid-width (and
mid-thickness) region, and craze-density in regions away
from the mid-width, which grew inwards from opposite sur-
faces. Now considering that high stresses are present in the
mid-thickness region of the sample during a tensile test, an
unstable crack nucleates and propagates through wedge and
craze leading to fibrillation in the center and tearing of array
of crazes away from the center (Fig. 7).
With increase in displacement rate (e.g. ∼500 mm/min;
strain rate ∼ 0.17 s−1 ), crazes grew rapidly from opposite
surfaces and fracture initiated near the core of the tensile bar,
and propagated outwards breaking through the crazed surface
on both sides (resulting in tearing of the crazed region) at ap-
proximately the same position along the length of the tensile
bar. At these high displacement rates, one half of the fracture
was predominantly crazing-tearing (Fig. 8a and b) and the
second half that separated from the mid-thickness leaving a
large void in the first part of the fracture surface was lay-
ered fibrillation (Fig. 8c). Even though at low magnification,
the fracture appears brittle in nature (Fig. 8a), but at sub-
microscopic level, tearing of array of crazes is involved. Also,
comparing the high magnification micrographs of crazed re-
gion at low and high displacement rates (Figs. 7c and 8b)
indicates some differences in tearing of the crazed region.
Fig. 8b suggests that tearing occurred at a higher strain rate
because of the high displacement rate of the tensile test result-
ing in a smooth and flat tearing of the crazed region. Also, the
reduced ductility accompanying craze formation at high dis-
placement rates is associated with craze embrittlement and
results in lowering of toughness compared to polymer that
exhibits enhanced plastic flow. Crazing is often considered a
precursor to brittle fracture [47], particularly in amorphous
polymers. In the present case, crazing occurs in association
with fibrillation, as two independent modes of deformation
and does not produce brittle fracture. Thus, percent wedging
 R.D.K. Misra et al. / Materials Science and Engineering A 384 (2004) 284–298 293

Fig. 8. SEM micrographs of the fracture surface of high-density neat polyethylene tensile tested at a displacement rate of 500 mm/min (strain rate ∼0.17 s−1 )
showing (a) one-half of the fracture surface at low magnification that is characterized by (b) crazing-tearing at high magnification. Note that while fracture
appears brittle at low magnification, it shows crazing-tearing at high magnification. (c) Second-half of the fracture that separated out leaving a large void in the
first-half exhibiting layered-type fibrillation.

and crazing modes of deformation are a strong function of the
deformation rate and the growth of wedge and craze involves
drawing of the surrounding undeformed polymer. In contrast
to wedging, crazing is not a ductile mode of deformation, the
final fracture occurs when tearing of the crazed material oc-
curs. In absence of crazing (100% ductile or wedge), failure
occurs when there is a complete lamellar breakdown in the
mid-thickness of the tensile bar.
From the above discussion and SEM observations, it can
be said that wedges that transform into severely deformed
fibrils, ridges/wrinkles (that nucleate because of stress relax-
ation) and crazing are the primary controlling mechanisms
of stress whitening with crazing dominating at high displace-
ment rates.
3.3.2. Microstructural evolution in calcium
carbonate-reinforced polyethylene composites
The sequence of deformation processes occurring in
5, 10, and 20% calcium carbonate-reinforced polyethy-
lene with increase in strain and at a constant displace-
ment rate of 50 mm/min (strain rate ∼ 0.017 s−1 ) are pre-
sented in Figs. 9–11. The plastic deformation at this low
displacement rate in calcium carbonate-reinforced polyethy-
lene composites initiated with nucleation of wedges and
ridges (Figs. 9a–11a). However, the density of ridges in-
creased with increase in percent calcium carbonate pre-
sumably because of increase in the number of stress con-
centration sites. Also, with increase in percent calcium
carbonate, greater stress relaxation associated with ridges
occurred. This is apparent from the increase in raised sur-
face feature associated with ridges (wrinkles). With increase
in strain, the ridges relaxed and disappeared, while the
wedges separated and pulled away from the surrounding
constrained matrix with consequent debonding/detachment
of mineral particles (Figs. 9–11b and c). In compari-
son to neat polyethylene, the fibrils were less severely
deformed and extensive curling of fibrils was not ob-
served.
294 R.D.K. Misra et al. / Materials Science and Engineering A 384 (2004) 284–298
Fig. 9. SEM micrographs of tensile deformed 5% calcium carbonate-
reinforced high-density polyethylene composites at a displacement rate of
50 mm/min (strain rate ∼ 0.017 s−1 ) showing (a) formation of wedges and
ridges at strains of: (a) ∼1.3; (b) ∼2, and; (c) tearing of wedges from the con-
strained matrix with debonding of calcium carbonate reinforcement particles
at a strain of ∼3.
At high displacement rates of 100 mm/min (strain rate
∼ 0.033 s−1 ) and greater, the deformation of the fibrils and
their separation from the matrix appears to have been ob-
structed by the ridges in a manner similar to neat polyethylene
(Fig. 5) leading to layered type of fibrillation. An illustration
of this for 20% calcium carbonate-reinforced polyethylene
composites is presented in Fig. 12. It is pertinent to indi-
Fig. 10. SEM micrographs of tensile deformed 10% calcium carbonate-
reinforced high-density polyethylene composites at a displacement rate of
50 mm/min (strain rate ∼ 0.017 s−1 ) showing formation of wedges and ridges
at strains of: (a) ∼1; (b) ∼3, and; (c) tearing of wedges from the constrained
matrix with debonding of calcium carbonate reinforcement particles at a
strain ∼6.
cate here that unlike neat polyethylene, in 5, 10, and 20%
calcium carbonate-reinforced polyethylene, crazing was not
observed. It is likely that calcium carbonate reinforcement
particles modify the local stress field such that crazing is in-
hibited. This is currently being examined.
The final fracture at all the displacement rates investi-
gated occurred by fibrillation. However, there was differ-
ence in the nature of fibrillation, which was dependent on
the displacement rate of tensile test and the percent cal-
 R.D.K. Misra et al. / Materials Science and Engineering A 384 (2004) 284–298
Fig. 11. SEM micrographs of tensile deformed 20% calcium carbonate-
reinforced high-density polyethylene composites at a displacement rate of
50 mm/min (strain rate ∼ 0.017 s−1 ) showing formation of wedges and ridges
at strains of: (a) ∼1; (b) ∼2, and; (c) tearing of wedges from the constrained
matrix with debonding of calcium carbonate reinforcement particles at a
strain of ∼3.
cium carbonate reinforcement. At low displacement rates of
50–125 mm/min (strain rate ∼ 0.017–0.04 s−1 ), the fracture
surface was non-layered or continuous fibrillation for all the
investigated 5, 10, and 20% calcium carbonate-reinforced
polyethylene composites. An illustration of non-layered fib-
rillation is presented in Fig. 13. At intermediate displace-
ment rate of ∼ 250 mm/min (strain rate ∼ 0.083 s−1 ), and
295
Fig. 12. SEM micrographs of tensile deformed 20% calcium carbonate-
reinforced high-density polyethylene at a displacement rate of 380 mm/min
(strain rate ∼0.125 s−1 ) showing formation of wedges and ridges at a strain
of: (a) ∼0.3; (b) ∼0.4, and; (c) tearing of wedges from the constrained matrix
with debonding of calcium carbonate reinforcement particles at a strain of
∼0.9.
with increase in percent reinforcement of calcium carbon-
ate, polyethylene composites exhibited increased tendency
towards completely non-layered or continuous fibrillation to
mixed non-layered + layered fibrillation and finally layered
fibrillation (Fig. 14). The center of the fracture surface (mid-
thickness) was non-layered and away from the center was lay-
ered fibrillation, in line with the presence of high hydrostatic
296 R.D.K. Misra et al. / Materials Science and Engineering A 384 (2004) 284–298

Fig. 13. (a) SEM micrograph of the fracture surface of 20% calcium carbonate-reinforced high-density polyethylene at a displacement rate of 125 mm/min
(strain rate ∼ 0.042 s−1 ) showing non-layered or continuous fibrillation.

Fig. 14. (a) SEM micrograph of the fracture surface of 20% calcium carbonate- reinforced high-density polyethylene at a displacement rate of 100 mm/min
(strain rate 0.033 s−1 ) showing mixed fibrillation mode of fracture: non-layered fibrillation in the center (a, b) and; layered fibrillation away from the center
(a, c).
 R.D.K. Misra et al. / Materials Science and Engineering A 384 (2004) 284–298 297

Fig. 15. SEM micrograph of the fracture surface of 20% calcium carbonate-reinforced high-density polyethylene at a displacement rate of 300 mm/min (strain
rate ∼ 0.1 s−1 ) showing layered fibrillation.

Table 2
Nature of fracture surface morphology of calcium carbonate-reinforced polyethylene composites tensile tested at different strain rates
Displacement rate of tensile test 5% CaCO3 –PE composite 10% CaCO3 –PE composite 20% CaCO3 –PE composite
(mm/min) (strain rate, s−1 )
50 (0.016) Non-layered fibrillation Non-layered fibrillation Non-layered fibrillation
125 (0.04) Non-layered fibrillation Non-layered fibrillation Non-layered fibrillation
250 (0.083) Non-layered fibrillation + commencement of Non-layered fibrillation + Layered fibrillation
layered fibrillation layered fibrillation
380 (0.125) Non-layered fibrillation + layered fibrillation Layered fibrillation Layered fibrillation

in the mid-thickness of the sample that promotes enhanced
deformation of fibrils.
At high displacement rates of ∼300 mm/min (strain rate
∼ 0.1 s−1 ), the fracture was a mixed type, i.e. layered +
non-layered for 5% calcium carbonate-reinforced polyethy-
lene composites (similar to Fig. 14), while for 10 and
20% calcium carbonate-reinforced polyethylene compos-
ites, it was predominantly layered fibrillation (Fig. 15). The
characteristics of the fracture surface are summarized in
Table 2.
From the above observations, it can be concluded that
at displacement rates greater than 50 mm/min (strain rate
∼ 0.017 s−1 ), addition of calcium carbonate to polyethy-
lene suppresses crazing (large number of tiny voids interdis-
persed between deformed fibrils). Instead wedge/ridge tear-
ing is the primary micromechanism of plastic deformation
in calcium carbonate-reinforced polyethylene that leads to
fibrillated fracture. Considering that voids present in crazed
zone are potential light scattering entities providing white
appearance (i.e. stress whitening), an important implication
of the addition of calcium carbonate is in the minimization
of stress whitening. In fact, calcium carbonate-reinforced
samples exhibited reduced susceptibility to stress whitening
(lower opacity) compared to unreinforced neat polyethylene.
It is striking to note that in the present study displace-
ment rates were varied from 50 to 380 mm/min (strain rate
0.017–0.125 s−1 ), while the extent of cold drawing in neat and
calcium carbonate-reinforced neat high-density polyethylene
varied by more than ten times and the stress–strain behavior
exhibited a notable change. This behavior is attributed to the
strain rate sensitivity of the investigated materials and the
change in the micromechanism of deformation with strain
rate. The strain rate sensitivity behavior is discussed in detail
in a recent work [48].
4. Conclusions
(a) The reinforcement of neat polyethylene with 5–20% cal-
cium carbonate increased the tensile modulus, however,
a clear discernible effect on yield strength was not appar-
ent.
(b) The addition of calcium carbonate to neat polyethy-
lene enhanced crystallization to a small extent,
298 R.D.K. Misra et al. / Materials Science and Engineering A 384 (2004) 284–298
but the increase in percent bulk crystallinity was
significant.
(c) The extent of cold drawing of polymer matrix decreased
with increase in strain rate of tensile test and with increase
in percent calcium carbonate reinforcement in calcium
carbonate-reinforced polyethylene composites.
(d) The reinforcement of neat polyethylene with calcium
carbonate changes the primary mode of plastic defor-
mation process from crazing-tearing in polyethylene
to wedge/ridge tearing in calcium carbonate-reinforced
composites. The ridges in calcium carbonate-reinforced
composites are formed due to stress relaxation of the
polymer matrix.
(e) The mode of fracture in neat polyethylene is crazing-
tearing and fibrillation, while in calcium carbonate-
reinforced composites, the mode of fracture is fibrillation.
However, the nature of fibrillation in polymer matrix (lay-
ered or non-layered) depends on percent reinforcement
and strain rate of tensile test. High strain rate and high
percent reinforcement favor predominantly layered fib-
rillation.
Acknowledgments
University of Louisiana grant # LEQSF (2003–05)-RD-
B-08 for the work presented here.
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