Polymer Toughness and Impact Resistance

WILLIAM G . PERKINS

Polyester Technical Center

Shell chemical c o m p a n y
130 Johns Avenue
Akron, Ohio 44305

This report is a review of the factors that influence the impact resistance of high
polymers, with an emphasis on crystalline polymers. The phenomenology of poly-
meric fracture is examined, including brittle and ductile failure, and the ductile-brit-
tle transition temperature ( D m . A n in-depth discussion of the effects of crystalline
morphology follows, with special attention given to the influence of spherulite size,
fillers, processing conditions, transitions/relaxations, and multilayer coextrusion.
Next, rubber phase addition is considered, including mechanisms, morphology, rub-
ber type and particle size, and test conditions. Finally, common impact test methods
are surveyed, including pendulum, falling weight, tensile impact, and tensile elonga-
tion tests.

INTRODUCTION cracks or crazes form, which coalesce into larger

P olymer toughness,, in the form of impact resis-
tance, is a measure of the ability of a material or
fabricated article to withstand the application of a
sudden load without "failure". Impact resistance is
therefore a complex function of geometry, mode of
loading, load application rate, environment (thermal
and chemical), material properties such as chain
length, packing, tacticity, alignment and bonding
forces, and, of course, the definition of what consti-
tutes failure. The measured impact strength of a poly-
mer must be the result of the sum of the contributions
of all processes that dissipate any of the energy of the
impact blow. and is probably the most critical mechani-
cal property of plastics, because it relates to the service
life of the part, and involves the increasqly important
matters of product safety and liability. Impact behavior
can g e n e d y be improved three ways: 1)By optimizing
crystalline morphology (for semicrystalline polymers).
2) By incorporating i t discrete rubbery p h a s e (via
blending or copolymerimtion). 3) By adding a (usually
fibrous) reinforcement to the polymer matrix.
The present review will discuss the first two tech-
niques, and also recount the various impact test meth-
ods commonly used to evaluate polymer toughness,
and their applicability and/or correlation to actual
end-use conditions. The third technique will not be
discussed.
PHENOMENOLOGY
General
Under an applied stress, chemical bonds are stressed.
As stress increases, they break, and small submicro-
cracks (1). After these cracks are thus initiated, they
then propagate to failure. A polymeric structure that
resists crack initiation may not resist crack propaga-
tion, and vice versa, so impact tests that focus on one
over the other may give misleading results regarding
the sample's impact resistance (2).There are two gen-
eral modes of failure: brittle fracture, characterized by
a linear relationship (as on a load-deflection plot) be-
tween impact load and sample deflection, and ductile
fracture, characterized by plastic yielding. This yield-
ing is manifested in the load-displacement curve as a
decrease in the slope of the load-displacement curve,
prior to failure. Brittle fracture is frequently a result of
highly localized crazing [crazes are pseudo-cracks, ori-
ented normal to the stress direction, and spanned by
cold-drawn elongated fibrils of the material, which
can carry load and thus maintain the structural in-
tegrity of the sample (3)], confined to a very small
volume of the material. Ductile fracture, on the other
hand, may be broken down into either multiple craz-
ing, wherein crazes are initiated in a comparatively
large volume of the polymer, i.e., a multiple deforma-
tion mechanism, or shear yielding (plastic flow with-
out crazing). If, upon examination of a fractured spec-
imen, it is not clear which mechanism is dominant, it
is usually because, under the given test or application
conditions, the mechanisms are competing, and no
single one is overwhelmingly favored. In measure-
ments of tensile strength or fatigue under tension, for
example, it is possible to get mixed failure modes,
with crazes and shear deformation zones occurring in
the same specimen (4). Although crazing has tradi-
tionally been associated with fracture in amorphous

POLYMER ENGINEERING AND SCIENCE, DECEMBER 1999, Vol. 39, No. 12 2445
 William G. Perkins
polymers, it has also been noted as a mechanism in
crystalline polymers (5, 6).Crazes have been observed
traveling both through crystalline spherulite centers,
and through the noncrystalline material between
spherulite boundaries (5).
A pioneer in fracture mechanics, Griffith (7) postu-
lated that rupture produces a new surface area and
for rupture to occur, the increase in energy required
to produce the new surface must be balanced by a de-
crease in elastically stored energy. To explain the large
discrepancy between the measured strength of mate-
rials and that based on theoretical considerations,
GriRth proposed that the elastically stored energy is
not distributed uniformly throughout the specimen,
but is concentrated in the neighborhood of small
cracks. kacture would thus occur via spreading of
the cracks, which originate in pre-existing flaws, or
defects, which in turn may include pre-existing cracks,
notches, embedded particles, and voids. Through the
stress concentration that they cause, material defects
are thus seen as the origin of crazes and cracks, and
defect irregularities in size, shape, position. and na-
ture generally are considered to be responsible for the
observed scatter of polymer ultimate properties.
GriBth's theories laid the groundwork for what would
become known as Linear-Elastic Fracture Mechanics
(LEFM) and are even today useful in studying brittle
materials. Since polymers are viscoelastic materials,
however, strict LEFM theory cannot be applied, and
the total work of fracture must include the various
forms of plastic deformafion, which appear prior to and
during failure (8,9). In particular, three points should
be considered (8):
1) Because of the relatively low yield stress values of
many plastics, plastic deformation at the crack
tip is far more likely to occur.
2) While a small degree of dissipative energy can be
accommodated in the overall work of fracture, it
is obvious that as this assumes greater signs-
cance, there is a much greater possibility that a
fracture mechanics approach will lose its general
validity.
3) Plastics properties such as fracture toughness
and yield stress are dependent on many variables
appropriate to fracture testing, and for a given
material, the test conditions necessay to ensure
validity are therefore quite restricted.
The bottom line is that the major problem in apply-
ing fracture theory to polymers is to assess the extent
to which the plastic deformation zone at the crack tip
influences the resulting fracture behavior (8).
Brittle Fracture
In brittle fracture, failure occurs in a brittle fashion
at both the microscopic (local)and macroscopic (bulk)
level. A familiar example of brittle fracture is the shat-
tering of ordinary (silica-based) window glass, when
hit by a stone. Although most polymeric materials are
less susceptible to brittle fracture than ordinary glass,
2446 POLYMER ENGINEERINGAND SCIENCE, DECEMBER 1999, Vol. 39, No. 12
they can all be made to undergo this phenomenon
under the nght set of conditions. For example, at ex-
tremely low temperatures (below -1OOOC) natural rub-
ber (NR) will shatter and experience brittle fracture
just like glass.
In brittle fracture, localized crazes initiate, grow,
and break down to give cracks at stresses below those
necessary to cause bulk shear yielding, and so lead to
brittle fracture often requiring only a relatively low
value of fracture energy. There is little or no large-
scale plastic flow during this process, since the mobil-
ity of the polymeric subunits is too low. Brittle fracture
has been explained in terms of (a)the aforementioned
defect mechanism (7) involving a "characteristic flaw
size," and (b) the energy required for bond breaking
(10).According to Bicerano (4), the defect mechanism
theory provides a better description of the fundamen-
tal physics of the phenomenon, whereas it has proven
easier to develop a simple predictive structure-proper-
ty relationship for the brittle fracture stresses of poly-
mers in terms of bond breakage.
DuctileFractare
Unlike brittle fracture, ductile fracture requires suf-
ficient mobility of the polymeric chain segments for
plastic flow to occur at a local (molecular)level. Both
multiple crazing and matrix shear yielding can there-
fore be considered to be ductile at a microscopic level.
On the other hand, at a macroscopic level, shear yield-
ing by homogeneous and continuous plastic deforma-
tion, is much more ductile than the heterogeneous
processes of (a)cavitation, 03) craze nucleation, propa-
gation and breakdown, and (c) crack propagation,
which are the stages of failure via crazing (4).Typical
parameters that favor ductile behavior are w, as
opposed to bisudal or trbxial conditions, elevated tem-
peratures, relatively low rates of deformation, and an
absence of agressive environments.
A rule of thumb is that, all other factors being equal,
the polymer with the most ductile mode of failure will
be the most useful one. Failure by either multiple
crazing or matrix shear yielding is therefore to be
favored over failure by brittle fracture. The desired
mechanism between multiple crazing and shear yield-
ing, however, is not always as clear-cut, and depends
on additional factors, such as whether the specimens
are notched or unnotched. but shear yielding is prefer-
able in most cases, being more efficient at dissipating
energy (4). Many brittle polymers are 'toughened" by
modification, for example by the incorporation of rub-
ber particles, as dicsussed below. Depending on the
nature of the polymer, toughening can occur by im-
parting either the ability to craze more effectively, as
in polystyrene (PSI (11).or by enhancing the ability to
more easily undergo shear yielding, as in polyamide
(PA) (12).
A good defmition of ductile (tough) and brittle (weak)
behavior comes from the stress-strajn curve. Brittle
behavior is designated when the specimen fails at its
 Polymer Toughness and Impact Resistance
maximum load at a comparatively low strain (<20?40)
(13). usually dissipating minimal energy. At the test-
ing speeds under which practical impact tests are
conducted, it is difficult to determine the stress-strain
curve, so impact strengths are customarily quoted in
terms of the measured fracture energy and fracture
surface appearance, of a standard specimen. It should
be kept in mind, as Ward (13) points out, that high
impact strength does not necessarily imply ductile
failure, nor does brittle fracture necessanly imply low
impact strength. Glass-reinforced polyester, for exam-
ple, can have an extremely high impact strength, even
though it fractures in a brittle manner. Generally
speaking, though, ductility imparts greater impact re-
sistance, in most materials.
Ductile-Brittle Transition
At some temperature, depending on the structure
and morphology of the polymer, the geometry of the
specimen, and the nature and speed of the test or other
energy input, a polymeric material undergoes what is
known as a ductile-brittle transition. Below this temper-
ature, known as the dudik-brittle transition temperature
(DB?T), the material breaks in a briffle (usually low im-
pact energy) manner: above this temperature, the ma-
terial breaks in a ductile (usually high impact energy)
fashion. Because polymeric transitions and relaxations
tend to shift to higher temperatures when the time
scale of the experiment is shortened, the ductile-brittle
transition will be shifted to higher temperatures as the
speed of the impact event is increased. Although a duc-
tile-brittle transition also occurs with most metals, with
plastics the transition fkequently occurs in the temper-
ature range critical for design purposes. Because all
plastics are brittle under certain conditions, the loca-
tion of the ductile-brittle transition is therefore of para
mount importance to the plastic part designer, who
must choose a material and part geometry such that
conditions inducing the switch to brittle behavior are
unlikely to occur duririg use.
A final consideration regarding polymer fracture is
the time-temperature superposition principle (14) and
how it influences the fracture mechanism. At low tem-
peratures, or high testing speeds, brittle fracture usu-
ally predominates, as it requires the least failure
stress. Measured strengths in this fracture regime are
considered brittle strengths. As temperature is raised
some arbitrary amount, (or test speed lowered), multi-
ple crazing next becoines dominant, followed by shear
yielding at still higher temperatures (4). Measured
strengths in these fracture regimes are commonly
known as yield strengths, since the specimen yields
(before flowing plastically). In other words, at low tem-
peratures the yield strength is higher than the brittle
strength, so failure is in the brittle mode. As the tem-
perature is increased, the yield strength decreases
faster than the brittle strength, and at some point (the
DEIT) falls below the brittle strength, and failure then
becomes ductile.
POLYMER ENGINEERING AND SCIENCE, DECEMBER 1999, Vol. 39, No. 12
CRYSTALLINE MORPHOLOGY
General
The impact properties of semicrystalline polymers
are normally relatively good compared with those of
glassy polymers. Although Tg and molecular weight
are still important, the most ovemding factor which
controls the fracture behavior is their morphology.
The mode of crystallization in a bulk polymer is gener-
ally spherulitic (15), the spherulites consisting of
skeletal crystalline lamellae or fibrils radiating from a
common center (16).As growth proceeds from these
bundles of fibers that fan out gradually like wheat
sheaves, the fibrils branch noncrystallographically
a n d assume spherical symmetry (16). Keith a n d
Padden (17) have shown that during crystallization, a
fractionation process occurs such that impurities, re-
jected by the growing crystallites, tend to diffuse away
radially from the spherulites rather than to accumu-
late between the lamellae. Although this accumulation
of impurities at the boundaries of spherulites tends to
separate the spherulites, they are, in fact, tied togeth-
er by molecules running through more than one
spherulite and known as intercrystalline links (18).
These intercrystalline links also reinforce individual
spherulites by joining the lamellae. The result is a
semi-continuous crystalline phase throughout the
polymer. The behavior of these tie molecules may be
compared with entanglements in amorphous thermo-
plastics: both are responsible for the strength of the
polymers and without them both types of polymer are
extremely weak.
Semicrystalline polymers usually exhibit high im-
pact strength if their glass transition temperature (TJ
is well below the temperature at which the test is car-
ried out. The impact strength in this case varies in-
versely with the percent crystallinity, although if the
crystallites are small and imperfect, they may actually
increase impact resistance (19).If the Tgis above the
test (or end-use) temperature, increasing crystallinity
again lowers the impact strength, provided the materi-
al is not oriented. It is likely that crystallites, in this
case, act as stress concentrators, causing the stress
acting on a small volume of the material to be much
greater than the average stress applied to the whole
sample. As a result, the material breaks at a stress
that is less than the expected critical value. Also,
crystallites are seen to reduce multiple crazing (20).
and shear yielding (2l),both energy-dissipative mech-
anisms of polymer matrices.
Spherulite Size
As mentioned earlier, unoriented semicrystalline
polymers tend to form spherulites (spherical aggre-
gates of crystallites) when either heated from below
their Tgor cooled from the melt. The size and number
of these crystalline structures have a profound influ-
ence on impact resistance. I t is generally agreed that
impact resistance is inversely related to spherulite size
(22-26). This may be due to the presence of strained
2447
 William G. Perkins
amorphous material between large spherulites, or to
defects within the spherulites themselves, formed
during growth.
Within limitations, spherulite size can be controlled,
either via crystal nucleating agents,or through changes
in processing conditions. Also, percent crystallinity
and spherulitic texture can be independently varied,
to optimize end-use properties.
Some early studies have shown the relationship be-
tween crystalline morphology and impact resistance.
Ohlberg et aL (22) studied crystallization in high den-
sity poly(ethy1ene) (HDPE), and found that Gardner
impact strength decreased from >6.9 Joules to 0.8
Joules as spherulite size increased from 3.5 to 6.8
pm. They also found that for a given spherulite size,
impact strength increased as the polymer molecular
weight decreased. In other words, to maintain a con-
stant impact strength using a higher molecular weight
polymer, the spherulite size had to be reduced. These
authors controlled spherulite size by altering the cool-
ing rate of their melt samples. Percent crystallinity
was not specified.
Hammer et aL (23),working with poly(oxymethy1-
ene) (POM) found that samples with larger spherulites
lost ductility as the testing rate was increased. Barrish
(24)noted that the size of spherulites grown under in-
dentical conditions influenced whether spherulites
would crack or be drawn out. He found that complete-
ly spherulitic films of isotactic poly(propy1ene) (PP)
cracked while smaller spherulites in incompletely
spherulitic films tended to be drawn out. Reding and
Brown (25) applied various thermal techniques to
poly(chlorotrifluoroethy1ene)(PCTFE) and observed
that the spherulites in their quenched and subse-
quently reheated polymer did not become as large as
those in the sample slowly cooled from the melt, nor
did the quenched and reheated polymer become as
brittle as the melt-cooled polymer. They further noted
that the greater brittleness of the slowly cooled poly-
mer almost certainly arose from the larger and greater
number of spherulites. Working with injection molded
PP and POM, Wright et al. (26) noted that for POM,
both yield force and total (impact) energy decreased
with increasing spherulite size. For PP, results were
masked by the existence of an impact transition in
the region of the selected test temperature (23C).but
this DBTT was seen to decrease with decreasing
spherulite size
Starkweather et al. (27), working with nylon 66
(PA66) and nylon 610 (PA610),observed that impact
strength decreased with increasing sample crystallinity,
and that at a constant level of crystallinity, impact re-
sistance increased with higher molecular weight, within
the approximate number-average molecular weight
(Mn) range of 12,000 to 24,000. Spherulite sizes were
not specified: however, these authors did show experi-
mental results that suggested that large spherulites
have an adverse effect on PA toughness only when their
diameter is an appreciable fi-action of the test section
thickness. In a related study, Starkweather and Brooks
2448 POLYMER ENGINEERING AND SCIENCE, DECEMBER 1999, Vol. 39, NO. 12
(28)evaluated the effect of remolding on the spherulite
size of PAM. They molded the the PA66 into test bars
that produced spherulites 25-30 pm in diameter. These
test bars were then cut up and remolded several times.
As the number of remolds increased, the spherulite
size decreased markedly.
Bessel et aL (29) investigated the effect of structure
and morphology on the mechanical properties of dry
nylon 6 (PA6).They found that the behavior depended
most strongly upon the degree of crystallinity, with
spherulite size having only a secondary effect. Speci-
mens with a degree of crystallinity in excess of 40%
were brittle, whereas at low levels of crystallinity
(<30%),the material was ductile.
Menges and co-workers (30)reviewed how mechani-
cal properties are affected by crystallinity, spherulite
structure, and spherulite size. They pointed out that
failure sites are found at boundary surfaces of lamel-
lae and become more prominent as the size,complete-
ness, and internal structure of spherulites increase.
Single large failure sites where fracture energy is con-
centrated promote much more microcrack initiation
than does a distribution of many small sites, wherein
the energy dissipation occurs in the largest possible
volume of material. These authors concluded that a
coarse spherulitic material tends to be more brittle
than a finely granular structure with the same pro-
portion of crystallites, and therefore a morphology
containing adequately small spherulites was recom-
mended for achieving the greatest possible impact
strength. It should also be kept in mind that the dis-
tribution of crystallinity, and the crystallite/spherulite
size will be influenced by the differential cooling rates
commonly observed between the surface and interior
of molded or extruded articles.
The effect of the fine structure of acetal resins on
mechanical properties was investigated by Hammer et
aL (23).who found the major effect was on toughness.
They observed that brittle failure usually consisted of
crack propagation along a spherulite surface, but that
it could also be found to propagate through a spheru-
lite. Ductility, on the other hand, seemed to consist of
a cold drawing from the surface of a spherulite. Sam-
ples with larger spherulites lost ductility as the testing
rate was increased. Both spherulite and crystallite
size decreased with decreasing quench temperature,
but the major effect on properties appeared to be that
due to variations in spherulite size.
Friedrich (31)studied PP having different molecular
weights and tacticities by using a variety of heat treat-
ments to produce morphologies ranging from fine
(-20pm dia.) spherulites to coarse (-500pm dia.)
spherulites. He found that cracks propagated most
easily at the interfaces between coarse spherulites.
The resistance to this type of failure increased with
increasing PP molecular weight, likely due to more
plastic deformation occurring at the spherulite bound-
aries, since higher molecular weight material has
more intercrystalline and interspherulitic links (tie
molecules).
 Polymer Toughness and Impact Resistance
Way and co-workers (32) found that spherulite size
had a pronounced effect upon the deformation char-
acteristics of PP. They presented stress/strain curves
in which PP spherulite size was varied by using differ-
ent heat treatments. The material with the largest
(-250pm dia.) spherulntes was brittle, but became
more ductile as t h e spherulite size was reduced.
Material with a spherulite diameter of only 92pm was
so ductile that it could 'be drawn to strains in excess
of 700%. The brittleness of the slow-cooled material,
with the largest spherulites, was attributed to segre-
gation of impurities and void formation at spherulitic
boundaries.
Working with HDPE and poly(butene- 1) (PB-1).
Haas and MacRae (33, 34) observed that both ductile
and brittle fracture in biaxially stressed films originat-
ed either at spherulite centers or at boundaries be-
tween spherulites. T h q speculated that material het-
erogeneities that originally nucleated the spherulites
were also likely to act as stress concentrators to initi-
ate cracks. They found an increasing tendency toward
brittle fracture with decreasing molecular weight, and
attributed this to a higher concentration of impurities,
and to fewer tie molecules available to connect the
spherulites, in the interspherulitic regions.
When evaluating the various aspects of morphology
and their influence on irnpact resistance (aswell as other
physical/mechanical properties), one must keep in
mind that these parameters are strongly interrelated,
and if one ignores this interaction, conclusions based
on a single parameter might not be entirely accurate.
FiUera
McGenity and co-workers (35)investigated the effect
of PP crystallization using talc and calcium carbonate
(CaCO,) fillers a t different loading levels. They fol-
lowed spherulite growth rate a n d determined the
number of nucleating sites per unit volume of poly-
mer, and per unit area of mineral surface. Talc values
were considerably higher than those for CaCO,, indi-
cating more efficient nucleating ability. The presence
of filler affected not only the nucleation and kinetics of
crystallization, but also the crystallinity and orienta-
tion indices and proportion of P-phase crystallites pre-
sent. Impact properbes were determined, in part, by
crack pinning and blocking by filler particles, stress
concentration at the edges of the filler particles, and
the nucleating ability of the filler.
In a n earlier effort by the same research group (36).
usmg mineral-filled PP, it was determined that impact
strength depends ori both the size and shape of the
filler, and is also aflected by micromorphology. These
researchers postulated that impact strength is en-
hanced by small, low-aspect-ratio filler particles,
whereas Large particles act as flaws that can initiate
cracks, and high-aspect-ratio particles have large
stresses near their edges that facilitate failure. They
also stated that the micromorphology of the matriv is
important, and is affected by the presence of the filler
POLYMER ENGlNEERl" AND SCIENCE, DECEMBER 1999, Vol. 39, No. 12
particles. They observed that poor impact strength
correlated with a high capacity for nucleation of crys-
tallization from the melt, a n d attributed this to
boundary layers between spherulites that were weak-
ened by the presence of filler particles.
Rocewing Condltioncl
A study by Murphy et d (37) focused on the effect
of injection molding conditions on the micromorphol-
ogy and impact strength of isotactic PP. Increasing
the melt temperature reduced the extent and depth of
a row nucleated lamellar shear band (found below
the highly oriented skin), and spherulite nucleation,
resulting in improved impact properties. Increasing
the mold temperature (to 70C) did not sigmficantly
affect the extent and width of the banded morpholo-
gy, but caused the formation of a transcrystalline
brittle surface layer which reduced the impact resis-
tance. A combination of high melt temperature, low
mold temperature, and fast injection time resulted in
optimum impact strength distribution along the melt
flow direction.
The effect of injection molding conditions on isotactic
PP and isotactic ethylene-propylene (EP) copolymers
was studied by Fujiyama and Azuma (38).For the high-
est impact strength specimens, they observed oriented
layers near the specimen center, formed by flow accom-
panied by crystallization shrinkage. They found it nec-
essary to balance mold gate size, holdmg pressure, vis-
cosity, and crystallization time, to obtain molded
articles with maximm tensile impact strength.
Ragosta and co-workers (39)investigated the corre-
lation of crystallization conditions, structure, and im-
pact properties for isotactic PP. They defined a critical
strain energy release rate (GJ, proportional to impact
strength, which decreased linearly with increasing
crystalline lamellar thickness for both annealed and
unannealed samples. They observed, concurrently,
that lamellar thickness increased and G, decreased,
with increasing crystallization temperature, and as-
cribed this to the fact that an increase in lamellar
thickness causes a decrease in the number of intra-
spherulitic links (18). leading to a decrease in G,,
since the latter is sensitive to both intra- and inter-
spherulitic link densities.
Another study on the effect of processing conditions
on impact strength was done by Fleischer and Brand-
rup (40). using extruded profiles of poly(viny1 chloride)
(PVC)/ chlorinated polyethylene (CPE) blends. They
found that processing at low temperatures resulted in
insufficient mixing and subsequent poor properties.
Higher processing temperatures caused disintegration
of WC particles and optimum mixing of the two phas-
es into a co-continuous morphology, providing excel-
lent impact strength. Raising processing temperatures
still further, to greater than 200"C, caused decompo-
sition of W C primary particles and resulted in phase
conversion to a sphere-in-matrix phase morphology,
and poor mechanical and rheological properties.
2449
 William G. Perkins
m M O - O M
The effect of structure on polycarbonate (PC)impact
strength was investigated by Wyzgoski and Yeh (41).
They proposed that the large decrease in impact
strength observed with annealed PC was not due to
changes in density or the (low temperature) p-transi-
tion, but rather seemed to be associated with in-
creased nodular structures restricting larger chain
motion.
Turley (42) also studied the relationship between
polymer structure and impact strength. He noted that
a transition shown by a maximum in the dynamic
mechanical damping curve does not always indicate
good impact properties. A maximum due to the mo-
tion of long segments of the main chain associated
with the Tg,however, is important. Secondary transi-
tions below Tg(and, of course, below the test tempera-
ture) usually contribute to good impact properties, as
long as the DBTT does not increase to a temperature
above the test temperature, due to the speed of the
test, and as long as the secondary transition is due to
movement within the main chain, not side chains (42,
43). Bisphenol-A polycarbonate is an example of a
polymer with a useful secondary transition below Tg
Turley showed that in a rubber-modified PS, the Tgof
the added rubber serves as a secondary transition or
relaxation that contributes to the impact strength of
the modified polymer. While the production of crazes
was not seen as the best way to improve polymer im-
pact strength, the energy required to generate them
does decrease the amount of energy (from the impact
blow) available for initiating and propagating large
rupture cracks. Any other gross deformation, tearing,
or plastic drawing during impact also lowers the
amount of energy available for rupture.
Multilayer Coartrclmion
One other aspect of morphology that relates to im-
pact resistance should be mentioned: micro- or multi-
layer coextmsion (44), a novel coextrusion technique,
which has been around quite some time (original
patents have expired), but has not as yet seen signifi-
cant commercial application. The process uses a se-
ries of dies, called layer-+lying devices, attached
to the ends of multiple extruders, which permit two
(or more) polymers of widely dissimilar solid state
properties to be combined into unique microlayer and
nanolayer structures with hundreds or thousands of
alternating layers. (If the layers become thin enough,
one is effectively dealing with surface chemistry and
physics.) The process is currently being utilized by
several research laboratories for fundamental studies
of phenomena such as interfacial interdiffusion, adhe-
sion, and impact behavior.
In one study using this technique, Sung et aL (45)
studied the behavior of PC and styrene/acrylonitrile
(SAN), materials that deform by shearbanding and
crazing, respectively, and that also exhibit the good
interfacial adhesion required for stress transfer under
2450 POLYMER ENGINEERINGAND SCIENCE, DECEMBER 1999, WoL 39, No. 12
conditions of high local strain. They noticed two types
of crazes in the SAN component of a composite sheet
consisting of 49 alternating layers of the two materi-
als, deformed in uniaxial tension: surface crazes and
so-called tunnel crazes. A transition from predomi-
nately surface crazing to predominately tunnel crazing
occurred as the PC-SAN layer thickness ratio was de-
creased, or as the strain rate was increased. Surface
crazes did not prevent localized yielding and stable
neck propagation, whereas tunnel crazes were associ-
ated with this loss of ductility.
These workers also observed that the surface crazes
produced microshecubandingin neighboring PC layers
where the crazes impinged on the PC-SAN interface. A
three-dimensional model of interactive surface crazing
and microshearbanding was proposed in which mi-
coshearbands initiate first in the PC layers and propa-
gate rapidly along the edges of the craze. When they
overtake the craze tip, they penetrate through the in-
terface and continue around the craze tip to entirely
engulf the craze. This terminates craze growth, and
further strain in the SAN layer is accommodated by
shear deformation.
In a variation of the microlayer technology, Yuan
and co-workers (46). working with sections cut from
various positions on the walls of a blow molded
HDPE/PA blend automotive fuel tank,obsenred that
the PA formed discontinuous layers, 'flakes," within
the composite. Using hod, Charpy, and falling dart
impact tests, the authors found that the impact
strength strongly depended upon the microstructure:
the more regular the layering of the PA flakes (from
the point of view of individual layer thickness and in-
terlayer distance), the higher the energy absorption
during impact.
RUBBER TOUGHElllIllJG
General
Rubber toughening should impart greater ductility.
improved crack resistance, and higher impact strength
to the material, accompanied by only a small loss in
stiffness and without a detrimental effect on thermal
stability. According to Partridge (47) a polymer might
be considered to be successfully rubber toughened if
its fracture resistance under a particular set of con-
ditions is increased by a factor of 10, while its low-
strain stiffness decreases by no more than about 25%.
The Tg of the matrix should not change. Other re-
searchers might accept less impact improvement in
order to maintain greater stiffness.
Because polymeric materials are viscoelastic, they
generally exhibit a geometry and strain-rate depen-
dent ductile/brittle transition. This has to be kept in
mind when using data for design purposes. Leevers
(48) recently presented a theory of impact and dynam-
ic fracture in semicrystalline polymers that correlates
impact resistance to bulk material properties. He con-
cluded that there appears to be no mechanism that is
truly independent of geometry or impact speed.
 Polymer Toughness and Impact Resistance
In addition to geometrical and rate considerations,
each rubber-toughened system h a s a temperature
limit, below which the toughening becomes ineffective.
This lower-limit temperature, at a given strain rate, is
dependent on the nature of the rubber and occurs
when the viscoelastic response of the rubber becomes
too slow to respond to the applied stress (49). The
rubber then behaves in an essentially glassy manner,
and any toughening contribution can only come about
by processes such as crack pinning (50),which ab-
sorb much less energy than shear yielding and multi-
ple crazing.
Mechanisms
Almost any engineering plastic can be made tougher
by the addition of a srnall amount of rubbery material.
One theory is that the rubber becomes stretched dur-
ing the fracture process and absorbs a great deal of
energy. Another theory proposes that the rubber par-
ticles act to introduce a multiplicity of stress concen-
tration points, promoting multiple crazing, which lead
to cracks which propagate during the fracture process,
requiring greater energy than a single crack, due to
the production of more new surfaces (relating the
fracture energy to the new surface area by GriIXths
(7)theory of fracture). Cheng et aL (51) propose that
the addition of a rubbery phase introduces cavitation-
al mechanisms that relieve the hydrostatic strain en-
ergy and enhance shear yielding of the matrix.
The concentration of stress which initiates local
yielding in the matrix is just the first step in a com-
plex process. As the overall applied stress increases,
the matrix will deform, and impact energy will be
dissipated by multiple crazing. by shear yielding, or
both. Whether a rubber-modified polymer deforms by
multiple crazing, shear yielding, or a combination of
the two depends entirely on the nature of the matrix.
When the craze initiation stress of the matrix is lower
than the yield stress, the failure mechanism is by
multiple crazing, and rubber toughening is mainly
achieved by the dispersed rubber particles acting as
craze initiators. ConveIsely, if the craze initiation stress
is tugher than the yield stress, the matrix will fail by
shear yielding, and toughening is then usually achieved
by the dispersed rubber particles acting as initiators
of shear bands. Mixed crazing and yielding is thought
to occur when the craze initiation stress and the yield
stress are comparable, or when certain interactions
occur between shear bands and crazes (52).
A popular model of rubber-reinforced polymer stress
response is the efiective area model of Ishai and Cohen
(53).The crack, craze, or shear band is assumed to
follow a surface of least resistance by passing through
the equator of each low modulus (or debonded) parti-
cle in its path, thus minimizing the area of matrix SIX-
face involved. Stress fields around individual particles
overlap, once a critical concentration of particles is
exceeded. The overall stress at which bulk yielding
can be initiated is therefore dependent on the particle
POLYMER ENGINEERINGAND SCIENCE, DECEMBER 1999,VOI. 39, NO. 12
volume fraction and spatial distribution, as well as on
the critical stress needed for the start of shear band
or craze growth in the matrix. Finally, the presence
and the nature of the rubber particles will influence
the strain rate/temperature dependence of yield in the
rubber-modified polymer, as well as post-yield proc-
esses such as creep, and fracture/fatigue resistance.
Bucknall(54)proposed that the rubber particles have
two separate but equally important functions. First,
under an applied stress, crazes are initiated at points of
maximum triaxial stress concentrations, which are
usually near the equators of the rubber particles. The
crazes then grow approximately normal to the maxi-
mum applied stress. Second, the rubber particles are
craze terminators, preventing the growth of very large
crazes. The result is that a large number of small
crazes are generated, in contrast with the small num-
ber of large crazes formed in the same polymer in the
absence of rubber particles. This multiple CI-aZing that
occurs throughout a comparatively large volume of rub-
ber-modified material explains the high energy absorp-
tion in fracture tests and the extensive stress whitening
that accompanies deformation and failure.
Hourston et aL (55) studied commercial grades of
rubber-toughened poly(buty1ene terephthalate) (PBT)
using various test procedures. Examination of frac-
tured samples via transmission electron microscopy
(TEM)revealed that stress whitening resulted from
cavitation of the rubber particles. Immediately behind
the fracture surfaces, extensive plastic yielding of the
matrix occurred, which distorted the rubber particles
into flattened ellipses.
Fumo and Nauman (56)used a process called com-
positional quenchuzg to produce a blend of a submicro
dispersion of hexafluoropropylene-vinylidene fluoride
(HFP/VDF) copolymer rubber in a poly(ether imide)
(PEI). Impact strength was sigruficantly improved, es-
pecially at elevated temperatures, ostensibly because
of the ability of the rubber particles to activate shear
yielding deformation in a large volume of the PEI
matrix near the tip of the propagating crack, thus
absorbing energy during fracture. Similar blends pro-
duced via extrusion and precipitation processes did
not perform as well.
The main failure mechanism of brittle polymers,
such as PS and poly(methy1methacrylate) (PMMA),is
the nucleation of voids and formation of localized
crazes, which lead rapidly to initiation and propaga-
tion of brittle cracks, causing catastrophic failure. At
room temperature, these polymers have yield strengths
higher than their breaking strengths, and thus have
low crack initiation and low crack propagation ener-
gies in impact, resulting in low unnotched and notched
impact strengths. They are rubber-toughened mainly
by increased matrix crazing, which allows fewer brittle
cracks to form (57).
On the other hand, the main fracture mechanism of
ductile polymers (which may be brittle under certain
test conditions), such as PA, poly(ethy1ene terephtha-
late) (PET), and PC, is either multiple crazing or matrix
2451
 William G. Perkins
shear yielding. Multiple crazing involves a large volume
of material that is able to absorb energy, whereas
shear yielding involves the creation of bands of highly
oriented, stretched material at 45" to the direction of
the applied stress. Shearbanding polymers have high
crack initiation energy, but low crack propagation
energy in impact, resulting in high unnotched impact
strength,but low notched impact strength. Notches, in
fact, usually result in brittle-type response under im-
pact conditions. Tanrattanakul et aL (58),for example,
found that with notched PET samples, the principal
deformation mechanism under all testing conditions of
temperature and rate was crazing,which resulted in
brittle fracture (an example of notch sensitivity). In
this case, plane-strain localized crazing took place be-
fore sufficient plastic flow could occur to relieve the
dilatational stresses in the interior of the sample (52).
This type of polymer (in its unnotched form) is rubber-
toughened mainly by increased matrix yielding.
Rubber particles have different effects on these two
types of polymer matrices. With brittle polymers, there
appears to be a n optimum rubber particle size at
which the toughness is greatest. This appears to be
because craze termination is important in the tough-
ening of this type matrix. Although small particles give
more termination sites per unit volume, they act with
lower efficiency at each site. With ductile polymers, the
critical rubber particle size depends on on the type of
rubber, and the rubber concentration, being smaller
for the lower concentrations (57).According to Yee and
Pearson (59) the rubber particles cavitate under im-
pact stress, relieving the buildup of hydrostatic ten-
sion. After cavitation the triaxial stresses disappear
and the matrix behaves as if it were under plane-stress
conditions, shear yielding more readily under this
stress state rather than the craze-favoring triaxial
state. The voids created by the cavitated rubber parti-
cles further act as stress concentrators.
Burgisi et aL (60) studied toughness enhancement
of PA 6 modified with different types of functionalized
elastomers. These authors point out that the neces-
sary condition for enhancement of impact strength is
that rubber particles must cavitate at a level of stress
lower than that required for crazing of the matrix, in
order to relieve triaxiality and pervent brittle fracture.
They further note that there is a lower limit of particle
diameter, below which cavitation does not occur, and
the impact behavior then drops off, toward that of the
unmodified matrix.
Investigating particle cavitation in rubber-toughened
PMMA, Ayre and Bucknall (61) proposed that the vol-
ume strain energy responsible for void formation in
the rubber phase is generated by both differential
thermal contraction and by mechanical loading. As
test temperature is reduced, the increasing matrix yield
stress causes rubber cavitation before (matrix) yield.
The energy barrier to cavitation at the yield point is
therefore progressively reduced as the temperature is
lowered. Void nucleation is thus the rate-controlling
step to rubber particle cavitation (61).
2452 POLYMER ENGINEERING AND SCIENCE, DECEMBER 1999, Vol. 39, No. 12
Wu (57) suggests that, with ductile polymers, there
is only one condition that needs to be satisfied to
achieve toughening: the critical interparticle distance
should be smaller than a certain critical value. That
value is seen as being a material property of the ma-
trix, provided the matrix itself can dissipate impact
energy by extensive shear yielding. The combination
of particle volume fraction and particle size by which
the critical interparticle distance is reached, is consid-
ered unimportant. For those polymers that fail by a
combination of crazing and shear yielding, a bimodal
size distribution of rubber particles is seen as the
most efficient way of providing crack blunting and
shear band initiation (62).
Some similar conclusions were drawn by Jiang et
aL (63).studying PP/ethylene-propylene-dienemono-
mer (EPDMI blends. They concluded that notched Izod
impact strength of the PP matrix could be improved
by decreasing the EPDM interparticle distance, if the
particle size remains unchanged. The effect was simi-
lar to increasing the test temperature. Plotting the
critical (for the DB?T) interparticle distance vs Tg-T,
they found that PA/EPDM and PP/EPDM fall on the
same curve, suggesting that there is a single master
curve for these parameters, under these test condi-
tions. This same laboratory also studied the strain
rate effect and found that the critical interparticle dis-
tance increased with decreasing strain rate (64).
Because the rubber particles merely initiate and ac-
celerate the yielding processes in a matrix placed
under stress, if the matrix cannot respond by exten-
sive yielding, it cannot be toughened. In other words,
the more ductile the matrix polymer, the more it can
be toughened. In thermosets, the distance (molecular
weight) between crosslinks is proportional to the
toughenability of the system (65). Increasing the
crosslink density lowers the fracture toughness at any
given temperature by shiftmg the Tgupward, and lim-
iting the total crack-tip strain that can be realized.
Bradley et aL (66)found that the temperature of maxi-
mum toughness was shifted some 50-120C lower in
rubber-toughened thermoset systems, compared to
untoughened systems, with the actual toughness of
the former systems being 4X higher. Hgh crosslink
density systems were found to be unresponsive to
rubber toughening at any temperature.
With thermoplastics, the entanglement density might
be expected to be equivalent to the thermoset cross-
link density, in terms of influencing the toughenability
of a given matrix polymer. The matrix needs to be ca-
pable of absorbing energy by shear yielding and/or
masssive crazing, if rubber toughening is to be suc-
cessful. In the absence of matrix yielding, such as in
tightly crosslinked thermosets, or at low tempera-
tures, all the energy that can be absorbed in yield and
fracture must be absorbed by the modifier particles.
This is achieved by cavitation and ductile tearing of
 Polymer Toughness and Impact Resistance
the particles, and usually provides only modest im-
provement in toughness (67).
Irrespective of the exact mechanism, the rubber
should be dispersed as discrete particles on a micro-
scopic scale and be well bonded to the rigid polymer
matrix (47). The particles can be incorporated via
blending a rubber with the matrix polymer, or by
copolymerizing a rubber with the matrix polymer, tak-
ing advantage of the natural segregation of immiscible
polymers (or chain sequence lengths in a block or
graft copolymer). Copolymerization is usually more ef-
ficient as an impact modifier than is blending (68), as
observed, for instance, in an early study (69)where
introduction of 2.5% lubber by g r a m increased the
impact strength of PS IOX,while introduction of the
same amount of rubber by blending increased the im-
pact strength only 2X.Grafling helps couple the rub-
ber to the (immiscible)matrix (70).
In a study by Lemstra et aL (71), electron beam irra-
diation of PS/EPDM blends, using a PS/poly(butadi-
ene) (PBD) block copolymer as a compatibilizer, result-
ed in a 2-3X increase in Izod impact strength. The
authors postulate that radiation-induced grafting of
the BD part of the block copolymer, located at the
rubber/copolymer interface, onto the dispersed EPDM
particles, was responsible for the improvement.
In the absence of radiation, the effect of compatibi-
lization on increasing the toughness of polymer
blends was discussed by Armat and Moet (72) using a
PA/PE blend and a maleic anhydride (MA) functional-
ized styrene-ethyleneJbutylene-styrene(SEBS) com-
patibilizer. They claimed a dual interfacial function for
the compatibilizer: (a) reducing the interfacial tension
of the system, resulting in reduction of the dispersed
phase particle size, and (b) enhancing the interfacial
adhesion through the formation of microbridges. The
dispersed phase thus coupled to the matrix in com-
patibilized blends can support a load and deform co-
continuously along with the matrix, causing extensive
yielding of the blend prior to its failure, and high ulti-
mate elongation. Similar improvements were seen by
Modic and Pottick (73), using a PA/PP blend with the
same compatibilizer.
The majority of blends and graft copolymers are
two-phase, and their morphology depends on the type
of molecular interaction and the resultant interface,
the rheology of the components, and the processing
history. As the interfacial energy between the phases
decreases, particle size will generally decrease and the
extent to which the dispersed phase droplets deform
under stress increases. Thus, when a two-phase poly-
mer blend is stretched, the droplets of dispersed
phase may form high-aspect-ratio fibrils (74). Co-con-
tinuous structures can be quite readily generated in
two-phase blends; however, such a structure can re-
duce its interfacial area and therefore its free energy
by relaxing to a morphology in which one phase is
dispersed in the other. If phase separation between
the rubber particles and the matrix does not occur,
the (dissolved) rubber will act as a plasticizer in the
POLYMER ENGINEERING AND SCIENCE, DECEMBER 1999, Vol. 39, No. 12
polymerized blend, in some cases improving impact
resistance, but most likely lowering stiffness and ther-
mal resistance to an unacceptable level. In general,
the rubbery phase must be semicompatible with the
polymer: compatible enough for good dispersion and
wetting to occur, but not so compatible as to create a
homogeneous or single-phase system.
The interface between the phases influences the
final blend properties. As mentioned above, rubbery
particles should be weU dispersed in order to act effi-
ciently as stress concentrators, and they should also
be well bonded to the polymer matrix, for efficient
stress transfer between the two phases. When cooled
from the melt, most rubbers will shrink more than the
polymer matrix, and debonding will thus occur in the
absence of good adhesion between the two phases.
Where the adhesion is good, the rubber will be in a
state of triaxial tension (75).In cases of blends, unless
the polymer reacts or interacts with the rubber, it is
usually necessary to use specific compatibilizers to
ensure a stable structure with a uniform distribution
of rubbery particles. As in other types of polymer
blends, the exact nature of the compatibilizer appears
to be highly system specific. This goal of maximking
adhesion and dispersion does not always apply. For
instance, where improved impact resistance is de-
sired, interfacial failure may itself provide a toughen-
ing mechanism by dissipating energy.
In order to optimize the interaction between the
rubber particles and the matrix, so-called core-shell
impact modifiers have been developed (61, 7680).
These usually consist of a rubbery core surrounded
by a shell designed specifically to interact with the
matrix polymer. The chemical composition of the shell
can be chosen to impart compatibility or chemical re-
activity with the matrix. This results in improved dis-
persion of the modifier during melt processing, and
provides good adhesion with the matrix (81).
Memon (78) shows that the impact strength of ther-
moplastics modified with core-shell impact modifiers
is a function of the interactions at the matrix/shell in-
terface. He used dynamic mechanical analysis to in-
vestigate the modifier/matrix interactions.
The toughening of PA6 with a MA grafted poly(ethy1-
ene-octene) rubber (shell)/semicrystalline polyolefin
(core) blend was investigated by Yu et al. (79).They
found that this modifier both processed better, and
also improved impact strength, over maleated polyeth-
ylene-octene rubber by itself. Matrix shear yielding
was the mode of energy dissipation, and the matrix
viscosity influenced the notched hod impact strength
via varying the size of the dispersed phase; high vis-
cosity promoted reduced modifier particle size, there-
fore improving its toughening effectiveness.
Lin et al. (80)studied the effect of shell composition,
core/shell crosslinking, particle aize, and modifier
concentration in epoxy resins toughened with a core-
shell modifier consisting of butyl acrylate as core and
MMA copolymerized with glycidyl methacrylate (GMA)
as a shell. Toughness increased with increasing shell
2453
 William G.Perkins
GMA content, smaller modifier particle size (< / =
0.25pm) and crosslinking of the shell.
Rubber Type
As a rubber particle stretches under stress, it ab-
sorbs ener@ and also stabilizes the ensuing crack
front or craze, whereas initial cavitation of the rubber
particle relieves the triaxial stress existing at the
crack tip, and thus enhances localized yielding of the
matrix. If the applied stress is increased further, the
crack tip may be bridged by the stretching rubber
particle, provided that there is sufficient adhesion be-
tween the rubber and the matrix, and that the particle
can stretch sufficiently rapidly in terms of the speed of
the crack advance. For this reason, It is desirable that
the rubber have as low a Tg as possible, while still
being able to fibrillate and maintain a degree of struc-
tural integrity in response to impact loading. For ex-
ample, styrene-butadiene rubber (SBR) was replaced
long ago by polybutadiene rubber (BR)as a toughen-
ing agent in high-impact polystyrene (HIPS)and acry-
lonitrile-butadiene-styrene(ASS), because BR has a
Tgof -85C whereas SBR has a Tgof only -50C and
therefore the BR imparts superior low-temperature
impact strength. A similar effect on impact strength
was seen when comparing a butyl acrylate-methyl
methacrylate-styrene (BA/MMA/S) graft copolymer
rubber to BR (82).
Another requirement of the rubber is that it should
be thermally stable, both during processing and sub-
sequent end use. Saturated rubbers resist oxidative
degradation better than unsaturated rubbers, but low
temperature impact toughness mght be impaired be-
cause their 2's are usually higher. Unsaturated rub-
bers may be used with appropriate antioxidants.
Working with rubber-toughened PA's, Borggreve et
al. (83, 84) found that the impact improvement of
their blends depended strongly on the type of rubber
used. This impact improvement could not be correlat-
ed with the tensile strength or the elongation at break
of the rubbers. The lower the initial modulus of the
rubber, however, the more effective it seemed to be as
a toughening agent (for PA6). The role of the rubber
particles was seen as relieving the hydrostatic pres-
sure at the crack tip by cavitation, rather than by the
more classical role as a stress concentrator. This view
is supported by the earlier observation of Gent and
Tompkins (85)that the cavitational stress of rubbers
in a triaxial stress state decreases with decreasing
elastic modulus of the rubber, thus allowing more
facile cavitation.
Wu et al. (86).using PC blends as an example, pro-
posed a model of stress distribution around the notch
in an hod impact test sample. They concluded that
there is no advantage in reducing the modulus of rub-
ber particles to less that 1/1000 that of the matrix.
Their model also predicts that the Tg of the rubber
dominates the DBTT.
2454 POLYMER ENGINEERING AND SCIENCE, DECEMBER 1999, Vol. 39, No. 12
Rubber Particle Sim
Commercial rubber-toughened thermoplastics typi-
cally have particles smaller than 3pm in diameter and
often smaller than 0.2pm (47). For each matrix mater-
ial there appears to be an optimum range of particle
sizes leading to the best toughness improvement.
Whatever the size of the particle, however, its essential
initial role is often to act as a stress concentrator.
Thus, if a material is subjected to a stress, the local-
ized stress experienced by the matrix material in the
immediate vicinity of a rubber particle will be magni-
fied. The m am will then yield locally, in response to
this localized stress field, avoiding brittle catastrophic
failure. Although voids in a matrix will also act as
stress concentrators, they, unlike rubber particles,
are unable to bear loads, and are therefore not effec-
tive toughening agents.
The optimum rubber particle size is related to the
nature of the subsequent matrix deformation mecha-
nism. According to B u c M (49).the rate at which the
matrix can respond to stress by forming oriented fibrils
(crazing) becomes the limiting factor in determining
impact resistance. This is because fibrillation is the
most rapid mechanism available for the extension of
the damage zone at the crack tip. Fibrils, which can
range from 5 to 50 nm in diameter, are the load-bear-
ing members of the craze (87). In HIPS, where such
fibrillation occurs during multiple crazing, particles
less than 1 pm are less effective in toughening the sys-
tem than are larger particles (88),allegedly because
small particles are less efficient in initiating crazes
than are large ones (89).Unmodified PA, on the other
hand, has no easy means by which it can fibrillate. It
is cavitation in the rubber particles which appears to
provide toughness in rubber-modified PA (=A) (90).
relieving the triaxial tension ahead of the crack. The
matrix between the voids then undergoes extensive
shear yielding, and fibrillation is achieved. This differ-
ence in intrinsic deformation mechanisms between
HIPS and FWPA is likely the reason the optimum rub-
ber particle size for toughening the latter (0.3pm) is
different from that of the former (-2 pm) (91).
ABS, because of its polar character, tends to deform
by shear yielding at low deformation rates, whereas
crazes are nucleated at higher deformation rates. Very
small particles tend to reduce its stiffness and gloss,
but increase its toughness. The optimum mean parti-
cle size for a good combination of toughness, stiffness,
and surface in ABS is about 0.3-0.5 pm (92).
In a study using PP modified with ethylene-propy-
lene rubber (EPR) in a slow-strain deformation tensile
test, Michler et al. (93)observed that the type of defor-
mation mechanism depended on the rubber particle
size. For a sample with an average EPR particle size of
0.3pm. void formation was followed by plastic defor-
mation of both rubber and matrix. Also, weak shear
bands formed in the matrix between particles, and in-
creased in intensity with increasing sample strain.
 Polymer Toughness and Impact Resistance
Shear flow in the matrix appeared either as shear
bands or as diffuse shear yielding. For a sample with
a n average EPR particle diameter of 1.6 pm, a well-de-
veloped @ W a r deformation morphology appeared,
suggesting a crazelike deformation mechanism. From
these and other observations, they concluded that the
major part of the energy applied to the specimen was
absorbed through the shear deformation process in
the matrix via a cavitation process: that is, the cavita-
tion process itself was not the major energy absorbing
mechanism, but provided the energy dissipating sites.
Both particle size and distance between particles were
seen as important to optimize the internal phase mor-
phology and thus improve toughness. The optimum
interparticle distance was seen as also being depen-
dent on temperature, the ideal distance decreasing
with decreasing temperature (94). Ideal particle sizes
in cornpatibiked systems tend to be inversely propor-
tional to both the amount added (53) and the func-
tionality (95)of the compatibilizer.
In a transparent plastic, the presence of micro-
scopic rubber particles often results in a loss of
transparency, due to light scattering by the rubber
particles, which are typically within the size range of
0.2 to 20 pm. This effect can be minimized and sur-
face gloss maintained by making the particle size
small (c0.2 pm) and by keeping the particles well
dispersed (92).
In a series of recent papers, Paul et aL (96-98) in-
vestigated the effect of matrix molecular weight on
rubber-toughened PA6 blends. They found that Izod
impact strength was affected, non-monotonically, by
the amount of functionality in the rubber and the
rubber particle size, which was in turn affected by
matrix molecular weight and melt viscosity, the higher
molecular weight and higher melt viscosity leading to
lower rubber particle size. These investigators also
found that the ductile-brittle transition temperature
decreased as the molecular weight of the PA6 matrix
increased, when compared at either constant rubber
functionality, or at constant rubber particle size.
Horiuchi et al. (99) studied the effect on impact
strength of functionalized SEBS triblock elastomers in
blends of PA6 and PC. They found that maximum im-
pact strength and maximum tensile strain at break
could be obtained when certain combinations of func-
tionalized and unfunctionalized SEBS were used.
They credit this behavior to higher interfacial strength
resulting from the combination of the two types of
elastomer.
The effect of rubber particle size on toughening be-
havior of PMMA modified with a core-shell type addi-
tive, made up of a poly(n-butyl acrylate) core and a
PMMA shell, was investigated by Cho et aL (76). They
found that maximum impact strength was obtained
for rubber particles with a 0.25 pm diameter regard-
less of the rubber phase content, and only a modest
improvement of the impact strength was achieved for
blends containing either 0.15 or 2 pm particles.
POLYMER ENGINEERING AND SCIENCE, DECEMBER 1999, Vol. 39, No. 12
Teat Conditions
Rubber-modified plastics exhibit effects of rate and
temperature of test, over and above those which are
normally expected in polymeric materials. This is be-
cause the viscoelastic behavior of both the matrix and
rubber needs to be considered, and also, the preferred
energy absorption mechanism of the matrix can be
different at different strain rates/temperatures ( 100).
For instance, morphology appears to be less critical in
controlling fracture in HIPS at low strain rates or
higher temperatures (101), suggesting that the parti-
cle size effect in this system has its origin in the kinet-
ics of deformation, rather than in any absolute inabili-
ty of small particles to toughen the PS matrix (47). In
rubber-toughened epoxies, on the other hand, the ef-
fect of rubbery particle morphology is more pro-
nounced at high temperatures or low strain rates
(102), in complete contrast to the HIPS results. There
is currently insufficient understanding of the effects of
test conditions on fracture in rubber-modified poly-
mers, and of the complex interrelationships between
morphological effects and test condition effects.
TEST METEODS
General
The impact strength of polymers may be evaluated
by various test methods, which usually entail the de-
livery of a sharp blow by either a hammer or by a pro-
jectile propelled at the polymer or dropped on it. In
these tests, the loading is very fast, on the order of at
least 300 cm/sec. Depending on the instrument, the
load imposed may be either tensile, compressive, or
flexural, with resulting fracture stresses being uniaxi-
al, biaxial, or triaxial (103).The impact resistance is
evaluated in terms of the energy absorbed by the
specimen during the impact process. One thing to be
considered is that no two test methods measure ex-
actly the same physical quantity, and, in fact, there is
no universal agreement as to what physical quantities
some of the methods actually measure (42).
A common practice is to regard the energy trans-
ferred to a polymer at break, or the area under a con-
ventional stress-strain curve, as a measure of its
toughness. However, one should be aware that two
polymers may have quite different stress-strain curve
shapes (say, brittle and ductile) indicating different re-
sponses to the impact loading, yet have the same area
under the curves. Also, two polymers may absorb the
same amount of energy when they break under the
impact of a projectile, yet absorb this energy in differ-
ent ways, predominantly either elastically or viscous-
ly, again exhibiting the same toughness, by virtue of
their load-deflection curves having the same area
under them, yet their mode of failure would be entirely
different. By changing the test temperature, in combi-
nation with fracture surface examination, the impact
strength evaluation can be extended for determination
of the DB?T.
2455
 William G. Perkins
Because fi-acture is complex and depends strongly
on the type of test and on the speed of testing, the
best method for evaluating a polymer employs condi-
tions similar to those of use. If this procedure is not
followed, the test may mislead the fabricator, because
some polymers behave poorly in conventional impact
tests using specially prepared specimens, but are,
nonetheless, useful materials for fabricated articles.
The resolution of these and similar contradictions en-
countered in the application of polymers to practical
uses requires detailed knowledge of both fracture
mechanisms and the different ways in which testing
techniques can influence them.
Impact strength is not a fundamental material prop-
erty-it depends upon specimen geometry and upon
the particular test method employed. Thus. it is diffi-
cult to correlate the results obtained from different
test techniques, and extremely difficult to correlate
the results from impact tests on specimens of the ma-
terial to the impact performance of the manufactured
article. The performance of a material or a structure
depends on local geometrical and morphological varia-
tions, and on processing conditions such as cooling
rate, shear stress, and melt-flow paths, which can
result in orientation and residual stresses. A struc-
ture produced by a given process may possess sig-
nificant morphological differences from (standard)
test specimens.
Pendulum Tests
Pendulum-type machines are used for notched or
unnotched specimens that may be of different sizes
and clamped as a cantilever (Izod)or as an unclamped
bar supported at both ends (Charpy).These tests are
also referred to as flexed-beam impact tests, and de-
termine the resistance to breakage by flexural shock,
in terms of the difference between the potential energy
of the striker before and after impact.
A mass is attached to the end of an arm that rotates
about a pivot point; a striker is placed near this mass.
The arm is raised to a predetermined position, and
when released, swings downward and strikes the speci-
men, which is either supported at both ends or mount-
ed rigidly in a vise or fixture. The precise mounting po-
sition and the type of fixture depends on the test. The
mass, length of the arm,and angle at the raised posi-
tion determine the amount of available energy, which
must be high enough to give a clean break.
After the striker breaks the sample at the bottom of
its swing, it continues to swing upward until all the
kinetic energy is exhausted. From the height it reaches
after impacting the sample, energy expended per unit
area can be calculated via either a calibrated dial
mounted in the plane of rotation, or through a trans-
ducer mounted on the striker or on the mounting block
to which the specimen vise is attached. Maximum
pendulum velocities (impact speeds) are 300400
cm/sec.
The notched Zzod test is frequently used to deter-
mine crack propagation resistance, because of the low
2456 POLYMER ENGINEERING AND SCIENCE, DECEMBER 1999, Vol. 39, No. 12
cost of the instrument, and test simplicity, conve-
nience, and acceptance by the polymer industry. The
test utilizes a cantilever-mounted bar or beam speci-
men, firmly clamped in a vertical position, with a hori-
zontal notch cut on the side facing the striker, which
impacts the sample just above the notch. The material
at the tip of the notch is subjected to a highly ampli-
fied state of triawial stress. Farther away from the
notch the stress state is one of plane, or biaxial stress,
and eventually, if the bar is wide enough, uniaxial ten-
sion (104).It is because of this triaxial stress state
that notched Izod test samples usually fail in a brittle
manner. Factors that increase the measured impact
strength (ductility) of a notched I d sample include
increases in the notch radius, test temperature or
sample molecular weight, or decreases in either the
test rate or sample thickness.
The notch tends to promote brittle failure because it
increases the DBlT (105).Some materials, which
stoutly resist crack initiation in use, are known to be
notch-sensitive,meaning that their notched impact re-
sults will be substantially lower than their unnotched
impact results, the notch acting as an artificial crack.
Polycarbonate and nylon are examples of notch-sensi-
tive polymers. Another is polypropylene, which nor-
mally has a DBTT between 0 and 20C (106), but has
a DBTT of about 100C when notched (107).Notched
sample tests are considered the most severe of the
toughness tests (108). as notches serve as stress con-
centrators; the smaller the notch radius, the larger
the stress concentration. Unnotched sample tests can
be used to determine both crack initiation and propa-
gation, and may be run by reversing the notched
specimen in the clamping vise.
The notched Charpy test utilizes a bar or beam
specimen mounted horizontally on a span support,
with a vertical notch cut on the side opposite the
striker-impact side, and struck centrally by the pen-
dulum, behind the notch. In a similar fashion to the
unnotched Izod test, ductile samples often will not
break, but bend, occasionally interfering with pendu-
lum clearance. Sample and notch specifications for
both tests are given in ASTM test method D 256.
Falling Weight Tedm
In these tests, a guided hemispherically-tipped
weight (tup) is dropped, under the force of gravity,
onto a specimen which is positioned over a circular
opening. The dart-drop or Gurdner impact tester is a
well-known example of this type of instrument, where-
as the more recently introduced Dynatup tester is sold
as a fully automated and computerized version. The
tup may be gradually increased in mass, or dropped
from increasing heights, in order to vary the impact
force. The maximum speed readily attainable is nearly
800 cm/sec, twice that of the pendulum-type instru-
ments. Samples are usually in sheet form (ASTM D
3029).although thermoplastic pipe (ASTM D 2444)
and f ilm (ASTM D 1709)are also tested via this type
apparatus. In addition to the load, the velocity of the
 Polymer Toughness and Impact Resistance
falling weight must be accurately determined, as sig-
nificant errors from frictional effects can result by as-
suming free fall. Yet: et al. (109) describe some other
caveats regarding falling weight (puncture) tests.
Many materials that give low (brittle) notched Izod
impact values fail at higher energy in a ductile man-
ner when tested in sheet form, due to differences in
the stress state and resulting material response. The
loading in a falling weight test is biaxial, and known
to be less severe than the triaxial stress state of the
Izod test (104).This type of test measures the energy
required to initiate a crack, as well as propagate it,
and so is much more forgiving of highly ductile mate-
rials than are the notched Izod and Charpy tests. The
cause of failure of sheet-type material in practice is
more likely to be revealed by a falling-weight impact
test than by a pendulum test (1lo), so these tests
tend to be a better guide to practical behavior, unless
the sample being evaluated contains ribs, sharp cor-
ners, or other stress concentrators.
Any anisotropy present, such as excessive orienta-
tion, leading to weakness in a given direction, is re-
vealed by the test. An oriented injection-molded speci-
men, for example, may fail with a single straight crack
at a relatively low energy, whereas a substantially m-
oriented compression-molded specimen of the same
material will likely fail at a much higher impact ener-
gy, with (energy-absorbing) cracks in several direc-
tions. An advantage of the falling weight test over the
Izod or Charpy tests is that the sample usually breaks
in its weakest direction. With the pendulum tests,
which generally use a highly oriented injection molded
specimen, the sample is always broken in its strong-
est direction.
Ten6ile Impact T e a
This type of test involves tensile loading of a speci-
men. The common configuration is a modified pendu-
lum impact test, using a 'dog bone" sample geometry.
One end is clamped in the pendulum head and the
other in a crosshead clamp. When the pendulum
swings down, the crosshead clamp holding the trail-
ing end of the sample 1s halted by an anvil, the sam-
ple breaks, and the pendulum head, now bearing half
the specimen, swings up to a height that is translated
into energy-to-break. Test protocol can be found in
ASTM D 1822. The test gives the energy, per unit
area, to fracture the sample, but does not differentiate
between two materials that produce the Same value,
one requiring a large force and little elongation to fail,
and the other just the oposite. The rate of sample ex-
tension, related to the specimen gauge length, has a
strong influence on the fracture mechanism encoun-
tered in the test. Higher loading rates, up to 2,500
cm/sec or more, can be achieved using hydraulically
or pneumatically driven instruments. These instru-
ments maintain constant velocity through the break,
and their rates are infirlitely variable from zero. They
also record the complete impact event.
POLYMER ENGINEERING AND SCIENCE, DECEMBER 1999, Vol. 39, No. 12
Tensile Elongation Test
Unlike the above tests, tensile elongation, which
generates the well-known stress-strain curve, is a rela-
tively slow-speed test, and is one of the least severe
toughness tests. This is because no notches are pre-
sent, the (usually) injection-molded specimens are
tested in their optimum (oriented) direction, and a
moderate rate of loading is commonly used. Also, the
imposed stresses in tensile loading tests are uniaxial,
whereas most materials are much more brittle in bi-
axial and triaxial states of stress than they are in uni-
axial loading (104, 109).As previously mentioned, the
area under the resulting stress-strain curve is as-
sumed to be a measure of the material's toughness,
but the relationship of this method to higher-speed
impact loading is not always predictable.
Test Method Summary
If more extensive information is needed, instrumen-
tation can be added to the above tests to define the
whole impact event by plotting load against time or
deformation. Several variables, such as load at failure,
energy-to-failure, time-to-failure, deflection at failure,
impact energy, and total energy, can be manipulated
to give a fuller understanding of the failure mecha-
nism(s) taking place. Transducers permit the measur-
ing of force continuously throughout the impact proc-
ess, separate the energy into the product of force and
displacement, and have shown that materials may
have different force-time curves but the same energy-
to-break. Apparent modulus, yield and ultimate
strengths, and energy at yield and break can be deter-
mined. Fracture toughness and ductility index, for
use in elastic and plastic stress analyses, can also be
derived (111). Detailed interpretation and theoretical
analysis of the instrumented falling weight impact test
are given in a paper by Reed (112).
Specimens for all the above tests are usually spe-
cially prepared, and thus are quite suitable for control
or material tests. I t should again be emphasized, how-
ever, that frequently a fabricated article performs dif-
ferently, as the fabrication process itself can have a
strong influence on the resulting impact strength. In
thin-walled injection moldings, for example, the flow
properties of the material during mold filling may be
more important than the basic impact properties of
the unoriented material, in governing the impact be-
havior of the molding. Specimen geometry is also im-
portant, because under shock loading, the rate of
stress buildup is governed by the article shape. Where
possible, the impact strength of the finished product
should be tested in addition to the usual control and
quality tests.
Bucknall (113) sums up the state of fracture inves-
tigation by observing that in order to fuuy understand
the many factors involved in impact fracture, it is nec-
essary to employ a wide range of experimental and
theoretical techniques, including force-time measure-
2457
 William G.Perkins
ments, high-speed photography, small angle X-ray
scattering, electron microscopy of fracture surfaces
and of sub-surface layers, and finite element analysis.
These techniques should then be combined with vari-
ations in the composition and morphology of the ma-
terial, in test temperature, loading rate, and specimen
geometry.
A more recent technique for evaluation of fracture
phenomena is that of micromechanics (114). As these
authors point out, one of the main objectives of micro-
mechanics is to express in a systematic and rigorous
manner the continuum quantities associated with an
infinitesimal material neighborhood in terms of the
parameters that characterize the microstructure and
properties of the microconstituents of the material
neighborhood. It allows a relationship to be developed
between a heterogeneous materials macroscopic prop-
erties and its microscopic morphology.
Unfortunately, there is at this point in time not
enough good characterization results to allow a com-
prehensive framework for the interpretation of poly-
mer toughness. As more work is done in the field,
hopefullly a clearer picture will emerge. As a final
word, several useful general references (115-1 19) are
available as comprehensive sources of information on
the topics reviewed herein.
CONCLUSIONS
Some general guidelines for improving the impact
resistance of a polymeric system are outlined herein:
Microscopically examine fracture surfaces to as-
certain the fracture mechanism and type of ten-
sile stresses experienced by the article of interest,
at the temperature of interest, under conditions
similar to its intended use.
Determine which standard laboratory impact
test(s) correlates with the type of fracture actually
observed.
Review current processing procedures and deter-
mine if the morphology imparted during fabrica-
tion (amount and type of crystallinity, orientation,
etc.) can be improved.
Investigate rubbery additives, including elasto-
meric ionomers, unsaturated rubbers, block &
graft copolymers, and core-shell modifiers con-
taining both unreactive and reactive shells. Also
consider rubber particle size, and salamistruc-
tures, which are generally best.
Investigate the introduction of backbone chain
unsaturation for crosslink sites, to both limit crys-
tallinity and help attain a fine cell structure. Pos-
sibly copolymerize with a small amount of unsat-
urated comonomer.
Investigate other (non-elastomeric)types of fillers.
Determine if hot filling, flash freezing, or other
post-molding handling procedures are imparting
2458 POLYMER ENGINEERING AND SCIENCE, DECEMBER 1999, Vol. 39, No. 12
frozen-in stresses or initiating fracture. An in-line
annealing step might be needed.
Consider other deformation mechanisms that
may provide enhanced ductility and impact resis-
tance, using only small amounts of modifier to
encourage such mechanisms.
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