A Review of

Polyet hy len e- Polyp r opylene Blend s

and Their Compatibilization
J. W. TEH and ALFRED RUDIN"
Institute for Polymer Research, Department of Chemistry, University of Waterloo, Waterloo,
Ontario, Canada N2L 3G1

JOHN C. KEUNG
Shell Canada Limited, Oakville Research Centre, Oakville, Ontario, Canada L6J 5C7

ABSTRACT m
A major stream of post-consumer plastics is a commingled blend of
polyethylenes and polypropylenes, which usually exhibits lower performance
compared with that of the homopolymers due to the incompatible nature of
polyethylenes and polypropylenes. Various studies have been carried out to
characterize the structure, morphology, mechanical, thermal, and rheological
behavior of this blend. The effect of processing, modification, and
compatibilization have also been studied by various workers. This article is a
review of the work done on polyethylene-polypropylene blends to help in
the understanding of this important blend. 0 1994 John Wiley & Sons, Inc.

waste into an individual single polymeric type by

various methods is costly and complete sorting is
economically nonviable and sometimes impos-

P ost-consumer plastics waste has become the

focus of legislation and environmental con-
cerns.I3 The major polymeric components of these
plastics waste streams are polyethylenes, polypro-
pylenes, styrenics, polyvinyl chlorides, and poly-
ethylene terephthalates. Separation of the plastics
* To whom correspondence should be addressed.
sible. Hence in the field of plastics recycling, we
are usually faced with a recycled product of a com-
mingled mixture. Due to the incompatible nature
of most polymer^,^,^ the commingled polymeric
mixtures are poor in their mechanical perfor-
mance, aging behavior, and resistance toward
thermal and chemical environment. In the case of
recycling of polyolefins, a commingled blend of
polyethylenes (consisting of linear low, low, and

Advances in Polymer Technology, Vol. 13, No. 1, 1-23 (1994)

0 1994 by John Wiley & Sons, Inc. CCC 0730-6679/94/010001-23
POLYETHYLENE-POLYPROPYLENE BLENDS
high density) and polypropylenes is inevitable. In
order to put these recycled commingled polyolefin
blends into effective and efficient use, a study is
needed to understand the structure, properties,
and processing behavior, their interaction and cor-
rela tion.
Early work on melt blending of polyolefins has
resulted in over 100 patents on the processes or
formulation for producing rheologically modified
polyolefins, as reported by Plochocki.6More recent
work on the rheological behavior of polyethylene-
polypropylene blends has been covered by
. ~ mechanical behavior of PE/PP blends
U t r a ~ k iThe
was first documented by Robertson and Paul8 and
later reported by Noel and Carley9and Deanin and
Sansone.'O The earliest study on the effect of
blending on the morphology was reported by Last
in 195911; however, a detailed study on PE/PP
blends' crystallization morphology and kinetics
was published only in 1980.12,*3 Various techniques
have been employed to study the compatibility of
the PE/PP blend^.'"'^ Correlation between struc-
ture and properties has also been extensively stud-
ied.2a-25 The following is an attempt to summarize
the work done on PE/PP blends to help in the un-
derstanding of this important blend.
Compatibility/Miscibility
between Polyethylene and
Polypropylene
Although both polyethylene and polypropylene
have many similarities in properties,26 the two
polymers are immiscible and incompatible in gen-
eral. The terms "immiscible" and "incompatible"
have been adopted here in line with the definition
by U t r a ~ k i where
,~ immiscible is defined thermo-
dynamically as the case when the Gibbs free en-
ergy of mixing AG, is greater than 0, whereas in-
compatible means that the blend gives properties
inferior to those of both the original constituents or
neat polymers. Addition of a small amount of
polyethylene or ethylene-propylene copolymer
into polypropylene improves the impact perfor-
mance of p ~ l y p r o p y l e n e , ~whereas
, ~ , ~ ~ addition of a
small amount of polypropylene into polyethylene
enhances transparency of solid polyethylene" (at
the expense of environmental stress cracking resis-
tance). Hence in very small amount, either for
polyethylene in polypropylene or polypropylene
2 VOL. 13, NO. 1
in polyethylene, blends of these two polymers can
be considered to be "technically" compatible.
Both polyethylenes and isotactic polypropylene
are semicrystalline, and both are capable of crystal-
lizing with lamellar structure and spherulitic mor-
phology. However, polyethylenes crystallize in an
orthorhombic form with a = 7.417 A, b = 4.945 A,
and c = 2.547 A, whereas polypropylene crystal-
lizes into an cr-monoclinic form (a = 6.65 A, b =
20.96 A, c = 6.50 A, p = 99"20') and p-hexagonal
form (a = 19.08 A, c = 6.49 A).27 Polyethylenes
exhibit melting points of 110-140"C, whereas a-PP
melts at 160-170°C and p-PP melts at 140-150°C.
From the distinct difference in crystalline structure
and large differences in melting point, we should
expect polyethylene and polypropylene to be in-
compatible in the solid state, unless interaction has
taken place and resulted in cocrystallization or inti-
mate epitaxial growth. A simple and fast method
to ascertain compatibility is to run a differential
scanning calorimetry test on the blend to find out
whether there is any shift in melting points and/or
change in enthalpy of f ~ s i o n . ' ~Wide-angle
,~* X-ray
diffraction of the blend should give information on
whether the two polymers have crystallized into
their own individual crystalline form independent
of one another.29 Optical microscopy studies on
microtomed thin sections, or melting and crystalli-
zation with a hot-stage microscope should reveal
the spherulitic morphology. 12,20,22
By measuring the thermal expansivities of poly-
ethylene, polypropylene, and blends of polyethyl-
ene and polypropylene, Zakin et aLI5have shown
that for all compositions of blends studied, no ap-
pearance of any additional transition region char-
acteristic of the blend was observed. The blends
exhibited the Tg of the polypropylene at -13-
-14"C, the position of which was little affected by
the presence of polyethylene.
Alle and Lyngaae-Jorgensen16studied the capil-
lary flow behavior of PEiPP blends over a range of
compositions and shear rates. Viscosity-shear rate
data yielded a master curve plot, with some scat-
ter, of reduced viscosity versus reduced shear rate
(Fig. 1). It was concluded that the PEiPP system
formed either a compatible blend in the molten
state under shear flow conditions or a melt mor-
phology which did not change over the tempera-
ture range studied. These reviewers are inclined to
favor the latter view.
Small-angle neutron scattering has been em-
ployed to study the phase morphology of a 50150
blend of HDPE and iPP by employing deuterium

loo r
n
lo-' r
10' lo2 1o3
Ik no/T
FIGURE 1. Master curve for PP/PE blends at all compositions obtained by plotting the reduced viscosity
against reduced shear rate at different temperatures: (0)PP; ( 0 )PP/PE-75/25; (a)
PP/PE-25/75; (A)PE. [After Reference 16, Figure 11, N. Alle et al., Rheol. Acta, 19, 94 (1980), with permission
from the publishers, Verlag GmbH & Co. KG.]
labeling to enhance contrast." The blend was pre-
pared by dissolution of the polymers in o-dichloro-
benzene and precipitation in methanol. Phase seg-
regation was observed for both the precipitated
blend and melt crystallized blends, where the
mean chord intercept lengths of both phases were
found to be between 1000 and 10,000 A. The phase
segregated morphology was also observed at
- 200"C, where the domain dimensions were found
to be of the same order as those observed in the
melt crystallized blends, indicating a two phase
structure for the melt. The radius of gyration of PE
in the blends was close to that in the homopoly-
mer.
Demont and coworkers18studied the thermally
stimulated creep of PE, PP, and ethylene-propyl-
ene copolymers and blends. The existence of four
amorphous phases was deduced; of these, the ma-
jor components were polyethylene and polypro-
pylene, again indicating that these polymers are
not miscible on a molecular level.
Lower critical solution temperatures (LCSTs) in
heptane have been measured of blends of PE, P I',
and EP copolymer. l9 In the case of block or random
copolymers, single LCST was obtained for the
whole range of ethylene contents. However, in the
case of PEiPP blends, two individual LCSTs were
ADVANCES IN POLYMER TECHNOLOGY
POLYETHYLENE-POLYPROPYLENE BLENDS
1oG 1o5 1o6
PP/PE--50/50; (m)
obtained corresponding closely to the LCSTs of PE
and PP, indicating incompatibility of the PE and
PP in semiconcentrated solution. The LCST of PP
in the PE/PP blends remained the same, whereas
the LCST of PE in the blends varied slightly with
PE contents, and was about 10" lower than that of
neat PE, In the case of PP with El' copolymer and
PE with EP copolymer, the LCST of the polymer
forming a separate phase was not altered by the
presence of the other polymer. This has been inter-
preted as partial compatibility between the copoly-
mer and PE. Incompatibility between PE and PP
was further substantiated by visual observation of
the solution kept at a temperature well above the
higher LCST, at 210°C, for a long time. In the case
of PE/PP blends, three phases were observed to
persist, whereas in the case of PP and copolymer
blends, only two phases remained.
We can conclude that from the cited different
techniques of differential scanning calorimetry,
X-ray diffraction, optical microscopy, thermal ex-
pansivities measurement, capillary rheometry,
small-angle neutron scattering, thermally stimu-
lated creep, and lower critical solution tempera-
tures, that incompatibility between polyethylene
and polypropylene has been established for the
blends in solution, in melt, and in solid state.
3
POLYETHYLENE-POLYPROPYLENE BLENDS
Polyethylene- Polypropyl ene
Phase Boundary
In the case of incompatible blends where the
constituents exist as separate phases, the phase
boundary becomes an important factor in control-
ling and determining the properties of the mate-
rials. This is especially true for mechanical perfor-
mance where stresses have to be transmitted
between the phases. In the case of PEiPP blends,
solidification from the melt normally will involve
crystallization of the PP phase followed by that of
the PE phase if the rate of cooling is not too
f a ~ t . 'In
~ ,this
~ ~case, two crystallization peaks will
be observed. During the process of PP crystalliza-
tion, growth of PP spherulites in a "homoge-
neous" melt of a mixture of PE and PP will involve
the propagating PP spherulite front encountering
domains of PE melt.12 The resulting morphology
will depend on whether the PE domains will be
expelled by the PP growing spherulite front, or
whether the PE domains will be engulfed and re-
main within the PP spherulite as occlusions. When
PE/PP blends are cooled rapidly from the melt,
simultaneous crystallization of the PE and PI' will
take place, and the phase boundary as well as
phase morphology will be different from those ob-
tained through slow cooling. We shall first look at
the boundary of the melt of PE and PP on a macro-
scopic scale, followed by an examination of the
phase boundary in the spherulitic morphology,
and finally at any epitaxial crystallization between
the PE and PP phase boundary.
Interpenetration of PE and PP across the bound-
ary in the melt state has been investigated by
A fine mixture of alcoholic suspensions of
polyethylene and polypropylene powder was fil-
tered through a fine sieve. After drying, the mix-
ture was subjected to compact melting at 160"C,
150 kb/cm2, for 3, 5, 10, 15, 20, and 60 min and
then quenched. The thickness of the interphase
layer was determined by phase-contrast micros-
copy. Interdiffusion of PE/PP was found to be
Fickian for the first 10 min, and the interphase
layer thickness was found to be 15-28 A. Another
investigation on PE/PP phase boundary was car-
ried out by Kryszewski et al.32Thin films of PP and
PE were sandwiched and heated to 180°C and then
thin sections were cut and subjected to different
heat treatments and observed with a cross-polar-
ized microscope. It was found that, depending on
4 VOL. 13, NO. 1
the melt temperature and the length of time of
heating, interdiffusion of the polymers in the melt
blend resulted in penetration of PE into PP phase
for distances up to 300 pm, while penetration of PP
into PE phase may be greater or less than this,
depending on the type of PE and the melt flow
index of the polymers.
It has been found, in general, that the spherulite
size of the PP in the blend is decreased by the
presence of PE.20,22The morphology at the phase
boundary of PE/PP blends was studied by Teh.22
Larger p-form PI' spherulites were found to de-
velop predominantly at the phase boundary (Fig.
2). An early study on the development and growth
of spherulitic morphology of the PEiPP blends was
carried out by Wenig and Meyer.I2 Optical micros-
copy showed that when the blends were crystal-
lized at 130"C, PP spherulites formed containing
PE droplets of some microns in size, the amount of
which increased with increase in PE contents.
These phenomena were studied in more detail
with a transmission electron microscope on rep-
licas of the blend and also with a scanning electron
microscope on impact fracture surfaces.33 It was
shown conclusively that the shape, size, and ori-
entation of PE occlusions remained undisturbed
during crystallization of the PI' spherulites. The
growing PP spherulite was unable to deform the
PE droplets or to push them ahead into the in-
terspherulitic boundaries. The PE droplets, how-
ever, hindered the spherulite growing front, caus-
ing distinct concavities. The PP lamellae, after
passing the PE occlusions, turned and surrounded
them to form line boundaries. Such boundaries in-
troduced weakened paths within the PP spheruli-
tes, and carbon replicas of the fracture surface re-
vealed intraspherulitic boundaries lying on the
fracture path.
In a further investigation, Bartczak and Ga-
l e ~ k showed
i~~ that during crystallization of PP
from PP/PE mixtures, the shape of the interface
changed from initially flat to highly developed
with many deep and branched influxes of the PE
flowing into the PP phase (Fig. 3). This was attrib-
uted to the change in polymer (PI') density during
conversion of the melt to solid. The resulting vol-
ume defect was compensated by the second poly-
mer (PE) flowing into the regions where this defect
cannot be remedied by the flow of melt of the crys-
tallizing polymer, which is prevented by spheru-
lites surrounding these regions. These authors
suggest that deformation of the interface is an al-
ternative to mutual diffusion to explain the thick-
 POLYETHYLENE-POLY PROPYLENE BLENDS

FIGURE 2. Boundary morphology of LDPE/PP showing overlapping of small PE spherulites with larger a-PP
spherulites and very large p-PP spherulites: (a) as crystallized at room temperature; (b) 113°C;(c) at 152°C;(d)
at 165°C. [After Reference 22,Figure 9, J. W. Teh, J. Appl. Polyrn. Sci., 28,605 (1983), with permission from the
publishers, John Wiley 8, Sons, Inc., New York.]

ening of the interface between crystallizable poly-
mers. As a result of such deformations the area of
the interface increases, leading to improvements in
the mechanical properties of this region.
a to the extent of up to 600 pm,32this is not the true
FIGURE 3. Schematic representation of
deformation of molten PE inclusion by growing and
impinging PP spherulites: (a) melt completely
occluded by spherulites and the inclusion; (b)
deformed inclusion after completion of
crystallization. [After Reference 34,Figure 6, Z.
Bartczak and A. Galeski, Polymer, 27,544 (1986),
with permission from the publishers, Butterworth
Heinemann Ltd. 0.1
Early work on epitaxial crystallization of macro-
molecules has been reviewed by Mauritz, Baer,
and H ~ p f i n g e rTakahashi
.~~ found that polyethyl-
ene failed to crystallize epitaxially from the melt on
uniaxially drawn and annealed polypropylene
~ u b s t r a t e s . However,
~~ later work by various
worker^^^-^^ has shown that under different spe-
cific conditions, epitaxial crystallization of polyeth-
ylene on a polypropylene substrate was observed.
This epitaxially grown crosshatch morphology has
been postulated to eliminate or modify the amor-
phous interphase by a crystal bridging mecha-
nism.40Epitaxy will be discussed in more detail in
a later section.
Although interdiffusion of polyethylene melt
and polypropylene melt has been shown to occur
interphase between polyethylene and polypropyl-
ene. The actual interphase thickness or layer could
more realistically be 15-28 A as found by let^.^^,^'
In the case of crystallization of PE/PP blends, the
interphase between the polypropylene spherulites
may not be linear, and this has been postulated to
be due to the squeezing over of the polyethylene
dispersed phase which is still in the melt form,
resulting in many deep and branched influxes.34

ADVANCES IN POLYMER TECHNOLOGY 5

POLYETHYLENE- POLYPROPYLENE BLENDS
On the other hand, for unrestricted freely growing
polypropylene spherulite fronts, the dispersed
droplets of polyethylene were encircled without
being pushed out or distorted. Epitaxy has been
shown to take place under specific conditions, and
the epitaxial interface morphology could only be
found in recrystallized or annealed blends sub-
jected to drawing or orientation.
Morphology of
Polyethylene-Polypropylene
Blends
Morphology of crystalline polymers is con-
trolled by the crystallization conditions. Thus mor-
phology obtained from crystallization under differ-
ent conditions may exhibit completely different
structures. On top of that, temperature of crystalli-
zation, rate of cooling, stress or strain orientation,
and annealing will also affect the morphology. In
the case of blends, composition and the type of
constituents will be another added factor.
The earliest study on the spherulitic morphol-
ogy of PE/PP blends was reported by Barton and
Rak.41A mixture of low density and high density
polyethylenes with atactic amorphous polypropyl-
ene in different weight ratios was dissolved in p-
xylene, and thin films were cast from 1% solution
on glass slides. Cross-polarized and phase contrast
optical microscopy were used to study the crystal-
line morphology developed under different ther-
mal conditions. For atactic polypropylene contents
greater than 50 wt%, only sporadic refractive for-
mations were observed. For blends containing less
than 50 wt% atactic PP, well-developed spherulites
were obtained for films crystallized from cast films
containing solvent. However, if the solvent was
completely removed prior to crystallization (crys-
tallization from melt film), the typical spherulite
morphology disappeared, and an extensive inter-
penetration of crystalline and amorphous granu-
lated morphology was obtained. Similar observa-
tions were also made in the case of high density
and isotactic p o l y p r ~ p y l e n e . ~ ~
Microheterogeneity was observed on micro-
tomed thin sections of bulk crystallized PE/PP
blends by the process of repeated melt pressing at
190°C followed by quenching in water and pelleti-
~ a t i o nHowever,
.~~ if the blends were annealed at
6 VOL. 13, NO. 1
190°C for 3.5 h, merging of the initially uniformly
dispersed phase inclusions occurred, giving rise to
a macroheterogeneous morphology. Lovinger and
Williams20found that for blends of less than 50%
polypropylene, interpenetrating networks of the
two polymers were observed, whereas for blends
containing more than 50% polypropylene, the
morphology was typified by polyethylene islands
dispersed in a polypropylene matrix. Spherulitic
morphology was observed for all blends, and the
size of the polypropylene spherulites was drasti-
cally reduced in the presence of polyethylene. This
decrease in size was also observed in the case of
crystallization of melt filmsz and cast films.24
However, in the case of binary blends of polypro-
pylene with EPR or PP/EPR/HDPEternary blends,
no decrease of polypropylene spherulite size was
observed, but the spherulitic structure of the poly-
propylene matrix was gradually disguised and ob-
literated.@ On the other hand, DOrazio et al.45
reported that addition of EPR to polypropylene
and high density polyethylene, HDPE to PI‘, and
HDPE/EPR to PI’ produced a decrease in the aver-
age size of the spherulites. The discrepancies men-
tioned probably reflect differences in EPR compo-
sitions which were not analyzed.
Morphology of the PE/PP blends crystallized at
temperatures well above the melting points of
polyethylenes has been studied by various work-
e r ~ . ~ ~As,discussed
~ ~ ~ earlier,
~ , ~ when” ~ the ~ well-
mixed PE/PP blends were cooled from tempera-
tures above the melting point of polypropylene to
a crystallization temperature well above the melt-
ing point of polyethylene, polyethylene dispersed
melt droplets were incorporated in the intra-
spherulitic regions, during the growth of polypro-
pylene spherulites. The number, dimensions, and
the shape of the polyethylene domains were de-
pendent on the composition, the thermal history,
and the crystallization t e m p e r a t ~ r e In
. ~ ~general,
the polyethylene occlusions increased in size with
increase in polyethylene content in the blends.
Blends that had been subjected to high tempera-
ture annealing prior to crystallization had coarser
polyethylene inclusions. l2 This had been postu-
lated to be due to the coalescence of the polyethyl-
ene dispersed phase due to diffusion, similar to
the case of bulk crystallized blends discussed
earlier.43Polyethylene domain size also increased
with increase in compression molding timez8and
increase in crystallization temperatures. l2 This
could be due to the lower viscosity and higher mo-
lecular mobility resulting in easier coalescence of

the polyethylene dispersed droplets. Blends con-
taining more than 50% polypropylene had inter-
connected morphologies.
At a high rate of cooling, a high density polyeth-
ylene and polypropylene blend exhibited a single
crystallization exotherm, whereas at slow cooling
rate, two crystallization exotherms were ob-
tained.l4lZ8 Crystallization of 70/30 and 50/50 poly-
propylene-polyethylene blends at 135°C and
127°C did not yield morphology exhibiting any sig-
nificant d i f f e r e n ~ e . ~ ~
Morphology of PE/PP blends containing p-nu-
cleating agents have recently been studied.% It
was found that the relative amount and size of the
p-spherulites formed were independent of the
blend compositions and were not affected by the
initial melt temperatures, when the blends were
crystallized at 135°C. However, the amount of p-
polypropylene was affected by the rate of crystalli-
zation. The number of polyethylene occlusions (in-
traspherulitic) was found to be higher in the
a-spherulites than the P-spherulites, whereas in
the region containing predominantly P-spheru-
lites, dispersed polyethylene domains were found
mainly at the interspherulitic boundaries. This was
confirmed from morphological observation with
scanning electron microscope on the films crystal-
lized from melt and subjected to etching. The dis-
persed polyethylene droplets were removed as the
amorphous interphase between the polypropylene
and polyethylene was preferentially etched by a
solution of chromium trioxide in concentrated sul-
phuric acid.
Morphology of PE/PP blends has also been
widely investigated with scanning electron micros-
copy.20,33,48,5c56 Tensile or impact fracture surfaces
under room temperature or liquid nitrogen condi-
tions were observed directly. When compression
molded blends containing less than 50% polyethyl-
ene were fractured under liquid nitrogen condi-
tions, two distinct phase structures were observed.
Islands of polyethylene were dispersed within a
continuous matrix of polypropylene. The size of
these islands decreases with decreasing polyethyl-
ene c ~ n t e n t . *The~ , ~polyethylene
~ phase was char-
acterized by very short lamellae, while the poly-
propylene phase had very broad and long
lamellae.20,54 In the case of a 50/50 blend, fracture
was through both the predominantly polyethylene
dispersed phase and the polypropylene matrix,
and both the polypropylene and polyethylene
phases were i n t e r c o n n e ~ t e d . ~On
~ , ~the
~ other
hand, for PE/PP compositions of much less than
ADVANCES IN POLYMER TECHNOLOGY
POLYETHYLENE-POLYPROPYLENE BLENDS
50% polyethylene, failure was initiated at the PE/
PP boundaries, as distinct spherical particles and
voids were observed. This was also observed for
an impact fractured 20/80 PE/PP blend at room
temperature, where drops of dispersed polyethyl-
ene and voids were observed.33The area occupied
by uncovered polyethylene droplets and voids was
much greater than the volume concentration of the
blend, suggesting that the fracture path was di-
rected toward the largest perimeters of embedded
polyethylene droplets. The dispersed PE droplets
appeared to increase in size with increased com-
pression molding time.51In the case of blends con-
taining more than 50% polyethylene, polypropyl-
ene became the dispersed phase,48and the fracture
surface morphology was similar, with increase in
size of polypropylene dispersed droplets as the
polypropylene contents increased.
Injection molded samples yielded a different
fracture surface morphology compared to com-
pression molded samples. Due to the high shear
flow and fast cooling conditions in injection mold-
ing, the dispersed phase may become elongated
ellipsoids or rods instead of spherical drop-
l e t ~ . The
~ ~ matrix
, ~ ~ phase
, ~ ~ may also be oriented in
the flow direction. Under room temperature ten-
sile failure, the sample underwent drawing prior
to fracture. Fracture surfaces showed coarse fibril-
lar morphology52for both the homopolymers and
the blends. No spherical dispersed phase was ob-
served, and the fracture surfaces of the blends ex-
hibited layered structures. Striations perpendicu-
lar to the deformation direction were also
observed. Compression molded samples contain-
ing a very finely dispersed polyethylene phase
may undergo drawing, and the fracture surfaces of
drawn blends gave similar fibrillar structure, while
samples that failed under liquid nitrogen condi-
tions had a dispersed droplets morphology.MBrit-
tle fractured surfaces of extruded and hot drawn
blends also had dispersed droplets m ~ r p h o l o g y . ~ ~
From the observation of the various studies, we
can conclude that for a PE/PP blend composition of
50/50, the interpenetrating morphology is predom-
inant. The size of the dispersed phase (polyethyl-
ene in polypropylene matrix or polypropylene in
polyethylene matrix) has been reported to range
from 0.1 to 20 pm. In general the size of the dis-
persed domains increased with increase in content
of the disperse phase, decreased with increased
extent of mixing, and increased with annealing or
slow cooling. The phase morphology is highly de-
pendent on the processing and thermal history.
7
POLYETHYLENE-POLYPROPYLENE BLENDS
IEpitaxial Crystallization of
PE/PP Blends
Homoepitaxy was obtained by hydrodynami-
cally induced crystallization and formed distinct
structure such as shish kebabs.58Expitaxy is sel-
dom observed in melt crystallization due to the
lower mobility of macromolecular chains that
tends to hinder the development of single crys-
t a l ~However,
.~~ in the case of PEiPP blends, epi-
taxial crystallization may be induced to take place
under special ~ o n d i t i o n s .In~ addition
~ ~ ~ , ~to ~the
~ of lamellalike PP crystals. However, the PE b-axes
requirement of lattice match, epitaxy in macromol-
ecules may also be restricted by the matching of
the lamellar thickness.68
Keller's study on oriented polymers obtained by
a special technique from a solution of a mixture of
polyethylene and polypropylene indicated the
presence of blended fibers of ribbonlike shape with
30-50 pm width and 5 pm thickness, with inti-
mately crystalline regions of each pure compo-
nent.69Epitaxy was ruled out as differential scan-
ning calorimetry showed that the blends gave a
superposition melting curve of the pure neat
homopolymers: a strong and sharp melting peak at
140.5"C corresponding to the polyethylene crystals,
a broad shoulder at 147°C corresponding to the
shish kebab structure of polyethylene, strong and
sharp melting peak at 168-171°C corresponding to
polypropylene crystals, and a broad shoulder at
180-190°C corresponding possibly to the extended
backbone chain PP shish kebab. An X-ray diffrac-
tion study also indicated the existence of separate
crystalline phases, and no amorphous scattering
was detected. However, the monoclinic phase of
polyethylene, found to be present in the pure
polyethylene fibers, disappeared when the poly-
propylene contents exceeded 30%. Electron mi-
croscopy failed to elucidate any detailed structure
in that study.
Nishio et al.70studied the crystallization behav-
ior of oriented blends of PE/PP (drawn at 90°C to a
draw ratio of 6) annealed at a fixed length at 155°C.
New orientation texture of polyethylene was pro-
duced during melt recrystallization. The (110)
plane was found to be perpendicular to the draw
direction. Lamellar structure was arranged with
the crystallite b-axes at an angle of 30-40" to the
draw direction. However, epitaxial crystallization
was ruled out based on work of earlier workers36
and also on the large mismatch between the lattice
a VOL. 13,NO. 1
spacings of polyethylene and polypropylene. The
authors instead attributed the observation to the
tilting of the growing polyethylene crystals by la-
mellar slippage due to shrinking forces generated
in the course of cooling. It was also argued that
crystallite b-axes will tend to orient perpendicular
to the flow direction when the polyethylene melt
was crystallized under compressive stress.
Kojima and Satake3*reported similar findings
for the drawn PE/PP blends subjected to different
heat treatments. After ion etching, cross-hatched
and twisted or layered textured inclusions of PE
crystals were observed to be situated within arrays
were found to be oriented in the direction of draw.
Epitaxial growth of polyethylene onto polypro-
pylene or polypropylene onto polyethylene has
been carried out by two methods: (a) annealing of
drawn blends of PE/PP or sandwiched films of PE/
pp37-38,6=6. ,and (b) vacuum deposition or cast film
crystallization of PE or PP onto single crystals or
oriented film of PP or PE.39,5942
Morphology of the epitaxially grown PEiPP
blends was very similar for both methods of prepa-
ration. Cross-hatched morphology developed by
epitaxial growth, where the crystalline lamellae
and chains were inclined at a significant angle
(about 50") to the substrate chain axis, was exhib-
ited by both PE onto oriented and PP onto
oriented PE.65 These epitaxially grown lamellae
had been analyzed by electron and X-ray diffrac-
tion. The epitaxial relationship has been estab-
lished for the (I0O)pE and (OZO)ipp contact planes.62It
was postulated that the PE chain axis was lying
parallel to the bisector of the angle made by the PP
chains oriented at 50" (half the monoclinic p angle).
The epitaxially grown PE chain will then interact
with rows of methyl groups that populate the (010)
planes of PP. The interrow distance of the methyl
groups is 0.505 nm apart, and in the (100) plane of
PE, the chains are 0.495 nm apart. Hence lattice
matching has been observed in this case. How-
ever, epitaxial crystallization has also been ob-
served between PE and p-PP,@and if the similar
model is applied for the (1010)ipp and (100)pE con-
tact planes, the structural analysis predicts the PE
chains to be inclined at 245" to the P I' chain axis.
This was not supported by experimental evi-
d e n ~ e .Epitaxy
~ ~ , ~ was observed mostly between
HDPE and PP, although it has also been reported
for LDPE and
Mechanical properties of expitaxially formed
PE/PP blends exhibited s y n e r g i ~ m . ~ ~This ,~,~~,~,~~

has been attributed to the bridging of the amor-
phous intercrystalline regions in the stacked lamel-
lar morphology by the epitaxially grown crystals of
the second component.
ICrystallization Kinetics of PE/PP
The crystallization kinetics of a crystalline
homopolymer is controlled by the type of nuclea-
tion, rate of nucleation, and rate of spherulite
growth, which in turn are dependent upon the
nucleating density, the degree of supercooling, the
temperature of crystallization, and the rate of cool-
ing.27,71-74
The crystallization behavior of a blend is
made more complex by the presence of a second
crystallizing or noncrystallizing component.
Crystallization kinetics may be studied with a
dilatometer, an optical microscope, or a differential
scanning calorimeter. Optical microscopy is used
to determine the radial growth rate of spherulite,
G, by measuring the size of the spherulite as a
function of time during isothermal crystallization:
G = dR/df (1)
The Avrami constants can be determined from op-
tical microscopy using the Avrami equation75:
1 - W,/W, = exp[-Kf"] (2)
where WJW, = X,,the fraction of material crystal-
lized after time t, and may be obtained from the
spherulite size measurement. The DSC has also
been employed in the study of rate of crystalliza-
tion by using the following equation:
X, = (dH/dt) dt/jr (dH/df) dt (3)
0 0
where the heat of crystallization, Ht, after time t is
used to determine the X,.The Avrami equation
may then be analyzed in the following form as
derived from eq. (2):
In[-ln(1 - X,)]= Zn(K) + n.ln(t) (4)
From a DSC study on isothermal crystallization
using the measurement of half-time of crystalliza-
tion (7112) of polyethylene and polypropylene, Mar-
ADVANCES IN POLYMER TECHNOLOGY
POLYETHYLENE-POLY PROPYLENE BLENDS
.
Jc!
N
r-
T, /K
FIGURE 4. Half-time of crystallization of PE and
PP. [After Reference 13, Figure 1, E. Martuscelli et
al., Makromol. Chem., 181, 957 (1980), with
permission from the publishers, Huthig 81Wepf
Verlag, Basel, Switzerland.]
tuscelli et al. l3 had identified three different ranges
of crystallization temperature (T,) corresponding
to three different types of crystallization behavior
of the PE/PP blends (Fig. 4).Below T, of 125"C, the
~ ~ of/ PE
2 and PP were of the same magnitude, and
a single crystallization exotherm was exhibited by
the blend, where simultaneous crystallization of
the PE and PP was observed. From T, of 125 to
127"C, two crystallization peaks were observed,
with PP crystallizing first and also much faster
than the PE. At T, above 127"C, crystallization of
PE did not occur or happened very slowly, and the
crystallization behavior corresponded to crystalli-
zation of PP in a melt mixture of PE and PP, giving
a single exothermic peak. On the other hand, in
the case of nonisothermal crystallization under a
constant cooling rate of 5"C/min, the thermogram
gave a peak for the PP crystallization exotherm fol-
lowed by a shoulder of the PE crystallization ex-
otherm, for blend compositions of more than 75%
(Fig. 5). However, it has been reported earlier
that physical blends of PE/PP crystallized simulta-
neously, giving a single exothermic peak at practi-
cally all blend compositions at a cooling rate of 2"C/
min.28 The analyses of the kinetics of
crystallization based on crystallization under iso-
thermal and constant rate of cooling conditions
may yield different results.
9
POLYETHYLENE-POLYPROPYLENE BLENDS

decreased with increase in PE content.77The same

conclusion was obtained from the primary nuclea-
tion density, N, (determined from spherulite
growth rate, G, and Avrami constant, K , from DSC
data) which was found to decrease monotonically
with the PE content47 (Fig. 7). This would imply
that the PP spherulite size would increase with
increase in PE content, which would be contrary to
the observation reported earlier where a reduction
of PP spherulite size was observed for the
blends.20,u However it should be noted that the
conditions of crystallization were different for the
isothermal crystallization at high T, ,47,77 and the
rapid cooling from melt.20,22This was substantiated
by a later on PE/PP blends crystallized
90 100 110 120 130 isothermally at temperatures below 127"C, where
TEMPERATURE ("C) simultaneous crystallization of PE and PP were
taking place. The nucleation density was found to
FIGURE 5. DSC thermograms during cooling for increase with increase in PE content in the blend. It
PP and various blends of PP/HDPE: (1) -( 1 was postulated that at crystallization temperatures
PP: (2) (-.-.-) 95PP/5HDPE; (3) (----- I above the melting point of PE, the heterogeneous
9OPP/lOHDPE; (4) (---) 8OPP/POHDPE; (5) nuclei migrated across the interphase boundary
(-.- ) 75PP/25HDPE. [After Reference 52,
Figure 1, A. K. Gupta et al., J. Appl. Polyrn. Sci., 27,
from PP melt to PE melt, hence a decrease in the
4669 (1982), with permission from the publishers,
John Wiley & Sons, Inc., New York.]

iPP-LDPE CF5

From an optical microscope study, the PP ' l o I P P "IoLDPECF5

100 0
spherulite growth rate in PE/PP blends under iso- 90 10
thermal crystallization conditions at crystallization A 70 30
temperatures above the melting point of PE was & 50 50
found to be constant and was unaffected by the
presence of the PE domains for blend composi-
tions of up to 50% PE'2,33,4a7,49(Fig. 6 ) . Spatial
hindrance to PP spherulite growth due to the pres-
ence of PE occlusions did not cause any change in
the growth rate. From a theoretical calculation,
based on a simple model of the PP crystallizing
front encountering a spherical PE occlusion, Ga-
leski et al.33 have shown that u p to 50% PE, the
growth rate was decreased by only 5% for two-
dimensional growth, which was near to the experi-
mental error involved. Inclusions were engulfed or 124 128 130 132 134 136
rejected by the growing spherulite depending on T, /'C
the difference in interfacial en erg^.^"^^ Rejection of
FIGURE 6. Spherulite growth rate of iPP/LDPE
inclusions will induce a considerable depression in
blends of different compositions at different
the spherulite growth rate. crystallization temperatures. [After Reference 47,
Optical microscope measurements of the num- Figure 3, E. Martuscelli et al., Makrornol. Chem.,
ber of PP spherulites formed under isothermal 185, 1041 (1984), with permission from the
crystallization temperature above the melting of publishers, Huthig & Wepf Verlag, Basel,
PE showed that the number of PP spherulites was Switzerland.]

10 VOL. 13, NO. 1


( a ) I P P 100%
1.5 2.0 2.5 3.0
log { ( t - t , ) / m i n )
FIGURE 7. Avrami plots of (a) iPP; (b) 80% iPP / 20% LDPE blend at different crystallization temperatures
[After Reference 47, Figure 5, E. Martuscelli et al., Makromol. Chem., 185, 1041 (1984), with permission from
the publishers, Huthig & Wepf Verlag, Basel, Switzerland.]
nucleation density of PP. On the other hand, at
crystallization temperatures below 127"C, the PE
crystals growing in the blend may cause additional
heterogeneous nucleation of PP spherulites. This
postulation was supported by electron microscope
observation on the interphase boundary of PE and
PP, where copious nucleation of polypropylene
was observed on the boundary growing inwards to
the PP melt, while for the PE phase, sporadic nu-
cleation was observed leading to semicircular
bands centered on the interface.78 Optical micro-
scope observation for blends crystallized isother-
mally at 135°C also showed an increase in nuclea-
tion density for the PE/PP blend.79From a constant
rate cooling crystallization study, Gupta et al.52
have postulated that the rate of nucleation of PP
was enhanced by the addition of PE as evidenced
by the increase in the initial slope of the exotherm
of constant rate cooling crystallization. Reduction
in size distribution of the PP crystallites was sup-
ported by the observation of the decrease of half-
width of the crystallization peak.
In the case of simultaneous crystallization under
isothermal conditions, from DSC results, the
Avrami coefficient, n, was found to increase signifi-
cantly (from 2.3 for pure PE to 3.2 for a HDPE/PP
blend). This has been attributed to a change from
instantaneous to sporadic nuc1eati0n.I~It was also
found that the kinetics of crystallization of polyeth-
ylene was greatly delayed by the addition of a
small amount of polypropylene (=lo% by weight).
ADVANCES IN POLYMER TECHNOLOGY
POLYETHYLENE-POLY PROPYLENE BLENDS
1.5 2.0 2.5 3.0
Log { ( t - t , ) / m t n ]
The overall rate of crystallization of the polypro-
pylene phase for isothermal crystallization at T,
high enough to prevent any polyethylene crystalli-
zation was found to be strongly depressed by the
. ~ ~ the PP spherulite
addition of p ~ l y e t h y l e n eSince
growth rate was found to be constant, this de-
crease in overall rate was due to a decrease in the
nucleation density. In the case of LDPE/PP blends,
the Avrami constant n was found to be between
2.2 and 2.7 for most of the compositions and crys-
tallization temperatures studied and was slightly
higher than that for pure PP ( n = 1.8-2.0).
It may be summarized that in the crystallization
of PE/PP blends, the PP radial spherulite growth
rate is independent of blend compositions, but de-
creases with increase in crystallization tempera-
tures. The nucleation density in the PP phase is
decreased while that in the PE phase is increased.
Hence for isothermal crystallization temperatures
above the melting point of PE, the crystallization
rate is decreased with increase in the amount of
PE. However, in the case of isothermal crystalliza-
tion at temperatures below the melting point of
PE, or crystallization at a constant rate of cooling,
there may be a migration of heterogeneous nuclei
from the PP phase to the PE phase, but the overall
number of heterogeneous nuclei is increased due
to the presence of polyethylene crystallites which
may act as additional nucleating centers for the PP.
Hence a reduction of PP spherulite size is observed
in PE/PP blends.
11
POLYETHYLENE-POLY PROPYLENE BLENDS

IMechanical Behavior of
Polyethylene- Polypropylene 6oo/
Blends
The dependence of the mechanical response of
a blend on composition may be described by
models of composite material^^,^^,^^,^^^ (Fig. 8).
For the modulus-composition relationship, for
continuity of strain at the interface, we have the
parallel Voigt model. For continuity of stress, one
may employ the series Reuss model.80The Nielsen
and Halpin modified Kerner equation has been ap-
plied to particulate filled polymer systems,81while
the Takayanagi modeP2 has been widely used in 0' ' I I
60
I

40
I

20
I
0 PE
100 80
the study of oriented crystalline-amorphous poly- 0 20 40 60 80 1OOPP
m e r ~A. ~more
~ practical approach is the Simplex COMPOSITION
equation ( E = El+l + E2+2 + which enables FIGURE 9. Synergism and negative deviation of
synergism or antagonism to be described by a posi- dependence of modulus of PE/PP blends on
tive or negative interaction parameter /3.R4 compositions. [After Reference 86, Figure 4,J. W.
In general it has been found that for PE/PP Teh et al., Proc. lnt. Plast. Conf.,Kuala Lumpur,
blends, the dependence of modulus on composi- Malaysia, 22-24 October, 1985.1
tion can be best described by the rule of mixture
Voigt model,8~2z~25~43,54~6~7 but an antagonistic ef-
fect22,55,88,69
and synergistic effect9,10,20,52,67
have also
been reported (Fig. 9). Synergism was observed in the case of HDPE/
PP blends but not in LDPE/PP blends. This could
be due to the closeness of the melting points of
HDPE and PP. The difference in observations from
12
I different workers could be due to the differences in
I
the molecular weight and the melt viscosity of the
10
resins used. However, the discrepancy observed is
most probably the result of different ways of prep-
r n 6 aration of the blends, as reflected in processing
2 and thermal history.86 As discussed earlier, pro-
2 6 cessing history will affect the phase distribution
0
H and final morphology of the blend. Hence com-
4 pression molding with slow cooling will result in
phase segregation due to coalescence of the dis-
2 perse droplets, and initial crystallization of the PP
E followed by simultaneous crystallization of PE and
PP which will usually yield larger spherulites. On
0.0 0.2 0.4 0.6 0.0 1.0 the other hand, injection molding will impart high
COMPOSITION shear to the melt blend, and will result in fine and
better intermixed dispersed morphology. The
FIGURE 8. Theoretical curves of modulus of rapid cooling in the cold mold will result in simul-
two-component composite: (I)simplex equation; (11)
rule of mixture, Voigt model; (111) Nielsen and Halpin
taneous crystallization of both the PE and PP
modified Kerner equation; (IV) rule of mixture, phase leading to smaller spherulites. Synergism in
Reuss equation. [After Reference 22, Figure 3, J. W. modulus observed in the case of HDPE/PP blends
Teh, J. Appl. Polym. Sci., 28,605 (1983), with has been attributed to the reduction in average
permission from the publishers, John Wiley & Sons, spherulite size of PP due to PE, an increase in crys-
Inc., New York.] tallinity, and formation of intercrystalline links.20

12 VOL. 13. NO. 1

 POLYETHYLENE-POLY PROPYLENE BLENDS

based on the actual final rupture cross-sectional

area for the blends will be much lower than that of
301 the homopolymers20~87 (Fig. 11). Hence depen-
dence of true tensile strength on composition will
/
then actually be described by negative deviation
0 20
a behavior in all cases. In the case of yield stress, the
I
dependence on composition again varies from
v)
Vl
negative d e ~ i a t i o n ’ ~ , ~to~ , linear
~ ~ , ~ ~depen-
w dency8J0tHand positive d e v i a t i ~ n . ” , ~Various
~,~~,~~
lx
I-
equations have been proposed by different work-
v, 10
ers to account for the dependency of yield stress
~ ~ 12). Positive deviation may
on c o r n p ~ s i t i o n(Fig.
be described by an interaction parameter 7, similar
o Point of rupture to /3 in modulus dependency in the Simplex equa-
tion. Negative deviation may be ascribed to the
0 0.1 0.2 0.3 0.4 0.5 0.6 ease of decohesion of the immiscible inclusions in
STRAIN a matrix, where the yield strength will decrease as
FIGURE 10. Typical uniaxial stress-strain curves a function of the volume fraction of the disperse
of: (A) PP; (B) 80PP/20PE; (C) 60PP/40PE; (D) phase. In the case of incompatible blends like PE/
40PP/60PE; (E) 20PP/80PE; (F) PE. [After Reference PP, negative deviation is expected. However, the
22, Figure 1, J. W. Teh, J. Appl. Polym. Sci., 28, 605 observed synergism in yield stress must arise from
(1983). with permission from the publishers, John some interaction between the PE and PI’ phases,
Wiley 8, sons, Inc., New York.] either an increase in crystallinity, a change in
spherulitic morphology, or an increase in tie mole-
cules and intercrystalline links.z0It has also been
postulated that a small amount of PE may decrease
Typical stress-strain curves of compression
molded polyethylene, polypropylene, and their
blends are shown in Figure 10. In the case of
homopolymers, after reaching the maximum stress - 150
at yield, the stress dropped slightly, followed by 0
a
necking and cold drawing at constant nominal I 4
I
stress up to several hundred percent strain after I
I 30 1 HDPE/PP
which strain hardening took place when necking G I m/*--m-b
z
g
L
had spread throughout the gauge length. This was W I
-7- -100
followed by ultimate rupture. In the case of PE/PP E
v)
blends, the specimen may break prior to or imme- m
diately after yielding, if yielding and necking were Y . I
I-

d,i
3
indeed observed. Hence elongation at break was
very small in the case of compression molded 8
-I
2c
\
\
\
LDPE/PP
c-
I
-
50
W
2
I-
blends. For injection molded PEiPP blends, cold 2 \
\
drawing was observed and elongation at break I / -

was higher depending on the compositions, but

failure was normally fibrillar with serious delami-
0
= 1c -
-
0
-‘
\
eL,- - A- -AN /

L I I I I I I
nation. 9o 100 80 60 40 20 0 PE
Variation of ultimate tensile strength of the 0 20 40 60 80 1OOPP
blends with composition was observed to follow COMPOSITION o/o

the rule of mixtures,8,86 but negative devia-

tion22,45,85,86,90
and positive deviation and syner-
gism9,10,20,52,87
were also observed. However, it
should be pointed out that reported ultimate ten-
sile strength was calculated based on the original
cross-sectional area, and the true tensile strength,
FIGURE 11. Nominal ultimate tensile strength and
true ultimate tensile strength of PE, PP, and PE/PP
blends as a function of composition. [After
Reference 87, Figure 5, J. W. Teh et at., Proc. Int.
Plast. Conf., Kuala Lumpur, Malaysia, 22-24
October, 1985.1

ADVANCES IN POLYMER TECHNOLOGY 13

 POLYETHYLENE-POLY PROPYLENE BLENDS
0 I
o 0.2 0.4 0.6 0.8 1 provement in bonding between the phases, from a
volume fraction of LLDPE
FIGURE 12. Dependence of yield strength on
composition of PE/PP blends, experimental data
(points) and different theoretical models (lines).
[After Reference 25, Figure 5, V. Flaris and 2. H.
Stachurski, J. Appl. Polym. Sci., 45, 1789 (1992),with months
permission from the publishers, John Wiley 8, Sons,
Inc., New York.]
the PP matrix plasticity, and the PE has a marked
reinforcing effect resulting in a delay in the neck
formation, and hence an increase in yield stress.85
Elongation at break, in all cases, has been found
to be markedly decreased for the blends compared
with the homopolymers. In the case of homopoly-
mers, the large elongation at break is due to the
ability of the semicrystalline polymers to be cold
drawn through an orientation process where la-
mellae are rotated toward the draw direction and
broken u p into microlamellae and submicroscopic
units. The multilayer lamellar crystal is destroyed
by tilting and slipping of the chains.92In the case of
the blends, interspherulitic boundaries between
the PE spherulites and PP spherulites are very
weak, and interspherulitic rupture occurs prior to
orientation of the lamellae and cold drawing in
most cases.
The mechanical behavior of PE/PP blends is
affected by the processing history and thermal and
orientation treatment. Repeated granulation of
compression molded blends, after 10 cycles,
yielded blends of mi~roheterogeneity.~~ Modulus
of the blends prepared in this way exhibited linear
dependency on composition. However, if the
blends were annealed at 190°C for 3 1/2 hours, a
sigmoidal curve for the modulus-composition re-
lationship was obtained. compression molded
blends premixed with a Brabender plasticorder
gave different tensile behavior when the mixing
time was ~ a r i e d . ~For~ , a~ PE/PP
~. blend of 50/50 from the publishers, Chapman & Hall, London.]
14
composition subjected to short mixing time (2
min), the sample failed immediately after yieldings
exhibiting very low elongation at break, whereas
for blends subjected to a longer mixing time (15
min), necking and cold drawing were observed af-
ter yielding and elongation at break was much
higher. However, for samples subjected to very
long mixing time (2 h), brittle failure was again
observed. Annealing at 135°C for 5 h of injection
molded PE/PP blends improved the yield stress
and m0dulus.8~This was attributed to some im-
scanning electron microscopy study of the fracture
surfaces. However, the yield stress and modulus of
the homopolymers were also improved by anneal-
ing. Injection molded HDPE/PP blends of 70130
composition after aging at room temperature for 3
exhibited a hardening effect and showed a
slight decrease in elongation at break, and a small
increase in ultimate and yield stresses, elongation
at yield, and modulus.94 The hardness of the
blends and neat polymers when quenched from
melt at 220°C did not show significant differences,
but was affected by annealing.95When the blends
were annealed at 138°C followed by quenching,
pure PP yielded a much higher hardness (87 MPa)
than pure PE (48 MPa), and the hardness of the
blends assumed values in between, exhibiting a
negative deviation from rule of mixture (Fig. 13).
On the other hand, when the blends were an-
nealed at 129"C, the hardness of pure PE (86 MPa)
was higher than that of pure PP (70.5 MPa), and
i
100
I I 1 I
0 2 5 50 75 100
XPP( %)
FIGURE 13. Deviation from linear dependency on
composition of microhardness of PE/PP blends.
[After Reference 95, Figure 1, J. Martinez Salazar et
al., J. Mater. Sci., 23,862 (1988),with permission
VOL. 13, NO. 1
 POLYETHYLENE-POLYPROPYLENE BLENDS

the hardness of the blends was again intermediate

between the hardness of the two pure compo-
nents. This was attributed to the mutual influence
of the PE and PP phase on the crystallization be-
havior of the PE and PP during the process of an-
nealing.
The effect of orientation on PE/PP blends has
been investigated by different ~ ~ r k e r ~ . ~ ~ , ~ ~ , ~ , ~ ~ , * ~ ~
A novel method of surface growth technique pro-
duced oriented blends where intimately mixed fi-
bers resulted in adsorbed surface layers and entan-
~ , " 50/50 blend was found to give a
g l e m e n t ~ . ~ The
fiber modulus of 20 GPa, lower than drawn PE
fibers but higher than drawn PP fibers. Extruded
blends with very little drawing exhibited isotropic FIGURE 14. Fracture surface of hot drawn PE/PP
characteristics from an X-ray diffraction study, and blends. [After Reference 98, Figure 7, P. Robson et
the tensile yield behavior was very similar to that al., J. Appl. Polym. Sci., 26, 3515 (1981), with
of injection molded blends. However, the tensile permission from the publishers, John Wiley 8, Sons,
strength and elongation at break were found to be Inc., New York.]
independent of the blend composition, but at a
value much lower than that of the homopoly-
m e r ~When . ~ ~ the blends were cold drawn at 60°C, can be described with the simple parallel Voigt
the drawn blends and the homopolymers gave model.
similar ultimate tensile strength^.^^ In the case of In summary, the mechanical properties of poly-
hot drawing, the tensile properties of the homo- ethylene-polypropylene blends exhibit rule of
polymers and blends were found to be dependent mixture dependency on composition in general,
on the draw temperatures, the draw ratios, as well except for the elongation at break. Compression
as the compositions of the blends.96The tendency molded blends give inferior performance com-
of both the PE and PP to fibrillate in the blends pared to injection molded blends. This is due to the
subjected to drawing was observed in the SEM tendency for phase separation or segregation to
(Fig. 14). The tensile behavior of extruded occur readily in the case of compression molding.
blends subjected to large melt draw down (from High density polyethylene, as a minor component
8.5 mm die diameter to a filament of 1.0 mm diam- in the blends, imparts synergism to the PE/PP
eter) was also reported by Sherman.55 The ex- blends, possibly due to the closeness in melting
truded filaments were subjected to further cold point of the two polymers, which enables simulta-
drawing at room temperature. The cold drawn neous crystallization of the PP and PE under rapid
blends exhibited a complicated tensile properties- cooling conditions. Processing conditions, such as
composition relationship. However, when the cold the degree of mixing, rate of cooling, orientation,
drawn blends were subject to annealing at 150°C at and annealing history, control the final mechanical
fixed elongation, the resultant blends exhibited a properties through development of different solid
linear relationship between modulus and tensile state morphology.
strength with composition. The observation was
explained in terms of continuous fiber composite
theory. In another study99films stretched at 110°C
at different draw ratios showed a decrease in ten- I Rheological Behavior of
sile strength with increase in PE contents, the de- Polyethylene-Polypropylene
crease being higher for the film drawn at a higher
draw ratio. In the case of compression molded 50/
Blends
50 PE/PP blends subjected to different extents of
cold drawing, the 10-s isochronal creep moduli of The melt rheological behavior of PE/PP blends
the blend were found to lie between those of the has been studied extensively.6,7,9,16,21,53,57,87,101-109
pure components.100 Analysis by crystal strain The dependence of the flow behavior on composi-
measurements indicated that the blend behavior tion is more complex than the dependence of me-

ADVANCES IN POLYMER TECHNOLOGY 15

POLY ETHYLENE-POLY PROPYLENE BLENDS
100 10' ld lo3
SHEAR RATE, 9 ,(set-1)
FIGURE 15. Plots of viscosity versus shear rate for
PE/PP blends at 180°C: (0)PP; ( 0 )PP/PE-75/25;
(0)PP/PE-50/50; (W) PP/PE-25/75; (A)PE. [After
Reference 16, Figure 1, N. Alle et al., Rheol. Acta,
19, 94 (1980), with permission from the publishers,
Verlag GmbH & Co. KG.]
chanical properties on composition. In order to
predict the rheological characteristics of a blend
from known rheological properties of the constitu-
ents, various blending laws have been proposed as
summarized by Plochocki in an early review,6 and
more recently by U t r a ~ k i ~and
, " ~ others."'
An early study by Alle et a1.I6 found that the
flow behavior of the blends follow closely that of
the pure polymers. The melt flow curves of the
blends were found to lie between those of pure
homo polymer^'^^^^^'^^'^^^'^^ (Fig. 15). However, it
has also been found that the flow curves of the
blends in some cases may be lower than both the
l a 1 IPP-IlHDPE-2
1 ./
"*,I
FIGURE 16. Viscosity versus blend composition at fixed shear stress for different iPP/HDPE blends of
different melt viscosity ratio. [After Reference 108, Figure 6, M. Fujiyama and Y. Kawasaki, J. Appl. Polym. Sci.,
42, 467 (1991), with permission from the publishers, John Wiley & Sons, Inc., New York.]
16
pure homo polymer^.^^^^^ In the case where there
was a cross-over of the flow curves for the PP and
PE, the flow curves of the blends were again lo-
cated in between, gradually changing from the
character of PP to PE with increasing content of
PE.lo8
The dependence of melt viscosity on composi-
tion at constant shear stress was found to be de-
pendent on the viscosity ratio of the pure poly-
mer104 (Fig. 16). Linear, negative deviation,
sigmoidal or minimum behavior had been ob-
served depending on the type of PP and PE and
the shear ~ t r e ~ ~ Melt . ~ viscosity
~ , ~ exhibiting
~ , ~ ~ ~ , ~ ~ ~
complex dependence on composition has also
been r e p ~ r t e d .In~ the
~ , ~case
~ ~ of two-phase poly-
mer blends, viscosity-composition curves may go
through a maximum and/or a minimum, depend-
ing on the level of shear stress applied. This has
been explained by considering the deformation
and elongation of the dispersed droplets in a flow
shear field.112Four types of behavior have been
proposed which account for (a) little interaction
between the disperse droplets and the matrix; (b)
phase inversion; (c) elongation of droplets into fi-
brils during flow; and (d) strong interactions
among droplets or interlocked morphology (Fig.
17).
The extrudate swell (defined as the ratio of the
extrudate diameter to the capillary diameter), a
measure of melt elasticity, has been found to be
dependent on composition, temperature, and
shear stress or shear rate.21,87J0k105,108 Earlier inves-
tigations have found that extrudate swell exhibited
lbl IPP-2lHDPE-2 1c.l iPP-3/HDPE-2
lo3/ , ,
0 50 100
@ ("lo)
VOL. 13, NO. 1

0 50 100 0 50
B (VOI'10) B ( VOI%)
FIGURE 17. Schematic representation of different
shapes of blend viscosity curves of (a) monotonous
increase (b) s-shaped curve (c) exhibiting a
minimum (d) exhibiting a maximum. [After
Reference 112, Figure 4.45, C. D. Han, Multiphase
Flow in Polymer Processing, Academic, New York,
1981, with permission from the publishers,
Academic Press, Orlando, Florida.]
temperature dependency behavior when plotted
against shear rate, but was independent of temper-
ature when plotted against shear stress.11s115
However, it has also been found that in the case of
10
lo4 lo5 104
FIGURE 18. Extrudate swell behavior of different PE/PP blends. [After Reference 104, Figure 8, A. Valenza et
al., Eur. Polym. J., 20, 727 (1984), with permission from the publishers, Pergamon Press Ltd, Headington Hill
Hall, Oxford OX3 OBW, UK.]
ADVANCES IN POLYMER TECHNOLOGY
POLYETHYLENE-POLYPROPYLENE BLENDS
polyolefins, other than linear low density polyeth-
ylene, high and low density polyethylene and
polypropylene all exhibited temperature depen-
dency both as a function of shear stress and shear
rate.87At constant temperature, extrudate swell in-
creased with increase in shear stress or shear rate
in most cases except for low density polyethyl-
enes, a polymer susceptible to shear modifica-
tion.l16 In the case of HDPE/PP blends, at 200°C
capillary extrusion, the extrudate swell behavior of
blends as a function of shear stress followed
closely that of the polypropylene when the blend
composition was more than 50% PP, and the
curves were similar to that of HDPE for blend com-
position less than 50% PP87,104 (Fig. 18). In the case .
of HDPE/PP blends investigated by Alle et a1.,21
the extrudate swell of the PP, PE, and 25/75 PE/PP
100 were found to be independent of temperature
when plotted against shear stress. The 50/50 and
75/25 blends, however, exhibited temperature de-
pendency, the extrudate swell increasing with in-
crease in temperature of extrusion. It is interesting
to note also that the 25/75 blend exhibited a mini-
mum when extrudate swell was plotted against
shear stress, whereas linearity was observed in all
other cases. Santamaria et al.Io5found that the ex-
trudate swell versus composition plot gave a broad
maximum, while Fujiyama and KawasakiIo8 ob-
served complex dependency of extrudate swell on
shear rate and composition, and the behavior was
found to be controlled by the viscosity ratio of the
constituent PE and PP.
An early study117has shown that melt fracture
los 1o4 lo5
rt (Pa)
17
POLYETHYLENE-POLYPROPYLENE BLENDS
of polyethylene may be improved by the addition
of ethylene-propylene copolymer to polyethylene.
The melt viscosities of polyethylene homopolymer
(MI = 0.4) and blend of polyethylene containing
4% of polyallomer (MI = 2.5) coincide at low shear
rates, indicating that the addition of polyallomer
did not change the melt index significantly. How-
ever, at a shear rate of 660s-', melt fracture is evi-
dent in the polyethylene, but not in the blend. The
melt elasticity of the blend (measured by extrudate
swell) is also lowered significantly.llg
Melt rheological behavior of blends cannot be
described by a simple additivity law, as the rheo-
logical behavior of the constituents may vary dif-
ferently with temperature and shear. Conse-
quently, the melt phase morphology may vary
with temperature, time, and shear rate, and this
will affect the melt flow behavior.
IModification of
Polyethylene-Polypropylene
Blends
The performance of an incompatible blend can
be modified through a reactive process with a per-
or improved by addition of a suitable
compatibilizer. Styrene-b-ethylene-co-butylene-b-
styrene has been used in a few investigation^,'^^-'^^
but the compatibilizer that has been widely investi-
gated for PE/PP blends is ethylene-propylene rub-
ber, EPR. 25,40,41,44,51,56,86,90,120,13&136
For 15/85 PE/PP blended with a roll-mill, the
modulus and yield strength increased to a maxi-
mum with the amount of peroxide added, and
then decreased with further increase in peroxide
content,120 However, impact strength was reduced
with addition of peroxide. In the case of blending
in an extruder, addition of peroxide led to deterio-
ration of properties. Addition of small amounts of
peroxide may lead to cross-linking and chain ex-
tension'37and hence improvement in modulus and
yield strength. At higher concentrations of perox-
ide, degradation reactions may become predomi-
nant, leading to a deterioration in properties. In
the case of extrusion blending, the high shear and
high temperature used may result in predomi-
nantly degradation reactions. From X-ray diffrac-
tion and DSC studies, crystallinity was found to
decrease with an increase in peroxide content. A
new melting peak for the DSC and a new diffrac-
18
0 0% Peroxide
v 0.1% Peroxide
0 1 % Pcroride
~
'" 0 25 50 75 loo
W t ' l o Of LDPE
FIGURE 19. The effect of increasing LDPE
concentration on the complex melt viscosities of
unreacted and peroxide reacted LDPE/PP blends.
[After Reference 123, Figures 5 and 6, D. W. Yu et al.
Adv. Polym. Tech.,10, 163 (1990), with permission
from the publishers, John Wiley & Sons, Inc., New
York.]
tion peak were also observed for the peroxide
modified blend.
It was found that at low concentrations of per-
oxide, only the PE component is cross-linked in all
composition of PE/PP blends.121However, cross-
linking between PE and PP or cross-linking of the
PP was enhanced when pentaerythritol tetrallyl
ether coagent was added. The melting and crystal-
lization temperatures of the PE and PP of the mod-
ified blends were found to decrease with increase
in peroxide concentrations.
In a recent study on peroxide modification of
PE/PP blends,122-126 it has been shown that PP un-
dergoes mostly chain-scission while PE undergoes
cross-linking reactions. Hence, depending on the
composition of the blend and the peroxide level,
the value of the melt viscosity and melt modulus of
the modified blends may be lower or higher than
the untreated blends (Fig. 19). The yield behavior
of the PE-rich blend was improved with peroxide
modification, whereas a lower yield stress was ob-
served for the peroxide modified PP-rich blend.'25
The initial dissimilarities in rheological properties
of the blend components can be adjusted to be-
come similar by peroxide reactions during com-
pounding, hence favoring efficient mixing.126
These fine morphologies of the reacted blends con-
tribute to an improvement in mechanical proper-
ties.
One of the major problems in the modification
of PE/PP blends with peroxide is the difficulty of
VOL. 13, NO. 1

controlling the degradation of the PP. Coagents
seem to be able to enhance cross-linking of PP or
PE with PP. However, more studies are needed to
find the optimum conditions for successful reac-
tive extrusion of PE/PP blends. A more successful
and simpler way is to add a compatibilizer to the
PE/PP blends, forming a ternary blend. This will
be discussed below.
Ternary Blends of Polyethylene,
Polypropylene, and
Ethylene-Propylene Rubbers
Incorporation of a more rubbery phase such as
polypropylene copolymer improves the impact
performance of the polypropylene.26 Ethylene-
propylene rubbers, including random and block
copolymers of ethylene-propylene and ethylene-
propylene-diene t e r p ~ l y m e r , ' ~ *and J ~ ~ethylene-
vinyl acetate c ~ p o l y r n e r s , ' ~have
~ ~ ' ~been
~ used to
improve the properties of polyolefins and also in
thermoplastic elastomers formulation.'49JMIn gen-
eral, the impact strengths of PP and PE are im-
proved with addition of random or block EPR,
while the tensile strengths are decreased. Similar
trends are observed in the case of addition of EPR
to blends of PE/PP.
It has been found that the tensile strength, ten-
sile yield, and modulus of PE, PP, and PE/PP
blends were lowered by the addition of an
EPR,45,56,s6,90J32JM except in one investigation
where addition of EPR caused a deterioration of
tensile strength in the case of PE and PP homo-
polymers, but resulted in an enhancement in ten-
sile strength in the case of PE/PP blends.45 This
was attributed to the premature rupture of the PE/
PP blends during cold drawing caused by the in-
stability of the flow probably due to the interac-
tions arising between crystallites of the two
polymers. Addition of EPR may reduce the insta-
bility of flow making the cold drawing process eas-
ier and more continuous resulting in an increase in
the tensile strength. The notched impact strength
of PE, PP, and PE/PP blends were enhanced by the
addition of EPR.U,86,90,131,132,134 Elongation at break
of PE/PP blends was also improved with the addi-
tion of EPR, but the elongation at break of the
homopolymers may be reduced.86
The improvement in impact behavior has been
postulated to be due to the compatibilizing effect
ADVANCES IN POLYMER TECHNOLOGY
POLYETHYLENE-POLYPROPYLENE BLENDS
of the EPR on the PE/PP b l e n d ~ . ~ From J ~ ~a ~ ~ J ~
detailed study of fracture surface morphology,
DOrazio et al. found that addition of EPR resulted
in homogenization of the materials, so that the dis-
persed phase observed in the binary blends was no
longer detected in the ternary b l e n d ~ . ~The
J ~ lfrac-
ture behavior also changed from a brittle crazing
mechanism to a combination of shear yielding and
multicrazing. Hence they concluded that EPR may
act as an "interfacial" or "emulsifying" agent, im-
proving the adhesion between the PE dispersed
phase and PP matrix. Affinity of PE for EPR was
found to be higher than that of PP for EPR as
shown by the presence of spherical domains regu-
larly distributed in the case of 15/85 EPR/PP
blends, but no disperse phase could be discerned
in the case of 15/85 EPR/PE blends.131From scan-
ning electron micrographs of microtomed sections
extracted with xylene, Stehling et found that
in the ternary blends, the dispersed phase may
exist as layered sphere structures of spherical PE
occlusions covered by layers of EPR in a PP matrix,
or as an interpenetrating structure of PE/EPR in a
matrix of PP, depending on the processing
methods (Fig. 20). This shell and interpenetrating
morphology of the PE/EPR phase had also been
reported by other ~ o r k e r s . ~The ~ ,interpene-
~~,~~
trating morphology was observed to be converted
to the shell morphology under prolonged heat-
ing51
The melt rheological behavior of the ternary
blends has been studied by Ha and Kim133and
Choudhary et al.lM Ha and Kim found that at a
given EPR concentration, minimum viscosity was
observed in the blends with equal amount of PP
and PE, and this has been ascribed to the phase
separation between the components due to the in-
herent heterogeneity. It was deduced also that PE/
EPR has slightly better compatibility than the PP/
EPR pair. Choudhary et a1.'% found that at low
concentrations of EPR, the melt viscosities of the
ternary blends were predicted by the log additivity
p r i n ~ i p l eHowever,
.~ a negative deviation from the
log additivity rule was observed at high concentra-
tions of EPR. This was attributed to a phase sepa-
ration at high concentrations of EPR. It was postu-
lated that at low concentrations of EPR, the EPR
functioned as an emulsifier at the surface of PE
particles, and the two additives have a tendency to
form composite EPR/PE particles in the PP matrix.
Crystallization behavior and morphology of
EPR/PP and EPR/PE have been r e p ~ r t e d . ' ~ ~ - ' ~ ~ , ' ~ ~
Crystallization of PE was unaffected by the pres-
19
POLYETHYLENE-POLYPROPYLENE BLENDS
PP Matrix
PEP
A. Layered Sphere Structure
PP Matrix
PEP-HDPE
B. Interpenetrating Structure.
FIGURE 20. Schematic illustrations of morphology
of composite EPR/PE particles in PP-rich ternary
blends: (a) shell (b) interpenetrating structure. [After
Reference 130, Figure 5, F. S . Stehling et al., J. Appl.
Polym. Sci., 26, 2693 (1981), with permission from
the publishers, John Wiley & Sons, Inc., New York.]
ence of a low crystallinity EPR when EPR was the
minor phase, but in the rubber-rich composition, a
common crystalline supermolecular structure was
obtained with a small reduction of crystallization
temperature as well as a melting point depression
of PE.Im In the case of amorphous EPDM, the crys-
tallite size or the fold period of PE was decreased
and this has been ascribed to a limited mixing of
the amorphous phase within the interlamellar re-
In the case of PP/EPR blends, addition of
an amorphous EPR resulted in an increase in the
equilibrium melting point of the PP, while the
spherulite growth rate was slightly reduced.139
20
When EPDM was added to PP, a delay in nuclea-
tion was observed while the rate of crystallization
was enhanced.143The proportion of a- and p-form
PP was also modified when EPDM was incorpo-
rated.
In the case of binary blend consisting of immis-
cible melts with one component crystallizing, the
resulting solid structure will consist of crystalline
and amorphous regions arranged in a manner de-
termined by that of the melt prior to crystalliza-
tion.I5l Inaba et studied the morphology of
polypropylene and ethylene-propylene copoly-
mer by spinodal decomposition and crystalliza-
tion. They found that a modulated structure (see
Fig. 5 of Ref. 152) developed above the melting
point of PP by the liquid-liquid demixing is con-
served during and after crystallization if the crys-
tallization rate is much faster than the rate of mu-
tual diffusion of the constituent polymer molecules
but is not conserved if the crystallization rate is
sufficiently slow compared with the rate of mutual
diffusion.
In the case of ternary blends of PE/PP/EPDM,
the &form PP was suppressed by the addition of
EPDM.51 However, in another study, where p-
form PP was originally absent in the PP/PE blends,
addition of EPDM seemed to enhance the forma-
tion of p-PP from the result of X-ray diffra~tion.’~~
The crystallinity of the PE was found to be reduced
to a larger extent while that of PP was found to be
almost unchanged by the addition of EPDM.*35
This was postulated to be due to the fact that com-
patibility between PE and EPDM was better than
that between PP and EPDM as evidence by the
solubility parameters of the three polymers (8pE =
8.83, 8 p p = 7.82, aEPDM= 8.36 [ ~ a l / c m ~ ] The
” ~ ) .ob-
servation was further supported by X-ray diffrac-
tion study. A recent DSC study on the ternary
blends showed that the peak melting temperatures
of PE and PP were not affected by the amount of
EPDM, but the crystallization rates and nucleation
rates were changed by the presence of EPDM.136
Dynamic curing of ternary blends of PE/PP/
EPDM has recently been s t ~ d i e d . The ~ ~ Jtensile
~~
strength and the modulus of the ternary blend
were found to decrease with increase in peroxide
contents for PP-rich blends. This has been attrib-
uted to the predominant mechanochemical degra-
dation reaction of the PP due to shear and peroxide
during the dynamic curing process. On the other
hand, in the case of EPDM-rich ternary blends, the
tensile strength and modulus were improved with
increasing peroxide concentration.
VOL. 13, NO. 1

In summary, studies on ternary blends of PE/
PP/compatibilizer are relatively few compared
with studies on binary blends of PE/PP. However,
it has been shown in general, that in the case of
EPR, the effect of the third component on the PE/
PP is influenced by the proportion of ethylene and
propylene in the EPR and the crystallinity and the
viscosity of the copolymer.
IConclusions
Polyethylene and polypropylene form complex
binary blends. A maximum of four separate phases
may coexist in the blends: PE-crystalline phase,
PP-crystalline phase, PE-amorphous phase, and
PP-amorphous phase. The situation is made more
complex by the polymorphism of PP where four
different crystalline structures may be formed. The
spherulite size, the lamellar thickness, the interla-
mellar amorphous zone, the perfection of the crys-
tallites, the final crystallinity, and the possibility of
epitaxial crystallization are additional factors to be
considered that will affect the final morphology
and properties of the blends. Processing condi-
tions, such as the degree of melt shearing, the
cooling rate, and annealing history, not to mention
the melt viscosity, the melt viscosity and elasticity
ratios of the blend components, the molecular
weight, and molecular weight distribution, will af-
fect the melt and solid morphology and hence the
final properties. Finally the addition of a third
component as a compatibilizer will double or triple
the factors to be considered with the added PE-
compatibilizer and PP-compatibilizer interactions
to be taken into consideration.
IAcknowledgment
The support of a grant from Shell Canada Lim-
ited and the Natural Sciences and Engineering Re-
search Council of Canada is gratefully acknowl-
edged.
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