Melt rheology, phase structure and impact

properties of injection-moulded samples of

isotactic polypropylene/ethylene-propylene
copolymer (iPP/EPR) blends: influence of
molecular structure of EPR copolymers

L. D'Orazio, C. Mancarella, E. Martuscelli* and G. Sticotti

Istituto di Richerche su Tecnologia dei Polimeri e Reologia de/CNR, Via Toiano 6,
80072 Arco Felice, Napoli, Italy

and P. Massari
Flimont SPA, Ferrara, Italy
(Received 22 December 1991; revised 4 June 1992)

Isotactic polypropylene (iPP) based blends containing as second component ethylene-propylene co__Eolymers
(EPR) having, for constant propylene (C3) content (wt/wt), different average molecular masses (M w and/or
Mn) and, for constant average molecular mass, different molecular mass distributions (MMD) were
investigated. The study was undertaken to establish the influence of the melt phase viscosity ratio p in
determining the average particle size of the EPR phase in the vicinity of the minimum expected according
to the Taylor-Tomotika theory for the average particle size versus log/~ function, when ~ is about equal
to unity (in previous studies we have in fact reached/~ values far above 1). Moreoever, we also report the
effects of molecular mass and molecular mass distribution of the EPR phase on the melt rheological
behaviour of iPP/EPR blends, on the mode and state of dispersion of the EPR phase in the melt, as well
as, in the solid state after iPP crystallization in injection moulded samples, on the crystalline lamellar
thickness and the thickness of the amorphous interlayer of iPP phase, and finally on the impact properties
of blend materials. It should be pointed out that the apparent viscosity of all the iPP/EPR blends investigated
is expected to obey the logarithm additivity rule that applies at constant temperature and shear rate. The
application of the Cross-Bueche equation revealed that the zero-shear viscosity t/o of these iPP/EPR blends
deviates positively from the logarithm additivity rule. Assuming that the crystallization of the iPP phase
freezes the morphology of the EPR phase, a strict correlation is confirmed to exist between the values of
EPR particle size and EPR particle size range, as measured by scanning electron microscopy on samples
in the solid state, and/~ value. The number average particle diameter (D,) and the particle size range of
the EPR phase (D) are found to increase with increasing /~ value as expected according to the
Taylor-Tomotika theory. Finally, when the iPP phase crystallizes from its blends with EPR under
non-isothermal conditions, the phase structure developed in the blends is characterized by lamellar thickness
and interlamellar amorphous layer thickness, respectively, lower and higher than that shown by plain iPP.

(Keywords: polypropylene; ethylene-propylene random copolymers; blends; rheology; phase structure; impact properties;
molecular structure)

INTRODUCTION state, on impact properties of injection-moulded samples,

direct correlations between molecular structure of EPR,
The results of an investigation concerned with isotactic
rheological behaviour of the blend system, size of rubbery
polypropylene (iPP) based blends containing as second
particles and impact resistance were drawn. It was found
component ethylene-propylene copolymers (EPR) having
that the values of the blend zero-shear viscosity (t/o) and
different propylene contents (C3) (wt/wt) and molecular-
of a characteristic relaxation time (~(blend)) parameter,
mass distributions ( M M D ) and, for fixed C3 content and
obtained by applying the Cross equation, decreased
M M D almost constant, different average molecular
with increasing dispersion coarseness of the minor
masses were reported in a previous paper 1. From
component, in agreement with results already obtained
such studies, aimed at establishing the influence of
while studying a different immiscible blend system
EPR molecular structure and composition on melt
made up of polyamide-6 and ethylene-vinyl acetate
rheology, on mode and state of dispersion of the minor
copolymer 2. The size and size distribution of EPR
component in the melt, as well as, in the solid
domains were determined from the value of the phase
viscosity ratio (#) irrespective of C 3 content along the
* To whom correspondence should be addressed EPR chain. The trend of the number-average particle

0032-3861/93/173671 l 1
~' 1993 Butterworth-Heinemann Ltd. POLYMER, 1993, Volume 34, Number 17 3671
Injection-moulded samples of iPP/EPR blends. L. D'Orazio et al.

diameter (D.) versus log # showed that D. decreased with properties by optimizing the molecular structure of the
decreasing log p, in agreement with expectation on the rubber.
basis of Taylor-Tomotika theory. Moreover, the average
particle size effective for iPP toughening was found to
be dependent on test temperature; for a temperature EXPERIMENTAL
higher than the Tg of EPR and close to Tg of iPP, such Materials
an average value was, in fact, lower than that effective
The materials used in this study were an isotactic
at room temperature.
polypropylene (iPP) made by Himont and five ethylene-
According to Taylor-Tomotika theory the diameter of
a cylindrical thread of a viscous liquid suspended in propylene random copolymers (EPR) supplied by Dutral.
The molecular characteristics of these polymers are
another one versus the logarithm of the melt-phase
summarized in Table 1.
viscosity ratio (p) function should show a minimum in
the vicinity of # = 1. The iPP and EPR samples used in
the previous study permitted us to reach p values far Blending and sample preparation
above 1; thus it was impossible to verify the minimum The iPP and EPR copolymers were mixed in a Banbury
in Dn versus log p function. Therefore, to assess the mixer at 200°C with a blending time of 5 min. Blends
effects of the melt-phase viscosity ratio when the two with composition iPP/EPR 80/20 (wt/wt) were prepared.
components have melt viscosity values close to each After blending, the materials were injection moulded by
other, i.e. in the vicinity of the minimum expected by the means of an injection press at 200°C with a mould
theory, we blended the same sample of iPP as used in temperature of 60°C.
the previous work (Moplen S30G) with three other
samples of EPR rubbers having, for constant C3 content Techniques
fixed at 43 % (wt/wt), suitable molecular masses (Mw and Oscillatory shearin9 flow properties. The oscillatory
M,). The previous studies showed, in fact, that up to such shearing flow properties, namely the complex viscosity
C3 content the range of particle size of EPR was mainly r/* (defined by r/*=r/'-ir/", where r/' is the dynamic
determined by # value. Moreover, to optimize the effects viscosity or the real part of the viscosity, ~/" is the
of the molecular structure of EPR phase, such copolymers
had, for constant average molecular mass (Mw or M,), imaginary part of the viscosity and i= x~-1), the storage
different molecular mass distribution (MMD). modulus G' (defined by G' = coq", where co is the frequency
In addition to what we studied in the previous work 1, of oscillation in radians per second) and the loss modulus
the effects of Ca content along the EPR chain higher than G" (defined by G"=coq'), of the homopolymers and
43% (wt/wt) have been analysed by adding to Moplen blends were determined at 200°C by means of a
S30G two samples of EPR having a C3 content of 50% Rheometrics Mechanical Spectrometer in the plate-plate
and 58% (wt/wt); such samples are characterized by Mw mode with an angular frequency ranging between 10-2
a n d 10 2 rad s- 1.
quite comparable to that shown by the EPR samples
with comparatively lower C3 content. Furthermore
a small-angle X-ray scattering (SAXS) investigation Calorimetric measurements. The glass transition
concerning the possible modifications induced by the temperatures Tv the observed melting temperatures T~
addition of EPR rubber to the intrinsic morphology of and the crystallinity index of plain iPP and its blends
iPP matrix has been carried out. with EPR copolymers were obtained by using a Mettler
In the present paper we report the results of studies TA 3000 differential scanning calorimeter.
dealing with the rheological behaviour in the molten state The following procedure was used: the samples of
at the processing temperature of this type of iPP/EPR plain iPP and iPP/EPR blends (about 15 mg) were heated
blend, with the mode and state of dispersion of the minor from - 100 up to 200°C at a rate of 20°C min -x and the
component developed in the solid state, after iPP heat (dH/dt) evolved during the scanning process was
crystallization, in injection moulded samples, with the recorded as a function of temperature. The Tg was taken
crystalline lamellar thickness and the thickness of the as the temperature corresponding to 50% of the
amorphous interlayer of the iPP phase, and with the transition. The observed melting temperature T~ and the
impact behaviour of the blend materials. apparent enthalpies of fusion AH* were obtained from
The final target of the research is to formulate the inflection point and area of the melting peaks
EPR modified iPP with enhanced and/or tailored respectively.

Table 1 Molecular characteristics and glass transition temperatures (To of neat isotactic polypropylene (iPP) and ethylene-propylene
copolymers (EPR)

Sample M--~× 10 a ~ x 103 M--~x 10a Mw/M . Ca Tg

(%wt/wt) (°C)

iPP 65 484 2782 7.4 - - 10

EPR 1 40 110 300 2.8 43 - 53
EPR2 70 180 500 2.8 50 - 55
EPR3 73 259 860 3.5 58 -
EPR4 50 200 800 4.0 43 - 49
EPR5 15 200 1000 13.3 44 -48

Molecular characteristics and glass transition temperatures (Tg)of neat isotacticpolypropylene(iPP) and ethylene-propylenecopolymers(EPR)

3672 POLYMER, 1993, Volume 34, Number 17

 Injection-moulded samples of iPP/EPR blends. L. D'Orazio et al.

Mode and state of dispersion of minor component. The Izod impact strength. Notched Izod impact strengths
mode and state of dispersion of the minor component were of the injection-moulded samples were measured by
investigated by means of a scanning electron microscope means of a Ceast pendulum in a temperature range from
(Philips SEM 501). The morphological analysis was - 4 0 up to 23°C according to ASTM D256. By SEM a
performed on fracture surfaces of blend samples broken fractographic analysis of such broken surfaces was also
at - 4 0 ° C after coating with gold-palladium. carried out.

Small-angle X-ray scattering. Small-angle X-ray RESULTS AND DISCUSSION

scattering (SAXS) studies were carried out on injection
moulded samples of plain iPP and i P P / E P R blends by Melt rheology of single components and blends
means of a compact Kratky camera equipped with a Dynamic viscoelastic properties of single components and
Braun one-dimensional positional detector. Ni-filtered blends. The logarithms of the modulus of the complex
Cu K s radiation, generated from a Philips X-ray viscosity (Iq*l), of the dynamic storage modulus (G') and
generator (PW 1730/10) operating at 40 kV and 30 #A, of the loss modulus (G") as functions of the logarithm of
was used. The raw scattering data were corrected the investigated frequencies for plain iPP and EPR
for parasitic scattering, absorption and slit smearing copolymers are reported in Figure 1. As shown, and as
using Vonk's method 3. The desmeared intensities were expected on the basis of results already obtained by
then Lorentz factor corrected 4 by multiplying by s 2 studying different iPP and EPR samples 1, for both iPP
(s = 2 sin ~/2). and EPR copolymers I~/*l values decrease, whereas G'

~, lO s 10 s @ 10 s l°s
104 U 104
!04 ~ 104
~, 103 ~, 103
10 3 103 ~ ,
10 ~ 10 z
© L~
10 ~ I 0z 10 ~ 10 z

0 -z lif t 10 0 101 10 z 10 -z 10 -I 10 0 101 10 z

oo(rad/sec) co(rad/sec)

I0s 10 s 1o s 10 s /...%

& 1o k) 10 4
10 4 10 4 ~v
b 10 3
b 10 3
10 3 10 3
10 z 1oz
"e-'
L~
i0 ~ 10 z lO' e 10 z
1 0 -z 1 0 -I 10 ° 10 ~ 10 2 10 -z 10 l 10 0 101 10 z
O0(tad/see) O0(rad/sec)

@ 10 s IO s

104 k)
10 4

..., 10a
Z 10 3

C
10 z

10 -z 10 -I 10 ° 101 10 z
co(rad/sec)
Figure I Logarithmof modulus value of complex viscosity (Iq*]),of dynamic storage modulus (G') and of loss modulus {Ca")values as functions
of logarithm of frequency for plain iPP (a), for plain EPR1 (b), for plain EPR2 (c), for plain EPR4 (d) and for plain EPR5 (e)

P O L Y M E R , 1 9 9 3 , V o l u m e 34, N u m b e r 17 3673
Injection-moulded samples of iPP/EPR blends." L. O'Orazio et al.
and G" values increase, with increasing frequency. Note Finally, it should be underlined that the dynamic
that the EPR1, EPR2 and EPR4, EPR5 samples show viscoelastic properties shown by the EPR samples
different rheological behaviour (compare Figures lb and characterized by broader M M D (EPR4 and EPR5) are
lc with Figures ld and le respectively). A larger reduction comparable to that shown by plain iPP.
in viscosity with increasing frequency and G' values higher Figure 2 shows the typical dependence of the logarithm
than G" values in the last investigated decade are of the modulus value of the complex viscosity (Ir/*])upon
exhibited by the EPR4 and EPR5 samples, whereas the the logarithm of the investigated frequencies for the
EPR1 and EPR2 samples show comparatively lower iPP/EPR blends; for the sake of comparison, also shown
depression of r/* with increasing frequency and G" values in each plot are the q logarithms obtained by applying
higher than G' values in the whole range of investigated the following logarithm rule, which applies at constant
frequencies (compare Figures ld and le with Figures lb temperature and shear rate9'X°:
and lc).
log r/= ¢~log r/1 + ¢2 log r/2 (1)
Taking into account that the average molecular mass
Mw dominates the viscosity at low frequency, whereas a where r/ is the viscosity of the mixture, r/1 and
molecular mass between M. and Mw appears to r/2 are the viscosities of the two components measured
determine the viscosity at high frequencys-s, the finding at the same temperature, and (I)l and (I) 2 a r e their
that different rheological behaviour is shown by samples volume fractions. As shown in Figure 2 and as expected,
having almost the same Mw and/or M. but different iPP/EPR melts are pseudoplastic in the whole range of
molecular-mass distribution (MMD) (compare the explored frequencies, i.e. r/values decrease with increasing
molecular characteristics of EPR2 with those of EPR5 frequency. It is, at the same time, very surprising to find
and EPR4 in Table 1) indicates that the dynamic that mixing iPP and EPR copolymers results in a
viscoelastic properties of EPR copolymers investigated decrease in blend viscosity according to equation (1).
are, at least in the range of explored frequencies, mainly Such unexpected results seem to suggest that in such
dictated by their MMD. With increasing Mw/M. ratio, iPP/EPR blends there is no mutual influence of the
the frequency at which non-Newtonian behaviour single components despite their melt immiscibility and
becomes apparent shifts to lower value and the melts heterogeneity.
show a higher sensitivity to frequency, a larger decrease The above finding disagrees with the results obtained
of r/* with increasing frequency occurring. by Danesi et al. ~1 by means of capillary rheometer and

4.4 4.4

4.0
R1 4.0 PR2

~-~ 3.6
m
s.6
A Theoretical "~ A Theoretical
3.2 • Experimental "~ 3.2 • Experimental
2.8 2.8
a b
2.a

LOG ( ~ ) LOG ((~)

a.4 4.4'

4.0 ~ / E P R 4 4.0 ~ 1 ~ EPR5

3.6 3.6
A Theoretical '~ i A Theoretical
3.2 • Experimental ~t~_ 3.2 • Experimental -~
~ r i F

2.8 2.8
C d
2.4 2.4
-s -2 -i 6 i s -3 -2 -i b i a
LOG (f,~) LOG ((4))
Figure 2 Dependenceof logarithm of modulus value of complex viscosity (Ir/*l)upon logarithm of frequencyfor iPP/EPR1 (a), iPP/EPR2
(b), iPP/EPR4 (c) and iPP/EPR5 (d) blends

3674 POLYMER,1993,Volume34, Number17

 Injection-moulded samples of iPP/EPR blends. L. D'Orazio et al.
5.5
by us 1 by means of Rheometrix on samples of blends
containing the same iPP, but different EPR copolymers, 5.0 z~"~c*z~" z*'A

showing that iPP/EPR blends are to be classified as ,~.Ac ~, o

negative deviation blends (NDB), i.e. the blend viscosity 4.5 A ~ .o-

decreases below the mean value of the viscosities of the zv,~"

two plain components. Taking into account that the EPR
copolymers used in this work have viscosity lower than
those previously used and close enough to iPP viscosity,
the conflict between the results suggests that very different 3.0 "~" Q --
rheological behaviours can be exhibited by iPP/EPR /. . ........ ~. .........

blends depending on the molecular structure of EPR

rubber component, i.e. depending on the melt-phase
viscosity ratio. Z.O
-3 -
I)
-
I1 I
0
[
1
I
2 3
The dependence of the logarithm of the elastic modulus Log c,J
G' and the loss modulus G" upon the logarithm of the Figure 4 Dependence of logarithm of loss modulus (G") upon
investigated frequencies of the iPP/EPR blends are shown logarithm of frequency for iPP/EPR2 blend
in Figures 3 and 4. It is to be noted that, in agreement
with the results already obtained 1, all the iPP/EPR blends
show the same G' and G" values in the whole range of Table 2 Application of Cross-Bueche equation to plain iPP and EPR
explored frequencies. At low frequency the blends copolymers and to iPP/EPR blends: values of zero shear viscosity (%),
containing the EPR copolymers with narrower M M D characteristic relaxation time (~) and m; the zero shear viscosity values
(EPR1 and EPR2) exhibit G' values slightly higher than calculated assuming log addivity rule for iPP/EPR blends (q~) are also
reported
that of the single components, whereas the blends
containing the EPR copolymers with broader MMD Sample r/o ~ m q~
show G' values intermediate between that of the single (P) (s) (P)
components (compare Figure 3a with Figure 3b). Such
findings could suggest that, in the first investigated iPP 164 100 0.722 2/3 -
EPR 1 218 390 0.267 4/7 -
decade, the amount of energy stored by a blend system EPR2 271 000 0.281 4/7 -
depends on the M M D of EPR and tends to increase on EPR4 331 016 1.735 4/7 -
decreasing the Mw/M, ratio. EPR5 307 500 1.761 4/7 -
iPP/EPR 1 188 000 1.110 4/7 174 053
iPP/EPR2 221 141 1.050 4/7 181 967
iPP/EPR3 171 615 1.089 4/7
a iPP/EPR4 287 356 1.143 4/7 189 622
iPP/EPR5 263 300 1.152 4/7 186 765

• 4
0 With increasing frequency the G' values shown by all
the iPP/EPR blends investigated approach that shown
by plain iPP.
In the whole range of explored frequencies the amount
of energy dissipated by all the iPP/EPR blends is
substantially the same as that dissipated by plan iPP, in
" [ -~.. agreement with our previous results 1.
1 I , I i I J I i I ,
Determination of zero-shear viscosity of single
-2 -1 0 1 2
Log components and blends. Taking into account that in
oscillatory measurements on polymer melts the frequency
(~0) becomes analogous to shear rate (7)12-15 and
b assuming an approximate equivalence of [r/*] and
5 apparent viscosity (r/.)lS-20, the zero-shear viscosity (r/o)
of both single components and blends was calculated by
using the following modified Cross-Bueche equation21:
~4
or/. = 1 + (2)
o z~~ where r/o is the zero-shear viscosity, ~ is a parameter
.a a .'~^"~'-~ i that according to Cross should correspond to the
characteristic relaxation time related to molecular mass
,~ . for the linear polymer solution and m gives a measure
2
of the shear thinning of the melt. According to Iwakura
et al. 22 for polymer melts ~ is related to the size of the
1 , I i I I I i I I I i apparent flow unit; the reciprocal of ~ corresponds to the
-3 -2 -I 0 1 2 a
shear rate at which r/. = r/o/2. The m values found for the
Log ~.)
single components to obtain linearity in plots of I/r/,
Figure 3 Dependence of logarithm of elastic modulus values (G') upon versus 7m are reported in Table 2. As shown for plain iPP
logarithm of frequency for iPP/EPR2 blend (a) and iPP/EPR5 (b) m assumes the value usually obtained for a polymer with

POLYMER, 1993, Volume 34, Number 17 3675

Injection-moulded samples of iPP/EPR blends," L. D'Orazio et al.

a M M D (2/3) 21; whereas for the EPR copolymers m values Table 3 Apparent melting temperatures (T~) of plain iPP and
are lower (4/7), indicating a less severe shear thinning in iPP/EPR blends and crystallinity index of the plain iPP and iPP
crystallized from its blends with EPR copolymers
the non-Newtonian region.
From the lines l/r/a versus ~m the zero-shear viscosity Sample T~ X~(blend) Xc(iPP )
~/o and a are easily obtained from the reciprocal of the (°C)
intercept and from the slope respectively. The t/o and a
values of the plain iPP and EPR copolymers are also iPP 169 37 37
iPP/EPRI 166 29 36
listed in Table 2. As shown, the plain iPP at 200°C has iPP/EPR2 167 31 38
a zero-shear viscosity lower than that of the pure EPR iPP/EPR3 167 28 36
rubbers and the r/o values shown by the EPR copolymers iPP/EPR4 168 29 36
are proportional to an average molecular mass greater iPP/EPR5 166 30 38
than Mw, likely between Mw and Mz (see Table 1). As far
as ~ values are concerned, the plain iPP shows a
relaxation time longer than that shown by EPR1 and samples comparatively lower Tg is shown by the samples
EPR2 samples and shorter than that shown by EPR4 having narrower M M D (EPR1 and EPR2).
and EPR5 samples. As the reciprocal of the parameter The d.s.c, thermograms of the injection moulded
corresponds to the shear rate at which r/a decreases to samples of the iPP/EPR blends show two distinct glass
half of r/o, shorter a values means that non-Newtonian transition temperatures (Tg) and a single endothermic
flow starts at larger shear rate. Thus the range of peak when heated from - 100 to 200°C. The Tg at lower
Newtonian behaviour of plain iPP is expected to be temperature corresponds to Tg of EPR phase, while that
smaller than that of EPR1 and EPR2 copolymers and at higher temperature to T~ of iPP phase; such a finding
larger than that of EPR4 and EPR5 copolymers. confirms that, also in the amorphous condensed phase,
The m, ~/o and a values calculated for iPP/EPR blends there is no miscibility between the two components.
are reported in Table 2; the zero-shear viscosity .values The temperature position of the endothermic peaks
for the blends obtained assuming the additivity logarithm (Tin), reported in Table 3, is characteristic of the melting
rule (r/~) are also reported. As shown for all investigated of the or-crystalline form of iPP. The apparent melting
blends the m parameter assumes the value of 4/7, temperatures shown by iPP crystallized from its blends
suggesting that the blend system undergoes a shear with EPR copolymers are slightly lower than that of plain
thinning less severe than that of plain iPP in the iPP, irrespective of the EPR molecular structure. Such a
non-Newtonian region. It is to be noted that these finding indicates that the melting behaviour of the iPP
iPP/EPR blends, as far as r/o is concerned, show a positive is to be considered independent of EPR and EPR
deviation from the logarithm additivity rule. Moreover, molecular structure; the perfection and thickness of the
the extent of such a deviation increases on increasing the growing iPP crystals are almost unaffected by the
EPR average molecular mass (M w or likely an average presence of the EPR rubbery phase, irrespective of its
molecular mass between Mw and Mz). Such a result molecular characteristics. Thus, according to previous
disagrees with that obtained in the previous work 1, results 21 iPP and EPR are confirmed to be immiscible
showing ~/o(blend) values with a large negative deviation in the molten state.
from equation (1). The Xc(blend ) values are lower than that of plain iPP,
The a values shown by all investigated blends are and the Xc(iPP ) values shown by the iPP phase
comparable to each other; such values are longer than crystallized in the presence of EPR phase strictly
that shown by plain iPP, indicating that, in these blend approach that exhibited by the neat iPP phase with no
systems, the transition from Newtonian to pseudoplastic dependence on EPR molecular structure (see Table 5).
flow starts at a frequency lower than that of plain iPP; Such findings, contrary to what was found while studying
an opposite result was obtained in the previous work 1. isothermally crystallized samples of different iPP/EPR
The different rheological behaviours shown by the blends 2a, indicate that when iPP crystallizes from
iPP/EPR blends studied in the present work, also in the its blends with EPR in non-isothermal conditions
absence of shear, are presumably related to the fact that the rubbery component does not interfere with the
for such blends the range of phase viscosity ratio (#), crystallization process.
defined as the ratio between the zero shear viscosity of
the amorphous polymer phase (t/S) and the zero shear Phase structure
viscosity of the crystallizable polymer phase (r/~), tends Mode and state of dispersion of the minor component.
closely to approach unity (see Table 4). In the absence of The analysis by SEM of the mode and state of EPR
shear it could be supposed that the system may be dispersion, generated in the iPP/EPR injection moulded
described in terms of a continuous two-phase model, samples, shows that in all investigated specimens a
where the macromolecules of one phase are physically layered structure developed in the direction perpendicular
entrapped into the macromolecules of the other phase. to the mould flow direction, according to the schematic
model reported in Figure 5. As shown in Figure 5, on
Thermal behaviour and crystallinity moving from the border towards the core of the sample
The glass transition temperatures (T~) shown by the three different layers are found:
plain iPP and EPR copolymers are listed in Table 1. The (1) a skin surface (S) where no domains of EPR
apparent melting temperatures (T~) of plain iPP and of dispersed phase can be observed. The thickness of such
iPP crystallized from its blends and the crystallinity index a layer ranges between 15 and 20#m, a higher skin
ofiPP/EPR blends (Xc(blend)) and ofiPP phase (Xc(iPP)) thickness (40 #m) being shown only by the blend sample
are reported in Table 3. As shown and as expected, the containing the EPR4 copolymer.
iPP Tg lies around - 1 0 ° C and the EPR Tg are located (2) an intermediate transition layer (I) where the
in the range - 4 8 to -55°C. Note that among EPR concentration of the EPR domains increases on going

3676 POLYMER, 1993, Volume 34, Number 17

 Injection-moulded samples of iPP/EPR blends. L. D'Orazio et al.

Figure 6) in agreement with the expectation on the basis

of the Rayleigh-Taylor-Tomotika theory 24-27. The
finding that the average size shown by the blend
containing the EPR5 copolymer does not agree with the
prediction of Taylor-Tomotika theory is presumably to
be ascribed to the larger M M D exhibited by such a
rubbery phase, which causes a coarser dispersion of
the minor component with a broader particle size
distribution.
Moreover, the transverse surfaces of all investigated
blend samples show, in the direction perpendicular to
the mould flow direction, concentric elliptical lines having
m
the centre of their axis coincident with that of the samples.
Such lines represent the profiles of the flow rate, frozen
because of fast cooling. It should be noted that along
such lines the EPR spherical-shaped domains tend to be
M.F,D. more or less deformed assuming an ellipsoidal shape with
the major axis oriented in the direction perpendicular to
the mould flow direction (see Figure 5).

"t/z :X
Super-reticular parameters of iPP. Typical Lorentz
corrected desmeared patterns for the neat iPP and
iPP/EPR blends are shown in Figure 7. As shown, both
Figure 5 Schematic model of layered structure generated in iPP/EPR desmeared SAXS profiles exhibit defined maxima. By
injection moulded samples applying Bragg's law, long periods (L), calculated from
the peak position, were obtained for all investigated
Table 4 Range of particle size, number average particle diameter (b-..)
and phase viscosity ratio (~) for iPP/EPR blends 0.65

Range of
Sample particle size D. p
(#m) (#m)

iPP/EPR1 0.14).4 0.25 1.33 ~ 0.50

iPP/EPR2 0.1-0.5 0.30 1.65
iPP/EPR3 0.1-0.4 0.25 -
iPP/EPR4 0.1-0.6 0.35 2.02
iPP/EPR5 0.4-1.2 0.80 1.87
[1~ 0.35

towards the core of the samples with gradient

characteristic. The thickness of such a layer ranges
between 20 and 25/~m, only blend sample with EPR4 0.20
0.0 0.2 0.4 0.8 0.8 1.0
copolymer showing a comparatively higher thickness
Log ( p )
(40 pm).
Taking into account that, generally, in flowing systems Figure 6 Plot of the number average particle size (D.) v e r s u s logarithm
of two immiscible polymers the low viscosity component of the melt phase viscosity ratio (p) for all investigated iPP/EPR blends
tends to become the continuous phase and to encapsulate
the high viscosity component, the findings that the 10000-
sample with EPR4 copolymer exhibits comparatively
higher thickness of both skin and intermediate transition
layers are to be related to the comparatively higher #
value calculated for the iPP/EPR4 blend, showing that 12000
the zero-shear viscosity of the plain iPP is twice as low
as that of the EPR copolymer (see Table 4).
(3) a core (C) showing an EPR droplet-like morphology. • 0000
The range of diameters of the EPR particles is reported
in Table 4 together with the number average of such
diameters (D.) and the # value of the blends. As shown,
4000
with the exclusion of the blend containing the EPR5
copolymer, the range of particle size and the average
particle size of the dispersed phase are determined by the
/~ value; those quantities increasing with #. Analogous
0 10 15 20
conclusions were already drawn while studying blends
based on the same iPP with different EPR copolymers 1. s-t0 3 ( A -I )
The trend of the D, values versus log/~ shows that D, Figure ? Typical dcsmeared SAXS pattern for the plain iPP and
decreases with decreasing log/~ (see Table 4 and iPP/EPR blends

POLYMER, 1993, Volume 34, Number 17 3677

Injection-moulded samples of iPP/EPR blends." L. D'Orazio et al.

samples. Assuming for the iPP spherulite fibrillae a t"800 -

two phase model, consisting of alternating parallel

crystalline lamellae and amorphous layers, from the L
values the crystalline lamella thickness (Lc) was calculated 800
by using the following relation: E-,.,
c~
Xc(iPP)L Z
Lc - (3)
(pc/p,)[1 - Xc(iPP)] - X¢(iPP) 4oo
E-,
where Xc(iPP) is the d.s.c, crystallinity index of the iPP E-',
phase, and Pc and p, are the densities of the crystalline
and amorphous iPP phase, respectively. Subtracting the •~ zoo

obtained L c values from the L values, the average

thickness of the amorphous interlamellar layer (L,) was
obtained. In this calculation, in agreement with what was ' ' ' ' l ' ' ' ' l ' ' ' ' l ' ' ' ' l ' ' ' ' r

found by SEM analysis, the rubbery domains were -60 -4-0 -20 0 20 40
assumed to be located in interfibrillar regions. Thus the T (°c)
crystallinity of iPP phase (Xc(iPP)) was considered and Figure 8 Notched Izod impact strength as a function of temperature
not that of the blend. for plain iPP and iPP/EPR blends: ( x ) iPP, (A) iPP/EPR1,
(O) iPP/EPR2, (f-I)iPP/EPR4, ('A') iPP/EPR5
The L, L c and L~ values of plain iPP (L(iPP), L¢(iPP)
and La(iPP)) and of iPP crystallized from its blends
with EPR copolymers (L(iPP/EPR), Lc(iPP/EPR) and
L,(iPP/EPR)) are reported in Table 5. As shown, the of the EPR copolymers ( - 40°C), no improvement in the
L(iPP) and L(iPP/EPR) values, within the experimental iPP impact strength is obtained, irrespective of EPR
error (+ 5 ,~), show no dependence on EPR molecular molecular characteristics (see Fioure 8). Such a result
structure and composition. Such a finding is in agreement agrees quite well with that obtained while studying
with results already obtained while studying isothermally different iPP/EPR blends z.
crystallized samples of different iPP/EPR blends 23. It is interesting to underline that, for test temperatures
It is interesting to underline that the thickness of the ranging between - 4 0 and -20°C, the fracture surfaces
crystalline lamella ofiPP crystallized from its blends tends of the plain iPP and of the iPP/EPR4 blend show
to decrease, whereas the thickness of the amorphous no stress-whitening phenomenon, whereas the fracture
interlamellar layer increases (see Table 5). Thus when iPP surfaces of all the remaining blend samples, except
crystallizes in the presence of EPR copolymers in the skin layer made of plain iPP, are more or
non-isothermal conditions, the phase structure developed less whitened. Particularly, the surfaces of the blend
in the blends is characterized by lamellar thickness samples containing the EPR1 and EPR3 copolymers
and interlamellar amorphous layer, respectively, lower are completely whitened; those of the blend samples
and higher than that shown by plain iPP. Such containing the EPR2 and EPR5 copolymers show only
morphological results agree with those obtained while slight whitening localized in the sample core.
studying isothermally crystallized samples of different Taking into account that, for a test temperature of
iPP/EPR blends 2a. In order to explain these results, we -40°C, iPP/EPR blend materials show no improved
assumed that EPR molecules with low molecular masses, strength, the stress whitening phenomenon is mainly to
because of their higher mobility, diffuse into the iPP be associated with cavitation during the test and/or a
interlamellar amorphous layer where they may form possible orientation contribution.
domains more or less interconnected with the amorphous The fractographic analysis of the broken surfaces of
iPP phase, thus increasing its thickness and hindering plain iPP and of iPP/EPR blends shows that all samples
the iPP crystal growth. at -40°C, as expected, break in a brittle fashion; the
fracture surfaces show a crack path where practically no
Impact behaviour matrix yielding takes place. Moreover, the broken
The notched Izod impact strength values for the plain samples of plain iPP show no fracture induction area,
whereas such an area, localized in the central part of the
iPP and the iPP/EPR blends investigated are reported
in Figure 8 as functions of test temperatures. As expected, notch front, is observed in all blend samples. The size of
the plain iPP shows very poor impact properties in the the fracture induction area is different, with no systematic
whole range of explored temperatures and, for test dependence on EPR molecular structure, the smallest
temperature below the glass transition temperature (T~) and largest area being shown respectively by the blend
sample containing the EPR4 and EPR2 copolymers (see
Figure 9).
Table 5 Long period (L), crystalline lamella thickness (L¢) and
amorphous interlammelar layer (La) of the plain iPP and iPP
For test temperature higher than EPR Ts and close to
crystallized from its blends with EPR copolymers iPP T, ( - 1 0 to 0°C), enhancement in iPP impact
behaviour results, dependent on the type of EPR
Sample L Lo dispersed phase (see Fioure 8). As shown in Fioure 8 at
(h) (A) ~) the temperature of 0°C, higher impact strength values
iPP 161 56 105 are shown by the blend samples containing the EPR2
iPP/EPR 1 168 45 123 and EPR4 copolymers; the same comparatively lower
iPP/EPR2 163 47 116 values are exhibited by all the remaining blend samples.
iPP/EPR3 174 45 129 The surfaces fractured at 0°C of the blend samples
iPP/EPR4 166 45 121
iPP/EPR5 172 48 124
containing EPR1 and EPR3 copolymers are completely
whitened, whereas the fracture surfaces of all the

3678 POLYMER, 1993, Volume 34, Number 17

 Injection-moulded samples of iPP/EPR blends. L. D'Orazio et al.

different degrees of dispersion (average particle size) (see

Table 4). It is likely that EPR particles ranging in size
between 0.30 and 0.35 #m are more effective for iPP
toughening, and/or in iPP/EPR4 and iPP/EPR2 blends
a more effective interparticle distance is achieved,
according to Wu 28. Such values of D-~,, able to optimize
the impact strength of iPP at 0°C, agree with that found
in the previous work ~.
For test temperatures close to room temperature,
the impact strength shown by the blend samples
containing the EPR2 and EPR4 copolymers is higher
than that shown by the remaining blend samples.
With increasing test temperature, the intensity of the
stress whitening phenomenon and the volume of material
involved increase strongly, with no dependence on
EPR type. Such a finding could suggest that, on
increasing test temperature, also multicraze formation
may occur. Therefore the fracture mechanism active, for
test temperature close to room temperature, could result
in a combination of shear yielding and multicraze
formation.

C O N C L U D I N G REMARKS
A study aimed at assessing the influence of the melt-phase
viscosity ratio (#) in determining the average particle size
of EPR phase dispersed into iPP matrix in the
vicinity of the minimum expected according to the
Taylor-Tomotika theory for the average particle size
versus log/~ function has been reported. Moreover the
effects of the molecular masses (Mw and M,) and
molecular mass distribution (MMD) of EPR phase on
Figure 9 SEM micrographs of fracture surfaces broken at -40°C of melt rheological behaviour of iPP/EPR blends on mode
iPP/EPR4 (a) and iPP/EPR2 (b) blends and state of dispersion of EPR phase in the melt, as well
as, in the solid state, on intrinsic phase structure of iPP
crystalline phase and on impact properties of injection
remaining blend samples exhibit whitening localized only moulded samples of blend materials were reported.
at the fracture induction area, and/or at the boundary It should be pointed out that the apparent viscosity
between the iPP skin and the intermediate transition of all the iPP/EPR blends investigated can be expected
layer according to Figure 5. It is interesting to underline to conform to the logarithm additivity rule that applies
that better impact properties, for test temperature of 0°C, at constant temperature and shear rate 9, indicating that
are shown by the blend samples that undergo stress in the melt there is no mutual influence of the single
whitening with lowest intensity (blend with EPR4 components despite their immiscibility and heterogeneity.
and EPR2 copolymers). Such a finding supports the Opposite results were obtained in previous work 1 and
suggestion that, at 0°C, a cavitation process, rather than by Danesi et al. 11, showing that iPP/EPR blends are to
multicraze formation, is associated with the observed be classified as 'negative deviation blends' (NDB). Taking
whitening. Therefore it can be supposed that, for test into account that the EPR copolymers used in this work
temperature approaching the iPP Tg, the observed have melt viscosity considerably lower than that of EPR
improvement in impact strength shown by the blend copolymers previously used and quite close to the
material could be due to yielding of the matrix. melt viscosity of the iPP, the conflict between the
The fractographic analysis of the surfaces of the blend results suggests that the iPP/EPR blends can exhibit
sample broken at 0°C reveals that the size of the fracture very different rheological behaviours depending on the
induction area, where the material breaks in ductile molecular characteristics of the EPR rubbery component,
fashion, depends on the type of EPR copolymer used. i.e. depending on the melt phase viscosity ratio defined
As shown in Figure 10, the smallest and largest as the ratio between the zero shear viscosity of the
induction areas are observed in the blend samples amorphous polymer phase and the zero shear viscosity
containing the EPR1 and the EPR2, EPR4 copolymers, of the crystallizable polymer phase.
respectively. The blend samples containing the EPR3 and The application of the Cross-Bueche equation
EPR5 copolymers show fracture induction area with revealed, moreover, that the zero-shear viscosity (%) of
comparable intermediate size (see Figure 10). As expected, these iPP/EPR blends deviates positively from the
the best impact properties are shown by the materials logarithm additivity rule (q~) and that the transition from
that at 0°C show largest fracture induction area (blends Newtonian to pseudoplastic flow starts at a frequency
with EPR4 and EPR2 copolymers). lower than that of plain iPP. These results are opposite
The very different behaviours of such EPR copolymers to that found in previous work ~ and support the
as impact modifiers is reasonably ascribed to the fact hypothesis that in the absence of shear the melt-phase
that in blends with iPP they give rise to domains with viscosity ratio (/~) is the main factor in determining the

POLYMER, 1993, Volume 34, Number 17 3679

Injection-moulded samples of iPP/EPR blends." L. D'Orazio et al.

Figure 10 SEM micrographsoffracturesurfacesbrokenat 0°C ofiPP/EPR1(a),iPP/EPR2(b),iPP/EPR3 (c),iPP/EPR4 (d)and iPP/EPR5 (e)blends

viscosity of the blend system and its viscoelastic expected according to the Rayleigh-Taylor-Tomotika
parameters. theory, are in agreement with that found in previous
Assuming that the crystallization process of iPP phase work 1.
freezes the morphology of the EPR phase, a strict Recall that the injection moulding process induces an
correlation is confirmed to exist between the values of anisotropic distribution of EPR dispersed phase in the
the EPR particle size and EPR particle size range, as direction perpendicular to the mould flow direction.
measured by SEM on samples in the solid state, and # Moving from the border towards the core of the samples,
value. The number average particle diameter (D.) and three different layers are found:
the particle size range of the EPR phase (D) are (1) a skin surface 15-20#m thick, where no domains
found to increase with increasing # value, with the of EPR phase can be observed;
exception of the EPR copolymer characterized by (2) an intermediate transition layer where the
the comparatively broadest M M D (13.5). Such results, concentration of the EPR particles increases on going

3680 POLYMER, 1993, Volume 34, Number 17

 Injection-moulded samples of iPP/EPR blends. L. D'Orazio et al.

towards the core of the sample with gradient characteristic; 2 Addonizio, M. L., D'Orazio, L., Mancarella, C. and
and Martuscelli, E. J. Mater. Sci. 1989, 24, 2939
3 Vonk, C. G. J. Appl. Crystallogr. 1975, 8, 340
(3) a core showing an EPR droplet-like morphology, 4 Alexander, L. E. 'X-Ray Diffraction in Polymer Science', Wiley,
droplet size being determined according to # value in all New York, 1969
investigated samples except the sample containing the 5 Ballman, R. L. and Simon, R. H. M. J. Polym. Sci. (A) 1964, 2,
EPR5 copolymer. This exception to the rule is reasonably 3557
ascribed to the very large M M D (13.5) shown by this 6 Ballman, R. L. Nature 1964, 202, 288
7 Graessley, W. W., Hazelton, R. L. and Lindeman, L. R. Trans.
copolymer and to the consequent broad particle size Soc. Rheol. 1967, 11, 267
distribution. 8 Graessley, W. W. 'Advances in Polymer Science', Vol. 16,
Moreover, when iPP phase crystallizes from its blends Springer-Verlag, Berlin, 1974
with EPR phase in non-isothermal conditions, the 9 Lee, B. L. and White, J. L. Trans. Soc. Rheol. 1975, 19, 481
l0 Utraki, C. A. and Kamal, M. R. Polym. Eng. Sci. 1982, 22, 96
intrinsic morphology of iPP matrix is modified by the 11 Danesi, S. and Porter, R. S. Polymer 1978, 19, 668
addition of rubbery component. Therefore the phase 12 Nielsen, L. E. 'Polymer Rheology', Marcel Dekker, New York,
structure developed in the blends is characterized by 1977
lamellar thickness and interlamellar amorphous layer 13 Han, C. D. J. Appl. Polym. Sci. 1986, 32, 3809
respectively lower and higher than that shown by plain 14 Han, C. D. J. Appl. Polym. Sci. 1988, 35, 167
15 Ferry, J. D. 'Viscoelastic Properties of Polymers', 2nd Edn.,
iPP. Wiley, New York, 1970
The value of D n able to optimize the impact strength 16 Nielsen, L. E. 'Mechanical Properties of Polymers and
of the iPP in the temperature range of 0-20°C was Composites', Vol. 1, Marcel Dekker, New York, 1974
confirmed to be 0.30-0.35 #m, in agreement with that 17 Cox, W. P. and Merz, E. H. J. Polym. Sci. 1958, 28, 619
18 Onogi, S.,Masuda, T. andIbaragi, T. KolloidZ. 1968,222,110
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between the impact strength and D. value and between 20 Verser, D. W. and Maxwell, B. Polym. Eng. Sci. 1970, 10, 122
D. value and # value, the impact behaviour of the iPP, 21 Cross, M. M. J. Appl. Polym. Sci. 1969, 13, 765
for a given test temperature, can be directly predicted 22 Iwakura, K. and Fujimura, T. J. Appl. Polym. Sci. 1975, 19, 1427
23 D'Orazio, L., Mancarella, C., Martuscelli, E. and Sticotti, G.
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24 Rayleigh, J. W. S. Proc. R. Soc. 1879, 29, 71
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