Effect of Nucleating Agent Incorporation on Mechanical,

Morphological, and Rheological Properties of In-Situ Copolymer

Polypropylene and PPH/POE Blends

Mansour N. Al-Otaibia, Azzedine Kioulb, and Saeed Al-Zahrania

a
King Saud University, Department of Chemical Engineering, Riyadh, KSA
b
SABIC Plastic Applications Development Center, SABIC, Riyadh, KSA
Email address of the corresponding author: m-n-otaibi@hotmail.com

Abstract. Toughening of homopolymer polypropylene (PPH) in the post reactor step by incorporating external elastomers
has become an attractive area of research. In this investigative work, PPH was post-reactor blended with different types of
Polyolefin elastomers (POE) that were selected based on the co-monomer type and density. The performance behavior of
PPH/POE blends with and without a nucleating agent was compared to in situ (in the reactor) modified PPH with Ethylene
Propylene Rubber (EPR). The addition of POE in PPH, increased toughness at room temperature and the stiffness of the
blends decreased. The addition of a nucleating agent was noted to improve the toughness and stiffness compared to their
non-nucleated counterparts, while the tensile strength remained unchanged. At -20 °C, the impact strength results showed
no significant improvement in PPH/POE blends with and without addition of the nucleating agent. The morphology analysis
have shown clearly phase separation of the blends components thus demonstrating the immiscibility of the blend systems.
The addition of the nucleating agent was seen to decrease the domain size of POE phase thus leading to the improvement
in the toughness properties of the blends. ICP materials have shown better mechanical properties and more uniform rubber
dispersion than the blends system. The rheological results of PPH/POE blends based on POE1 (butene co-monomer) and
POE4 (octene co-monomer) indicate that increase POE content leads to an increase in the blends viscosity across the shear
range. However, the trend was different in blends containing copolymers POE2 and POE3.
Keywords: homopolymer polypropylene (PPH), impact copolymer polypropylene (ICP), POE, EPR, blends, impact
modification, mechanical properties, morphology.

INTRODUCTION
Polypropylene is one of the most important thermoplastic materials used in a wide variety of application such as
packaging, consumer goods, building, and automotive in view of its easy processing, low density, chemical resistance,
and low cost. At low temperatures, the applications of PP are limited due its low impact resistance [1-2]. To remedy
this problem, a new family of polypropylene known as Impact PP was developed by incorporating a rubber phase
(EPR) in the reactor (in situ modification). The process of producing impact copolymer polypropylene in situ takes
place in two stages. In the first one, the homopolymer polypropylene is produced in the first reactor and in the second
stage, ethylene-propylene rubber (EPR) is produced in presence of the homopolymer polypropylene in the second
reactor [3]. However, incorporation of an elastomer (EPR, EPDM, and POE) by blending with homopolymer
polypropylene outside the reactor is also used as a method to improve the impact resistance of PP materials [3-7].
Nucleating agents are known to increase number of crystallization sites in semi-crystalline polymers, resulting in an
increase in overall crystallization rate, a decrease in the spherulite size and an increase in crystallization temperature
thus decreasing the production cycle time during polymer conversion. The purpose of this work was to study the effect
of nucleating agent incorporation on the blends properties and compare the morphology and toughness/stiffness
balance properties of PPH blended with different types of POE (different co-monomer / different density) to those of
in situ reactor blends (ICP).

MATERIALS AND TESTING

Table 1, shows the polymers used in this work. The mentioned PPH was used as a matrix resin for the blends. An
impact polypropylene (ICP) with total rubber content of around 15% was used as a benchmark against the PPH/POE
blends. An alpha nucleating agent was used with dosage of 300 ppm.
 Table (1). Polymers used in this work with melt index, density, and co-monomer types.
Polymer MFR ( g/10min @ 230 °C, 2.16 kg) Density (kg/m3) Co-polymer type
PPH 24 906 -
POE1 2.5 862 C2-C4
POE2 7.25 870 C2-C4
POE3 1.85 885 C2-C8
POE4 0.823 868 C2-C8
ICP 21 905 In-situ modified

In this work, PPH/POE Blends were prepared with and without a nucleating agent. POE contents in the blends
systems were selected as 10, 15, and 20 wt. %. The compounding work was carried out on a KraussMaffei co-rotating
twin-screw extruder. The screw diameter of the latter was 25 mm with an L/D of 56. The screw speed and the cutter
speed were 500 rpm and 2800 rpm respectively. The palletization step was done using an underwater cutter at a water
temperature of 40°C. The test specimens were prepared using KraussMaffei KM50/380 EX injection molding with a
30 mm screw diameter and 26.7:1 L/D ratio.
Flexural test was performed according to ASTM 790 using (Zwick/Roell Z010) with a compression load cell at
constant crosshead speed 1.36 mm/min.
Notched izod impact tests were done according to ASTM D256 at room temperature and at -20 °C using
Zwick/Roell HIT50P pendulum type impact tester. The dimensions of test bar is (64 × 12.7 × 3.2 mm), notched depth
is 10.2 mm, and the notched type is A.
The morphologies of the blends were analyzed based on molded sheet bars using scanning electron microscope
(SEM-FEI Quanta 200) at an accelerating voltage of 20 kV. The cryo-fractured surface of each specimen was etched
by xylene at room temperature for 15h in order to remove the rubber phase. Then, the specimens were dried and coated
with a thin layer of gold.
The rheological properties of the samples were characterized with ARES made by TA using parallel plate
geometry. The viscosity was measured at 230 °C. The limits for the rotation angular frequency was varied between
0.1 and 100 rad/s.

DISCUSSION
From flexural modulus data presented in Figures 1 and 2, it can be noted that the moduli of the PPH/POE blends
decreased upon the incorporation of the elastomer phase. This is expected due to the incorporation of soft particles
(dispersed POE phase) which have lower elastic modulus than that of the PPH matrix. This can also be attributed to
the fact that crystallinity of the PPH matrix is lowered by the incorporation of the elastomer phase [7-9]. The ICP
material presented a marginally higher flexural modulus compared to PPH/POE blends with 15% elastomer content.
This could be attributed to the better compatibility between EPR and matrix in ICP as compared to PPH/POE system
in addition to higher crystallinity of the PPH matrix in presence of the EPR phases. The incorporation of the nucleating
agent was seen to improve the flexural moduli of all blend systems as compared to their non-nucleated blends. This is
related to the fact that the nucleating agent reduces the spherulite size of the polymer crystals [10-11], reduces their
size distribution, and slightly increases the crystallinity of the blend. The nucleated ICP sample have shown noticeably
higher flexural moduli than PPH/POE blends with 15%. loading of POE. This is related to the better compatibility of
PPH/EPR in ICP as compared to PPH/POE systems and to the increase in crystallinity of the matrix phase.

Figure 1. Flexural modulus for non-nucleated blends. Figure 2. Flexural modulus for nucleated blends.

The notched izod impact results are summarized in Figures 3–6. There is significant improvement in impact
strength with the increase of the POE content at room temperature. On the other hand, the ICP presented superior
impact properties compared to PPH/POE blends at the same level of elastomer content (15%). Therefore, it can be
deduced that EPR introduced in polypropylene during the in-situ polymerization is more effective in improving the
impact strength of PPH than POE copolymers introduced during post-reactor compounding. This is most probably
related to the better dispersion and compatibility of right particle size and size distribution of the EPR phase in ICP
systems as compared to their compounded PPH/POE equivalents. The addition of the nucleating agent to PPH/POE
blends was seen to improve the notched izod impact of the systems. This effect could be related to the type of the
nucleating agent used, the reduction of the PPH matrix spherulite sizes, and the increase in their size homogeneity. It
is important to note also from the test results that POE with butene co-monomer (POE1 and POE2) imparted higher
impact values compared to POE with octene co-monomer (POE3 and POE4) in presence of the nucleating agent and
this could be attributed to the copolymer chemical structure (co-monomer content, co-monomer distribution,
branching size) and also to its higher MFI that might have imparted lower PPH/POE viscosity ratio [7, 10, 12-13]. At
-20 °C, the impact strength results showed no significant improvement in PPH/POE blends with and without addition
of the nucleating agent and this could be due to the ductile-brittle transition-taking place at this temperature. On the
other hand, the ICP impact strength values, with and without nucleating agent were shown to be superior at low
temperature (-20 °C) compared to the blend systems. This could be related to the fact that the EPR phase in ICP
possess better ductility and toughness than POE particles.

Figure 3. Izod impact at RT for non-nucleated blends. Figure 4. Izod impact at RT for nucleated blends.

Figure 5. Izod impact at -20 °C for non-nucleated blends. Figure 6. Izod impact at -20 °C for nucleated blends.

From the SEM micrographs, it is observed that all blends presented continuous and dispersed phases for all
systems. The SEM micrographs of blend systems of POE1 and POE2 have shown that the dispersed phase was finer
than that present in blends of POE3 and POE4. This could be due to the better compatibility of the POE with butene
copolymers with PPH [14]. It is also worth noting that copolymers with the highest MFI values (lower viscosity) have
imparted the finest dispersed phase in the blends investigated. This is probably due the fact that the homopolymer
phase will encounter less resistance in breaking up the lower viscosity dispersed phase during compounding and
moulding (high shearing at the gate). In ICP it was observed that the EPR dispersed phase was more homogeneous in
size and shape (round) and was in between the phase sizes developed in (POE1 and POE2) and (POE3 and POE4)
blends. This is mainly related to the better compatibility of the EPR copolymer with PPH and possibly to the right
viscosity ratio of the PPH/EPR system compared to PPH/POE blends. The addition of the nucleating agent was
observed to modify the morphology of the dispersed phase in some PPH/POE blends. In the SEM micrographs (Figure
10), it can be seen that the dispersed phase in blends based on POE1, POE2 and POE3, presented highly elongated or
fibrillary shape, while in POE4 based blend the dispersed particles were oval. However, the EPR phase in ICP is round
and remained unchanged compared to ICP without nucleating agent. These morphologies could be explained by the
fact that the lower viscosity copolymers, POE1, POE2 and POE3 have developed elongated morphologies during
samples moulding (shear induced particles orientation and stretching) using injection moulding followed by
subsequent faster cooling in the mould under the influence of the nucleating agent (faster crystallization or high
undercooling). This effect was not observed in ICP material and POE4 copolymer based blends, probably due to the
difficulty in stretching and freezing the high viscosity dispersed phase. It is important to mention here that the
improvement in impact strength at 23 °C of the nucleated samples based on POE1, POE2 could have been due to the
formation of the fibrillar-dispersed phase.
POE1 POE2 POE3

POE4 ICP

Figure 7. SEM images for fractured and etched surfaces of 15% POE for non-nucleated blends.

POE1 POE2 POE3

POE4 ICP

Figure 8. SEM images for fractured and etched surfaces of 15% POE for nucleated blends.

From viscosity graphs, POE1 and POE2 have demonstrated less shear thinning (especially POE2) compared to
their counterparts POE3 and POE4. However, at lower shear values and approaching the zero shear conditions the
octene-based copolymers presented non-Newtonian plateau and shear yielding especially for copolymer POE4. This
could be due to the fact that the latter have longer chain branches, broader molecular weight distributions (MWD) and
possibly more co-monomer content responsible for entanglements and disentanglement at quiescent and at higher
shear conditions, respectively [15]. With POE4 and POE1, it was noticed that an increase in copolymer content has
led to an increase in the blends viscosity across the shear range. This could be due to the higher viscosity of the
copolymers incorporated in PPH. However, the trend was different in blend containing copolymers POE3 and POE1.
It was noted that the highest and lowest viscosities were observed in blends containing 15 and 20% POE, respectively.
With 10% POE content ranging in between of 15% and 20% POE level. This phenomenon could be explained by the
fact that POEs with lower molecular weights will impart lower viscosities to PPH based blends at above a certain POE
content. Similar phenomenon was reported by Na Sang [16].

1000
Without nucleating agent 1000 With nucleating agent
Viscosity (Pa.s)

Viscosity (Pa.s)
100 100

10 10
0.1 1 10 100 0.1 1 10 100
Frequency (rad/s) Frequency (rad/s)
PPH POE1 POE2 PPH POE1 POE2
POE3 POE4 ICP POE3 POE4 ICP

Figure 9. Viscosity curve for 15% loading PPH/POE blends and ICP without/with nucleating agent.

CONCLUSION
• Flexural modulus decreased with increasing the POE content in PPH in the presence and absence of nucleating
agent. The ICP material presented a marginally higher flexural modulus compared to the PPH/POE blends with
15% elastomer content.
• The in-situ polymerization (ICP) is more effective in improving the impact strength at low temperature than
PPH/POE blends prepared during post- reactor compounding.
• The morphological investigation indicated that all PPH/POE blends and ICP system were immiscible in the ratios
investigated.
• From the ARES test, it was noted that the blends materials have presented higher viscosities than PPH across the
entire frequency range.

ACKNOWLEDGMENTS
The author would like to express his sincere thanks to SABIC and King Saud University for their support.

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