Polymer Testing 24 (2005) 613–619

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Material Properties
Effects of testing parameters on the mechanical properties
of polypropylene random copolymer
Senol Sahin, Pasa Yayla*
Mechanical Engineering Department, Engineering Faculty, Kocaeli University, 41040 Kocaeli, Turkey
Received 24 January 2005; accepted 2 March 2005

Abstract
The effects of temperature on the impact resistance and hardness of polypropylene random copolymer are studied for a
wide range of temperatures. The variations in the mechanical properties with a wide range of strain rates are also evaluated.
Finally, the variations in mechanical properties as a function of time after production are studied.
q 2005 Elsevier Ltd. All rights reserved.

Keywords: Polypropylene random copolymer; Mechanical properties; Physical properties; Storage time; Strain rate

1. Introduction 2.2. Specimen preparation

There is a vast literature on processing, morphology,
testing and ultraviolet (UV) degradation of polypropylene
(PP) [1–3]. However, the literature lacks results on the effects
of storage time, outdoor ageing time and the addition of
different master batches at different ratios on the mechanical
properties. This may be connected to the fact that those
investigations are very rigorous and time-consuming. For
these reasons, the aim of this paper is to study the influence of
testing parameters on the mechanical and thermal properties
of injection moulded polypropylene random copolymer
(PP-R) samples with different storage times.
2. Experiments
2.1. Materials
The polymer used in this study is a natural colour PP-R,
produced by Borealis s.a, trade name RA 130E, and supplied
in granular form. The properties of the polymer are given in
Table 1.
* Corresponding author. Tel.: C90 262 335 1148; fax: C90 262
335 2812.
E-mail address: pyayla@kou.edu.tr (P. Yayla).
0142-9418/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymertesting.2005.03.002
A specially designed injection mould was used to
produce test samples. The configuration of the moulded
test samples is depicted in Fig. 1.
All the test samples were injection moulded on a ERAT
FE 130/95 injection moulding machine. Table 2 shows the
specification, set parameters of the machine and the
moulding conditions. Unless otherwise mentioned, before
testing all the samples were conditioned at room tempera-
ture for a period of 30 days.
2.3. Tensile tests
The tensile test samples were dumbbell-shaped with
dimensions of 156!10!4 mm, complying with ISO 527-1
(1993) standard. Tensile tests at various speeds were carried
out on the samples. A Zwick Z10, screw-driven universal
tensile/compression testing machine equipped with a data
acquisition system, was utilised to carry out the tensile tests.
Unless otherwise mentioned, a 50 mm/min test speed was
used. For strain rate effect investigation, a wide range of
speeds from 1 to 1000 mm/min were used. An extensometer
was utilised to determine the elastic modules. Tests were
carried out at a temperature of 23 8C. From at least three
614 S. Sahin, P. Yayla / Polymer Testing 24 (2005) 613–619
Table 1
Typical properties of polymer used in this study
Property Value
3 rectangular with dimensions of 80!10!4 mm, conforming
Density (kg/m ) 900
Melt flow index 21.6 N, 230 8C (g/min) 0.20
Vicat softening temperature (8C) 65
Yield stress (MPa) 25
Elastic modulus (MPa) 840
specimens for each test series, average values for yield
stress, sy, tensile strength, sB, elastic modulus, E, strain-to
yield, 3y, and strain-to-break, 3B, were deduced using the
testing program of the controlling computer.
2.4. Charpy impact tests
Impact fracture energy is an important parameter
characterizing toughness of materials. Impact values
represent the total ability of the material to absorb impact
energy, which is composed of two parts: (a) the energy
required to break bonds, and (b) the energy consumed in
deforming a certain volume of the material. With conven-
tional impact testing equipment (without instrumentation), it
is practically impossible to measure separately these two
parts. Instrumented impact testing provides valuable
information on energies involved in the fracture process,
giving individual evaluation of energy for crack initiation
and energy required to propagate the crack through the
material, which is not possible with the conventional Charpy
impact test. In many materials, the formation of the crack at
the notch root occurs just prior to or at the peak load.
Therefore, it is a reasonable approximation to define the
energy up to the peak load as the ‘crack initiation resistance’
[4]. Similarly, post-peak energy is also defined as the ‘crack
propagation resistance’ of the material. For many industrial
applications, the temperature dependence of impact strength
Fig. 1. Configuration of injection moulded test samples for (a) tensile (4 mm), (b) Charpy impact (4 mm), (c) hardness (3.3 mm), (d) Vicat
softening temperature (4 mm) and (e) colour tests samples.
is very interesting and has attracted considerable attention,
not only from industry, but also from academic circles [5].
The geometry of the Charpy impact test samples was
to the ISO 179/1eA (2000) standard. A single-edge 458
V-shaped notch (tip radius 0.25 mm, depth 2 mm) was
milled in the bars with a fly-cutter using a milling machine.
A series of Charpy impact tests were carried out for a wide
range of temperatures according to ISO 179/1eU (2000). For
setting the test temperature, a mixture of liquid nitrogen and
acetone at different ratios was used. The test samples were
kept in the cooling medium for at least 30 min before
testing.
The Charpy impact tests of the notched specimens were
conducted at a wide range of temperatures ranging from K
75 to 85 8C, employing a Ceast Instrumented Charpy Impact
Tester (Code 6545/000) at an impact speed of 2.93 m/s. The
Charpy impact energy evaluation was based on the linear
elastic fracture mechanics (LEFM) analysis to determine
impact strength of materials as proposed by Plati and
Williams [6]. Charpy impact energy Cv is given by
U
Cv Z (1)
BDF
where U is the absorbed energy by the sample, B and D are
the width and thickness of the samples, respectively, and F
is the sample geometry-dependent calibration factor.
Bearing in mind the advantages of instrumented Charpy
impact tests, both the crack initiation energy, which is
consumed up to the maximum force, and the total impact
energy, which is the conventional Charpy impact energy,
dissipated during whole impact process, were calculated.
2.5. Hardness test
Hardness is defined as the resistance of a material to
deformation, particularly permanent deformation,
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Table 2
Specification and set parameters of the injection moulding machine
used in this study
Parameters Value
Screw diameter (mm) 45
Screw L/D 3.1
Number of barrel heaters 3
Injection volume (cm3) 22
Injection rate (cm3/s) 5.2
Screw speed (rpm) 5
Injection pressure (MPa) 10
Nuzzle temperature (8C) 215
Mould surface temperature (8C) 40–50
indentation or scratching. In general, the most widely used
methods to measure hardness are Rockwell and Shore. The
Rockwell method is usually used for harder materials and is
derived from the increase in depth impression as the load on
an indenter is increased from a fixed minor load to a major
load. The Shore (or Durometer) method, regulated by ISO
868 (2003), has scales for both softer rubbers and plastics.
In this work, Shore D hardness tests were performed at
different temperatures using a Zwick 3100 Shore D
Durometer hardness tester. All results are the average of
three measurements.
3. Results and discussion
3.1. Tensile tests
The tensile behaviour and ultimate mechanical proper-
ties are very important characteristics of semi-crystalline
polymers. These macroscopic properties are known to very
closely depend on the strain rate, thus an understanding of
strain rate dependence of their deformation behaviour is
important for encouraging their wide use in engineering and
structural applications [7]. Strain rate has a complicated and
dramatic effect on materials deformation processes because
the energy expended during plastic deformation is largely
dissipated as heat. This process was observed to be more
prominent at higher loading rates that are associated with
adiabatic drawing than during lower loading rates where
isothermal drawing occurred [8]. In general, three stages of
plastic deformation were suggested in tensile tests of semi-
crystalline polymers [9,10]: (1) pre-neck deformation of
micro-spherulitic structure that proceeds in the whole
sample, (2) large deformation in the neck, which transforms
the micro-spherulitic structure to fibrillar structure, and
lastly (3) post-neck deformation of the fibrillar structure. In
general, in the neck, the polymeric material softens
drastically for a very short period, which is associated
with a decrease of plastic modulus. However, as the neck
develops and exceeds a limiting zone, the morphology
changes to that of a fibrillar structure with increase in plastic
modulus, termed as strain-hardening.
615
Fig. 2. Variation of stress–strain response with respect to crosshead
speed for natural PP-R material.
Typical stress–strain curves of the PP-R samples tested
at different crosshead speeds are given in Fig. 2. The test
samples were not broken at 600% elongation at crosshead
speeds up to 25 mm/min, but for the higher test speeds, the
samples were ruptured at lower % elongation and had a
value of about 38% at crosshead speed of 1000 mm/min. At
lower test speeds, the PP-R samples formed a very marked
and stable neck with a wide stress-whitening zone; as the
test proceeded, the necked zone extended throughout the
whole test gauge to the point of rupture at very large
deformation values. At this stage, due to strain-hardening
there was a gradual increase in the stress as the test
proceeded up to rupture. As the test speed increased, the
stress-whitening zone narrowed and, at very high crosshead
speeds, the remainder of the gauge length was not plastically
deformed.
The effects of crosshead speeds on the variations in
‘yield stress’, ‘yield strain’ and ‘elastic modulus’ are given
in Figs. 3–5, respectively. The behaviour of these proper-
ties with log(crosshead speed) was linear and suggested
that, like other semi-crystalline polymers, the mechanical
properties of PP-R is also very strain rate-sensitive. It has
been pointed out that the slope in these figures might vary
from one semi-crystalline material to another and could be
a good indication to define the strain rate dependency of
material [8].
3.2. Impact tests
The effect of temperature on the variation of force–time
signal obtained from instrumented Charpy impact tests were
depicted in Fig. 6, showing remarkable change in nature of
the force–time signal as the temperature changes. Fig. 6
shows that up to about 25 8C, almost all of the energy is
616 S. Sahin, P. Yayla / Polymer Testing 24 (2005) 613–619

Fig. 5. Variation of elastic modulus with crosshead speed for

injection moulded samples produced from natural PP-R material.
Fig. 3. Variation of yield stress with crosshead speed for injection
moulded samples produced from natural PP-R material.
attention as the pipes get rather fracture-sensitive at lower
consumed at crack initiation stage, and the energy consumed temperatures.
during crack propagation stage becomes visible for The Charpy crack initiation and crack propagation
temperatures above 50 8C. At temperatures above 75 8C, fracture resistance evaluation are given in Fig. 8. The figure
the specimens were partly fractured, while below this shows that up to the lower transition temperature of 0 8C,
temperature they were completely fractured. about 90% of impact energy is consumed to initiate fracture,
The variation of Charpy impact energy with temperature but the trend changes as the test temperature increases,
is given in Fig. 7, giving relatively constant impact strength
between K75 and 0 8C and then the impact strength rapidly
increases with increasing temperature. After 90 8C, it
becomes impossible to break the sample into two. The
phenomenon of characteristic brittle–ductile transition starts
after 0 8C, indicating the fact that the impact strength
deteriorates dramatically as the temperature approaches
from higher values to 0 8C. These results are practically
important from two points of view. First, in practical
applications, pipes made from PP-R could be used down to
water freezing temperatures, and secondly, transportation
and installation of the pipe at lower temperatures are
possible. Thus, these two important points require particular

Fig. 4. Variation of yield strain with crosshead speed for injection Fig. 6. Temperature effects on the force–time response obtained
moulded samples produced from natural PP-R material. from instrumented Charpy impact tests for natural PP-R material.
 S. Sahin, P. Yayla / Polymer Testing 24 (2005) 613–619
Fig. 7. Temperature effects on the total Charpy impact energy (Cv)
for natural PP-R material.
implying that crack propagation energy is higher than the
crack initiation energies for temperatures above 50 8C. For
higher temperatures, the crack initiation consumes only
about 35% of the total impact energy.
3.3. Hardness tests
The variation of Shore D hardness values of the PP-R
samples with temperature is given in Fig. 9. As expected, the
material gives higher hardness values at lower temperature.
Moreover, at the Charpy impact transition temperature of
0 8C, the trend in hardness variation changes, with a steeper
decrease above 0 8C.
3.4. Storage time effects
It is widely known that the properties of polymers may
not remain constant but could vary after processing. As a
Fig. 8. Temperature effects on the Charpy impact crack initiation and propagation energies for natural PP-R material.
617
semi-crystalline material, the properties of PP changes
caused by physical ageing continue on a logarithmic
timescale for a very long time and can still be detected
after months and even years, especially in the cases of
modulus and toughness [11]. The feature could be even
more pronounced for semi-crystalline polymers such as PP-
R. Thus, most of the testing standards require that the test
specimens have to be conditioned for a certain time before
testing. Despite this pre-conditioning, in practice it is not
known how important the pre-conditioning is and how the
mechanical properties vary during the conditioning period.
The variations in yield strength and Charpy impact
resistance of the injection moulded PP-R samples
with respect to room temperature ageing time just after
the injection process were investigated and the results are
shown in Fig. 10. The figure shows that the yield strength
increases gradually after injection; with an increase of about
20%, and stabilises after about 1.500 h storage time.
Regarding the total Charpy impact energy, the effect of
time gets more striking; the impact resistance starts
diminishing just after production, and this reduction
continues for about 1.500 h, reduces about seven times,
and then remains more or less stable. This figure shows a
considerable change in the values of these properties with
time, suggesting that the crystallisation ratio of the material
does not remain constant after production but changes can
be observed for a long period of time after its processing
(this will be demonstrated in a future publication).
4. Conclusions
This paper outlines experimental results from tensile tests
at different crosshead speeds and instrumented Charpy
impact tests on notched samples of polypropylene random
618 S. Sahin, P. Yayla / Polymer Testing 24 (2005) 613–619
Fig. 9. Temperature effects on the Shore D hardness for natural PP-
R material.
Fig. 10. Variations in yield strength (sy) and total Charpy impact
resistance (Cv) with storage time after the injection.
copolymer over a wide range of temperatures. Special
attention was focused on the changes in the tensile properties
over a long period of storage after injection.
Regarding the effects of testing parameters on the
mechanical properties of polypropylene random copolymer,
the following conclusions could be drawn:
(1) The tensile properties of the materials are fairly rate--
sensitive. The properties such as the yield stress, elastic
modulus and yield strain of the material increase with
strain rate. The variations of these properties with log
(crosshead speed) were linear and it is envisaged that the
slope in these figures might very from one semi-crystal-
line material to another and could be a good indicator to
define the strain rate dependency of semi-crystalline
polymeric materials.
(2) The Charpy impact crack initiation and propagation
resistances of the material are rather sensitive to the test
temperature. For lower temperatures of up to 0 8C,
relatively brittle behaviour has been observed. The effect
of an increase in temperature becomes visible after 0 and
above 85 8C the material becomes too ductile to break.
(3) The Shore D hardness of the natural PP-R material is
diminished with increasing temperature. The decrease in
hardness becomes more remarkable after the lower
transition temperature of 0 8C.
(4) The ageing behaviour of polypropylene at room
temperature is rather striking and should not be ignored
in the testing of plastics. Changes in the yield strength
and Charpy impact energy of the PP-R material caused
by storage time continue on a logarithmic timescale for a
very long time and become fairly stable after about 2
months after the injection. The yield strength increases
and impact strength decreases with the storage time. This
observation is quite important from an industrial point of
view. In the plastic pipe sector, for all the quality control
tests, particularly hydrostatic pressure and tensile tests,
samples are conditioned at least 24 h before the tests are
commenced [12]. Despite this pre-conditioning time set
by the standard, it becomes evident that the 24 h
conditioning time is not long enough to have stabilised
mechanical properties.
Acknowledgements
The authors are greatly indebted to colleagues at both
industrial as well as university laboratories for their positive
interest, and especially to Turkkablo A.S., Emas A.S., and
Arili Pipelife Plastik Sanayi A.S. of Turkey. Dr P.S. Leevers
of Imperial College and Prof. E. Cavusoglu of Arili Plastik
are also appreciated for their valuable discussion and
comments on the manuscript. The raw materials supplied
by Borealis S.A. are gratefully acknowledged.
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