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Study of the PENT test conditions for reducing failure times in high-
resistance polyethylene resins for pipe applications

Article  in  Mechanics of Time-Dependent Materials · February 2011

DOI: 10.1007/s11043-011-9151-z

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Mech Time-Depend Mater (2012) 16:105–115
DOI 10.1007/s11043-011-9151-z

Study of the PENT test conditions for reducing failure

times in high-resistance polyethylene resins for pipe
applications

Carlos Domínguez · Rafael A. García · Marcelo Aroca ·

Alicia Carrero

Received: 9 November 2010 / Accepted: 12 August 2011 / Published online: 23 September 2011
© Springer Science+Business Media, B. V. 2011

Abstract A thorough study of the physical conditions in the Pennsylvania Edge Notch Ten-
sile (PENT) test, such as stress and temperature, is carried out in order to reduce the long
test times observed in new bimodal and multimodal polyethylene grades (third and fourth
generation grades) which may withstand hundreds or thousands of hours at the standard con-
ditions (80◦ C, 2.4 MPa). The results show how on increasing the temperature up to 90◦ C and
the applied stress up to 2.8 MPa, the failure time may be reduced by a factor of 6. Special
attention should be paid to the n and Q parameters of the Brown and Lu equation, because
variations in those parameters could dramatically change the result of the comparison be-
tween different systems depending on the temperature and stress value.

Keywords PENT test · Slow crack growth · Polyethylene · Failure time reduction · Pipe
material

1 Introduction

High-density polyethylene (HDPE) is the most commonly used pipe material for the trans-
portation and distribution of water and natural gas. In view of the critical nature of this
application both, proper long-term performance and reliability are required to fulfill ev-
ery time more rigorous specifications. After a certain period of time, a polyethylene pipe
can fail in a brittle manner under a load well below its yield stress. This failure mech-
anism, named slow crack growth (SCG), involves the formation of a craze at a point of
stress concentration and the subsequent growth and final fracture (Chan and Williams 1983;
Lustiger and Markham 1983; Brown et al. 1991). In order to measure the resistance of

C. Domínguez () · R.A. García · A. Carrero

LATEP-GIQA, Departamento de Tecnología Química y Ambiental, ESCET,
Universidad Rey Juan Carlos, 28933 Madrid, Spain
e-mail: carlos.dominguez@urjc.es

M. Aroca
Centro de Tecnología REPSOL, Ctra. de Extremadura, Km. 18, 28931 Madrid, Spain
106 Mech Time-Depend Mater (2012) 16:105–115

a polyethylene resin to the SCG process, the PENT test was developed by Lu and Brown
(1992) at the Pennsylvania University and next standardized in ASTM F1473. So far the
PENT test has been widely used for assessing and comparing the resistance to SCG of
polyethylene pipe compounds used primarily for gas applications in the USA and Europe.
Nowadays, this standard has been also included in ISO 16241.
The standard conditions established for the PENT test are 2.4 MPa and 80◦ C. The tem-
perature of 80o C is very used in most test methods because the failure mechanism under
these conditions is valid will be representative of that takes place at lower operating tem-
peratures (Brown and Zhou 2005). On the other hand, the specifications for polyethylene
gas pressure pipes (ASTM D2513) point that the resistance for a PE100 (PE3408) grade
must be higher than 100 hours at 2.4 MPa and 80◦ C. In order to be comparable to current
PE 100 resins in the market, the PENT value should be greater than about 500 h (third and
fourth generation grades) under the standard conditions of 80◦ C and 2.4 MPa (Brown and
Zhou 2003). Currently, the highest resistance grades have values of thousands of hours, and
therefore the PENT test at the standard conditions becomes insufficient.
When a resin is being developed it is very important to have a result of the SCG resistance
as soon as possible, 500 hours or more being a very long time. In the search for stricter
conditions, Dreze and Scheelen suggest that the SCG failure mechanism is the same at
95◦ C and 80◦ C (Dreze and Scheelen 1998). In the same way, Brown suggests 90◦ C as the
superior limit temperature for the PENT test (Brown and Zhou 2003). However, in another
work, Brown points out that the temperature should be lower than 90◦ C (Brown 2007).
Considering these discrepancies, this work tries to get more information about the physical
conditions of the PENT test, such as stress and temperature, in order to reduce the long
failure times exhibited by the new materials.

2 Experimental

2.1 Materials

Two commercial PE80 (second generation) and a PE100 (third generation) grades, kindly
supplied by Repsol company, have been studied in this work. PE80B and PE100B are
ethylene-butene copolymers, Ziegler-Natta based catalyst and PE80A is an ethylene-hexene
copolymer, chromium based catalyst. All the samples contain an additive which is a com-
mercial formulation of phenolic and phosphitic antioxidants, both in 1500 ppm. Table 1
summarizes the main properties of these materials.

Table 1 Polymer physico-chemical properties

Material Comonomer SCB Mw Mw /Mn Density Crystallinity Flexural Yield

type contenta (kg/mol) (–) (g/cm3 ) (%) modulus stress
(%mol) (MPa) (MPa)

PE100B 1-butene 0.55 222 24.7 0.9580 64.2 1220 25.7

PE80B 1-butene 0.53 198 16.2 0.9578 64.1 1260 26.1
PE80A 1-hexene 0.78 155 12.2 0.9527 58.3 980 22.5

a SCB content measured by 13C NMR

Mech Time-Depend Mater (2012) 16:105–115 107

2.2 Specimen preparation

To carry out the PENT test, 10 mm thick plaques were compression molded in a laboratory
hydraulic press at 180◦ C and a nominal pressure of 200 bars and slow cooled during more
than 5 hours at a rate of approximately 0.5◦ C/min up to room temperature. While cooling,
the pressure was allowed to decrease naturally in accordance with ASTM F1473. Specimens
of 50 × 25 × 10 mm were machined from the plaques and following notched by slowly
pressing a razor blade into the specimen at a speed of about 200 µm/min. Side notches of
1 mm and front notch of 3.5 mm were made according to the previously stated international
standard in order to have a fracture under plane strain conditions which contributes to the
formation and evolution of the craze (Brown and Bhattacharya 1985).

2.3 Molecular and physical characterization

To estimate the molecular mass and the molecular weight distribution of the samples, GPC
measurements were carried out on a Waters Alliance GPCV 2000 equipped with refractive
index and viscometer detectors. The molecular exclusion was made by three columns, two
Pl-gel 10 µm Mixed-B and one 10 µm 106 Å. 1,2,4-trichlorobenzene was used as solvent
at 145◦ C and the flow rate was 1.0 ml/min. The instrument was calibrated against narrow
standard polystyrene samples, and the molecular weights were obtained by universal cali-
bration.
Thermal measurements were carried out at a heat rate of 10◦ C/min with a DSC calorime-
ter Mettler-Toledo 822e. To assess the actual value of crystallinity of the tested materials,
samples were cut from the core of the specimens used for the PENT test. The degree of crys-
tallinity was calculated from the melting enthalpy values of the samples, using as reference
a value of 290 J/g for the enthalpy of fusion for an ideal PE crystal.
Densities were determined in a gradient column with water and ethanol according to ISO
1183-2 previously calibrated with floating glass beads of well-known densities at 23◦ C. To
carry out the density determination the samples were previously compression molded and
crystallized at 15◦ C/min.
Tensile and flexural tests were developed in a universal testing machine (MTS Alliance
RT/5) at 23◦ C and a 50% relative humidity. Tensile test were carried out on the dumbbell-
shaped specimens at a crosshead speed of 50 mm/min as ISO 527-2:1993 indicates. The
yield stress was determined as the first maximum in the stress-strain curves. Flexural tests
were accomplished on the rectangular bars samples with a three-point bending geometry
according to the ISO 178:2001 standard at a crosshead speed of 2 mm/min.
An INSTRON 3800 Series PENT Tester was used to evaluate the SCG resistance. In
the PENT test described in ASTM F1473, a single edge notched test specimen is exposed
to a constant load at a well controlled temperature value. The time to failure is measured
with a timer. The PENT test was performed in air, where the degradation problems are less
significant in comparison with the test carried out in water. Afterward the PENT test, the
fracture surfaces were observed by environmental scanning electron microscopy (Philips
XL-30) at 0.5 Torr and 15 kV. Since no extensive surface preparation in this type of mi-
croscopy is required, a more accurate observation of the fracture surface of the sample is
allowed.
108 Mech Time-Depend Mater (2012) 16:105–115

3 Results and discussion

3.1 Effect of the applied stress

Depending on the applied stress (σ ) a sample may fail in a brittle, ductile or under a mixed
failure mode. Figure 1 shows the results for the PE80A sample at 80◦ C, where the three
modes are displayed. The brittle failure mode belongs to the region below a certain critical
stress value (σc ), where the material fails following a SCG process. As has been previously
reported by Lu and Brown (1990a, 1990b) in the SCG region the failure time is proportional
to σ −n , where n is a constant term for each region.
Figure 2 depicts the stress versus failure time curves for the three tested materials at
80◦ C. In the SCG region, the n value ranges between 2 and 5 depending on the material.
Due to this fact, the comparison of two materials could be different depending on the applied
stress. In this case, analyzing the failure time at a 3 MPa stress, the PE80A sample exhibits
higher failure time than PE80B sample, but this trend is just the opposite at stresses below
2 MPa, where the PE80B is tougher. This important result implies that the PENT test should
be performed at different stresses in order to evaluate not only the failure time but also the
n value.
Figure 3 shows the failure surfaces of the PENT specimens characterized by ESEM at
2.4 MPa and 80◦ C. All the samples present a fibrillar morphology which indicates that a
SCG process has taken place (Lu and Brown 1997). On the other hand, the sample PE80A
shows a sharp initial blunting process with broad arrest lines, which is due to the step-wise
failure mode, while the other materials present a quasi-continuous failure mode morphology
(Parsons et al. 1999, 2000). The higher SCB content of the PE80A sample, with the resulting
lower density and crystallinity values, contributes to the blunting process that takes place
at the tip the notch, favoring the step-wise failure mode (García et al. 2008). In the same

Fig. 1 Failure modes as function of the applied stress: (1) ductile failure, (2) mixed mode, and (3) brittle
failure
Mech Time-Depend Mater (2012) 16:105–115 109

Fig. 2 Stress vs. failure time

curves at 80◦ C

Fig. 3 Fracture surfaces at 2.4 MPa and 80◦ C

way, the lower density value, with its respective flexural modulus and yield stress, of the
PE80A implies a lower σc value. Quasi-continuous and step-wise modes are brittle failure
modes, taking place in both cases in the SCG region of the stress versus failure time curve
(Lu and Brown 1990a, 1990b). For the PE80A sample, the increment in the SCG rate at
high stress values is partially inhibited by the blunting phenomenon, which reduces the
stress concentration at the tip of the notch and therefore the n value.
110 Mech Time-Depend Mater (2012) 16:105–115

Fig. 4 Stress versus failure time

at different temperatures
(PE100B)

Fig. 5 Stress versus failure time

at different temperatures
(PE80A)

3.2 Effect of the test temperature

The SCG is a thermally active process so, generally, the failure time is reduced when the
temperature is increased. The temperature and stress effect is taken into account in the well-
known Brown and Lu equation (Brown and Lu 1995):

tf = Aσ −n exp(Q/RT ) (1)

where A, n and Q are constants for a given resin.

In Figs. 4, 5 and 6 the stress and temperature effect for the studied samples have been
represented. Although the higher temperature pointed out by the different standards is 80◦ C,
the study at higher temperatures, as 90◦ C and 100◦ C, has been considered on this study to
reduce the long failure times exhibited by the new bimodal polyethylenes. From the trends
displayed by the three stated graphs it follows that between 60 and 90◦ C the behavior of the
materials is quite similar, showing the SCG region a good parallelism for all of them. This
important result suggests that the mechanism is the same at 90◦ C that a lower temperature,
Mech Time-Depend Mater (2012) 16:105–115 111

Fig. 6 Stress versus failure time

at different temperatures (PE80B)

Fig. 7 Time to failure against

1/RT in the brittle region at
2.7 MPa

being the failure time appreciably shorter. However, the behavior for the PE100B sample
at 100◦ C is very different. As Fig. 4 shows, the tendency for the SCG region at 100◦ C is
sharply different with respect to the other temperatures, probably because the first stages of
the melting processes are occurring at this temperature. An interesting conclusion, drawn
from these results, is that the PENT test could be performed at 90◦ C, therefore substantially
decreasing the test times.
Beyond these observations and when failure time is plotted against 1/RT for a certain
stress value inside the SCG region (2.7 MPa for Fig. 7), the activation energy value (Q, (1))
may be determined. Due to the similarity in the n values, the activation energy will be in-
dependent of the stress in the brittle region. The obtained values for the different materials,
are comprised between 96 and 121 kJ/mol, these differences imply that when two materials
are compared at a certain stress value, the result may be different depending on the temper-
ature. Actually, comparing PE80A and PE80B at 2.7 MPa, the failure resistance for PE80A
is higher only at temperatures above 60◦ C. Therefore, when several materials are compared,
the activation energy value should be determined in order to avoid wrong conclusions.
112 Mech Time-Depend Mater (2012) 16:105–115

Fig. 8 Master curve of stress

plotted against failure time for a
reference temperature of 23◦ C

On the other hand, it is important to note that the PENT tests were performed between
60 and 90◦ C, while the real operating temperatures are in the vast majority of the cases
below these values, and as consequence the activation energy should be always determined
to enhance the information about the resins long-term properties.
As observed for the n value, the sample PE80A shows an activation energy significantly
lower than PE80B and PE100B, which means that the SCG process in this material is less
influenced by the temperature. This fact can be related with the appearance of a certain
blunting processes in PE80A.
From the obtained results and using the Brown and Lu equation, the failure time at room
temperature could be estimated for the SCG region at the studied stresses, being the results
showed in Fig. 8. The n values for every curve in such graphic correspond to the average of
the previously obtained values for each temperature.
From a comparative point of view, it can be seen how the ratio between PE80A and
PE80B is totally different from the obtained value at 80◦ C showed in Fig. 2, being the
resistance for the PE80B higher than the PE80A at the analyzed stresses. This observation
demonstrates the importance of achieving the activation energy, which should be calculated
with experimental data at least at three different temperature values.

3.3 Aging and thermo-oxidative processes analysis

In order to check the influence of the aging and thermo-oxidative processes on the differ-
ent specimens, OIT and DSC experiments were carried out over the compression molded
plaques used for the PENT test after different aging times at 23◦ C. The OIT was measured
at 210◦ C in an oxygen atmosphere following the conditions proposed by Frank et al. (2009).
Table 2 shows the results obtained for the different resins. Additionally, the tested speci-
mens at two different conditions, 90◦ C and 2.0 MPa (failure times from 30 to 300 hours)
and 60◦ C and 2.4 MPa (failure times from 600 to 3000 hours), respectively, were also an-
alyzed by means of OIT and DSC tests. The same results of OIT, crystallinity and melting
temperature, were obtained as for the raw materials not subjected to any test, just storing
during 35000 hours.
The high OIT values, which do not show any significant variation even after 35000 hours,
guarantee the long-time stability of the materials during the PENT test at the analyzed tem-
Mech Time-Depend Mater (2012) 16:105–115 113

Table 2 Oxidation induction times and DSC analysis

OIT (min) Crystallinity (wt%) Melting temperature (◦ C)

Material 100 h 15000 h 35000 h 100 h 15000 h 35000 h 100 h 15000 h 35000 h

PE100B 27 26 27 64.5 64.0 63.8 136.6 135.9 135.5

PE80B 25 24 25 64.1 63.0 63.5 136.4 136.7 136.9
PE80A 30 31 32 58.5 57.7 58.8 132.9 132.9 133.0

Table 3 PENT time results

tPENT (2.4 MPa−80◦ C)
Material 2.4 MPa–80◦ C 2.8 MPa–90◦ C tPENT (2.8 MPa−90◦ C)
Failure time Failure time
(hours) (hours)

PE100B 355 56 6.3

PE80B 48 9.8 4.9
PE80A 75 24 3.1

peratures. Moreover, the absence of any significant post-crystallization signal on the aged
materials implies that the mechanical properties will remain almost unaffected.
Another phenomenon that has not been taken into account for predicting the resistance
the SCG at lower temperatures and long times is the local crack tip aging concept, reported
by Pinter and Lang (2003), which suggests that the high stresses approaching the mate-
rial yield and the craze stress near the crack tip help and accelerate the thermo-oxidative
degradation of the material. Although the results shown in Table 2 suggest that the stabilizer
formulation used for that resins minimize the degradation of the polymer, a certain influence
and variation of the predicted results, displayed in Fig. 8, could exist. Nevertheless, this work
is intended to study more rigorous experimental conditions to reduce the PENT failure time
obtained at the standard conditions (80◦ C and 2.4 MPa reported by ASTM F1473 and ISO
16241). Prediction of the failure times at room temperature is out of the scope of this work.
Figure 9 shows the ESEM failure surfaces for the PE80B sample, testing at 2.4 MPa and
different temperatures in the range of 60 up to 90◦ C. Images show that for all the tempera-
tures, the fibrillar surface extended to more than half of the entire fracture surface, being this
fact a clear evidence that the SCG process took place. Previous results of our group showed
that when the fibrillar region extended to more than 30% of the fracture surface, the SCG
process is occurring, becoming the main failure process (Domínguez 2009). In addition, it is
in order to point out that the initial blunting process in PE80B material, which could inhibit
the initial craze, is almost negligible in all the range of temperatures studied.

3.4 Test time reduction

Table 3 summarizes the standard PENT failure time results at 80◦ C and 2.4 MPa versus the
obtained at 90◦ C and 2.8 MPa, their ratios being also established. The results show how the
failure time is lowered in all the cases, achieving a noteworthy reduction by a factor of 6 in
the case of sample PE100B. As also shown, the time reductions values were not the same
for each material, which proves that the determination of n and Q values are always critical
to compare different resins.
114 Mech Time-Depend Mater (2012) 16:105–115

Fig. 9 PE80B fracture surfaces at 2.4 MPa and different temperatures

4 Conclusions

In the present work, the stress and temperature variables have been studied for different
materials in order to reduce the long failure times that new bimodal resins present in the
PENT test. Based on the results obtained, a more strict condition of 2.8 MPa and 90◦ C has
been proposed. Under this condition, the PENT failure time may be reduced up to 6 times.
On the other hand, and special attention should be paid to the values of the parameters n
and Q. Variations in those parameters could dramatically change the result of the comparison
between different systems depending on the temperature and stress value. Therefore, when
two different systems are being compared, at least three different stress and temperature
values should be tested in order to have well determined n and Q parameters.

Acknowledgement The authors acknowledge Repsol company for kindly providing the materials and
funding for this research.

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