Mechanics of Time-Dependent Materials 5: 67–78, 2001.

67
© 2001 Kluwer Academic Publishers. Printed in the Netherlands.

Relation of Slow Crack Growth Failure

Time to Structure of HDPE

E. NEZBEDOVA, J. KUCERA and A. ZAHRADNICKOVA

Polymer Institute Brno, Tkalcovska 2, CZ-656 49 Brno, Czech Republic;
E-mail: kucera@polymer.cz

(Received 15 March 1999; accepted in revised form 21 January 2000)

Abstract. Long-time brittle failure limits the lifetime of polyethylene pipes for water and gas dis-
tribution. The same type of failure was observed in single-edge-notched tensile specimens under
plane strain conditions. The crack opening displacement (COD) was measured as a function of
time and temperature, and the time to complete fracture (tf ) was measured. An empirical failure
time extrapolation relation based on temperature was developed using the Arrhenius equation. The
experimental and extrapolated data for 80◦ C were found to correlate very well. Using this relation,
structural parameters were characterised by the Stepwise Isothermal Segregation/Differential Scan-
ning Calorimetry (SIS/DSC) method. The correlation between fracture and structural parameters was
found.

Key words: crack growth, PENT test, polyethylene, structure

Nomenclature
A = stress-frequency factor
Ac = anisotropy factor for brittle failure
COD = crack opening displacement (mm)
DSC = differential scanning calorimetry
FST = full scale test
GPC = gel permeation chromatography
1H = enthalpy of fusion (J·g−1 )
HDPE = high density polyethylene
NPT = notch pipe test
PE = polyethylene
PENT = Pennsylvania notch test
Q = activation energy (kJ·mol−1 )
R = gas constant (J·mol−1 ·K−1 )
SCB = density of short chain branches (CH3 /1000C)
SDR = standard dimension ratio, nominal ratio of the outside diameter to the wall thickness
SENT = single edge notch tensile specimen
SIS = stepwise isothermal segregation
T = temperature (◦ C)
tf = time to failure (min)
tf † , tf k = time to failure for crack growth perpendicular, parallel to the extrusion direction (min)
68 E. NEZBEDOVA ET AL.

1. Introduction
The lifetime of plastic pipes is controlled by material, service temperature, defect
sizes, environment, and loading factors (Tränker et al., 1996). It is well known
(Egan and Delatycki, 1995) that the structure of polymer chains, mainly (a) mo-
lecular weight and distribution, and (b) number, type, and distribution of short and
long chain branches, are the primary material factors. Further, the structure and
morphology of the polymer are influenced significantly by processing (palletising,
pipe extrusion). Structure, together with temperature, environment, and loading
conditions, determine the type of fracture.
Polyethylene can fail at pipe service temperatures under low stresses in a brittle
mode after a long period of time. The failure mode is called ‘long-term brittle
failure’ (Lu and Brown, 1992). The crack initiation stage and slow crack growth
play an important role in determining the lifetime (Tränker et al., 1996; Huang and
Brown, 1988).
The currently used quality check test for slow crack growth (ISO 13479, 1997)
generally takes 1000 hours, after which the test is terminated. Similarly, to qualify
a new resin, the conventional hydrostatic pressure test must last 104 hours (ISO
1167). Some accelerated tests, utilising fracture mechanics, have been developed
during the last ten years (Lu and Brown, 1992; ISO/TC 138/SC 4N. 144, 1998).
The PENT test developed by Lu and Brown (1992) produces the same type of
brittle fracture that occurs in pipes after a long time in service.
The main aim of this study was to judge the quality of pipes being in service for
a long time. The structure of the resin of PE pipes was characterised by the Step-
wise Isothermal Segregation/Differential Scanning Calorimetry (SIS/DSC) method
(Adison et al., 1992; Nezbedova et al., 1997, 1998) and gel permeation chromato-
graphy (GPC) (Nezbedova et al., 1998) in an attempt to link structure with service
performance.
The PENT test was used to determine the time to failure (tf ) of the resin. Further
fracture parameters can be estimated from the crack opening displacement (COD)
as a function of time: (i) the time of the beginning of brittle fracture (tb ) as the
inflection point of this function, (ii) the minimum rate of COD (min d(COD)/dt)
(Nezbedova et al., 1997). Only tf was measured for the purpose of this work. The
extrapolation of tf data from higher temperatures to 20◦ C enables one to judge the
fracture parameters at temperatures expected in service.

2. Experimental
A set of pipes supplied by the Czech Gas Company was investigated. The pipes,
having been in service since 1969, had an outside diameter from 40 to 225 mm
(SDR 11). Samples taken from the pipe’s surface were analysed by SIS/DSC, some
of them also by GPC analysis. The reason for using GPC analysis was to exclude
bimodal materials because the SIS/DSC record for bimodal materials is the same
as that for the homopolymer with a unimodal distribution (Nezbedova et al., 1998).
RELATION OF SLOW CRACK GROWTH FAILURE TIME TO STRUCTURE OF HDPE 69

Figure 1. An example of a DSC record after using the SIS procedure. The sample taken from
a HDPE pipe after ten years in service – sample No. 14.

The SIS procedure is described in detail in Adison et al. (1992) and Nezbedova et
al. (1997). The principle of this procedure is the fractionation of the sample during
the course of a selected temperature programme. The DSC record (following SIS)
gives several peaks according to the number of temperature pauses, which reveals
the short branch distribution (Figure 1). The location and the area of these peaks
correspond to the average density of short chain branches (SCB) in each individual
fraction and to the representation of this fraction in the polymer, respectively.
Peak I corresponds to a homopolymer fraction in the polymer and indicates the
stiffness of the resin. Too low a content of the homopolymer fraction decreases
stiffness, too high a content of the homopolymer fraction supports brittle fracture.
Peak II corresponds to a copolymer fraction with a very low content of SCB and
a relatively high molecular weight. Peak III corresponds to a copolymer fraction
with a higher content of SCB and a medium molecular weight. Fraction IV that
crystallised during cooling of the sample to room temperature, consists mostly of
low molecular weight chains with a high content of co-monomer.
The method of Lu and Brown (1992) was applied to evaluate parameters of
‘long-term brittle failure’. The geometry of the specimens was single edge notch
tensile specimen (SENT). The shape and dimensions of the specimens are shown
in Figures 2a and 2b. The specimens were machined from the pipes parallel to
the extrusion axis (Figure 2a) and perpendicular to the extrusion direction axis
(Figure 2b) as recommended in ISO/TC 138/SC 4N. 144 (1998). The notch depth
was chosen to minimise the failure time without producing excessive creep on the
remaining ligament. The notch was made by pressing a fresh razor blade into the
specimen at a constant speed of 330 µm·min−1 . The specimens were conditioned
for 40 hours prior to testing. It was found (Lu and Brown, 1992) that a notching
speed of less than 500 µm·min−1 does not affect the lifetime.
70 E. NEZBEDOVA ET AL.

Figure 2. The shape and dimensions of specimens machined from a pipe.

The kinetics of the failure process was observed under a constant nominal ap-
plied stress of 2 MPa and temperature 80 and 40◦ C, respectively. Only specimens
which had the shortest time to fracture at 80◦ C were examined at 40◦ C. The COD
was measured with the aid of an optical microscope (Figure 3) in the middle of the
notch and measured at the surface of the specimen and at the bottom of the notch.
The COD versus time curves measured at the surface and at the bottom of the
notch were similar, but a difference in the slope of the initial curve parts was found
(Nezbedova et al., 1997). For the purpose of this paper, only the COD measured at
the surface of the specimen were considered. The error of this COD measurement
was about 2 µm.
The testing conditions are important for the following reasons: the temperat-
ure of 80◦ C is usually the highest temperature for testing polyethylene, because
significant morphological changes occur above 80◦ C. The nominal stress of 2 or
2.4 MPa (recommended by Lu and Brown, 1992) is about the upper limit at 80◦ C
for production of the same type of brittle fracture as occurs at room temperature
under long-time service conditions. The test under these conditions is one of the
quickest for PE in air under constant load.
The measurement at two temperatures enables the time to fracture to be ex-
trapolated to other temperatures. The method based on the Arrhenius equation
(Equation (1)) was used for this extrapolation.
 
Q
tf = A · exp , (1)
R · (T + 273◦ C)

where A is an empirical parameter (called the stress frequency factor) which in-
cludes the effect of nominal stress and branch density (Brown and Lu, 1990), Q is
the activation energy, T is the temperature in ◦ C and R is the gas constant.
RELATION OF SLOW CRACK GROWTH FAILURE TIME TO STRUCTURE OF HDPE 71

Figure 3. The COD measuring equipment: an open temperature chamber, two specimens in
grips, a weight, the microscope with measuring eyepiece, and a lighting optical cable.

3. Results
Two parameters for basic structural classification were chosen (Nezbedova et al.,
1998): (a) the average density of SCB, and (b) the value of the ratio 1H1 /1H2 ,
where 1H1 and 1H2 are the enthalpy of fusion connected with the peaks I and II
respectively (see Figure 1). The parameter SCB was calculated from the following
equation
X
4
133.2 − Tpeak i 1Hi
SCB = · , (2)
i=1
1.6 1H
where Tpeak i is the temperature of fusion of the fraction i (see Figure 1), 1Hi is
the enthalpy of fusion connected with the peak i, and 1H is the total enthalpy
of fusion. The values of Tpeak i and 1Hi were determined from DSC records with
the aid of a peak analysis software. The GPC analysis confirmed that none of the
analysed samples was bimodal.
The results of the PENT tests are summarised in Table I for 80◦ C and in Table II
for 40◦ C, respectively. The times to produce complete fracture (tf ) are desig-
nated by tf † and tf k for crack growth perpendicular (axial specimens) and parallel
(tangential specimens) to the extrusion direction, respectively. Some typical COD
measurements for axial specimens (tf † ) are shown in Figures 4 and 5. As expected,
tf † > tf k holds for each pipe because the molecules are generally oriented parallel
72 E. NEZBEDOVA ET AL.

Table I. The specimen dimensions, the structure parameters, the activation energy Q for selected
samples, the time to fracture, and the anisotropy factor at 80◦ C.

Number Outside SCB 1H1 /1H2 Q Type of Wall Notch tf † Ac =

diameter [kJ·mol−1 ] specimen thickness depth tf k tf † /tf k
[mm] [mm] [mm] [mm] [min]

1 110 3.98 0.33 – ax 6.01 2.52 4268 7.36

tn 6.10 2.54 580
2 110 2.97 2.43 – ax 6.36 2.63 269 5.72
tn 7.56 2.94 47
3 110 4.40 2.43 – ax 6.42 2.63 297 2.43
tn 6.47 2.65 122
4 110 0.46 6.32 65 ax 6.45 2.65 106 1.58
tn 6.45 2.65 67
5 110 2.20 3.72 – ax 6.48 2.65 122 2.14
tn 6.56 2.68 57
6 110 1.34 10.21 98 ax 6.99 2.79 112 4.48
tn 6.37 2.63 25
7 110 3.14 3.38 102 ax 7.10 2.80 114 1.46
tn 6.94 2.76 78
8 110 1.26 8.74 65 ax 7.45 2.92 84 1.22
tn 7.40 2.89 69
9 160 1.95 1.74 – ax 9.22 3.34 145 1.04
tn 9.41 3.38 139
10 160 1.15 4.6 62 ax 9.31 3.36 56 1.10
tn 9.54 3.41 51
11 160 1.66 2.79 – ax 9.86 3.50 374 2.83
tn 9.39 3.38 132
12 160 1.45 4.41 112 ax 10.07 3.54 105 1.50
tn 10.09 3.54 70
13 160 3.19 3.21 106 ax 10.24 3.57 89 1.14
tn 10.25 3.59 78
14 225 4.27 0.72 – ax 13.52 4.25 33968 2.01
tn 13.41 4.23 16882
15 225 4.16 2.27 – ax 14.24 4.39 246 1.48
tn 14.38 4.41 166
RELATION OF SLOW CRACK GROWTH FAILURE TIME TO STRUCTURE OF HDPE 73
Table II. The specimen dimensions, time to fracture and the anisotropy factor at
temperature of 40◦ C.

Number Outside Type of Wall Notch tf † Ac =

diameter specimen thickness depth tf k tf † /tf k
[mm] [mm] [mm] [min]

4 110 ax 6.57 2.68 7294 2.45

tn 6.23 2.57 2973
6 110 ax 6.47 2.65 1442 2.56
tn 6.77 2.73 563
7 110 ax 6.96 2.79 8866 5.79
tn 6.95 2.79 1531
8 110 ax 7.68 2.97 1367 1.31
tn 7.94 3.02 1044
10 160 ax 9.51 3.41 1129 2.99
tn 9.90 3.50 378
12 160 ax 9.98 3.52 14389 3.03
tn 9.96 3.52 4744
13 160 ax 10.42 3.61 10494 2.44
tn 9.56 3.43 4298

to the extrusion direction and the crack growth is generally slower in the direction
perpendicular to the orientation. The crack growth anisotropy factor based on the
lifetime, Ac = tf † /tf k , varies from 1.0 to 7.4 at 80◦ C. This range is wider than that
published in Lu et al. (1994) for similar experiments. The range depends on the
processing conditions and the grade of the PE resin, and can be affected by small
variations in initial crack depth and uniformity.
Equation (1) was applied to the experimental data for 80 and 40◦ C. If we sup-
pose that A is temperature-independent, we can calculate Q for each pipe and
crack orientation when the tests were conducted at both temperatures. We have
taken the time of failure at 40◦ C as the characteristic parameter of a pipe and the
crack direction. It was denoted tf (40). When the values of Q are plotted versus
ln{tf (40)}, they are well approximated by a straight line (Figure 6)

Q = a + b · ln{tf (40)}, (3)

with a = −66.2, b = 18.7 corresponding constants.

The stress frequency factor A can be evaluated for each tf (40) applying Equa-
tion (1). Plotting A versus tf (40), it was concluded (see Figure 7) that an approx-
imation to a straight line is again reasonable:

ln(A) = c + d · ln{tf (40)}, (4)

74 E. NEZBEDOVA ET AL.

Figure 4. An example of COD dependencies versus time at 80◦ C.

Figure 5. An example of COD dependencies versus time at 40◦ C.

where c = 25.44, d = −6.20. Then Equation (1) was rewritten as

a + b · ln{tf (40)}
ln(tf ) = c + d · ln{tf (40)} + . (5)
R · (T + 273◦ C)
Equation (5) was used for extrapolation of the time to failure at 20, 40, 60, 80◦ C
(Figure 8). The extrapolation was compared with the experimental data measured at
80◦ C for different pipes at both directions. A good correlation in the range of meas-
RELATION OF SLOW CRACK GROWTH FAILURE TIME TO STRUCTURE OF HDPE 75

Figure 6. The dependence of activation energy Q versus the logarithm of time to failure at
40◦ C for different pipes.

Figure 7. The dependence of stress frequency factor A versus time to failure at 40◦ C for
different tested pipes.
76 E. NEZBEDOVA ET AL.

Figure 8. The extrapolation of time to failure for different temperatures (straight lines). This
is compared with experimental data at 80◦ C.

ured times was found. It seems that for room temperature (20◦ C) and longer times,
the extrapolated data are shifted to significantly long failure times. Unfortunately,
we have no independent experimental data to confirm this trend. A discussion of
this problem was found in Tränker et al. (1996) where the authors concluded that
all data at 20◦ C are shifted to significantly longer (factors of 2–10), compared with
the experimental data obtained directly at 20◦ C.
Correlation between structural parameters and the time to failure is very diffi-
cult. We tried to correlate the logarithm of tf to SCB with respect to results pub-
lished by Brown and Lu (1990). We obtained a more complicated graph (Figure 9).
The dependence of tf for 80◦ C is simple for SCB < 3; it can be approximated by a
straight line for all values of a second structural parameter 1H1 /1H2 . Above this
value, the data split into two branches. The samples with 1H1 /1H2 > 1 (a high
share of homopolymer fraction) lie on the original straight line, but the samples
with 1H1 /1H2 < 1 (a low share of homopolymer fraction) lie on another branch
which represents a substantial increase in time to failure from 500 to 104 min,
which agrees qualitatively with results obtained by Brown and Lu (1990).

4. Conclusions
• The measured anisotropy factors differed over a wide range (1–7.4) for the
pipe material.
RELATION OF SLOW CRACK GROWTH FAILURE TIME TO STRUCTURE OF HDPE 77

Figure 9. The correlation between time to failure tf † (80) and SCB. The enthalpy ratio
1H1 /1H2 serves as a secondary structural parameter.

• The dependence of the activation energy and the stress-frequency factor on

the failure parameter tf (40) were evaluated. An extrapolation of failure data
was provided on this basis. This extrapolation is in good agreement with the
experimental data at 80◦ C in the range of measured times. There is somewhat
of an overestimation of failure times at temperatures of 20◦ C and below.
• The log(tf ) depends linearly on SCB for SCB < 3. For SCB > 3 the data
split into two branches corresponding with the other structural parameter
1H1 /1H2 .

Acknowledgement
The authors thank the Czech Gas Industry for the sponsorship of this project.

References
Adison, E., Ribeiro, V. and Deffieux, A., ‘Evaluation of the heterogeneity in linear low-density
polyethylene comonomer unit distribution by differential scanning calorimetry characterisation
of thermally treated samples’, Polymer 33, 1992, 4337–4342.
Brown, N. and Lu, V., ‘The kinetics and microscopic processes of long term fracture in poly-
ethylene piping materials’, Annual Report 1989–90 GRI90/0104. University of Pennsylvania
Philadelphia, PA, 1990.
78 E. NEZBEDOVA ET AL.

Egan, B.J. and Delatycki, O., ‘The morphology, chain structure and fracture behaviour of high-
density polyethylene’, J. Mater. Sci. 30, 1995, 3307–3318.
Huang, Y.L. and Brown, N., ‘The effect of molecular weight on slow crack growth in linear
polyethylene homopolymers’, J. Mater. Sci. 23, 1988, 3648–3655.
ISO/TC 138/SC 4 N. 144, ‘Notch tensile test to measure the resistance to slow crack growth of
polyethylene resins (PENT)’, first version of ISO document, 1998.
Lu, X. and Brown, N., ‘A test for slow crack growth failure in polyethylene under a constant load’,
Polymer Testing 11, 1992, 309–319.
Lu, X., Zhou, Z. and Brown, N., ‘The anisotropy of slow crack growth in polyethylene pipes’,
Polymer Engrg. Sci. 34, 1994, 109–115.
Nezbedova, E., Salajka, Z. and Kucera, J., ‘Relation between toughness and structural parameters of
PE-copolymers’, in International Conference Welding Technology, Materials Testing, Fracture
Mechanics and Quality Management, Vol. 2, S. Felber, T. Varga and J.L. Zeman (eds), Vienna
University of Technology, 1997, 507–515.
Nezbedova, E., Zahradnickova, A. and Kucera, J., ‘Long time brittle fracture in HDPE’, in
Polymerwerkstoffe ’98, Vol. 1, H.-J. Radusch and J. Vogel (eds), Martin-Luther-Universität,
Halle-Wittenberg, 1998, 457–466.
Tränkner, V., Hedequist, V. and Gedde, U.W., ‘Structure and crack growth in gas pipes of medium-
density and high-density polyethylene’, Polymer Engrg. Sci. 36, 1996, 2069–2076.