Development of a validation method for the use of Miner’s Rule

in predicting the oxidative resistance of polyolefins

J. Paschal1, J. Hassinen2
1
Bodycote Testing Group, Melrose Park, IL
2
Bodycote Polymer AB, Nyköping, Sweden

Abstract

With the implementation of NSF Protocol P171 in 1999, and subsequent adoption of ASTM
F 2023 in 2000, Miner’s Rule has been used extensively in developing estimations of cross-
linked polyethylene (PEX) pipe lifetimes when exposed to varying system conditions in the
presence of chlorinated water. Previous work in this area demonstrated that Miner’s Rule
can be effectively used and validated for some polyolefins under standard hydrostatic test
conditions, but that significant deviations can also occur depending on the material. This
paper presents the results of similar work towards a validation method for Miner’s Rule,
specifically focused on flowing systems with an aggressive water matrix to accelerate
oxidation of the polymer. The use of Miner’s Rule proved to be a reasonable approximation
for some materials, but as with the earlier work, overly optimistic for other materials. The
paper also discusses the proposed method to be incorporated into the applicable ASTM
products standards for PEX and polypropylene (PP) piping and minimum criteria established.

Introduction
The Miner’s Rule method for determining cumulative damage to pipes subjected to varying
temperature conditions is widely used in predicting stress-rupture performance, as well as the
classification of service conditions given in various ISO standards. Previous work in this
area demonstrated that Miner’s Rule can be effectively used and validated for some
polyolefins under standard hydrostatic test conditions, but that significant deviations can also
occur depending on the material (1). This work was based solely on hydrostatic testing. A
summary of the results from that study are given in Table 1.

Table 1 – Summary of previous Miner’s rule data

Material Cycle Approx. Test time, Relative Timea
hr
MDPE 105°C (7 days) – 90°C (14 days) 4 000 80-99%
MDPE 95°C (7 days) – 80°C (28 days) 11 000 89-96%
PB 110°C (7 days) – 95°C (14 days) 21 000 95-110%
PB 105°C (7 days) – 90°C (14 days) 33 000 88-118%
PEX 110°C (7 days) – 95°C (14 days) 11 000 57-78%
PEX 105°C (7 days) – 90°C (14 days) 17 000 62-68%
a
Relative time is the ratio of test fail time to the time predicted by Miner’s rule

With the implementation of NSF Protocol P171 (2) in 1999, and subsequent adoption of
ASTM F 2023 (3) in 2000, Miner’s rule has been used extensively in developing estimations
of cross-linked polyethylene (PEX) pipe lifetimes when exposed to varying system
conditions in the presence of chlorinated water. For this reason, the test methodology used in
this study differs from the previous work in that the water is flowing, and has been
specifically treated to provide a very aggressive oxidative environment.

Miner’s Rule is a method of estimating the cumulative damage to a pipe exposed to varying
pressure and/or temperature conditions (4). The method can only be applied to specimens
exhibiting the same failure mechanism. Different failure mechanisms must be evaluated
separately. In this study, the mechanism in all failures was Stage III oxidative degradation.

The use of Miner’s Rule in evaluating plastic piping is applicable to what has been termed
“traditional domestic” systems, where the water is assumed to be at a temperature of 60°C for
25% of the exposure time, and 23°C for the remaining 75% of the exposure time. For the
testing conducted in this study, elevated temperatures were used to accelerate the failure
times. The temperatures used were 100°C and 115°C. In the first case, the specimens were
maintained at the lower temperature for 75% of the time, and the higher temperature for 25%
of the time, as is assumed in the traditional domestic model. The second series of tests
reversed this cycle such that the higher temperature was used for 75% of the exposure. This
was done to further accelerate the testing. In summary:

Series 1 – 75% at 100°C, 25% at 115°C

Series 2 – 75% at 115°C, 25% at 100°C

In both cases, the temperature was cycled in 28 day periods (75% = 21 days, 25% = 7 days).
This cycling continued until failure occurred in each specimen.

Testing

Three cross-linked polyethylene (PEX) materials were used in this study. Samples of all
three were tubing coils from commercial production (i.e. not lab-controlled samples). The
three samples represented the three methods of cross-linking PE materials – peroxide
(Material A), silane (Material B), and electron beam (Material C).

Testing was conducted using equipment complying with the requirements of ASTM F 2023-
04 Standard Test Method for Evaluating the Oxidative Resistance of Crosslinked
Polyethylene (PEX) Tubing and Systems to Hot Chlorinated Water. The requirements
regarding sampling, specimens, and exposure condition tolerances were also followed.

The testing consisted of placing specimens on the chlorine exposure test stands at a constant
internal pressure (4 bar, 58 psig) and constant flow rate (54 L/hr, 0.24 gpm). The
temperature was then cycled with a period of four weeks, the first three weeks at one
temperature, and the fourth week at the alternate temperature (see Fig. 1).
 Series 1, 75% at lower temp

120
110
100
90
Temperature, °C

80
70
60
50
40
30
20
1 2 3 4 5 6 7 8
Week (7 days)

Series 2, 75% at higher temp

120
110
100
90
Temperature, °C

80
70
60
50
40
30
20
1 2 3 4 5 6 7 8
Week (7 days)

Figure 1 – Temperature cycling for each test series

The test conditions and sample information are given in Table 2. The results of testing are
given numerically in Table 3 and graphically in Figure 2 for exposure at the lower
temperature for 75% of the time (Series 1). Table 4 and Figure 2 provide results for exposure
at the higher temperature for 75% of the time (Series 2). The predicted values for the
materials shown in the tables were calculated using Miner’s rule and the applicable 3-
coefficient regression equation:
Ê1ˆ Ê Log (σ ) ˆ
Eq. 1 Log (t ) = C1 + C 2 Á ˜ − C 4 Á ˜
ËT ¯ Ë T ¯
Where hoop stress, _, is in MPa and temperature, T, is in Kelvin. The values of the
coefficients, C1, C2 and C3 were determined based on testing of the respective materials.
For Materials A and C, a limited dataset was obtained using the six test condition
requirements of ASTM F 2023 (2 stresses levels at each of 3 temperatures), but with only a
single data point at each condition. For Material B, the coefficients were based on a full F
2023 dataset previously tested. That is, the F 2023 data for Materials A and C were obtained
from specimens taken from the same coil as used in the Miner’s rule testing. The F 2023
data for Material B had been generated previously and was not duplicated in this study.

After calculating the predicted times at temperatures of 100°C and 115°C using the
applicable stress level for the specimen, the predicted time for the temperature cycling was
determining using Miner’s Rule as follows.

100% 100
Eq. 2 Time, hr = =
a Ê 25 75 ˆ
∑i t i ÁÁ + ˜˜
i Ë 25 t 75 ¯
t

Values for t25 and t75 are the calculated times for the temperature at that portion of the cycle.
For example, t25 is the time calculated for a temperature of 115°C using Equation 1, in Series
1 because Series 1 has the temperature set at 115°C for 25% of the total exposure time. In
Series 2, the value for t25 is calculated using a temperature of 100°C because 25% of the
exposure time was at 100°C.

Table 2 – Test conditions

Description Requirement (F 2023) Test condition
Fittings NA Brass
Tubing NA _-inch nominal size, SDR 9
Free chlorine, mg/L (ppm) 2.5 – 5.0 4.0
pH 6.5 – 8.0 6.8 ± 0.2
Oxidation-reduction potential > 825 >825
(ORP), mV
Flow velocity, ft/s (m/s) > 0.12 (0.036) 0.43 ft/s (0.13)
Flow rate, gpm (L/hr) > 0.06 (14) 0.24 gpm (54)
Conditioning time, hr 1–3 1
Test pressure, psig (MPa) 58 (0.40)
 Table 3 – Test Results, Series 1 (75% of time at 100°C)
% of
exposure Fail Predicted
Temp., time at Stress, Time, Fail Relative
°C temp. Specimen Material MPa hr Time, hr Timea
115 25% A-4 A 1.52 673 1022 66%
100 75% A-5 A 1.52 734 1022 72%
A-6 A 1.52 736 1022 72%
B-4 B 1.49 4143 4550 91%
B-5 B 1.48 4127 4566 90%
B-6 B 1.47 4161 4583 91%
C-3 C 1.46 1370 1330 103%
C-4 C 1.46 1968 1330 148%
a
Relative time is the ratio of test fail time to the time predicted by Miner’s rule

75% @ 100°C

1.6

1.5
Stress, MPa

1.4
100 1000 1350 4500

Time, hr

A-Time, hr vs A-stress, MPa

A-Pred, hr vs A-stress, MPa
B-Time, hr vs B-stress, MPa
B-Pred, hr vs B-stress, MPa
C-Time, hr vs C-stress, MPa
C-Pred, hr vs C-stress, MPa

Figure 2 – Series 1 data

 Table 4 – Test Results, Series 2 (75% of time at 115°C)
% of Fail Predicted
Temp., exposure Stress, Time, Fail Relative
°C time at temp. Specimen Material MPa hr Time, hr Time
115 75% A-1 A 1.52 770 564 137%
100 25% A-2 A 1.50 349 569 61%
A-3 A 1.50 477 569 84%
B-1 B 1.48 1872 2276 82%
B-2 B 1.47 1806 2284 79%
B-3 B 1.47 1875 2284 82%
C-1 C 1.46 718 680 106%
C-2 C 1.46 708 680 104%

75% @ 115°C

1.6

1.5
Stress, MPa

1.4
100 550 700 2300 5000

Time, hr
A-Actual
A-Predicted
B-Actual
B-Predicted
C-Actual
C-Predicted

Figure 3 – Series 2 data

Discussion

With the exception of specimen A-1, the relative times for Material A were reasonably
consistent with the previous hydrostatic work done on PEX materials. In this chlorine
exposure work the times were 16-39% lower than predicted by Miners rule, whereas in the
hydrostatic testing the times were 22-43% lower. This suggests that the use of Miner’s rule
is probably optimistic for these materials, and that such use should be validated for each
material formulation, or that an additional design factor may need to be incorporated into the
model. Additional work that may provide better validation for this material may be to use
lower temperatures or lower stresses to extend the test duration.

The Material B test times were approximately 9% lower than the predicted failure times in
Series 1 and were approximately 19% lower in Series 2. Previously reported data comparing
Miner’s Rule predictions with actual fail times of two PEX materials showed a decrease of
22% to 43% in actual fail time vs. predicted values. The previous testing was conducted at
temperatures of 110/95°C and 105/90°C with the cycle consisting of one week at the higher
temperature and two weeks at the lower temperature. Series 1 testing most closely simulated
this cycle from the previous work, with the higher temperature occurring for the shorter
period of time as is assumed in the “traditional domestic” model. In this case, the current
material had better performance (9% vs. 22-43%) than what would be expected based on the
earlier work. Additionally, the Series 2 data showed equivalent or better performance (18-
21% vs. 22-43%) which indicates the temperature cycling can be reversed thereby allowing
an accelerated test condition.

Material C was the only material to have all data points exceed the fail times predicted by
Miner’s rule. However, variations of 3-6% from the calculated mean value as seen with
specimens C1, C2 and C3 would be considered within the experimental variation of this type
of testing for individual data points.

The principal use of Miner’s rule related to this work is for predicting an extrapolated time to
failure under operating conditions of 0.55 MPa (80 psig) continuous internal pressure and a
temperature of 60°C (140°F) for 25% of the time and 23°C (73°F) for the other 75% of the
operating time. Table 5 provides the calculated time to failure for these conditions for each
material, and the reduction in time based on the relative times from Series 1 and 2. It should
be noted that the values in Table 5 are simply mathematical calculations, and that the
increase for Material C is within the experimental variation and not indicative of an actual
performance improvement.

The typical minimum extrapolation requirements are 50 or 80 years depending on the

standard or certification criteria being used. In either case, a reduction in extrapolated time
due to lack of validation of Miner’s rule would not affect the material acceptance for these
materials tested.
 Table 5 – Miner’s Rule Extrapolation
0.55 MPa internal pressure, 25% @ 60°C, 75% @ 23°C

Miner's Rule
extrapolation, Series 1 Series 2
Material years reduction reduction
A 35 23 22
B 501 453 396
C 61 63 64

This type of analysis could be used to specify if and when a validation of the Miner’s rule
model is necessary. For example, if the requirement was an 80-year minimum extrapolation,
validation could be required if the extrapolated time did not exceed this minimum by 25%
(100 yr). If that occurred, then validation testing could be done to confirm whether the
application of Miner’s rule to the specific material in question requires the use of an
additional design factor. This reduction in extrapolated years would then be compared with
the minimum requirements.

Conclusions

The use of a very aggressive oxidizing test fluid, resulting in shorter test durations, provided
results comparable to the earlier work done with hydrostatic testing. This confirms the
applicability of Miner’s rule as a damage assessment tool for oxidative resistance testing.

In both test series the test results for Materials A and B were less than the Miner’s rule
predictions. As such, an additional safety or design factor for this product may be
appropriate, depending on the initial extrapolation values and specification criteria. This is
consistent with the original conclusion of the earlier work done on hydrostatically tested
samples, but perhaps with a design factor greater than 0.5, depending on test conditions and
material.

Reversal of the temperature cycling such that 75% of the cycle is at the higher temperature is
a viable means of accelerating the testing. There was some slight negative variation for
Material B, and no significant variation for Materials A and C (excluding the oulier data).

Validation of the assumption or applicability of Miner’s rule is material-specific, and should

be considered when relying on this as part of the extrapolation model.
References
1. Leijstrom, H., Iwarfson, M., Results and experiences obtained by Studsvik from long-
term pressure tests on plastic pipes for validation of Miner’s Rule
2. NSF Protocol P 171 – Chlorine Resistance of Plastic Piping Materials
3. ASTM F 2023-04 Standard Test Method for Evaluating the Oxidative Resistance of
Crosslinked Polyethylene (PEX) Tubing and Systems to Hot Chlorinated Water
4. ISO 13760, Plastics pipes for the conveyance of fluids under pressure – Miner’s rule –
Calculation method for cumulative damage