Solar Energy 170 (2018) 988–990

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Solar Energy
journal homepage: www.elsevier.com/locate/solener

Aging behavior and lifetime assessment of polyolefin liner materials for T

seasonal heat storage using micro-specimen
⁎
Michael K. Grabmanna, , Gernot M. Wallnera, Klemens Grabmayera, David Nitscheb,
Reinhold W. Langa
a
Institute of Polymeric Materials and Testing, University of Linz, Linz, Austria
b
AGRU Kunststofftechnik GmbH, Bad Hall, Austria

A R T I C LE I N FO A B S T R A C T

Keywords: The paper deals with the lifetime assessment of polyethylene (PE) and polypropylene (PP) liner materials for
Polyolefin liner material seasonal heat storages. Temperature loading profile was estimated for a storage type with maximum tempera-
Seasonal heat storage tures of 85 °C in September and minimum temperatures of 50 °C in March. Aging experiments in hot air or water
Polymer degradation at elevated temperatures were carried out using micro-sized specimen. The aging indicator strain-at-break was
Lifetime
monitored. From experimental data at elevated temperatures endurance times at service-relevant temperatures
were extrapolated using an Arrhenius approach. By weighting the endurance times with the loading profiles and
assuming cumulative damages, lifetime values were deduced. The investigated PP random copolymer liner
material exhibited a significant better long-term performance than the well-established PE liner material.

1. Introduction
Common polymeric liner materials for hot water seasonal heat
storages are based on polyethylene raised temperature resistance grades
(PE-RT) or polypropylene random copolymer grades (PP-R) (Novo
et al., 2010; Pfeil and Koch, 2000). A ductile material behavior in the
service temperature range between 40 and 95 °C (Novo et al., 2010;
Wallner et al., 2013) as well as weldability, waterproofness and re-
sistance to hydrolysis are required. The long term stability of poly-
olefin-based liner materials against thermo-oxidation is essential to
ensure functionality and durability of hot water heat storages at service
temperatures up to 95 °C for at least 15–20 years (Schramm and
Jeruzal, 2006; Paranowska and Pedersen, 2016). Compared to appli-
cations of such materials for hot water piping, the maximum service
temperatures and the exposure times are significantly higher for sea-
sonal storages. Hence, special attention has to be given to the in-
vestigation of polyolefines accounting for the more demanding tem-
perature loading profile.
The main objective of this paper is to investigate the aging behavior
and to assess the lifetime of two different polyolefin grades using micro-
sized specimen. A well-established PE grade should be compared to a
novel PP random copolymer liner material. Temperature loading pro-
files were estimated for a medium temperature heat storage type with a
maximum temperature of 85 °C in September and a minimum tem-
perature of 50 °C in March. The technological parameter strain-at-break
was determined for micro-sized specimen after exposure to hot air or
water at elevated temperatures of at least 95 °C. Using an Arrhenius
approach, endurance times at service-relevant temperatures were cal-
culated. For lifetime assessment the theoretical loading profile and the
extrapolated endurance times were combined using the Miner’s rule
(Wallner et al., 2016).
2. Methodological approach
2.1. Materials and specimen
A commercial PE-RT grade and a novel PP-R grade were selected for
the investigations. The grades exhibit a base stabilization commonly
used in piping applications. The specific type and amount of stabilizers
is described and discussed in Grabmayer et al. (2014, 2015). The PE-RT
material was compression molded and the PP-R grade was extruded to a
2 mm thick sheet by AGRU Kunststofftechnik GmbH (Bad Hall, Austria).
100 µm (PE-RT) and 50 µm (PP-R) thick micro-sized specimens were
manufactured from the sheets by automated, CNC-aided edgewise
planning (Grabmayer et al., 2014). The specific heat capacity of both,
PE-RT and PP-R grades is around 2.000 J/(kg K) in the operating
temperature range of a seasonal storage (Mark, 2009). Negligible aging
induced changes of the specific heat capacity were detected until ma-
terial embrittlement. Using differential scanning calorimetry, specific
melting enthalpy values of about 85 and 50 J/g for the unaged PE-RT

⁎
Corresponding author.
E-mail address: michael.grabmann@jku.at (M.K. Grabmann).

https://doi.org/10.1016/j.solener.2018.06.046
Received 7 September 2017; Received in revised form 2 May 2018; Accepted 11 June 2018
Available online 22 June 2018
0038-092X/ © 2018 Elsevier Ltd. All rights reserved.
M.K. Grabmann et al.
and PP-R specimens, respectively, were determined. The embrittled
specimens revealed increased specific melting enthalpy values of about
110 J/g for PE-RT and 66 J/g for PP-R. Similar effects were observed by
Kahlen et al. (2010c) for semi-crystalline polymers as a result of en-
hanced tendency of crystallization behavior due to aging induced chain
scission. Hence, the specific heat storage capability is a factor of 2 lower
compared to the conventional storage medium which is water. The
main purpose of the polyolefin liner is to ensure the water tightness of
seasonal hot water storages. The heat storage performance of the liner
with a common thickness of up to 3 mm is negligible for such appli-
cations.
2.2. Aging conditions and characterization
The specimens were aged in hot air and deionized water in a Binder
FED 53 (Tuttlingen, Germany) heating chamber with forced circulation.
Hot water aging was carried out in closed stainless steel vessels (0.4 l).
The deionized water was changed whenever specimens were removed
from the steel vessels. The aging temperatures were 115, 105 and 95 °C
as well as 135, 115 and 95 °C for PE and PP, respectively.
To assess the aging behavior, tensile tests were carried out at am-
bient conditions using a screw-driven universal testing machine with a
test speed of 50 mm/min. As established by Wallner et al. (2004) as
well as Kahlen et al. (2010a,b,c,d) for various polymeric materials used
in solar energy engineering the ultimate mechanical properties strain-
at-break or tensile strength are highly sensitive indicators to monitor
both, physical and chemical aging phenomena. As aging indicator, in
this study strain-at-break was determined by the drop of ultimate strain
(εb) below the yield point (εb < εy).
2.3. Modeling of service relevant loading conditions
A heat storage type with maximum temperatures of 85 °C during
summer and minimum temperature of 50 °C was assumed. The tem-
perature load profile is depicted in Fig. 1.
2.4. Lifetime assessment
For lifetime estimation a cumulative damage approach was used
established by Wallner et al. (2016) for black-pigmented PP solar ab-
sorber materials. The main elements of the approach are the simulation
of temperature loading profiles, the extrapolation of aging data and the
cumulation of damages of different temperature levels. The experi-
mental aging data gathered at elevated temperatures were extrapolated
to service relevant temperatures using the linear Arrhenius fit approach
100
Heat storage type
medium
90
80
Temperature [°C]
70
60
50
40
30
01 03 05 07 09
Month
Fig. 1. Theoretical loading conditions for the heat storage.
Solar Energy 170 (2018) 988–990
assuming a specific degradation mechanism in the temperature range.
ISO 2578 recommends a linear Arrhenius extrapolation approach to
assess the service lifetime of polymeric materials. Furthermore, for
calculated endurance time values of more than 50 years the maximum
endurance time was kept constant at 50 years. This is in agreement with
recommendations given by Leijström and Ifwarson (1998).
A cumulative damage model according to ISO 13760 was used for
lifetime assessment. The assumed annual temperature loading profile
was transformed to a frequency distribution (h/a vs. temperature) in
5 K steps. The lifetime was deduced by weighting the temperature de-
pendent, extrapolated endurance times with the frequency distribution.
A more detailed description of this methodological lifetime assessment
is given by Wallner et al. (2016).
3. Results and discussion
3.1. Aging of the polyolefin grades in hot air and water
Unaged PE-RT material revealed a highly ductile behavior with
initial strain-at-break values of about 900%. A significant drop in strain-
at-break to values of about 500% appeared after initial physical aging
within the first 14 days in hot air and deionized water. Embrittlement in
hot air was obtained for PE-RT after 917 days. A more pronounced
aging behavior was observed for the PE-RT grade in hot deionized
water. At 115 °C the ultimate failure time was 77 days, which was a
factor of about 10 lower than for aging in hot air at 115 °C. Based on
these results it was decided to use the aging data in hot deionized water
for lifetime assessment of the PE-based liner material.
The investigated PP random copolymer revealed also a ductile
material behavior with strain-at-break values of about 250% in the
unaged state. After hot air aging at 135 °C ultimate failure was attained
after 113 days. The embrittlement time in hot water was a factor of
about 2 higher (221 days). For the investigated exposure temperatures
(135, 115 and 95 °C) PP-R exhibited a more critical oxidative de-
gradation in hot air. Consequently, hot air aging data were used for
lifetime assessment of PP-R.
Table 1 depicts the embrittlement times of the investigated liner
grades in the more critical environment water for the PE material and
air for the PP grade. Comparing the materials at the same exposure
temperatures of 115 or 95 °C, longer failure times (factor 6–8) were
deducible for the PP random copolymer.
3.2. Endurance times and estimated lifetimes
The experimental embrittlement times at elevated temperatures
were fitted using an Arrhenius approach and extrapolated to service-
relevant temperatures. Fig. 2 illustrates the reciprocal temperature
(K−1) over the derived endurance limits for the investigated PE and PP
grade. The dashed vertical line depicts the assumed 50 years cut-off
limit.
Due to the significant longer embrittlement times at 95, 115 and
135 °C for the PP grade also a better aging performance was deduced for
the service temperature range. For time-to-embrittlement of PP-R the
Table 1
Embrittlement times for PE-RT in hot water at 95, 105 and 115 °C and for PP-R
in hot air at 95, 115 and 135 °C.
Material & condition Temperature [°C] Failure time [d]
PE-RT (in water) 115 77
105 105
95 178
11
PP-R (in air) 135 113
115 483
95 1372
989
M.K. Grabmann et al.
150
2,4
120
2,6
Temperature [°C]
90
2,8
1/Temperature [1000/K]
60 3,0
3,2
103 104
Time-to-embrittlement [h]
Fig. 2. Experimental failure times for micro-sized PE-RT and PP-R specimen
and extrapolated endurance times at service relevant temperatures.
linear Arrhenius lifetime extrapolation resulted in endurance times of
about 12 years at 80 °C and about 50 years for 60 °C. PE-RT exhibited at
80 °C significant lower endurance times of < 1 year.
A significant difference between these data and the discussed data
from Paranowska and Pedersen (2016) is obvious. The extrapolated
endurance times for PE and PP/PE grades are at about 7 and 2 years at
80 °C, respectively. This divergence can be explained by the used ma-
terial and stabilization packages as well as by the differences of the
experimental setup. Paranowska and Pedersen (2016) used an aging
setup with separated exposure media (water and air) on each side of the
specimen, whereas in this work the more critical exposure medium was
selected. Furthermore, thickness effects could also affect the calculated
endurance times (macro- vs. micro-sized specimen).
The lifetime for the micro-sized specimens was deduced by
weighting the temperature dependent endurance times with the tem-
perature loading profiles assuming cumulative damages (Miners rule).
The estimated lifetimes were 1 year for PE-RT specimen and 16 years
for the PP-R grade. The calculated lifetime for PP-R is significantly af-
fected by the constant endurance time of 50 years that was assumed for
temperatures below 60 °C. Without this assumption, predicted lifetimes
would be much higher (∼25 years) for PP-R.
4. Summary and conclusion
The ultimate failure times defined by strain-at-break values below
yield point were achieved after 77–1372 days, significantly dependent
on the environmental condition (air or water), the temperature (95 up
to 135 °C) and the polyolefin grade. Interestingly, the aging behavior of
the PE-RT grade was much better in hot air and more critical in hot
water. For PP-R the opposite effect was ascertained with a significantly
better aging behavior in hot water. Hence, for lifetime estimation the
most critical environment hot water was used for PE grade while the
Solar Energy 170 (2018) 988–990
hot air aging data were considered for the investigated PP material. The
50 years
PE-RT deduced lifetimes for the investigated micro-sized specimen were about
PP-R
1 year for the PE grade and 16 years for the PP grade.
Acknowledgment
This research work was performed in WP-03 of the cooperative re-
search project SolPol-4/5 entitled “Solar-thermal systems based on
polymeric materials” (www.solpol.at). This project is funded by the
Austrian Climate and Energy Fund (KLI:EN) within the programme
“Neue Energien 2020” and administrated by the FFG. The authors wish
to express their acknowledgements to David Nitsche (AGRU
Kunststofftechnik GmbH, Bad Hall, A) for the cooperation, especially
for making available the compounds.
105 106
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