Solar Energy Materials and Solar Cells 186 (2018) 29–41

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Solar Energy Materials and Solar Cells

journal homepage: www.elsevier.com/locate/solmat

Review of accelerated ageing test modelling and its application to solar T

mirrors
⁎ ⁎
Coralie Avenela,b, Olivier Raccurta, , Jean-Luc Gardetteb, , Sandrine Theriasb
a
Univ. Grenoble Alpes, CEA LITEN, Thermal, Biomass and Hydrogen Department, Thermodynamic and Solar Systems Laboratory, F-38054 Grenoble, France; INES, F-
73375 Le Bourget du Lac, France
b
Université Clermont Auvergne – CNRS - SIGMA Clermont, ICCF F-63000 Clermont–Ferrand, France

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

Keywords: Solar mirrors for concentrated solar power (CSP) plants are expected to last at least 30 years. As this delay is far
Solar mirrors too long to obtain useful information regarding in-service degradation, accelerated approaches to weathering
Concentrated Solar Power (CSP) testing are performed by manufacturers and research laboratories in order to quickly assess the lifetime of
Ageing test commercial or new technologies. However, most published studies that have been performed in the CSP field are
Acceleration factor
based on phenomenological approaches. The characterization of the degradation, which mostly considers re-
Modelling
flectance loss, has rarely been linked to physical or chemical processes that are responsible for the degradation of
Lifetime prediction
properties. Furthermore, the general laws that can be established from these data to establish material behaviour
are empirical.
Ageing tests have been used for many years in other fields, particularly in the domain of polymeric materials.
The impacts on the material properties of stress factors such as temperature, irradiation and humidity have been
extensively studied, and models have been proposed for different kinds of materials, even though most are based
on empirical observations. One of the goals of this article is to determine how these models could be applied to
the weathering of solar mirrors, and as such, the goal of this paper is to provide a critical review of the various
models that are most used and accepted by the scientific community. All of these models include material-
dependent parameters, and the values that have been determined in these studies are reported here to list their
order of magnitude.

1. Introduction [14,15]. Issues involving durability then become a bottleneck in

1.1. Solar mirrors for CSP
Concentrated solar power (CSP) plants are a carbon dioxide-free and
renewable way to produce energy in which sunlight is concentrated by
mirrors on an absorber that heats a fluid. The different kinds of CSP
technologies and their historical developments have already been re-
viewed [1–9] and therefore are not presented here. Power plants only
use direct normal irradiation (DNI) and consequently must be installed
in specific locations that meet several requirements such as high DNI,
large plane land, etc. Trieb et al. [10] determined potential locations for
CSP plants on Earth, which are shown in Fig. 1.
Obviously, the stress factors within these locations are rather ag-
gressive (light, temperature, humidity, etc.), and as a consequence, the
exposed materials are susceptible to rapid degradation of their prop-
erties [11–13]. It is known that plants are profitable only if the lifetime
of their components, and in particular that of mirrors, exceeds 30 years
bringing products to the market.
Durability can be defined in many ways, but the most generally
accepted definition is that durability is the period of time during which
a product in its service environment will survive before requiring re-
placement or maintenance. The weathering resistance of mirrors ex-
posed to all of these stresses should then be evaluated to predict whe-
ther or not a technology is adapted to an implantation site. Mirrors can
be classified as 3 types including glass, aluminium and polymer mirrors
[16,17]. Glass mirrors can be monolithic or laminated. All of these
structures are shown in Fig. 2. Several plants using glass monolithic
mirrors have been installed and exploited since the 1980s [9,18–21],
and little degradation has been observed on the mirrors. However,
mirror technologies have evolved since, and new mirrors in the market
are different from those installed in these plants [22]. Indeed, the
backing system of paints used to contain large amounts of lead to im-
prove stability; nevertheless, recent environmental regulations require
a drastic decrease in lead content, or even complete removal [23]. As a

⁎
Corresponding authors.
E-mail addresses: olivier.raccurt@cea.fr (O. Raccurt), luc.gardette@uca.fr (J.-L. Gardette).

https://doi.org/10.1016/j.solmat.2018.06.024
Received 9 April 2018; Received in revised form 7 June 2018; Accepted 12 June 2018
0927-0248/ © 2018 Elsevier B.V. All rights reserved.
C. Avenel et al.
Fig. 1. Map of potential locations for CSP plants [10].
Fig. 2. Structures of (left to right) monolithic glass [11], laminated glass, aluminium [33] and polymer mirrors [34] with a magnitude order of layer thicknesses.
consequence but also in order to reduce costs, manufacturers have
developed new coatings [24], new designs [25] and new technologies
(or have updated the old ones), aiming to make the devices lighter and
easier to shape. These adaptations include aluminium [26–29], polymer
[30–32] and glass laminated mirrors, and their efficiency and durability
over the course of 30 years has not yet been proven.
The back side of monolithic mirrors is protected by a paint system.
The binder of such paints is a polymer or a mix of polymers, holding
together other elements such as inorganic fillers and pigments, which
provide desired protective properties such as anti-UV, oxygen and
water barriers [33]. Laminated mirrors contain a polyvinyl butyral
(PVB) layer to affix the two glass parts together. Polymer mirrors, as
their name suggests, have a polymer top layer and often a polymer
substrate. Only aluminium mirrors do not contain polymers. In this
regard, it seems relevant to base the study of mirror lifetime on the
methodologies and models developed in the polymer field.
On the other hand, all solar technologies are confronted with more
or less similar environmental conditions, and so it is also relevant to
base this review on solar fields such as photovoltaic and solar thermal
technologies.
1.2. Methodology for service life prediction
Reliable methodologies are required to provide quantitative lifetime
durability projections that support correct design decisions at the ear-
liest phases of product development. Relevant data should be obtained
in shortened times, and one could expect that this would allow for
30
Solar Energy Materials and Solar Cells 186 (2018) 29–41
establishing models to predict the lifetime and the performance evo-
lution of the product under normal use [34].
The goal of any accelerated weathering test is to increase the rate of
degradation of material properties. Methodologies must be developed
in order to assess the fate and the lifetime of new mirror technologies.
As stated above, this kind of methodology already exists in other do-
mains, with general methods developed by statisticians [34–36] or
methods applied in research fields such as those of polymers, paints and
coatings [37–39] or microelectronic fields [40,41], even for other solar
technologies [42,43]. All of these domains have a technological ma-
turity that is greater than that of CSP, and many of durability studies
have already been performed [44–46]. This could help in establishing
novel procedures that could be applied to the specific case of mirrors. In
particular, the experience gained in the domain of polymers is a sub-
stantial asset, which has proven that an appropriate combination of
testing conditions and set of methods assessing weather-induced
changes allows for a better understanding of property changes.
A general methodology for evaluating durability and lifetime can be
explained in the 4 steps described below [34,43]:
Define a performance requirement and a way to monitor the func-
tional properties that are associated with the performance.
Identify environmental conditions to define the main stress factors
that are responsible for the loss of properties and measure their level in
a representative location. This allows establishing a hierarchy of the
stress factors that considers a probability of occurrence at the applica-
tion site. Meteorological data from sites all over the world are mon-
itored, in particular in the framework of weather prediction and can be
C. Avenel et al.
Fig. 3. The specular reflectance in which θi is the incident angle and φ is the
acceptance angle [51].
easily accessed. Nevertheless, these global data must be handled with
care because they correspond to the ambient atmosphere and not to the
material itself. As an example, black materials are heated by a strong
irradiation and so their temperature is often higher than the ambient
temperature [47]. This is why the microclimate of the samples of in-
terest must be monitored in order to obtain a more realistic assessment
of the degradation on site. Furthermore, the microclimate should be
determined with a real system during operating, rather than with a lone
sample exposed on the site, because the system itself modifies the en-
vironment of the materials and components.
Laboratory ageing tests allow determination of the impact of each
factor on the product, and so determines which stresses are the most
aggressive. If a particular stress has no direct impact on the product,
there is no real need to take it into account, except if the stress inter-
feres with the other stresses, for example enhancing their effect. Every
factor previously identified is then applied at a higher level than in use
conditions in order to accelerate degradation. Because accelerated
testing is expected to provoke the degradation of the exposed materials
in conditions that are relevant of the environmental use conditions, but
at higher rate, the real degradation mechanisms must be known in
order to assess whether or not acceleration modifies the mechanisms.
This information can come from natural exposure of samples performed
in parallel with accelerated tests, or from the experience gained from
existing systems. A long time is required for both methods.
The final part aims at correlating accelerated ageing data with
natural weathering data, taking into account the level of the various
stresses applied to the materials. The goal is to use mathematical
models based on physical or chemical principles reported in the lit-
erature to propose equations that allow for a better prediction of the
long-term degradation of the properties. Even if mathematical model-
ling occurs in the end of the methodology, models should be specified
while planning the ageing tests. Indeed, all variables needed in the
chosen model must be monitored during the test. If they are not, ageing
tests may lead to useless modelling data.
Steps 2 and 3 constitute a risk analysis, which allows establishing a
hierarchy of the stress factors. This hierarchy includes the two fol-
lowing parameters: sensitivity of the material to each stress factor and
the level of the stresses encountered on a typical location of the ap-
plication, which can be obtained from environmental data [43].
1.3. Stress loading
Once a stress has been chosen, it can be applied in several ways;
constant, cyclic, step, progressive and random methods exist [34].
Constant stress is the most common and simple of these methods.
Sample batches are run at a constant level of constraint, and several
levels are chosen judiciously. This method should allow for the lifetime
prediction at low levels if the degradation varies linearly with the stress
level [34].
31
Solar Energy Materials and Solar Cells 186 (2018) 29–41
Many products are submitted to cyclic variations during utilization.
Environmental conditions in particular are cyclic, because of the nat-
ural alternation of day and night and of the seasons each year. This is
why it is sometimes considered that a test with cyclic conditions is
relevant to simulate such in-service conditions [34].
During a step-stress test, a constant stress is applied on a batch of
samples for a given time. If samples do not fail, the stress level is in-
creased to a higher constant level for a new period, and so on step-by-
step until all the samples fail. This method leads to failures in a rela-
tively short time compared to other methods. However, rapid failures
may be unrepresentative of in-service degradation. Furthermore,
modelling such a test is complex because it must account for the cu-
mulative effect of degradation. Step-stress interpretation needs a so-
phisticated computer programme. Thus, the mechanism must be the
same during all steps [34]. An example of such a model and its appli-
cation to electrical insulation cables was published by Nelson [48].
Progressive stress testing is similar to step-stress testing, except that
the stress is increased continuously. Consequently, the limits and
complexity are of the same level [34].
In some in-service conditions, the stress load can be random. An
example is building structures or planes that are submitted to wind
variations. Such a test can be designed using in-service data, such as the
mean or median of the stress, its amplitude over a day or a year, etc. To
model the results, the test is usually regarded as a constant stress test,
using the mean value applied over the test period [34].
1.4. Methodology applied to solar mirrors
To the best of our knowledge, the methodology described above has
not yet been applied to mirrors. Nevertheless, some steps can be taken
using data that are available in the literature. The advancement of each
step is presented below.
1.4.1. Step 1
In the case of mirrors, the relevant functional property of interest is
the specular reflectance, which is defined in Fig. 3. A first guideline
[49] to monitor this property has been published in the literature, but
the methods to properly perform the measurements are still under
discussion in the involved scientific community [50–52].
1.4.2. Step 2
Critical constraints applied to solar mirrors during power plant ex-
ploitation have been identified using the experience gained from in-
stalled plants and the analysis of stresses at the various sites. The main
stress factors were identified, and obviously temperature, humidity,
irradiation (both global and UV), rain, dew, wind, sand and dust come
into play. In specific cases, other factors are also involved, such as
saline mist in coastal areas, chemical pollutants from nearby industrial
sites, etc [12,53].
1.4.3. Step 3
Ageing tests that are currently used for mirror testing have been
recently reviewed [16,54–56] as the main studies performed on all
kinds of solar mirrors [16]. These tests include thermal cycling, damp
heat, humidity and condensation tests, irradiation tests with UV or
global solar spectrum, neutral and copper accelerated acetic acid salt
spray tests, acid rain and Kesternich tests. Nevertheless, there is cur-
rently no consensus or proof that the current ageing tests are relevant.
Commonly used procedures come from other domains such as the
photovoltaic [57] and paints [58–61] fields, but the performance cri-
terion used in these domains cannot be easily transposed to the domain
of CSP [55]. For example, one could erroneously conclude that the
device is not degraded only because “no major visual damage” [62] is
observed, which is in many cases wrong. Thus, these studies are almost
all only phenomenological and comparative, so none of the observed
degradation has been linked to a physicochemical process. This is why
C. Avenel et al. Solar Energy Materials and Solar Cells 186 (2018) 29–41

standard ageing tests that account for the results obtained from ac-
celerated ageing tests of mirrors and their correlation with the results
from natural exposure must be established. It is essential to assess that
the mechanism involved in accelerated tests and in natural exposure are
similar, otherwise any attempt to transfer the data from the lab to the
ground would be meaningless. Several actors in the CSP field are trying
to establish relevant standard procedures [55,63] in order to test mir-
rors with appropriate accelerated ageing tests and to obtain an esti-
mation of their lifetime, but even if many studies were done, the im-
pacts of stress factors on mirrors would still have to be ranked.
discussed. As varying the stress load over the testing time noticeably
complicates the modelling work, this article reports only models with a
constant stress or a stress assimilated to a constant value. In this article,
we will also discuss the possibility and the relevance of using these
relationships to obtain a drastic improvement of lifetime prediction of
mirrors for CSP plants.
This kind of review article already exists in the other fields men-
tioned above, such as in electronics [64] and photovoltaic (PV) tech-
nologies [65]. Some studies review several stress factors [64,65],
whereas others are focused on one stress factor of interest [41,66].

1.4.4. Step 4 2. Mathematical models with one stress factor

Furthermore, once ageing tests are proven to reproduce the actual
degradation mechanism, it will be necessary to determine the accel-
eration factor of accelerated ageing vs. natural ageing. The goal would
be to ensure that the performed test is sufficient to simulate 30 years or
a mirror's lifetime, or even more.
The global acceleration factor A of a test compared to an application
site is defined as the ratio between the time t s needed to reach a spe-
cified extent of degradation and the time of accelerated test tt to reach
the same amount of degradation, defined by Eq. (1) [34,43]:
ts
A=
tt
Nevertheless, the time of degradation at site ts is seldom known
because the mirror technologies are built with the goal of lasting at
least 30 years in harsh environmental conditions. It is for this reason
that a better understanding of the impact of the level of the relevant
stress factors on the degradation properties is necessary. Degradation in
real conditions, which results from the application of low constraint
levels, is assumed to follow the same laws as those established for high
constraint levels, and an extrapolation of the time to reach a certain
extent of degradation can be made.
1.5. Purpose of this review
In this article, we report mathematical relationships that were es-
tablished in other fields in order to model the effects of the three stress
factors that were previously identified. These laws were empirical or
sometimes based on rational approaches. To simplify the reading,
symbols used in all equations were homogenised and summarised in
Table 1 with their usual unit. Since accelerated ageing tests should be
performed first with only one stress factor at a time in order to identify
the impact of each stress factor independently, the first part of the
presented models is about the modelling of each identified stress factor.
Then, in the second part, the question of how to mix several factors that
can be involved and how to model the coupling of these factors is
2.1. Temperature
2.1.1. Constant temperature
Temperature is a common factor that accelerates the degradation of
a material because the kinetics of chemical processes vary with tem-
perature. Most of the experimental data obtained with the temperature
stress factor are modelled with the Arrhenius relationship [34,64,65],
shown in Eq. (2), assuming that a chemical degradation process is
controlled by a reaction rate constant k [67]:
(1) −Ea
k = γ . exp ⎛ ⎞
⎝ R. T ⎠ (2)
where the pre-exponential factor γ is a constant called the frequency
factor, T is the absolute temperature in Kelvin, and R is either the
Boltzmann's constant or the universal gas constant, depending on units
used for the activation energy Ea. The parameters Ea and γ are the
characteristics of a defined product or material. The frequency factor γ
is obtained from the collision theory (see the book The Theory of Rate
Processes [68] for a detailed explanation). The activation energy re-
presents the minimum amount of energy needed to pass an energy
barrier and achieve a single-step chemical process.
However, most of the degradation processes that occur in real cases
are by far more complex and occur at different steps and with different
activation energies. The difficulty then becomes to determine if the
global process can be approximated by the Arrhenius law over the
entire range of temperatures of interest. This is relevant if the reaction
rate is limited by one slower step, and so the calculated activation
energy represents the activation energy of this particular step. The re-
sulting value is not an activation energy properly linked to one physical
or chemical process, and so it takes different names in the literature,
such as global, apparent, experimental or quasi-activation energy
[64,68].
The acceleration factor aT calculated from this law is given by Eq.
(3) [43]:

Table 1
Meaning of symbols used in equations. Units of the parameters are an indication and can be adapted to the others in the equation used.
Symbol Unit Name Symbol Unit Name

A – global acceleration factor T K temperature

ai – partial acceleration factor of stress factor i Ts K temperature on site
B, C, D – constant Tt K temperature in test
ci mol.L−1 concentration in chemical compound i ts h time on site
ch chemical stress tt h time in test
Ea J.mol−1 thermic activation energy tf h time to failure
k h−1 kinetic constant tw h time of wetness
Is W.m-2 light irradiation on site w – liquid water
It W.m-2 light irradiation in test
I0 W.m-2 optimal intensity α – reaction order constant
m, n – material-dependent constant β % humidity activation energy
p – Schwarzschild's coefficient β’ %−1 humidity activation energy
R J.mol−1.K−1 perfect gas constant γ h−1 frequency factor
RD mol.h−1 rate of degradation (or reaction) θinc ° incidence angle
RHs % relative humidity on site θdec ° declination angle
RHt % relative humidity in test φ mrad acceptance aperture

32
C. Avenel et al.
−E 1 1 to apply this relationship.
aT = exp ⎜⎛ a ⎛ − ⎞ ⎞⎟
⎜ ⎟
R T T (3)
⎝ ⎝ t s ⎠⎠
The Arrhenius relationship has been applied to describe the fate of
numerous materials and experiments such as polymers [34–36,38],
inorganic [69] and organic [70] PV devices, and even old glass solar
mirrors technologies [13]. Nelson said “in certain applications, if the
Arrhenius life relationship does not adequately fit the data, the data are
suspect rather than the relationship” [34]. Although it works well for
many cases, some limits must be kept in mind:
• Activation energy assessment: the apparent activation energy cal-
culated from data describes a global phenomenon, but it ideally
should be linked to a physical or chemical process to assess the
validity of the obtained value [64,68].
• One predominant degradation mechanism: if more than one reac-
tion occurs competitively and if they have different activation en-
ergies, the Arrhenius model will fail to describe the degradation
process [71].
• One degradation mechanism over the range of temperatures: the
Arrhenius relationship describes the reaction rate of a single de-
gradation mechanism; consequently, all temperatures used to esti-
mate the apparent activation energy are assumed to lead to the same
degradation mechanism. When the dominant process varies over the
temperature range of interest, as well as the related activation en-
ergy, several models must be used to describe the material beha-
viour: one for each interval of temperature, taking the correct ac-
tivation energy [72–74]. As an example, it is known that in the case
of polymer oxidation, non-Arrhenius behaviours can be observed,
which have different origins, presences of transitions within the
range of investigated temperatures, existences of different processes
with different activation energies, etc [74]. It is even said that the
kinetics of ageing polymers usually do not follow the Arrhenius law,
except in some cases [75]. During data analysis, it is then necessary
to verify that there is no variation in the apparent activation energy
with temperature, and therefore no variation of the degradation
process, because the extrapolation of accelerated tests to outdoor
climatic conditions is done over a wide range of temperatures
[64,68].
In a case in which the Arrhenius law fails to fit the experimental
data, other models have been developed. A thermodynamic model
based on quantum mechanics and involving free energy, heat and en-
tropy of activation was developed by Glasstone, Laidler and Eyring
[68]. The simplest form is known as the Eyring Eq. (4). It is based on the
Arrhenius equation but contains one more term, FT, which is a function
of temperature. In general, the literature considers FT = Tm, with 0 ≤ m
≤ 1 [64–66].
−Ea
k = FT . γ . exp ⎛ ⎞ variations between years.
⎝ R. T ⎠ (4)
For the typical ranges of temperature that are adopted for ac-
celerated tests, the factor m has a relatively small effect because it is
generally close to 0, so the relation given in Eq. (4) becomes the Ar-
rhenius equation. Furthermore, the values of both parameters are cal-
culated from experimental data only, and so one value strongly depends
on the assumed value of the other. Indeed, the effects of Ea and m on the
reaction rate tend to compensate and the resulting acceleration factor is
similar to that of the Arrhenius relationship [64]. This acceleration
factor is described by Eq. (5), where C is a material-dependent constant
[43]:
m
T 1 1
aT = ⎛ t ⎞ .exp ⎜⎛C ⎛ − ⎞ ⎞⎟
⎜ ⎟ ⎜ ⎟
T
⎝ ⎠
s ⎝ ⎝ Tt Ts ⎠⎠ (5)
The same precautions as for the Arrhenius law must be kept in mind
33
Solar Energy Materials and Solar Cells 186 (2018) 29–41
A semi-empirical method was proposed to calculate the activation
energy, in the case of simple gas reaction [68,76–78]. Then, activation
energies calculated using this method were compared to experimental
determination for several gas reactions, and found to be in good
agreement enough [78]. According to this work, activation energy for
gas reactions ranges from about 0–480 kJ mol-1 [78]. A value of zero
means that the kinetic of the process does not depend on temperature
[68,78]. Even if the method works for simple molecules with few
atoms, it can be complicated to apply it on complex reactions. More-
over, both calculation and experimental determinations contain hy-
pothesis or uncontrolled parameters leading to uncertainties in the final
values that should be kept in mind [68,76–78].
Experimental activation energies were reported for thermoplastic
degradation mechanisms [79]: 10–30 kJ mol-1 for yellowing, 0–20 kJ
mol-1 for gloss loss depending on the kind and colour of resin, about
60 kJ mol-1 for photooxidation of polyethylene. Activation energy for
photooxidation of automotive coatings was assumed to be about
20–34 kJ mol-1 [47]. A review of activation energies for the degradation
of different properties of several polymeric materials shown that it
varies from 28 to 210 kJ mol-1 [80].
For PV devices, assessments of activation energy range from 60 to
100 kJ mol-1 [81,82]. Activation energies between 30 and 90 kJ mol-1
were associated to degradation of organic PV devices [70]. However,
the activation energy is not always evaluated for the PV device of in-
terest, and a range is often taken for further analysis, mostly between 0
and 200 kJ mol-1 [83–86].
The thermic degradation of solar absorbers was assessed to have an
activation energy of 140–210 kJ mol-1 [87,88]. This value was asso-
ciated to an oxidation mechanism [88], in agreement with tungsten
oxidation activation energies of 142 and 153 kJ mol-1 found in another
study [89].
The temperature can be considered as a full stress factor, but it is
also a specific case. Indeed, temperature is always present, whatever
the level, and it is known to play a role in reaction kinetics.
Consequently, a rise in temperature will contribute to an acceleration of
any degradation initiated by other stresses, and this is why the models
for other stresses have frequently been established taking into account
the temperature. These models aimed at describing the effect of the
other stresses in the first place and the temperature is incorporated in
the mathematical relationship, but it is not considered as a second stress
factor in its own right, such as humidity or irradiation would be. This is
why they are not considered to be coupling models by their authors,
and so in this review, they are classified as one stress factor models.
2.1.2. Cycling temperature
During outdoor use, the material is exposed to dramatic variations
in temperature. Indeed, the temperature varies according to day and
night alternation and seasonal alternation; thus, there are also small
Regarding this fact, a constant temperature test does not seem re-
levant to simulate the outdoor behaviour of a material. Indeed, thermal
cycling induces damages that are different than those resulting from
exposure to a constant temperature. The Coffin-Manson relationship (6)
is most commonly used to model the temperature cycling behaviour
[34,64,90],
C
N=
(ΔT )n (6)
where N is the number of cycles, ΔT is the temperature range and C and
n are constants that are dependent on properties of the material and the
test used. The acceleration factor from this relation is described by Eq.
(7):
n
ΔT
aT = ⎛ t ⎞
⎜ ⎟
ΔT
⎝ s⎠ (7)
C. Avenel et al. Solar Energy Materials and Solar Cells 186 (2018) 29–41

An empirical extension of this relationship has been established to where p is the Schwarzschild's coefficient, also called the p-coeffi-
account for how the cycling frequency and the maximum temperature cient. When Schwarzschild established this law, he assumed that the p-
impact the ageing of the material. The Coffin-Manson relationship be- coefficient had a constant value of 0.86, which fitted reported experi-
comes Eq. (8), where freq is the cycling frequency, m is a property of the ments well. Nevertheless, it appeared in later experiments that the p-
material, Ea is a quasi-activation energy, and Tmax is the maximum coefficient depends on the studied material and that it could even vary
temperature reached during the cycle [64]. within a batch of the same material, and in some cases, it also changes
with the radiant flux range [46].
C 1 −Ea×11605 ⎞
N= × × exp ⎛⎜ ⎟ The reciprocity law should be considered as a specific case of the
(ΔT )n (freq)m ⎝ Tmax ⎠ (8) Schwarzschild's law with p = 1. Experiments made on the reciprocity or
All of these models contain parameters that depend on the tested Schwarzschild's laws have been reviewed by Martin et al., [46] who
material, and so the difficulty is to estimate them accurately. In parti- reported a list of all the values of p found in the literature. In the do-
cular, since the (apparent) activation energy is in the exponential main of photography, the study of photoconductive materials and of
factor, a little change in its value induces a large variation in the ac- photodegradation of materials, p ranges between 0.5 and 1, but there
celeration factor. are some cases where it may reach 1.2 [46].
The acceleration factor based on Schwarzschild's law can then be
2.2. Irradiation calculated by Eq. (11), assuming that p is constant over the entire range
of intensities [43]:
Degradation due to light irradiation is usually called photo- ts I
p

degradation. The impact of light on the properties of materials has been aI = = ⎛ t⎞

⎜ ⎟

tt ⎝ Is ⎠ (11)
studied in numerous fields [46,64], but it is mainly in the photographic
domain that methods to quantify the effect of the physical parameters Reciprocity and Schwarzschild's laws are the most used to describe
were first developed [91,92]. Models have subsequently been applied to the photoresponse of materials, but other models have been developed.
other fields such as medicine, biology or environmental ageing tests. Although most of them are seldom used, a few have gained acceptance
The basic law used in photodegradation is the reciprocity law, [46]. One is a graphical technique proposed by Halm which is based on
which says that the same dose produces the same effect, independent of Kron's catenary Eq. (12), where I0 and C are constants that vary ac-
the dose rate. In other words, sources of light of different intensities I cording to the material. This model describes the behaviour of de-
produce the same amount of degradation under different times of ex- gradation in the case of a reciprocity failure. The constant C governs the
posure t if the multiplication of irradiation by time results in a constant shape of the curve and can vary within the range of intensity, whereas
value. This means that the product of a photochemical reaction is only I0 corresponds to the optimal intensity, at which a minimum amount of
dependent on the total energy employed, which is the product of irra- exposure is required to produce a given degradation. It corresponds to
diation and time and is independent of the two factors separately. This the minimum of the curve on the graph [46,92,94].
is illustrated in Fig. 4, which shows different exposure regimes with C −C
varying intensity and time but with the same integrated area, indicating log (I × t ) = constant+log ⎡ ⎛I⎞ ⎛I⎞ ⎤
⎢ I0 + I0
⎜ ⎟ ⎜ ⎟
⎥
the same dose of irradiation. The photoresponse of a material is as- ⎣⎝ ⎠ ⎝ ⎠ ⎦ (12)
sumed to be the same in each case according to this law. The first ex-
The historical development and all of the experiments associated
periments to establish the reciprocity law were published in 1859 by
with this law are well reviewed in Chapter VI of the book written by
Bunsen and Roscoe [46,91,92].
Mees [92], so they are not described here. At low intensities, this
However, there are many cases that clearly show deviation from this
equation can be reduced to (13). This representation is shown in Fig. 5
law. In particular, the law often fails when very low or high intensities
[46,92].
are used [46]. Schwarzschild showed in 1900 that the law should in-
stead consider the product I ×t 0.86 [93]. log (I × t ) = constant −ClogI (13)
This empirical model was generalized later as the two equivalent
forms (9) and (10) [46]: The linear form of this equation is given by Eq. (14), and it is a
1
specific case of the Schwarzschild's equation with p = 1 ± C [92].
I × t p = constant (9)
1
(10) I × t1 ± C = constant (14)
Ip × t = constant
Other common graphical representations include log (I × t ) vs. log (t )
and log (I ) vs. log (t ) plots. Another solution is merely to represent
log (photoresponse ) vs. log (I ) . If a straight line is obtained,

Fig. 4. A selection of radiant flux VS exposure times for testing the law of re- Fig. 5. Halm's graphical method for presenting reciprocity data in which the
ciprocity, in which the integrated areas for each exposure regime are identical. logarithm of the dosage (log It) necessary to produce a fixed photoresponse is
When the reciprocity law is obeyed, the photoresponse is the same [48]. plotted against the logarithm of radiant intensity (log I) [48].

34
C. Avenel et al.
Schwarzschild's law is obeyed and the slope provides the p-coefficient. If
it is not the case, Schwarzschild's law may still be obeyed but the p-
coefficient varies within the material or with the irradiation flux. These
representations are particularly used to link the photoresponse of a
material with the UV environmental exposure. To do this, they can be
adapted to include temperature and humidity effects [46].
Even if the literature is abundant on the subject, especially in the
photographic field, many of the published data have to be handled with
care. On one hand, before the 1970s, controlling the irradiant flux and
knowing its value could be difficult because almost no device was
available to monitor this parameter. On the other hand, measuring the
photoresponse of the exposed materials was complex and sometimes
consisted of subjective assessment, due to the lack of accurate mea-
surement devices [46].
The reciprocity law and the reciprocity breakdown model only ac-
count for the total amount of light received by the material. However,
the wavelength distribution of the light to which the material is sub-
mitted also plays a part in degradation [95]. Polymers in particular are
sensitive to specific wavelengths, because chemical bonds only absorb
light with a wavelength below or equal to a specific value [96,97].
Consequently, a large cumulative dose of light with a long wavelength
can cause no damage to a polymer material, whereas a small dose of
short wavelength light can cause significant damage [95]. This is why
the wavelength distribution of the laboratory sources of light used to
perform accelerated ageing tests must be known precisely, especially
the short wavelength part.
The temperature must be controlled carefully during experiments
because it has been shown that the degradation of polymer materials is
accelerated by temperature [95].
Bauer et al. developed several models [47,95,98–100] to predict the
photooxidation of polymer materials. The authors worked in the auto-
motive domain and specifically studied the ageing of coatings exposed
to light. In this domain, South Florida is a reference site for natural
ageing [95]. The photooxidation rates of polymers in different locations
around the world were compared to the data obtained in the case of
exposures in South Florida, and on this basis, relative models of ageing
were extrapolated. The simplest model only uses the UV dose of the
exposure sites, whereas a second model includes the temperature of
samples and a third adds the humidity effect [95].
2.3. Humidity
2.3.1. Degradation mechanism due to humidity
Humidity can participate in the degradation processes and at least
often accelerates these processes, especially corrosion mechanisms and
some chemical reactions that provoke degradation of the materials.
Indeed, moisture can lead to corrosion if there is a path to the corrosion
site, a contaminant and an electrical potential difference [64–66]. At
least two steps are involved in the corrosion process: diffusion of water
molecules to the corrosion site and the corrosion reaction itself.
In the case of microelectronic packaging, the Lawson experiments
showed that diffusion was not the rate limiting step, but that it was the
corrosion reaction itself [101]. In this specific case, modelling only the
corrosion reaction can be accurate enough to represent the degradation
process and allow for simplification of a model that can quickly become
complex [66].
Nevertheless, another experiment was led by Gunn et al. [102] on
plastic encapsulated bipolar integrated circuits, and results showed that
the degradation process was limited by the diffusion process of water
through the passivation layer of the devices. Identical components were
passivated by quartz or by silicon nitride, and then they were aged in an
accelerated test with temperature and humidity. The activation en-
ergies for the degradation, using the Arrhenius relationship only, were
106 and 29 kJ/mol, respectively for the two passivation layers, and this
difference was explained based on the different kinetics of water dif-
fusion processes in these materials. The authors proposed a mechanism
35
Solar Energy Materials and Solar Cells 186 (2018) 29–41
for the degradation due to the corrosion that includes the following four
steps [102]:
1) permeation of water through the plastic encapsulant, usually mod-
erately fast,
2) diffusion of moisture through the passivation layer, usually low,
3) transport of contaminant ions by water, usually moderately fast,
4) electrochemical corrosion of the metal, usually fast once initiated.
2.3.2. Relative humidity vs water vapour pressure
Another difficulty to take into account with the moisture effect is
that it can be modelled using the partial vapour pressure of water,
which describes the amount of water present, or the relative humidity
(RH) which is usually expressed in percent and is defined as [64,103]:
Vapour Pressure
RH = × 100
Saturation Vapour Pressure (15)
Identifying which parameter, between relative humidity and water
vapour pressure, is the most relevant has been discussed a lot in the
literature [41,66,103–105]. In another study from the microelectronic
field, Gunn et al. [104] designed several experiments with a goal to
determine it. They kept vapour pressure constant while varying tem-
perature and so the relative humidity because saturation vapour pres-
sure is temperature dependent. The results showed that degradation is
faster when relative humidity increases, even if the temperature is
lower and the water vapour pressure is constant [104]. This agrees with
an earlier result from Striny and Schelling [105] for a dynamic random
access memory (DRAM) and an aluminium metallized N-type metal-
oxide semiconductor (NMOS) integrated circuit. They compared four
kinds of relationships to model the effect of humidity on these devices.
They demonstrated that the ones based on relative humidity and on an
Eyring law, presented below by Eqs. (16) and (17), fitted the data better
than the one with vapour pressure. Furthermore, they represented these
four models as a function of humidity and temperature to determine the
dependence on each factor in order to assess their reliability at low
humidity. This analysis confirmed the exclusion of the model using the
water vapour pressure because of physical non-sense at low humidity
[105].
The relative humidity has been accepted as the parameter that is
used in accelerated tests modelling, rather than the usual thermo-
dynamic parameter that is the vapour pressure, because its effect on
corrosion's progress seems to be independent of temperature [64–66].
For this reason, only the models using relative humidity are presented
in this review.
2.3.3. Eyring based models
The two models developed by Striny and Schelling from the Eyring's
law are shown by Eqs. (16) and (17), where tf is the time to failure and β
and β’ are an activation energy term for humidity (others terms have
been described before and can be found in the Table 1) [105]:
E β ⎞
t f = C . exp ⎛ a +
⎝ R. T RH ⎠ (16)
E
t f = C . exp ⎛ a − β′.RH ⎞
⎝ R. T ⎠ (17)
When applied to the data reported in the article published by Striny
and Schelling [105], Eq. (16) leads to Ea = 67 kJ/mol and β = 528%,
whereas Eq. (17) leads to Ea = 77 kJ/mol and β’ = 0.12%-1. Even if
both fit the humidity test data, model (16) has a behaviour at low
humidity that is more relevant than model (17), so it has been selected
by the authors. The accelerated factor so obtained is described by Eq.
(18) and takes into account the temperature and relative humidity.
E 1 1 1 1 ⎞⎞
aT, RH = exp ⎛⎜ a ⎛ − ⎞+β ⎛
⎜ ⎟ ⎜ − ⎟ ⎟
R
⎝ ⎝ Ts Tt ⎠ ⎝ RH s RHt ⎠⎠ (18)
C. Avenel et al.
Another result of the work by Gunn et al. [104] is that degradation is
different between high and middle levels of humidity, and such that the
linked processes are represented by different activation energies. This
highlights the possibility that the degradation of the devices may be
different at in-service conditions, which commonly have a relative
humidity that is even lower. Consequently, the extrapolation of lifetime
from the results obtained with high humidity tests must be handled
with care, and degradation mechanisms must be studied closely and
compared to data obtained from natural ageing [104]. Keeping in mind
these considerations, the authors applied model (16) that was estab-
lished by Striny and Schelling [105] to their data. They found an ac-
tivation energy for the global process of approximately 29 kJ/mol and a
β constant of 296% [104].
Park et al. [106] also applied model (16) to the degradation of PV
modules under humidity and temperature ageing tests, using form (19):
−Ea β ⎞
RD = C . exp ⎛ − gradation was similar in a test performed at 80 °C / 80% RH, which
⎝ R . T RH ⎠ (19)
They found Ea to be 47 kJ/mol and β to be 281.86%, which are of
the same order of magnitude as the results of other previous studies.
An acceleration factor to describe the humidity stress aH is given by
Eq. (20), which is based on the Eyring-Flood relationship where β is a
material-dependent constant and RH is the relative humidity during test
(RHt ) or in service (RHs ) conditions [43]:
1 1 ⎞⎞
aRH = exp ⎜⎛β ⎛ −
⎜ ⎟ ⎟
⎝ ⎝ RHs RHt ⎠ ⎠ (20)
This acceleration factor is the same type as that presented by Eq.
(18) and developed by Striny and Schelling [105], but without the
temperature effect.
2.3.4. The Peck model
Another model has been established by Peck for epoxy packages of
microelectronic devices, which corresponds to Eq. (21) where n is a
material-dependent constant [107]:
E where u is the electrical resistivity of PVB, C and n are constants con-
t f = (RH )n . exp ⎛ a ⎞
⎝ R. T ⎠ (21)
They found values of n between –2.5 and –3.0, with Ea between 74
and 78 kJ/mol. The acceleration factor is then given by Eq. (22), as-
suming that n and Ea values are constants over the range of temperature
and humidity. They found an acceleration factor of almost 20 for a test
at 130 °C / 85% RH compared to one at 85 °C / 85% RH, taking Ea
= 78 kJ/mol [107].
RH
n
E 1 1 global activation energy of the product. The tests were performed for
aRH = ⎛ s ⎞ . exp ⎜⎛ a ⎛ − ⎞ ⎞⎟
⎜ ⎟ ⎜ ⎟
⎝ RHt ⎠ ⎝ R ⎝ Ts Tt ⎠⎠ (22)
A more recent study [108] showed that photovoltaic modules aged
in a damp heat test (85 °C, 85% RH) obey to a similar law with a
constant pre-exponential factor. They determined Ea to be 86 ± 11 kJ/
mol and n to be –2.2 ± 0.8. The authors also compared these values to
data from the literature for microelectronic devices and found them to
be consistent [108].
Another study was done by Park et al. [106] on PV modules, using
form (23):
−Ea
RD = C . (RH )n . exp ⎛ ⎞ vations and assumptions which are not presented here because they are
⎝ R. T ⎠ (23)
They found n to be 3.82, using Ea = 47 kJ/mol. It is apparent that n
is positive in this case because the model considers the degradation rate
instead of the time to failure. Some mathematical changes easily show
that the two forms lead to the same result, depending on where the
minus sign is placed. This model leads to the same acceleration factor as
before, described by relationship (22).
This model is well accepted and is currently noted as the Peck's
36
Solar Energy Materials and Solar Cells 186 (2018) 29–41
model in general books on ageing tests methods and modelling [34,90],
as well as in studies regarding the humidity effect [41,109].
2.3.5. The T + HR correlation
This empirical correlation was first developed for plastic packages
for semiconductors devices to relate failure rate with temperature and
relative humidity [110]. This study compared outdoor exposure in
Panama to the method 106 of the MIL-STD-202 standard [111] for la-
boratory testing. It has been shown that 10 cycles are equivalent to at
least 6 months of exposure in a tropical environment, which equates to
a laboratory to field acceleration factor of 18. Thus, field data were
obtained operating the device in a coastal area, so the authors noticed
that the acceleration factor could be even greater compared to inland
operation because of the device sensitivity to saline mist.
Because this test method is performed by a cycle, it is difficult to
model. Consequently, the authors made the assumption that the de-
seemed reasonable according to their experimental data and to the
literature, but with an acceleration factor of only 7.5 compared to the
Panama site.
They found that the degradation rate RD of the investigated plastic
encapsulated device depends on the sum of the temperature T and the
relative humidity RH of the test, according to Eq. (24) [110]:
RD = exp (C + n (T + RH )) (24)
where C and n are material dependent constants.
Desombre studied the degradation mechanisms that occur on PV
modules and found the same empirical ageing correlation (24) that
agreed well with the contact corrosion phenomenon [112].
Later, Cuddihy studied the electrical resistivity of polyvinyl butyral
(PVB) during ageing tests at several temperature and humidity levels
[103]. PVB is often used as an encapsulant material for PV modules. He
applied the previous model to his data, changing the degradation rate
for the electrical resistivity of PVB and using form (25):
ln (u) = C − n (T + RH ) (25)
taining an activation energy term, T is the temperature in degrees
Celsius and RH is the relative humidity in percent.
Because it fitted the data well, the author tried to demonstrate that
this empirical observation had some theoretical validity. He assumed
that this behaviour was derived from the Arrhenius relationship to
model temperature and used the relative humidity parameter to ac-
count for the water vapour pressure. Varying the temperature and
maintaining the same amount of humidity allows calculation of the
30, 40 and 50 °C at 54%, 80% and 100% relative humidity. The plot of
the electrical resistivity of the PVB against the relative humidity level
for the 3 temperatures forms straight lines and allows extrapolation of
the electrical resistivity of the PVB for the 3 temperatures at a theore-
tical level of 0% RH. Then, the author used these values to calculate a
global activation energy of the PVB corrosion of approximately 47 kJ/
mol, accounting only for the temperature and not the humidity.
According to the previous model, the author plotted electrical re-
sistivity as a function of T(°C)+RH(%) and obtained a good con-
vergence of data into a single straight line. Then, he tried to find
physical laws to explain this empirical observation. After some deri-
detailed in the original publication, he obtained a complex model based
on theoretical relationships such as the Arrhenius equation and ther-
modynamic concepts. He next simplified this model into the model
(25), which seems to prove that this empirical model has a fundamental
basis. In the end, they found a global activation energy approximately
50 kJ/mol for the PVB corrosion reaction, which was consistent with
their previous graphical determination of 47 kJ/mol [103].
Even if the model works well for these experiments, this kind of
C. Avenel et al.
relationship has also been studied by Striny and Schelling to model the
ageing of dynamic random access memory in plastic packages, and they
observed a poor correlation in their data [105]. Indeed, the model is
based on empirical observations made for specific data, and its validity
for other materials must be carefully verified. To do that, an experi-
mental plan such as the one proposed by Cuddihy [103], with 3 tem-
peratures and 3 humidity levels, can be performed. This kind of ex-
perimental plan has also been used for photovoltaic modules [106], for
example. Thus, the final relationship has disharmonious dimensions
(for example, degrees Celsius are added to percent) and that can be
hazardous or not physically consistent.
2.4. Others stress factors
While the three stresses presented above are considered to be the
main parameters, other constraints exist in the environment. They can
vary according to specific locations, for example saline mist is a strong
stress factor in coastal areas but is almost non-existent inland.
Pollutants, especially sulfur dioxide, are also specific stress factors be-
cause of their strong concentrations near industries but weaker con-
centrations in wild areas such as deserts.
When a material is used in environmental conditions, it may be
exposed to liquid water such as dew and rain. This stress is also specific
because it is dependent on climatic conditions: the rate of rain is quite
different in sand deserts than in tropical climates. Thus, the impact of
liquid water is different from the impact of humidity and necessitates its
own model. A common acceleration factor to describe the liquid water
stress a w is Eq. (26) [43], where tw is the time of wetness during test
(t w, t ) or service (t w, s ) conditions:
tw , t
aw =
tw , s
This law is based on the assumption that degradation only occurs
during wet periods and stops when there is no more liquid water in
contact with the material.
The acceleration factor for a stress provoked by chemicals such as
pollutants or saline mist is given by Eq. (27), where c i,t , cj,t , c i,s and cj,s
are the concentrations of a chemical compound i or j during the test or
in service conditions, respectively, and αi and αj are reaction order
constants [43]:
αi αj
ci, cj,
× ⎜⎛
t⎞
ach = ⎜⎛
t⎞
⎟ ⎟ ×…
⎝ ci, s⎠ c
⎝ j, s⎠
The relationship can be adapted to the number of chemical com-
pounds that take part in the degradation process.
Another way to calculate the acceleration factor of a test compared
to an application site for degradation due to corrosion is to use a re-
ference metal that has a degradation similar to the studied material.
Data for reference materials are available in the literature, and so de-
gradation rates during real ageing tests can be found for several loca-
tions. Then, the time needed to reach the same extent of corrosion in
the test is compared to the site according to the definition of the ac-
celeration factor (see Eq. (1)) [43].
Modelling the atmospheric corrosion of a material, even a simple
metal, is quite complex. The degradation mechanism involves several
stress factors in which saline mist is usually preponderant, but tem-
perature and humidity are also aggressive. The role of wind has also
been demonstrated, because it carries salt particles far away from the
sea [43].
To the best of our knowledge, no model has been properly devel-
oped for such stress factors, due to the high complexity and the speci-
ficity of phenomena.
Solar Energy Materials and Solar Cells 186 (2018) 29–41
3. Coupling several stress factors
The simplest hypothesis to couple several stress factors is to assume
a linear interaction between them. So, relationship (28) has been pro-
posed, where the global acceleration factor A is the product of all
models established for each stress [43].
A = aT × aRH × aI × ach × … (28)
However, sometimes a synergic effect can occur between several
stress factors, and global degradation does not behave according to the
previous law. To take this into account, empirical relationships can be
established to model the degradation that occurs during a test using all
stress factors of interest. Relationship (28) can be a starting point in this
case, and some terms to model interactions will be added.
A model was developed by Jorgensen et al. [53] to link the loss of
reflectance to the three main stress factors: temperature, light and hu-
midity. The effect of temperature is taken into account by the Eyring
model and humidity is taken into account by an Eyring-based model.
D
Δρ = C . IUV . T −ne− T e RH (B + T )
E
(29)
A similar model was used by Lee et al. [113] to model the loss of
specular reflectance, and it can be generalized to all kinds of de-
gradation with time.
Ea
RD = C . IUV . e− R . T . e B . RH . t (30)
The first model proposed by Bauer [47,95,99] to predict the pho-
tooxidation rate of automotive coatings at several locations (see above)
was completed a second time by the author in order to include the
temperature effect, and a third time to include the effect of the hu-
midity. This last model is based on the empirical law (31):
RD, relative = 1 + 0.2 RH (31)
(26)
4. Assessment of outdoor parameters
Once a model has been validated and the global activation energy
has been determined, the acceleration factor can be calculated using the
temperature of the site of interest. Nevertheless, several ways to obtain
this value exist and can readily affect the lifetime prediction.
The first and most common value used is the mean value of the
ambient temperature over the course of a year. Indeed, meteorological
data at many sites over the world are monitored, in particular in the
framework of the weather prediction, and can easily be accessed.
However, the mean temperature is not a relevant parameter, because
(27) the degradation rates do not vary linearly with temperature.
Consequently, the degradation rate can be dramatically faster with a
high amplitude of temperatures than the one calculated with the mean
temperature. This is the case for all of the processes that are thermally
activated, such as chemical reactions and diffusion process. In such
cases, it is necessary to define a new average temperature to use for
service life prediction.
Tencer et al. [114] proposed to calculate an effective temperature
that would be defined as the temperature which would lead to the same
degradation of the component if it was exposed to a constant tem-
perature, rather than varying temperatures. They assumed that the time
of exposure could be divided into discrete equal intervals, because in
practice the measure is often done with an equal interval of time. Thus,
the temperature is continuous in a classical climate model, and they
assumed that the rate of degradation follows the Arrhenius equation. In
the end, the authors proposed the following Eq. (32):
−Ea
Teff =
t
⎣
1
Rln ⎡ t ∫0 exp ( ) dt ⎤⎦
−Ea
R.T (32)
Because this equation depends on Ea, different materials and com-
ponent technologies will have different effective temperatures, and
37
C. Avenel et al.
therefore different rates of degradation in similar conditions of ex-
posure. Thus, the same material can have several effective temperatures
because it depends on the failure mechanism of interest, usually the
fastest, which can vary according to the exposure conditions.
Pickett and Sargent [79] used an effective temperature defined as
the irradiance weighted average temperature. Their hypothesis was that
even if the temperature varies outdoors, there should be a constant
effective temperature which would result in the same amount of de-
gradation after exposure to the same amount of sunlight. This hy-
pothesis is mathematically represented by Eq. (33).
Ea ⎛ 1 1 ⎞
∑ I Δt = ∑ Iexp ⎛⎜ ⎜
R ⎝ Teff
− ⎟⎞ ⎟ Δt
T⎠
t t ⎝ ⎠ (33)
The same method was then used by Dumbleton and Haillant [82].
Although it is easier to know the air temperature of a site, the true
temperature of interest is that of the exposed sample. One way to obtain
that temperature is exposing a sample for a long period of time, at least
a complete year, on the application site and monitoring its temperature
variations. Nevertheless, in most cases, such experiments cannot be
performed because of a lack of time and accessibility to real sites.
Another method used by Bauer et al. [95] includes estimating the
material temperature Tmat using the air temperature Tair, a constant C
that is a function of the material colour and the declination angle θdec
with relationship (34):
Tmat = Tair + C . cos (θdec ) (34)
5. Discussion
As discussed in the introduction, solar mirrors contain polymers,
except for aluminium mirrors. Specific attention should be paid to
polymer parts, even if the specular reflectance seems to be stable. As an
example, works on monolithic mirrors [115–117] have shown that their
top paint colour changed during ageing tests under temperature before
any loss of specular reflectance could be observed. Thus, this colour
change indicates a modification in the paint structure, which has been
evidenced by infrared spectroscopy with an Attenuated Total Re-
flectance module (FTIR-ATR).
In the current testing procedures, solar mirrors are not often tested
at constant temperature [16,55,118] because of a poor representa-
tiveness of temperature outdoor variations and because the community
is not yet aware of modelling methods. A cycling temperature test is
usually used instead, because it is assumed that it would better mimic
the natural day and night cycle [16,55,56,118]. The maximum tem-
perature reached in the test must be chosen carefully, and should not
exceed or even be too close to the transition temperature of the poly-
mers used in the device.
As shown before, polymers are sensitive to irradiation, in particular
UV irradiation, and so the paint system of mirrors will be degraded by
exposure to sunlight. When the binder is deteriorated, fillers and pig-
ments are released and can no longer play their protective role [33].
Solar mirrors from different manufacturers have been aged by exposing
the front or back face to irradiation, and the composition of paints were
monitored by FTIR-ATR spectroscopy [119]. Results have shown that
the loss of specular reflectance was faster with the back side exposed,
but only for mirrors whose paint was damaged by irradiation. For those
with a few changes in paints, the loss of specular reflectance was similar
with the front and the back face exposed.
At least two steps are involved in the corrosion process: diffusion of
water molecules to the corrosion site and a corrosion reaction. In the
case of monolithic glass mirrors, the silver layer is protected by a
system of paints that act as a coating. Water must then diffuse through
this barrier or by the edges, which are not always sufficiently protected.
A comparison can be made between the electronic devices with plastic
packages and monolithic mirrors: the paint system and the copper layer
38
Solar Energy Materials and Solar Cells 186 (2018) 29–41
can be seen as the protection system formed by the plastic encapsulant
and the passivation layer, whereas the silver layer would be the elec-
tronic part. The functional property of electronic devices is the electric
conductivity, whereas the one of mirrors is the specular reflectance.
Both properties are governed by the central part of the structure: the
electronic part is surrounded by the encapsulant, whereas the silver
layer is protected by glass or aluminium on one side and coatings on the
other side. As demonstrated in the two studies mentioned above
[101,102], the rate-limiting step depends on the material or on device.
As a consequence, the conclusions regarding the limiting step and the
associated activation energy cannot be directly applied to the case of
mirrors, but the methodology to determine it can be used for mirrors
and provides an order of magnitude for activation energies of these
processes.
Many studies [105,106] consider several models, usually among the
3 kinds presented above (Eyring, Peck and T + HR), and apply them to
their experimental data in order to determine which one is the best
adapted to their specific case. The basic way to identify the best model
would be to determine the degradation mechanism and the related
physical law. In practice, this is a difficult task, which is why studies try
to correlate experimental data as well as possible to existing models.
Laminated mirrors contain a PVB layer, consequently its degradation
might be correctly modelled by the T + HR model that has previously
been used to model the degradation of the electrical resistivity of PVB
[103].
While the relationships were discussed here for glass and polymer
solar mirrors, they could be applied to aluminium mirrors as well as to
other materials. The point is that for each new material, the degrada-
tion mechanism should be identified by material characterizations, and
the kinetic parameters should be determined experimentally and then
be correlated to this mechanism. Nevertheless in practice, the identi-
fication of such mechanism is hard and necessitates a long period of
analysis with a lot of complementary characterization methods. The
complete mechanism is then rarely known, but some clues can be given
by similar degradations observed with some well-chosen analysis.
The minimum and maximum values of the four kinetic parameters
Ea, β, n and p reported in this paper are summarised into the Table 2,
separately for each field of application.
A stress-step method has been applied to solar polymer mirrors
[113,120]. Workers used the Ultra-Accelerated Weathering System
(UAWS) developed by NREL and ATLAS [113,121]. The acceleration
factor of the device is assumed to be 63 compared to the South Florida
example. They concluded that testing plans should be developed using
this device and that statistical procedure adapted to these experiments
would be necessary, but complex to develop [113,120].
It is well known that polymer degradation is sensitive to the initial
polymer composition, in particular to the presence of photooxidation
catalysts, and thus to the conditions of polymerization. As an example,
see the work published by Gerlock et al. [97] This is of paramount
importance for the study of mirrors, because the back system of pro-
tective paints has a composition that depends on the manufacturer and
Table 2
Kinetic parameters ranges from literature with the associated field, where Ea is
in kJ/mol, β is in %, and n and p have no unit.
Parameter min max field / application
Ea 0 480 gas reactions
Ea 0 210 polymers
Ea 0 200 PV
Ea 140 210 solar absorbers
β 290 530 microelectronic
β 282 – PV
n −3 − 2.5 microelectronic
n −4 − 1.5 PV
p 0.5 1.1 photodegradation of materials
C. Avenel et al.
can even change based on a specific batch of samples. Indeed, as the
current market is still new, the production of mirrors is not stabilized
yet and manufacturers adapt their production methods and materials.
6. Conclusions
The different relationships used in the literature to model the effect
of the main environmental constraints on solar mirrors is reviewed, and
their application to the various technologies of solar mirrors is dis-
cussed. The impact of temperature is usually modelled by the Arrhenius
law, sometimes by the Eyring law which contains one more term that
does not drastically change the results. The degradation mechanisms
must be determined and should not vary over the range of temperature
including accelerated tests and service life. The effect of irradiation is
usually modelled by the reciprocity law or is generalized using the
Schwarzschild's law. Short wavelengths of light are more energetic and
can induce degradation which would not occur in outdoor conditions,
so the spectral distribution of lamps used in accelerated tests must be
monitored to ensure that they do not contain short wavelengths that are
not present in the solar spectrum. Modelling humidity effects seems to
be more complex, and three empirical models are still being used in the
literature: Eyring-based model, Peck's model and T + HR correlation.
These models are more or less adapted to different cases, and they all
should be used in new studies in order to determine which has the best
fit with the experimental data.
Accelerated tests may be designed for two distinct purposes: to try
to be as representative as possible of outdoor conditions but with a
faster degradation rate, or to determine the material-dependent con-
stants used in modelling. The first rule to be followed is that the ob-
served mechanism must be the same as the outdoor predominant me-
chanism. Determine the whole mechanism needs a lot of in-depth
characterization so in practice, most of studies only gives elements of
comparison between outdoor and indoor exposures.
Acknowledgement
The research leading to this article has received funding from
French national funding from Agence Nationale de la Recherche on the
program Investissements d’Avenir (no. ANR-11-EQPX-0014) and from
the Auvergne region.
Declarations of interest
None
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