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Ares(2019)1407650 - 01/03/2019
721452 — SOLAR-TRAIN — H2020-MSCA-ITN-2016

SOLAR-TRAIN
Photovoltaic module life time forecast and evaluation

H2020-MSCA-ITN-2016 - Grant Agreement No. 721452

Start date: September 1st, 2016 –Duration 48months

Coordinator: Dr. Karl-Anders Weiß, Fraunhofer Institute ISE, Freiburg, Germany

D4.4 : REPORT ON ALTERNATIVE TECHNIQUES FOR IDENTIFICATION OF DEGRADATION

PRECURSORS
Due date 28/02/2019
Author(s) Djamel Eddine Mansour, Chiara Barretta, Nikoleta Kyranaki,
Stefan Mitterhofer, Aziz Nairi
Workpackage No. and Leader 4 - Aziz Nairi
Date released by WP leader 01/03/2019
Date released by Coordinator 01/03/2019

DISSEMINATION LEVEL
PU Public 
CO Confidential, only for members of the consortium (including the Commission
Services)

NATURE OF THE DELIVERABLE

R Report

W Websites, patents, filling, etc.

E Ethics

O Other 
HISTORY
Author Date Related to WP/Task Comments
Djamel Eddine 20/02/2019 4/4.4
Mansour
Chiara Barretta
Nikoleta Kyranaki
Aziz Nairi

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SUMMARY
Keywords PV modules, Failure modes, degradation mechanisms, degradation
precursors, nondestructive testing, lamination process, PV materials
properties

1. Content of Deliverable

This document presents in a first part, some examples of the current state of the art of the quality
control tests performed in a production line to ensure the module’s quality. In a second part, is
discussed the key materials properties and characteristics that should be measured and/or detected
in order to have a better estimation of the module durability. In a third part, SOLAR-TRAIN efforts to
investigate and develop innovative detection methods of degradation precursors are presented.

2. Quality controls in the industry:

Quality control tests applied in a PV module manufacturing line should check specifically the
characteristics of the individual materials used and to control of the process applied for their
modification into the final product. Among the key aspects for the long-term duration of PV modules,
optimum encapsulation process is the most critical; however every step is usually submitted to
quality inspections.

Accepting that all materials in the BOM are in specifications and with appropriate storage conditions,
different tests are applied to control the lamination process that will allow the modules to support
the outdoor conditions. Most common control techniques used are destructive so usually they are
applied to witness laminates, processed with exactly the same process and at the same time than the
regular production, but with structures prepared for checking individual control parameters for the
full lamination process.

Usually in a continuous operation mode 24/7, tests are applied per laminator and per shift.
Frequency can vary depending on the manufacturing volume, being higher with the highest use of
equipment.

The lamination process is mainly controlled by two specific tests:

1) Gel content determination (primary method): is a direct determination of the gel content
based on the measurement of the unsolved non cross-linked material. Long duration test,
typically from 8 to 24 hours allows absolute gel content value determination, if the EVA
sample has been adequately obtained and processed. Precision of the result is affected by
the multiple weight steps and changes between filtering and drying furnace, together with
the use of dangerous solvents. Detailed description appears in standard IEC-62788-1-6:2017
[1].

An alternative with shorter process time is the modification to that process developed by the
manufacturer STR and adopted by industry in general.

A secondary method for this EVA curation determination is the Differential Scanning
Calorimetry (DSC) [1]. This method is a fast mean of determining the adequacy of the gel
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content on the laminates; however it should be calibrated with the gel content results
obtained out of the primary determination method.

2) Adherence tests: The Peel-off test, as described in [2], investigates the adhesion between
different layers rigid-flexible or flexible-flexible of the PV module stack. Backsheet-EVA, EVA-
glass and EVA-cell adhesion are tested. In order for the module to accomplish the expected
durability, acceptance criteria (N/cm) exist for every one of the interfaces. This procedure is
not valid for rigid glass-glass encapsulated modules

Both tests are destructive, so they require a specific laminate with test structures to measure and
that must have been processed at the same time than the regular product. If not, destruction of PV
modules is required.

Industry has some other specific tests directly related to the EVA material that include checking the
quality of the UV filter in the material or the specific shrinkage conditions, however those are checks
on a per material lot received bases more than in the regular manufacturing activity.

3. Key degradation precursors to investigate.

i. EVA’s crosslinking degree:

The crosslinking degree of the EVA is a key parameter to monitor to obtain a durable module [3][4],
[5]. Lamination (or encapsulation) is a production step when the laminate is brought to high
temperature in order to activate the crosslinking reaction.

If it’s too high, the stiffness of the EVA will be too high and might accelerate delamination due to
dynamic mechanical stress (wind or thermal cycling). Also, a high crosslinking degree is known to
lower the volume resistivity of the EVA, increasing the leakage current and therefore the risks of PID
(potential Induced Degradation) appearance [4].

If it’s too low, the elastic module of the EVA will be too low and will lower the adhesion strength
between of the laminate, increasing the risk of delamination occurrence Moreover, peroxides
(initially introduced in the EVA’s composition to catalyze the crosslinking reaction) might not be
completely depleted; these peroxides are known to be photodegraded into chromophores,
participating in the yellowing of the EVA.

For the EVA, the admitted optimal crosslinking degree is around 85%.

ii. Water permeability:

As stated in the D4.2, water ingress into a module is known to participate in several degradation
modes, like corrosion, delamination or PID [4]. For the water to get into the laminate, it must travel
through the back sheet or from the edges of the modules through the sealants materials. Water
permeability varies with the climatic conditions and the materials degradation. As such, the capacity
of determining the water quantity that a laminate will let through and the speed at which the water
ingress will occurs is a key to extrapolate on the durability of a module in the field.

iii. Additives:
The chemical components added in the composition of the encapsulation materials or the backsheet
have side effects and provoke unexpected degradation mode. For example, too much peroxide in the
EVA composition will result in residual peroxides after the lamination process, and as seen above,

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provoke early yellowing by photo-degradation. Furthermore, it has been seen that some type of UV
absorber (initially implemented to protect the EVA from UV photo-degradation) without the use of
HALS [4] could suffer from an autocatalytic photo-degradation reaction.

On the backsheet side, it has been observed that the type of TiO2 used as white colorant in some
Back-sheet (PP or PA outer layer) is the origin of the chalking degradation mode recently observed in
the field. The TiO2 is known to be photo-catalyzed by UV light which creates some radicals able to
react with the surrounding polymeric chains resulting in the back-sheet embrittlement and cracks [6].

The detection of such additives and the understanding of their unexpected effects on the module
materials could help explain and avoid future degradation of modules in the field.

4. SOLAR-TRAIN Progresses towards precursors detection:

a) Encapsulant Crosslinking degree determination

An in-line monitoring of the EVA gel content of every PV module produced will significantly
contribute to the process quality control. Three non-destructive techniques have been explored; it
will help us to gain insights into the EVA curing process and optimize the encapsulation regarding
long-term reliability.

In this work, samples with different lamination process (Table 1) were tested using the three
techniquess presented below:

Table 1:Curing time and temperature used in the lamination process of Glass-EVA-Backsheet configuration

LAMINATION
SAMPLES LAMINATION TEMP (°C)
DURATION (MIN)
1* 10 160
2* 7 160
3* 5 160
4* 3 160
5* 3 140

i. Raman Spectroscopy (front side of the Module)

Raman spectroscopy has been used as a fast and non-destructive method to investigate the activity
of the remaining peroxide cross-linker under different curing duration. An example of a depth
profiling Raman spectra of four EVA layers laminated in a Glass-EVA(x4)-Backsheet coupon is
presented in Figure 1. The key point of this observation is the Raman intensity ratio of the peroxide
vibration (869 cm-1) and the carbonyl stretching vibration (629 cm-1). This ratio corresponds to the
number of the crosslinks (or reticulation between polymer chains) formed, which is related to the
EVA’s gel content [7,8]. A calibration data from an external method is needed. Here, Soxhlet
extraction and Differential Scanning Calorimetry DSC have been performed using the same
lamination parameters.

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Figure 1:Depth profiling Raman spectra after lamination of backsheet-EVA-glass samples

ii. Ultrasonic detection (Back side of the Module)

The laminates (Combination of layers of materials issued from the lamination process) are placed flat
into a water tank and scanned through the backsheet by a Scanning Acoustic Microscope (SAM) HD²
(PVA TePla Systems GmbH) using a 30 MHz transducer at ambient conditions as shown in Figure 2.
The spectral response of the materials is called a “reflectogram”, each layer of the laminate possess
its own response depending on its mechanical properties and can therefore, be identified. The
reflectrograms of the laminates have been recorded and the arrival times of the “echoes”
corresponding to the encapsulant are used to process the data. As the crosslinking degree greatly
influence the mechanical properties of the encapsulation material. The change of the recorded
„time of flight“ (time to receive the echo from the material) uniformity can be related to the
lamination duration [9].

Figure 2: Picture of The laminates being scanned by an acoustic transducer. Both sample and lens are immersed in distilled
water.

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iii. Mechanical indentation (Back side of the Module)

In this study a linear mechanical loading using a depth control is applied from the backsheet side. The
indentation depth is servo-controlled all along the testing sequence and the resulting force evolution
is measured. In this example, a hold of the maximum indentation depth was defined in order to
measure the sample’s relaxation, in other words the evolution of the normal load over time that
must be applied to maintain the defined indentation depth [10]. The indentations are performed on
the outer surface of the backsheet by means of an Ultra Nano-indentation Tester UNHT3 (Anton Paar
GmbH) using a spherical diamond indenter tip with blunt geometry shape (Figure 3). The obtained
viscoelastic response is the sum of the backsheet and encapsulant responses. And therefore the
stress relaxation response of the is correlated to the encapsulant cross-linking degree [11]

Figure 3:Schematic representation of the spherical indentation technique

b) Humidity ingress detection

i. Humidity sensors:
To analyse the water ingress in mini-modules and encapsulants, sensor strips containing miniature
temperature (T) and relative humidity (RH) sensors [12] are encapsulated in various laminates. The
sensors used are Sensirion SHT-25 and SHT-W2. Both have been shown to be resistant to the high
lamination T and able to measure the humidity in the encapsulant accurately. The strips are
connected to a PCB containing the necessary readout electronics. A custom software is used to
evaluate the measurement results.

This technology has been used in various setups to analyse humidity ingress in different materials, for
different material parameters (for example after different lamination times), in different climates
and to test new methods of humidity ingress measurements.

Figure 4: Left: Stack being prepared for lamination. Right: Three backsheet-EVA-glass samples
connected to the data acquisition reader.

shows the first setup with the SHT-25 sensors. Here, three sensors have been encapsulated at
different depths in a backsheet-EVA (2 layers)-glass laminate. One sensor has been placed directly at
the backsheet-EVA interface, one between the two EVA layers, one at the EVA-glass interface. Three
laminates were encapsulated, with two different backsheets, and two different lamination durations.

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Sensors #1 #2 #3

Figure 4: Left: Stack being prepared for lamination. Right: Three backsheet-EVA-glass samples connected to the data
acquisition reader.

This setup has enabled us to analyse the ingress and egress curves at various temperatures (40°C,
60°C and 85°C) in a climatic chamber. RH has been controlled in two sets of steps (between 40% and
65% and between as 40% and 85%).

A similar setup has been used for the study of the moisture ingress and egress in PV laminates
encapsulated with different types of EVA layers and PET back sheets. Ingress from 20% RH to 85% RH
and the opposite egress, are measured in a climatic chamber.

ii. Humidity indicators:

Further experiments with the same materials will analyse another method of humidity ingress
detection using humidity indicator cards. The change in colour of the humidity indicator cards due to
moisture exposure is measured by a portable spectrophotometer. For the matching of the variance
of colour to humidity measurements, a detailed calibration is first performed. To achieve this,
laminates with the structure [EVA-humidity indicator card-EVA-glass] (Figure 5) are stabilised in an
environmental chamber sequentially at different relative humidity conditions. The corresponding
colour change of the humidity indicator card to the relative humidity of the chamber, is plotted on a
CIE L*a*b* colours referential. The already established miniature sensor strips will be used as
calibration tools.

Figure 5: Humidity indicator cards encapsulated in glass-EVA-EVA structure.

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iii. Outdoor measurements:

The same type of setup has been designed for outdoor water ingress/egress monitoring. Three types
of material combinations were used to build the mini-modules:

A. A white PET backsheet with EVA as encapsulation material

B. A white PET backsheet with TPO as encapsulation material
C. A black PET backsheet with the same EVA as A.

The three mini-modules are mounted together on a rack to complete this setup. Five such setups
have been built, four will be used outdoors in different climates (see Table 2) and one will be used in
a climatic chamber to analyse the sensor layout in controlled conditions.

Figure 6: Sensor strip encapsulated in a mini-module for outdoor ingress measurements

Table 2:Location of the outdoor water ingress setups

Place T RH
Ljubljana Moderate Humid
Bolzano Moderate Moderate
Rome Warm Morderate
Singapore Hot Humid
Ljubljana Climatic chamber

c) Acetic Acid detection

Acetic acid is a product of EVA degradation and as its production follows an autocatalytic reaction
pathway; once acetic acid is formed, it can lead to occurrence of degradation modes such as
delamination and corrosion of metallic components. Therefore, it is important to early detect acetic
acid as a precursor for further degradation modes.

Here, a non-destructive method is proposed. PH indicators can be laminated within PV module

samples. Intact, pH indicators are subject to change in their optical properties (colour) when the pH
of the surrounding environment changes. Optical properties can be measured by means if UV-Vis
Spectroscopy and plotted on a CIE L*a*b* colour referential to obtain a calibration curve that
correlates pH values to colour coordinates.

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Figure 7: Left: calibration curve. Right: sample configuration, pH indicators laminated within two EVA sheets

The method is still under development and further analysis are required, but it look already
promising because the indicators have suffer any degradation during lamination and prodived
information of pH changes before and after lamination. This method might be used, for example, in
production processes to monitor quality of lamination.

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References
[1] IEC-62788-1-6:2017. Measurement procedures for materials used in photovoltaic modules. Part 1
– 6: Encapsulants: Tests Methods for determining the degree of cure of Ethylene Vinyl Acetate

[2] Peel test MST 35 of IEC-61730-2:2016

[3] K,Agroui; G Collins; G Oreski (2015): Effect of crosslinking on EVA-based encapsulant properties
during photovoltaic module fabrication process. Rev.Energies Renouv, vol 18 2015

[4] Köntges, M., Oreski, G., Jahn, U., Herz, M., Hacke, P., & Weiß, K.-A. (2017, May). IEA PVPS -
Assessment of Photovoltaic Module Failures in the Field.

[5] S.Jonai; K.Hara; (2015): Relationship between cross-linking conditions of ethylene vinyl acetate
and potential induced degradation for crystalline silicon photovoltaic modules. Jpn J appl Phys nº 54

[6] P, Gebhardt et al. (2018): Backsheet Chalking – Theoretical Background and Relation to Backsheet
Cracking and Insulaton Failures. 35th EUPVSEC Brussels,24-28 September 2018

[7] Peike, C.; Phondongnok, C.; Kaltenbach, T.; Weiss, K.-A.; Koehl, M. (2014): Nondestructive
determination of the cross-linking degree of EVA by Raman Spectroscopy. In Open Journal of
Renewable Energy and Sustainable Development.

[8] Schlothauer, Jan C.; Peter, C.; Hirschl, C.; Oreski, G.; Röder, B. (2017): Non-destructive monitoring
of ethylene vinyl acetate crosslinking in PV-modules by luminescence spectroscopy. In J Polym Res 24
(12), p. 203.

[9] Gerritsen et al., 2014. Control of encapsulation and interconnect quality in PV-modules using
scanning acoustic microscopy. 29th EUPVSEC.

[10] ASTM International (2015). ASTM E2546 - 15 Standard Practice for Instrumented Indentation
Testing. Conshohocken: ASTM.

[11] John Lloyd and al, Non-destructive measurement of the degree of cross-linking of EVA solar
module encapsulation, 2011 IEEE

[12] M. Jankovec et al. “In-Situ monitoring of moisture ingress in PV modules using digital humidity
sensors.” IEEE Journal of Photovoltaics 6.5, pp. 1152-1159, 2016.

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