International Journal of Adhesion & Adhesives 74 (2017) 144–154

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International Journal of Adhesion and Adhesives

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

Use of master curves based on time-temperature superposition to predict MARK

creep failure of aluminium-glass adhesive joints
⁎
E.A.S. Marquesa, , R.J.C. Carbasa, Fábio Silvab, Lucas F.M. da Silvac, D.P.S. de Paivad,
Fernão D. Magalhãesd
a
Instituto de Ciência e Inovação em Engenharia Mecânica e Engenharia Industrial (INEGI), Rua Dr. Roberto Frias, 4200-465 Porto, Portugal
b
Bosch Termotecnologia, SA- Cacia, 3800-533 Aveiro, Portugal
c
Departamento de Engenharia Mecânica, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal
d
Departamento de Engenharia Química, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal

A R T I C L E I N F O A BS T RAC T

Keywords: Advancements in materials technology and the use of innovative designs have led to extensive application of
Durability adhesive bonding techniques in the electric appliance industry. While the static strength of such joints is
Creep sufficient for the intended applications, long term durability remains a major concern, mainly due to creep
Silicones effects. Conventional creep testing can be performed at the service temperature but it is a long test that can take
Glass
decades, although it can be accelerated using high temperatures. In this work, glass-aluminium joints were
studied under static and creep loads. Glass-aluminium specimens were subjected to creep testing at various
temperatures. Using the time temperature superposition principle, the results of these individual creep tests
were combined in a master curve that approximates the creep behaviour of the adhesive joint in a long time
period. These master curves were used to guarantee a minimum service life of the joint.

1. Introduction
The durability of adhesively bonded joints is a research topic of
significant importance, which has been gaining relevance as adhesive
bonding is more widely adopted by several different industrial users,
among them the home appliance manufacturers. In this industry, a
recent drive to use high performance materials such as tempered glass
and aluminium in home appliances combined with aesthetic concerns
(i.e., no visible fasteners or brackets) has led to the implementation of
alternative joining techniques such as adhesive bonding. However, the
complex nature of the time-dependent (viscoelastic) behaviour of
polymeric adhesives [1] leads to significant difficulties in making long
term behaviour predictions. As these products will operate continu-
ously for very large periods of time, creep becomes a significant design
factor. Manufacturers are therefore demanding a simple and reliable
method to determine the creep behaviour of an adhesive joint and
ensure that their product will not fail during its work life [2]. However,
the determination of creep damage is still a largely experimental
process that requires a significant amount of time and resources to
provide useful results. New equipment is still being devised with the
aim of simplifying the process of creep testing adhesive joints [3]. Due
to the time-scales involved, testing creep in real-time is impossible, as
long term creep tests of the finished products are totally impractical, as
the joints might have failure times measured in decades. Nonetheless,
if the tests are performed at temperatures significantly above the
service temperature, this will accelerate the creep process and might
allow the determination of results in a practical amount of time [4]. The
time-temperature superposition principle (TTSP) is one of the most
commonly used methods, able to combine the data from shorter tests
performed at various temperatures into a master curve, able to describe
the creep performance of an adhesive joint [5]. This principle was first
identified by the work of Leaderman [6]. This principle makes use of
the fact that for many materials the creep compliance versus logarithm
of time curves have the same shape for different temperatures, but the
increases in temperature have the effect of shortening the time scale.
Eventually it was determined by Tobolsky and Andrews [7] that this
relationship can be used to combine individual creep compliance
curves and assemble a curve that fully represents the creep deforma-
tion of an adhesive or material at any desired temperature.
To create a master curve a specimen must be subjected to a
constant load at a certain temperature. The creep of this specimen
must be registered in a graph with time given in logarithm scale.
Several experiments are performed at different temperatures, register-
ing a creep curve for each temperature. To construct the master curve,

⁎
Corresponding author.
E-mail address: emarques@fe.up.pt (E.A.S. Marques).

http://dx.doi.org/10.1016/j.ijadhadh.2016.12.007
Accepted 17 October 2016
Available online 06 January 2017
0143-7496/ © 2017 Elsevier Ltd. All rights reserved.
E.A.S. Marques et al.
a reference temperature has to be first defined. The individual creep
curves obtained at each temperature are then shifted along the time
scale and, starting with the reference temperature, superposed to
obtain a master curve. The adjustment of the curves must be such
that there is a smooth transition between the individual curves. It is
sometimes difficult to ensure that there is a smooth overlap of master
curves and some materials might require not only the horizontal time
shift, but also a vertical time shift. These materials are classified as
thermorheologically complex materials [1,7,8].
It must be remembered though, that the TTSP creep study does not
produce an exact model but an approximation and that the creep
behaviour of an adhesive joint is the result of various coincident factors
that act on a given adhesive joint. The creep results must be interpreted
accordingly and sufficient margins must be introduced to account for
these effects. The accuracy of master curves depends on the following
factors [9]:
• Variation of the shift factors with temperature.
• Existence of the same creep mechanism at the different tempera-
tures tested.
• The initial strain rate applied to the specimens.
• Variation in humidity.
• State of the polymeric material (glassy rubbery or on the transition
zone).
• Rate of application of heat to achieve the desired temperature level.
The creep of highly plastic silicone adhesives was previously studied
by Geiss and Voigt [10], and significant creep strain was identified.
However, no master curve was derived from this work, therefore no
long term durability prediction was made.
In this work, two silicone based adhesives were mechanically tested
in joints to assess the joint strength they can provide. Surface
treatments as well as curing times were also object of study. One of
the two adhesives was then subjected to creep tests at various
temperatures and, using the time-temperature superposition principle,
this data was then used to build master curves and draw conclusions
regarding the durability of the joint.
2. Experimental procedure
The experimental process of this work was divided into several
stages, which are described in detail in this section of the document.
The first stage describes the material selection process and lists the
main properties of the adhesives and substrates selected. A section on
the measurement of surface energy follows, performed to assist in the
selection of surface preparation. The next step consists in the testing of
SLJ with varied surface conditions, with the aim of determining an
optimal surface preparation of each of the adhesives under considera-
tion. Concurrently, peel tests were also performed, both with the aim of
determining joint strength and also assessing the curing time profile for
each of the adhesives. After this initial phase, creep tests were started,
using varied temperatures to accelerate the process and enable the
construction of a master curve, which was then used to perform
durability predictions. Lastly, a chemical analysis was performed to
allow a better understanding of the chemical processes behind the
creep behaviour for both adhesive.
2.1. Materials
The first stage of this work consisted in the study of the strength of
the metal-glass joints using two different adhesives. The initial selec-
tion of the adhesive was based on the specific demands placed upon the
adhesive by the intended application:
• Sufficient mechanical strength to sustain the typical assembly and
service loads of the equipment.
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International Journal of Adhesion & Adhesives 74 (2017) 144–154
• Ability to bond highly dissimilar materials (glass and aluminium).
• Minimum amount of preparation performed to the bonding sur-
faces.
• Minimum curing time.
• Resistance to service and transport temperatures (−20 °C to
+90 °C).
• Resistance to humidity during the service life.
Due to these requirements, it was decided to pursue the use of a
flexible adhesive. These adhesives have been shown to be capable to
effectively accommodate large mechanical deformations or thermal
expansions [11,12]. In addition, as adhesive joints in appliances
typically handle small loads and have large bonding area available,
they do not require the use of the stiff and high strength adhesives
common in structural applications. Silicone based adhesives fulfil these
requirements sufficiently well [13] and two different room temperature
vulcanizing (RTV) adhesives of this family were provided for analysis: -
a specially designed RTV silicone developed by Pactan without a
commercial reference and a RTV silicone produced by Loctite, with
the commercial reference 5366. The Loctite 5366 is an acetoxy cure
system RTV with a tin catalyst. No detailed information is available
about the curing system of the Pactan adhesive due to its custom
formulation. According to the manufacturer's data, these two adhesives
have distinct surface preparation requirements. The Loctite adhesive
only requires a surface cleaning while the Pactan adhesive requires the
application of a primer.
As previously mentioned, the substrates used for this work are
tempered glass and powder coated aluminium. The glass used is a
tempered glass with a serigraphy layer on one side that provides colour
to the glass panel. The glass is available in black and white colours.
These two different coloured glasses have slight differences in the
morphology of the surface opposite to the coloured face, as the black
glass panels have a slightly rougher surface. As it is impossible to cut
tempered glass, the panels used for these tests were of the smallest size
that could be supplied by the glass manufacturer (panels of 150 mm by
300 mm).
2.2. Substrate surface energy
The surface energy of the substrates was measured as a first step in
the compatibility study between substrates and adhesives. Substrates
with low surface energy will generally lead to worse wetting and
therefore might require surface treatments. However, this is not always
the case and a complementary study of surface treatments must also be
performed. For this purpose, the surface energy was determined by
measuring the contact angle on various surfaces [14]. Small samples
(20×20 m2) of glass and aluminium were tested on a DataPhysics OCA
(San Jose, CA, USA) contact angle measurement system.
2.3. Single lap joint tests
After the measurement of the surface energy, the next step
consisted in the production of single lap joints to directly assess the
ability of the adhesives to bond the intended substrates. The single lap
joint test is a simple but powerful test that quickly allows comparisons
between the performance of both adhesives. As previously stated, due
to the use of tempered glass a standardized single lap joint specimen
geometry could not be used. An alternative specimen geometry was
then devised, where two 25 mm wide aluminium substrates were
bonded to a single glass panel A special clamp was adapted to hold the
glass securely to an Instron 3376 (High Wycombe, United Kingdom)
universal testing machine. The testing speed used was 1 mm/minute to
ensure a quasi-static loading condition. While the use of a single glass
substrate for two different specimens may influence results in most
cases, in this specific instance there should be no noticeable influence,
as the large stiffness of the glass combined with the high ductility of the
E.A.S. Marques et al.
Fig. 1. (a) Single lap joint specimen geometry (dimensions not to scale); (b) general aspect of the single lap joint specimens.
silicone adhesive means that the stress state in the glass substrate will
not be significantly affected by the relatively small loads used.
Fig. 1 illustrates the specimen dimensions and general aspect,
including the bonded area and the thicknesses employed. The small
overhang between the aluminium and glass (where there is no
adhesive) is necessary because a spacer is located there during the
curing process to ensure a constant 1 mm of adhesive thickness. The
joints were cured for a total of 30 days at room temperature and with a
relative humidity of 70%.
A large number of single lap joints were tested in this phase as not
only adhesive and substrate type was varied but alternative surface
treatments and conditions were also considered. The surface states
considered were selected to represent a variety of conditions that might
be encountered in industrial operations, ranging from contaminated
surfaces to surfaces that were treated using the adhesive manufacturer
recommendation. A list of these substrate conditions follows:
• Optimal (per manufacturer recommendations)
1. Pactan – Cleaning agent and primer
2. Loctite – Cleaning agent only
• Supplied
1. Pactan and Loctite – Substrate surfaces as supplied
• Contaminated (due to handling)
1. Pactan and Loctite – Substrates subjected to repeated contact
with hands and without further cleaning
• Degreased
1. Pactan - Use of a cleaning agent
2. Loctite – Not-applicable – same as optimal case
• Primer only
1. Pactan - Primer applied without previous cleaning.
2. Loctite – Not applicable – no primer is available for this
adhesive.
For these SLJ tests, a total of 64 tests were performed, correspond-
ing to two different adhesives (Pactan and Loctite), 5 different surface
states (5 conditions for Pactan and 3 conditions for Loctite), 2 glass
types (black and white glass) and 4 samples per type.
2.4. Peel tests and curing time determination
The curing time of an adhesive joint is a critical parameter that
must be well understood before industrial application, having signifi-
cant influences in production line design, storage requirements and,
ultimately, product cost. This phase of the work assessed the influence
of curing time on the strength of both adhesives under study. The cure
of silicone sealants is controlled by the rate of water intake, which
depends on the area and thickness of the film as well as the relative
humidity of the surrounding air [15]. Therefore, any comparison
should be performed in geometrically identical joints with controlled
humidity and temperature. The methodology employed consisted in
additional peel tests performed on specimens with varied curing times,
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International Journal of Adhesion & Adhesives 74 (2017) 144–154
ranging from 5 days (the minimum required by the silicone suppliers)
up to a maximum of 30 days. The joints were cured at room
temperature in a room with relative humidity maintained at a constant
70%.
The testing procedure employed was a peel test, which also allowed
to assess the adhesive behaviour under this type of loading. As
described for the single lap joints specimens, the use of tempered glass
precluded the use of standardized specimens. Alternatively, aluminium
substrates were bonded on the face of a single panel of glass. The 25
mm wide aluminium substrates were formed into an “L” shape to allow
the test to introduce loads that are perpendicular to the adhesive layer.
Although it would be preferable to use flexible substrates to ensure that
a pure peel load could be obtained, the metal substrates employed in
the peel joints use the same material, surface preparation and dimen-
sions of the production joint and therefore their use allows a more
direct correlation with the behaviour of the finished product. The tests
were performed in the same universal testing machine used for the SLJ
tests, described in the previous section. Fig. 2 shows the configuration
of the specimens used and their geometry.
As described for the SLJ tests, due to large difference in stiffness
between the adhesive and the glass substrate, the use of one glass panel
for three specimens should not have significant influence on the
mechanical behaviour of the joints. A sliding testing tool was designed
to hold the glass panel and align each of the aluminium substrates with
the load cell of the universal testing machine (shown in Fig. 3). The
large clamp area provided by this tool allows the glass substrate to be
tightly held without any risk of breakage.
For this test, a total of 32 peel tests was performed, corresponding
to two different adhesives (Pactan and Loctite), three different curing
times (5 days, 8 days, 30 days), 2 glass types (black and white glass)
and 4 samples per type.
2.5. Creep testing
Creep testing was performed with the aim of assessing the long-
term behaviour and durability of one of the adhesives tested (Pactan).
There are various standards available to study the creep of adhesives
and adhesive joints. ISO 899 standard [16] is useful when studying the
creep of bulk plastic materials, but cannot be directly applied to
adhesive joints. Another standard, ISO 15109 [17] measures the time
to failure of an adhesive joint under constant load. This standard does
not provide the recording of the shear strain caused by the creep and is
therefore unsuitable for creating creep master curves. ASTM D 1780
standard [18] is much more complex as it allows the measurement of
creep for metal-metal adhesive joints under accelerated conditions and
due to the combined effects of time, temperature and tensile stress.
Due to the specific geometry and substrates of the specimens used
in this work, the chosen procedure does not follow any of these
standards directly. The specimens used for this work consist of a glass
panel on which four painted aluminium adherends are bonded. Fig. 4
illustrates the geometry of the joints manufactured for the creep test.
E.A.S. Marques et al.
Fig. 2. (a) Peel specimen geometry (dimensions not to scale); (b) general aspect of peel specimen.
Each glass panel therefore contains four complete joints.
This specimen configuration was again chosen due to the impossi-
bility of cutting the tempered glass into smaller substrates. As
described for the SLJ and peel procedures, the use of four specimens
per glass substrate was again thought to be inconsequential to the
results, especially given the small loads involved. While it would be
preferable to use only one glass panel per substrate, this would make
large scale testing inside the thermal chambers impossible. To ensure
the complete cure of the specimens, a cure cycle of 30 days at room
temperature and 70% of relative humidity was used. The smaller
bonding area used for these specimens (when compared with the peel
test specimens) ensures that a time of 30 days is sufficient for complete
cure.
The specimens were fixed in a structure specifically designed for
this purpose. Each specimen was subjected to a load selected to
represent a stress level approximately 100 times higher than that
found in the final production joint (1900 g of weight applied to each of
the four aluminium bars, corresponding to a constant load of 18.6 N).
The specimens were then placed in a temperature controlled chamber
(Weiss Technik SB 500, Reiskirchen-Lindenstruth, Germany) For each
joint the deformation caused by the creep effect was regularly
Fig. 3. Experimental testing setup for peel testing. a) overview; b) specimen detail.
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International Journal of Adhesion & Adhesives 74 (2017) 144–154
measured and recorded. This value was measured with a digital
calliper. An overview of the test configuration can be seen in Fig. 5.
The creep tests were performed at various temperatures. A list of
the joints tested in the test series is shown in Table 1. In this table the
temperatures of the tests and the number of joints tested at each
temperature are shown.
2.6. Chemical analysis
A chemical analysis was performed with the aim of identifying
possible thermally induced changes in the chemical or physical proper-
ties of the material during the creep tests. Three tests were performed
for this purpose.
Fourier transform infrared spectroscopy (FTIR) analysis was per-
formed on the Pactan adhesive samples that were previously subjected
to creep tests at four different temperatures (room temperature, 60 °C,
75 °C and 100 °C). For this test a Bruker Corporation Vertex 70
(Billerica, MA, USA) tester was employed, using the attenuated total
reflectance sampling technique. Differential scanning calorimetry
(DSC) and dynamical mechanical analysis (DMA) tests were used to
search for thermally induced changes in the adhesive, such as phase
E.A.S. Marques et al. International Journal of Adhesion & Adhesives 74 (2017) 144–154

Fig. 4. Schematic representation of the studied specimen.

Table 2
Surface energy measured for the substrate surfaces.

Substrate material Surface energy [mJ/m2]

White coloured tempered glass 43.58

Black coloured tempered glass 54.92
Aluminium with powder coating 32.69

3. Results

3.1. Surface energy measurement

The results for the substrate surface energy measurement proce-

dure are listed in Table 2.
These are relatively low values, generally indicating that these are
surfaces which are hard to bond. To provide a satisfactory bond, the
surface energy of the adhesive should be lower than the surface of the
substrates to be bonded [19]. For epoxy adhesives, the surface energy is
around 47 mJ/m2 [20] which precludes the use of this type of material
Fig. 5. Creep specimens inside a test chamber.
without a very effective surface treatment method. However, silicones
typically have a surface energy of 20 mJ/m2 [21], which should be
Table 1 sufficient to assure good adhesion in optimal conditions. While this
Creep test temperatures and number of specimens tested.
data appears to supports the adhesive type selected for this work,
Temperature White glass Black glass tensile and shear tests with experimental specimens are still funda-
mental to confirm these results.
Room temperature 4 joints 4 Joints
60 °C 8 joints 8 Joints
75 °C 4 Joints 4 joints 3.2. Single lap joint test results
100 °C 4 joints 4 Joints

changes of its constituents. Unlike those tested in the FTIR procedure,
the Pactan adhesive samples used in these tests were freshly cured and
untested.
The DSC test was performed from a temperature of 20 °C up to
200 °C, covering all the temperatures studied in the experimental creep
test. The apparatus used for the DSC test was a Netzsch STA 449 F3
(Selb, Germany). Nitrogen was used to create an inert atmosphere
during the DSC testing. The DMA test was performed from a
temperature of −100°C up to 150 °C and the apparatus used was
Netzsch DMA 242 E Artemis. Liquid nitrogen was used to cool down
the sample and gaseous nitrogen to introduce an inert atmosphere.
The results of the single lap joint tests are presented in this section.
Figs. 6 and 7 show the lap shear strength for each of the substrate
types.
As expected, the results generally show that the adhesive joints
tested lose strength for the cases where the glass and substrates were
subjected to contamination and not cleaned. It is also evident that the
joints bonded with Pactan adhesive only require cleaning and that the
application of primer does not change in any significant way the joint
strength.
Table 3 shows the typical fracture surfaces for single lap joints of
both adhesives with different surface states.
The fractures surfaces of the specimens that have led to lower
strengths (mainly for the contaminated and as supplied cases) present
an adhesive type of failure, especially for the Pactan adhesive. These
results indicate that the process of production and painting of the

148
E.A.S. Marques et al.
Fig. 6. Failure load as a function of the surface state (black glass).
Fig. 7. Failure load as a function of the surface state (white glass).
substrates can lead to very unfavourable surface conditions that if left
unmodified will lead to premature joint failure. As such, there is a clear
necessity to clean the bonding surfaces and assure that there is no
further contamination along the production line. When optimal con-
ditions are present, both adhesives exhibit cohesive failure in the
adhesive layer, although with very distinct failure loads (joints with
Loctite are 3 times stronger than joints with Pactan). Given that
cohesive failure occurs in both cases, this demonstrates that the
Loctite adhesive is clearly stronger.
3.3. Curing time determination
Fig. 8 shows the strength evolution obtained with the three curing
times studied, for each adhesive and glass type. The value shown is the
normalized strength, obtained by dividing the peak load by the width of
the bondline (25 mm).
According to the data in Fig. 8, that there is a greater variation of
joint strength with curing time for the Pactan adhesive than for the
Loctite adhesive. The Loctite adhesive is substantially less sensitive to
curing time. After the initial 5-day curing period there is no significant
increase in the joint strength. Also noticeable is the difference between
the failure load of the joints with Loctite adhesive and black glass and
joint with the same adhesive but with white glass. This effect was found
to be repeatable, as it is also found for the single lap joints and
indicates that, only for this adhesive, the glass colour has clear
influence in the ultimate failure loads. This might be due to the
different surface morphology previously described, which provides
more anchoring effect.
Figs. 9 and 10 show the fracture surfaces and, consequently, the
evolution of the curing process with time. The evolution of the curing
process is more evident for the Pactan adhesive (Fig. 9), due to the fact
that this adhesive requires more time to achieve full cure, with direct
reflection on the joint strength. The central section of the adhesive
layer is clearly not cured for 5 and 8 days of cure. As this section is
further from the borders of the adhesive layer, there is more difficulty
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International Journal of Adhesion & Adhesives 74 (2017) 144–154
for water molecules to flow through the adhesive and complete the
curing process. Due to this correlation of curing with the adhesive layer
geometry, smaller and thinner adhesive layers will necessarily have
faster curing times.
For the adhesive joints bonded with the Loctite adhesive (Fig. 10)
this evolution is not as evident, as after 5 days the curing process can be
considered almost complete. The failure surface appearance is very
consistent, although it exhibits some degree of adhesive failure.
3.4. Creep curves
In this section the creep curves for each temperature and specimen
type are presented. Each creep curve shown in this section is an
averaged curve, being obtained by calculating the average measured
strains for all the specimens experimentally tested at one given
temperature, while discarding the results of the specimen with larger
deviation from the average. This process has an inherent large
dispersion which increases with the passage of time. To exemplify this,
Fig. 11 shows a typical dispersion distribution for an experimental
creep curve used in this work.
The average creep curves for the black glass specimens are shown
on Fig. 12
Fig. 13 shows the average creep curves for the white glass speci-
mens.
Generally, the progression of the creep rate follows the expected
behaviour, increasing as the temperature increases. However, there is
an anomalous behaviour for the creep curves obtained at 60 °C. Instead
of the gradual increase in creep rate, the tests at 60 °C (for both types of
glass) have shown a creep rate higher than that of the specimens tested
at the temperature immediately above (75 °C). These tests were
repeated and the same behaviour was identified which might suggest
the existence of a visco-elastic phenomenon that is altering the creep
properties of the material around this specific temperature.
3.5. Master curves
After the individual creep curves were obtained, the master curve
can then be built. Two fundamental steps are necessary to build a
master curve. The first step consists on a manual adjustment of the
creep curves obtained at each temperature so that a larger and more
complete curve can be obtained, comprising of all the individual curves
at each temperature. Manual adjustment must be performed on the
time axis and each curve (corresponding to a temperature level) must
be individually adjusted. Fig. 14 exemplifies the manual adjustment
process of various creep curves for the tests of specimens with black
glass substrates. The curves for each temperature are shifted by a
shifting factor, at, which corresponds to the horizontal shifting (in the
time axis) of the curves.
This step might not be sufficient to ensure a smooth master curve,
as some materials also require adjustment on the vertical plane,
something that was also necessary for the studied data. This was in
part due to the discrepancies in the initial deformation mentioned in
Section 3. However, this is not the only cause, as the literature
describes the case of materials, called thermorheologically complex,
that require adjustments on the vertical axis to correctly fit the master
curve [1,5,6]. The authors of these articles explain that the vertical
shifting is necessary due to hygroscopic effects and thermal contrac-
tions and expansions. All these factors can, therefore, be potentially
present on the tests performed.
To guide the adjustments, the Williams-Landel-Ferry equation [22]
must be used. This equation allows the calculation of the required
horizontal shifting that must be applied to an individual creep curve so
that it fits the master curve.
−C1 (T − Tr )
log at =
C2+(T − Tr ) (1)
E.A.S. Marques et al.
Table 3
Typical fracture surfaces for single lap joints of both adhesives with different surface states.
Fig. 8. Peel joint strength as a function of curing time.
This expression corresponds to the equation of a straight line,
where the xx axis is given by (T–Tr)/log(at) and the yy axis
corresponds (T−Tr). T is the temperature of the creep curve that is
being adjusted and Tr is the reference temperature (the temperature of
the base curve). The constant C1 is the slope of the equation and the
constant C2 is the y-axis intercept.
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International Journal of Adhesion & Adhesives 74 (2017) 144–154
The reference temperature is the creep curve that functions as the
base for the master curve. It is on this base curve that the other creep
curves, obtained at different temperatures, are added to produce the
final master curve. In this work, the selected reference temperature is
the room temperature, which means that the full master curve will
correspond to an extrapolation of the creep curve at room temperature
for a substantially larger period of time. The reference temperature is
usually chosen to match the temperature at which the adhesive joint
will be subjected under service conditions. For polymers, and in case
the glass transition temperature (Tg) is considered as the reference
temperature, the C1 and C2 constants are known to have a universal
value of 17 and 52 respectively [23].
An alternative method to estimate the durability could consist on
the selection of a reference temperature above room temperature and
then other add creep curves to obtain a master curve starting at that
reference temperature. This master curve could be then shifted back to
the room temperature (again using the Williams-Landel-Ferry equa-
tion). The new, shifted curve should correspond to a durability
prediction for room temperature and could be validated with experi-
mental data at room temperature, which in this case would act as a
validation test would not be used to construct any master curve. Due to
the relatively small number of tests of this experimental campaign, the
selected strategy was instead to use the room temperature as reference
E.A.S. Marques et al. International Journal of Adhesion & Adhesives 74 (2017) 144–154

Fig. 9. Fracture surfaces of Pactan adhesive peel specimens with different curing times. a) 5 days of cure; b) 8 days of cure; c) 30 days of cure.

so that more information could be used to construct the master curve.

In a graphical representation of the Williams-Landel-Ferry equa-
tion, the horizontal shifting of each experimentally obtained creep
curve corresponds to a single point in a graph. This plot can be
effectively used to adjust the horizontal shifting factors so that each one
of this factors respect the equation. Table 4 lists values of horizontal
shifting (log10 at) applied to the creep curves of specimens with black
glass substrates.
Table 5 lists the values of horizontal shifting (log10 at) applied to
the creep curves of specimens with white glass substrates.
Fig. 15 shows an example of the plots obtained with the application
of the Williams–Landel–Ferry equation, in this case for the tests using
black glass. The C1 and C2 constants are obtained from the equation of
the straight line that best fits the experimental points corresponding to
Fig. 11. Dispersion of a representative averaged creep curve (black glass, 60 °C).
each creep curve.
Table 6 lists the C1 and C2 constants obtained with the straight line
equations shown above.
Based on this fitting procedure of the experimental creep curves,
the respective master curves can then be produced. Fig. 16 shows the
master curves for the white glass and Fig. 17 shows the master curves
for the black glass. In each of the figures the individual curves used to
build the master curve are identified by their testing temperature
(room temperature, 60°, 75 °C and 100 °C).
An important subject of discussion during the course of this study
was the influence of the glass type (black or white) on the joint strength
and durability. In order to answer this question, the two master curves
obtained are represented together in Fig. 18. This graph shows that the
master curves are quite consistent, with minor differences in behaviour
between black glass and white glass.
Fig. 12. Average creep curves for tests made with black glass specimens.

3.6. Durability predictions
Different approaches can be employed to use creep data do obtain
durability predictions. For example, with knowledge of the experi-
mental response of a bonded joint to creep recovery tests, a visco-
elastic and visco-plastic behaviour law can be defined for the adhesive
joint [24]. For larger time scales, considering the creep curves as an
extrapolation of room temperature data to a larger time-scale, one can
consider the time corresponding to the last point of these curves as the
minimum expected durability of the joint [25].
For the highest temperature curves studied in this test (100 °C), at
the time of test stoppage there was no failure of any specimen in each of
the creep curves used to build the master curve. Should the test
continue, it was expectable that the 100 °C specimens would last an
additional period of time before they would eventually fail. It can be

Fig. 10. Fracture surfaces of Loctite adhesive peel specimens with different curing times. a) 5 days of cure; b) 8 days of cure; c) 30 days of cure.

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Table 6
C1 and C2 values for each glass type.

C1 C2 (K)

White Glass 3.86 −219.25

Black Glass 2.88 −212.11

Fig. 13. Average creep curves for tests made with white glass specimens.

Fig. 16. Master curve for the white glass specimens assembled from room temperature,
60°, 75 °C and 100 °C curves.

Fig. 14. Example of the adjustment process using at factors. Data shown is for black
glass specimens.

Table 4
Values of horizontal shift factors (log10 at) for black glass specimens.

Horizontal shift log10 at

Tested temperatures 60 °C 0.78

75 °C 1.14
100 °C 1.93 Fig. 17. Master curve for the black glass specimens assembled from room temperature,
60°, 75 °C and 100 °C curves.

Table 5
Values of horizontal shift factors (log10 at) for white glass specimens.

Horizontal shift log10 at

Tested temperatures 60 °C 0.75

75 °C 1.13
100 °C 1.90

Fig. 18. Comparison between the master curves of the two types of glass tested.

concluded that for this case we do not have an exact idea of the time to
failure but have instead a minimum time period where we can expect
no failure to happen. As described by Chang et al. [26], this is always a
conservative approach, as the durability of the actual specimens can be
longer. Fig. 19 shows how the maximum time to failure can be derived
from the master curve data. According to these results, at least 20 years
of service life can be expected before creep induced failure.

3.7. Chemical analysis results

Fig. 15. (T−Tr) versus (T-Tr)/log(at) plot for the black glass master curve.

The FTIR test was performed for four samples of the Pactan
adhesive that were subjected to creep testing at different temperatures.

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E.A.S. Marques et al.
Fig. 19. Durability predictions obtained from master curve data.
Fig. 20. FTIR analysis of Pactan adhesive (curve shown is for the room temperature
sample).
(room temperature, 60 °C, 75 °C and 100 °C). The FTIR analysis did
not identify any significant changes between the samples, therefore no
chemical transformations are thought to have occurred during the
creep testing phase. Fig. 20 shows the absorbance peaks detected. The
peaks found are consistent with a silicone based adhesive.
The results for the DSC test are shown in Fig. 21. Inside the tested
temperature range there is no significant change in the chemical
properties, with no discernible peak in the TGA data and a gradual
increase in the heat flow.
The DMA results are shown in Fig. 22. The results show the
evolution of the storage modulus and the tan delta of the material as a
function of the temperature. The increased sensitivity of the DMA
apparatus, especially using its tan delta measurement capability, allows
the identification of some regions of interest along the temperature
range. The main peak in the tan delta curve allows the identification of
the glass transition temperature (Tg), which is located around −69°C.
As previously shown, there is an inconsistency in the creep for
results from the specimens tested at 60 °C, with higher creep strains
than those found for temperatures above. While the peaks correspond-
ing to the Tg are located outside of the tested range of temperatures, a
small secondary peak and plateau is located from room temperature to
Fig. 21. DSC data for the Pactan adhesive.
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International Journal of Adhesion & Adhesives 74 (2017) 144–154
Fig. 22. DMA data for the Pactan adhesive.
Fig. 23. DMA data for the Pactan adhesive (detail of tan delta curve).
around 60 °C. Fig. 23 is a zoomed view that shows this area in more
detail.
This plateau, while considerably smaller than the peak that caused
by the Tg,, may be the underlying cause for the anomalous behaviour
previously described. It is possible that a secondary phase change,
perhaps caused by a component of the adhesive, may be happening at
this temperature and this leads to a distinct creep behaviour at
temperatures near the 40–60 °C range.
4. Conclusions
This work investigated the factors that influence the overall
strength and durability of an aluminium-glass bond. Several mechan-
ical tests were performed, comparing different materials and surface
preparations. Creep tests at various temperatures were also performed
to assess long term durability using the time-temperature superposi-
tion concept. The main conclusions that can be drawn from this work
follow:
• The data from the surface energy measurement demonstrates that
the materials under study have generally low surface energies. While
this might lead to severe adhesion problems with most adhesives,
with the use of a silicone adhesive there a small but important
difference in surface energy between the substrates and the adhe-
sives that allows bonding without complex surface treatments.
• Single lap testing indicates that the strength of joints treated with
the optimal surface preparation method is similar to the strength
values obtained for joints which only had simple cleaning of the
substrate surface. The lowest joint strengths were found for the
joints which had the bonding surfaces untreated (the supplied state)
or contaminated. These conclusions were found to be valid for both
adhesives studied.
E.A.S. Marques et al.
• Curing time testing demonstrates that the Pactan adhesive is
significantly more sensitive to the curing time than the Loctite
adhesive. While the Loctite adhesive exhibits little gains in strength
during the 30 days of curing tested, the Pactan adhesive has a more
gradual progression and was observed to not be fully cured during
the first days of cure, which leads to much reduced joint strengths
when compared with the results of specimens cured for 30 days.
• There was a lack of coherency on the initial strain measurement. It
can be concluded that the initial measurement procedure must be
improved and standardized as to minimize such errors.
• The creep rate was generally found to increase with higher tem-
peratures, allowing the construction of the master curve, although
vertical adjustments were still required. For the 60 °C temperature,
there was an anomalous behaviour, with the creep rate being higher
than the rate found for higher temperatures. A detailed chemical/
physical study was performed to better understand this effect. FTIR,
DSC and DMA tests were performed for this purpose. Although the
results for the FTIR and DSC tests were non-conclusive, with no
significant change in the chemical/physical properties of this
silicone adhesive, the DMA test detected a peak corresponding to
the Tg and a secondary peak and plateau that extends to the 60 °C
temperature. This phenomenon may be the cause for the anomalous
behaviour detected in the 60 °C creep test.
• The creep curves for the black glass specimens and the white glass
specimens did not exhibit clear differences. It can therefore be
concluded that, for the adhesive used, the type of glass does not
cause a significant change in long term durability.
•
Using the master curve, which corresponds to an extrapolation of
the creep period to a larger time scale, it can be concluded that the
tested joints have a minimum expected durability of 20 years.
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