Progress in Organic Coatings 173 (2022) 107175

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Progress in Organic Coatings

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

Curing-induced internal stress in epoxy coatings: Effects of epoxy binder,

curing agent, filler, initial solvent concentration, curing temperature, and
relative humidity
Qiong Li , Claus Erik Weinell , Søren Kiil *
The Hempel Foundation Coatings Science and Technology Centre (CoaST), Department of Chemical and Biochemical Engineering, Technical University of Denmark,
(DTU), Building 229, DK-2800 Kgs. Lyngby, Denmark

A R T I C L E I N F O A B S T R A C T

Keywords: Curing-induced internal stresses in epoxy coatings are highly influenced by the type and concentration of product
Internal stress ingredients and the conditions applied. In this work, the effects on the curing-dependent modulus and the in­
Fillers ternal stress development of the epoxy/crosslinker chemistry, curing temperature, relative humidity, filler
Curing temperature
conditions, and initial solvent concentration, are studied. Analytical methods include the attenuated total
Relative humidity
Initial solvent concentration
reflection-Fourier transform infrared (ATR-FTIR) technique, dynamic mechanical thermal analysis (DMTA), a 3D
optical profilometer, and beam deflection.
An elevated curing temperature (35 or 45 ◦ C) resulted in a smaller elastic modulus and, despite an accelerated
curing reaction and a higher final reactant conversion, only a slight increase, around 0.2 MPa, in the average
internal stress. An increased relative humidity (from 35 to 60 %), also resulted in a smaller elastic modulus and
less volumetric shrinkage and internal stress. However, at 90 % relative humidity, the internal stress, due to an
enhanced final reactant conversion, was higher than observed at 60 % RH.
The presence of either BaSO4 or CaCO3 filler in the formulation reduced the final reactant conversion and
volumetric shrinkage, but resulted in a higher elastic modulus and internal stress.
When the solvent concentration increased from zero to 20 vol%, the final conversion, although extra volu­
metric shrinkage was introduced by the solvent evaporation, increased from 0.72 to 0.85, while the internal
stress decreased from 1.25 to 0.6 MPa.
Guidelines for how to optimize coating formulations and curing conditions, to avoid internal stress, are
presented.

diethylenetriamine (DETA), cycloaliphatic polyamine, poly­

1. Introduction
To maintain the service performance of infrastructures in heavy-duty
environments, two-component epoxy coatings are widely used [1–4].
However, curing-induced internal stress can be a potential threat to the
performance, because it can provoke the formation of premature cracks
in anticorrosive coatings [5,6]. During the curing process, the volu­
metric shrinkage, induced by simultaneous solvent evaporation and
cross-linking, is restricted and leads to an in-plane internal stress [5,6].
This stress is influenced by the choice of coating formulation, as well as
the curing and substrate conditions [5–8].
Abdelkader et al. [9] investigated the influence on internal stress of
five different curing agents: 4, 4'-methylenedianiline,
aminoimidazoline, and a polyamidoamine adduct. They found that the
molecular structure of the curing agents has a great influence on the
development of the curing-induced internal stress, but the mechanism
and a quantitative relationship remain unsolved. Wen et al. [10]
investigated the development of internal stress in UV-curing of multi­
functional acrylate and methacrylate coatings and discovered that the
curing-induced internal stress increased with increasing reactant func­
tionality and decreasing monomer chain length.
Croll [11] investigated the influence of solvent on internal strain in
clear epoxy coatings. Results showed that the coating thickness has little
influence on the residual strain in coatings cured with a faster evapo­
rating solvent, and that the residual strain exhibited a slight dependence
only on the solvent content. On the other hand, for coatings formed

* Corresponding author.
E-mail address: sk@kt.dtu.dk (S. Kiil).

https://doi.org/10.1016/j.porgcoat.2022.107175
Received 24 May 2022; Received in revised form 24 August 2022; Accepted 2 September 2022
Available online 8 September 2022
0300-9440/© 2022 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
Q. Li et al.
Nomenclature
ATR-FTIR Attenuated total reflection Fourier-transform infrared
spectroscopy
DMTA Dynamic mechanical thermal analysis
BaSO4 Barium sulfate
D50 The value of the particle diameter when the cumulative
percentage reaches 50 %
CaCO3 Calcium carbonate
DETA Diethylenetriamine
PVC The pigment volume concentration
CPVC The critical pigment volume concentration
BFDGE Diglycidyl ether of bisphenol F
DGEBA Diglycidyl ether of bisphenol A
MXDA m-Xylylenediamine
MPMD Methylpentamethylen diamine
WFT Wet film thickness
Vt The current coating volume
V0 The initial coating volume
Greek
λ The ratio of PVC to CPVC
using slow-evaporating solvent, the residual strain increased with
increasing coating thickness.
The pigment volume concentration (PVC) and the critical pigment
volume concentration (CPVC) in coatings also influence the develop­
ment of internal stress. For most coating systems applied at PVC < CPVC,
the internal stress increases with the increase of PVC, while for PVC >
CPVC, the internal stress decreases with the increase of PVC. The reason
is that the presence of pigment particles changes the elastic modulus and
Poisson's ratio of the coating system, because the modulus for the pig­
ments is much higher than that of the binders [12]. Inoue et al. [13]
investigated the influence of fillers on the curing-induced internal strain
and the viscoelastic properties for melamine-alkyd resin coatings. Their
results showed that the coating elastic modulus and the internal stress
increase with increasing filler concentration.
The relative humidity of the surrounding air also has a significant
influence on the development of curing-induced internal stress. Initially,
water absorption makes the coating swell with an associated compres­
sive stress development in polyurethane-, epoxy-, and alkyd/melamine-
based coatings. The curing-induced (tensile) internal stress, for some
coatings, exhibited a relaxation in humid conditions [13–16].
In summary, most previous investigations focused on one parameter,
two at most, such as the effect on internal stress of the epoxy resin type,
hardener type, pigmentation conditions, initial solvent concentration,
curing temperature, or post-curing relative humidity. However, indus­
trial coatings have a complex composition and are cured under a variety
of conditions. To map the influence on internal stress development and
the coupling to the above mentioned parameters, a more comprehensive
investigation is required.
Aiming at industrial guidelines to lower internal stress in coatings,
the present work quantifies the dynamics between reactant conversion,
mechanical coating properties, and internal stress. Parameters of inter­
est are the molecular structures of binders and hardeners, filler type and
concentration, initial solvent concentration, curing temperature, and
relative humidity of the surrounding air. The experimental strategy is to
use infrared spectroscopy, an optical 3D profilometer, dynamic me­
chanical thermal analysis (DMTA), and a battery of beam deflection
devices to quantify, in parallel, the curing-induced internal stress, the
curing kinetics, the volumetric shrinkage, and the mechanical property
evolution.
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Progress in Organic Coatings 173 (2022) 107175
2. Experimental
2.1. Materials and coating preparation
A series of anticorrosive coatings, listed in Table 1, with an amine/
epoxy functional group stoichiometric ratio of 1.0 was prepared. The
binders include a solvent-free diglycidyl ether of bisphenol F (BFDGE)
epoxy resin supplied by Hexion Inc., USA with an epoxy equivalent
weight of 169 g/mol, and a solvent-free diglycidyl ether of bisphenol A
(DGEBA) with an epoxy equivalent weight of 187 g/mol supplied by
KUKDO, South Korea. To prepare an adducted MXDA-BFDGE with 7.5
mol% of the amine in the curing agent reacted, MXDA-BPA and MPMD-
BFDGE, solvent-free m-xylylenediamine (MXDA) and methyl­
pentamethylen diamine (MPMD), supplied by Sigma-Aldrich, USA, were
used. The molecular structures of BFDGE, DGEBA, MXDA and MPMD are
shown in Fig. 1.
The solvent in the formulation was xylene provided by Borup Kemi,
Denmark. Barium sulfate (BaSO4, D50 = 3.5 μm and a Mohs hardness of
3.5), supplied by SIBELCO, Belgium, and surface treated calcium car­
bonate (CaCO3, D50 = 2.6 μm and a Mohs hardness of 3.0), supplied by
OMYA, Switzerland, were used as fillers with different λ (i.e. the
pigment volume concentration, PVC, divided by the critical pigment
volume concentration, CPVC) values.
In order to control the wet film thickness (WFT), an Elcometer 3580
casting knife film applicator was used, and the applicator could adjust
film thickness from zero to six mm with increments of 10 μm. The WFT
was set to 300 ± 10 μm, which is a typical (for instance chemical pro­
cessing plants) heavy-duty, epoxy-based coating thickness.
2.2. Curing conditions
To control the curing temperature and relative humidity, the BFDGE
cured with adducted MXDA-BFDGE solvent-free coatings were stored in
an Aralab climate chamber. The five different curing conditions, listed in
Table 2, were designed to investigate the influence of curing tempera­
ture and relative humidity on curing-induced internal stress of coatings.
2.3. FTIR spectroscopy
To monitor the epoxy conversion degree, the coatings were applied
on a 0.1 mm thick plastic substrate (supplied by Erhvervsskolernes
Forlag, Denmark), and the samples were stored in an Aralab climate
chamber for 120 h with controlled temperature and relative humidity.
The reactant (epoxy) conversion as a function of curing time was
monitored with a Thermo Scientific Nicolet is50 ATR-FTIR
Table 1
The nine different coating formulations used in the analyses.
Name of Description
formulation
BPF-MX BFDGE cured with 7.5 % adducted MXDA-BFDGE, no solvent
BPA-MX DGEBA cured with 7.5 % adducted MXDA- DGEBA, no solvent
BPF-MD BFDGE cured with 7.5 % adducted MPMD-BFDGE, no solvent
10 % volume BFDGE cured with 7.5 % adducted MXDA-BFDGE, including
solvent xylene as solvent, 10 % volume solvent
20 % volume BFDGE cured with 7.5 % adducted MXDA-BFDGE, including
solvent xylene as solvent, 20 % volume solvent
BaSO4-λ0.2 BFDGE cured with 7.5 % adducted MXDA-BFDGE, including
BaSO4 as fillers, λ = 0.2, no solvent
BaSO4-λ0.3 BFDGE cured with 7.5 % adducted MXDA-BFDGE, including
BaSO4 as fillers, λ = 0.3, no solvent
BaSO4-λ0.5 BFDGE cured with 7.5 % adducted MXDA-BFDGE, including
BaSO4 as fillers, λ = 0.5, no solvent
CaCO3-λ0.3 BFDGE cured with 7.5 % adducted MXDA-BFDGE, including
CaCO3 as fillers, λ = 0.3, no solvent
BFDGE: diglycidyl ether of bisphenol F; MXDA: m-xylylenediamine; DGEBA:
diglycidyl ether of bisphenol A; MPMD: methylpentamethylen diamine.
Q. Li et al. Progress in Organic Coatings 173 (2022) 107175

Fig. 1. Molecular structures of binders and curing agents used in the investigation.

2.4. Dynamic mechanical thermal analysis (DMTA) measurements

Table 2
The five different curing conditions used in the experiments.
DMTA tension test was used to track the elastic modulus of coatings
Sample name Curing condition on a 0.1 mm thick plastic substrate (Erhvervsskolernes Forlag, Denmark)
23 ◦ C Sample cured at 23 ◦
C and a relative humidity of 35 % and free film samples at different curing times were prepared and cut
35 ◦ C Sample cured at 35 ◦
C and a relative humidity of 35 % into rectangular geometry. The oscillation-time ramp procedure, using
45 ◦ C Sample cured at 45 C and a relative humidity of 35 %
an advanced rheometer DHR-2 (TA Instruments) with a frequency of 1
◦

60 % RH Sample cured at 23 ◦
C and a relative humidity of 60 %
90 % RH Sample cured at 23 ◦
C and a relative humidity of 90 % Hz, was performed for 5 min at 23 ◦ C.

2.5. Curing shrinkage measurement

spectrometer. Due to the potential occurrence of a carbonation reaction
at the coating surface, the ATR-FTIR spectra for each free film sample
The curing shrinkage measurements were conducted using an optical
was measured at the coating-substrate interface. For all experiments,
3D profilometer (KEYENCE VR-3000), and the method to calculate the
three replicates were used. Details on calculation of the epoxy group
volumetric shrinkage was described in our previous work [17].
conversion from ATR-FTIR spectra, can be found in previous work [17].

2.6. Internal stress measurements

A deflection method was used to monitor the curing-induced internal

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Q. Li et al.
stress, and the coatings were applied on 0.1 mm thick 316 L stainless
steel shims with a length of 200 mm and a width of 15 mm (Fig. 2a).
Prior to application, the substrates were cleaned with ethanol. Using an
Elcometer 3580 applicator, the coating thickness was controlled to 300
± 10 μm. The coated samples were placed horizontally in a climate
chamber with controlled temperature and relative humidity, until the
samples reached gelation. To omit the influence of gravity and make use
of the laser position sensors (Fig. 2b), samples were fixed vertically with
a clamp, allowing deflection at the free end. The method of using the
deflection method to record the curing-induced internal stress in coat­
ings was described elsewhere [17].
3. Results and discussion
The influence of binder and hardener types on the curing-induced
internal stress will now be described, followed by the effects of filler
conditions, initial solvent concentrations, curing temperature, and
relative humidity.
3.1. Effects of binder and hardener on the curing-induced internal stress
The effects of binder and hardener types on the coating properties
during curing, including conversion, elastic modulus, volumetric
shrinkage (defined as the ratio of the current coating volume to the
initial coating volume minus one, Vt/V0–1), and internal stress, are
shown in Fig. 3.
During the first 10 h, the epoxy conversion of the BPF-MX and the
BPA-MX coatings do not show much difference. Following this, the
epoxy conversion of the BPA-MX coating increases from 0.71 to 0.76
after 24 h, and finally reaches a value of 0.79 after 120 h. For the BPF-
MX coating, the epoxy conversion increases from 0.71 to 0.72 after 24 h
and converges to a value of 0.72 after 120 h. However, after 10 h a
slightly higher epoxy conversion in the BPA-MX coating was observed,
which can be attributed to the presence of the highly reactive 2-
Fig. 2. (a) Schematic illustration of a coated metal deflection sample (top view). (b) The device chamber with 16 parallel samples, mounted vertically at the top end.
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Progress in Organic Coatings 173 (2022) 107175
(chloromethyl) oxirane molecule, an impurity remaining from the epoxy
synthesis, and the side reaction between the hydroxyl and the epoxy
groups in the BPA-MX coating.
The elastic modulus of the BPA-MX coating only increases from 0.2
GPa at 6 h to 0.97 GPa after 120 h. This is smaller than the elastic
modulus of the BPF-MX coating, which increases from 0.9 GPa at 6 h to
2.1 GPa after 120 h. Due to the missing methyl groups in the BFDGE
structure (relative to DGEBA), this binder has a slightly higher reac­
tivity, but the DGEBA molecule has an added hydroxyl functionality (see
Fig. 1), which can lead to a higher final epoxy conversion through side
reactions. Therefore, a tighter and stiffer 3D structure with a larger
elastic modulus is developed in the BPF-MX coating.
The rate of change of the relative volumetric shrinkage, for the BPF-
MX and the BPA-MX coatings, is fast from 3.5 to 7.5 h. After about 120 h
of curing, the shrinkage ceases. With the final relative volumetric
shrinkage of the BPA-MX coating reaching a value of − 0.032, which is
slightly higher than that of the BPF-MX coating (− 0.028). This can be
attributed to the somewhat higher final epoxy group conversion for the
BPA-MX coating.
The measured internal stress in the BPF-MX coating is much larger
than that of the BPA-MX coating; the internal stress in the BPF-MX
coating increases fast from zero MPa at 3.5 h to about 1 MPa at 20 h
and then slowly increases to 1.25 MPa after 120 h. Conversely, the in­
ternal stress in the BPA-MX coating increases fast from zero MPa at 3.5 h
to 0.5 MPa at 20 h and then slowly goes up to 0.8 MPa after 120 h. When
taking the evolution of epoxy conversion, elastic modulus, and relative
volumetric shrinkage together, although the BPA-MX coating exhibited
a higher final epoxy conversion and relative volumetric shrinkage, the
internal stress of the BPA-MX coating is significantly smaller than for the
BPF-MX coating. This can be explained by the much smaller elastic
modulus of the BPA-MX coating.
For the effect of hardener type, it can be seen (Fig. 3, right hand side)
that during the first 4 h, the epoxy group conversion of the BPF-MX and
the BPF-MD coatings do not show much difference. After that, the epoxy
Q. Li et al. Progress in Organic Coatings 173 (2022) 107175

Fig. 3. Curing transients showing the effects of binder type to the left (i.e. the 300 μm solvent-free BPF-MX and BPA-MX coatings) and the effects of hardener (i.e.
300 μm solvent-free BPF-MX and BPF-MD coatings) to the right. Conditions were 23 ± 0.5 ◦ C and 35 % RH. Note that in this case, the epoxy conversion represents the
coating-substrate interface conversion. In all the plots, standard deviations with errors bars are shown. The inserts in the two top figures are magnifications of the first
12 h.

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Q. Li et al. Progress in Organic Coatings 173 (2022) 107175

group conversion of the BPF-MD coating increases from 0.66 to 0.79

after 24 h and finally reaches 0.84 after 120 h. The epoxy group con­
version of the BPF-MX coating, on the other hand, increases from 0.61 to
0.72 after 24 h and finally reaches 0.72 after 120 h. The aliphatic
MPMD, because of the slightly higher reactivity than the aromatic
MXDA molecule, reaches a higher conversion after 4 h.
Although a slightly higher epoxy conversion in the BPF-MD coating
was observed, the elastic modulus of the BPF-MD coating increases from
0.92 GPa at 6 h to 0.99 GPa after 120 h. This is much smaller than the
elastic modulus of the BPF-MX coating, which increases from 0.9 GPa at
6 h to 2.1 GPa after 120 h. The aromatic backbone in the MXDA, which
increases the stiffness of the BPF-MD coating, is the cause of this [18].
For the BPF-MX and BPF-MD coatings, the rate of the relative volu­
metric shrinkage is fast from 3.5 to 7.5 h, and then the shrinkage slows,
with a fluctuation within a narrow range, after 120 h of curing. The final
relative volumetric shrinkage of the BPF-MD coating reaches a value of
− 0.037, which is slightly higher (i.e. more negative) than that of the
BPF-MX coating (− 0.028). This is attributed to the higher final epoxy
group conversion of the BPF-MD coating.
The measured internal stress in the BPF-MX and the BPF-MD coatings
are very similar during the first 20 h and after that, the internal stress in
the BPF-MX coating increases slowly from 1 MPa at 20 h to 1.25 MPa
after 120 h. For the BPF-MD coating, the internal stress increases from 1
MPa at 20 h to 1.75 MPa after 120 h. This can be explained by the higher
conversion and volumetric shrinkage in the BPF-MD coating, even
though the elastic modulus of this coating is smaller than that of BPF-
MX. Although a very limited increase in the epoxy conversion of BPF-
MX, BPA-MX, and BPF-MD coatings after 48 h is seen, the crosslinking
reactions still proceed. If sufficient reaction time is allowed, a final
epoxy conversion of close to 100 % can be expected, and this gradual
increase is reflected in the simultaneous increase of the internal stress.
In summary, the internal stress depends highly on the conversion,
elastic modulus, and volumetric shrinkage. When evaluating the curing-
induced internal stress with the beam deflection method, the effects of
conversion, elastic modulus, and volumetric shrinkage should be taken
into account, and each of these parameters are critical for an under­
standing of the development of internal stress.

3.2. Effect of filler conditions on the curing-induced internal stress

The transients of coating formulations with different fillers are

shown in Fig. 4. Here, the filler-free sample shows the largest final
conversion and little difference can be seen for the filler-containing
samples BaSO4-λ0.2, BaSO4-λ0.3, BaSO4-λ0.5, and CaCO3-λ0.3. The
slight decrease in the conversion of filler-containing samples can be
attributed to the flexibility loss induced by the particles [19].
For the elastic modulus, during the first 72 h, the filler-containing
samples exhibit higher elastic moduli and the values increase with an
increasing λ value for BaSO4 filler-containing samples. The elastic
modulus of BaSO4-λ0.5 and CaCO3-λ0.3 are practically equal and
overlap. After 72 h, the elastic modulus of BaSO4-λ0.2 and filler-free
samples show little difference and ends up with the smallest modulus
(around 2 GPa).
The volumetric shrinkage decreases with increasing λ value for
BaSO4 filler-containing samples because the fillers induce rigidity and
thus progressively reduce the relative volumetric shrinkage [19,20]. For
CaCO3-λ0.3, the relative volumetric shrinkage during the first 48 h is
much smaller than for filler-free samples. After that, the samples
maintain almost the same value and ends up with the smallest final
volumetric shrinkage.
The filler-containing samples show larger internal stress and for
BaSO4 filler-containing samples, the measured values increase with
increasing λ value. This agrees with previous research [12,21,22]. For Fig. 4. Transients of the 300 μm solvent-free BPF-MX coatings with different
the CaCO3 filler-containing sample, the internal stress comes to a filler conditions. Cured at 23 ± 0.5 ◦ C and 35 % RH. Note that in this case, the
epoxy conversion represents the coating-substrate interface conversion. In all
plateau after around 20 h and the internal stress of BaSO4-λ0.3 is much
four plots, standard deviations with errors bars are shown.
larger than for CaCO3-λ0.3, indicating that internal stress is more

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Q. Li et al. Progress in Organic Coatings 173 (2022) 107175

susceptible to a BaSO4 filler-containing coating. This can be attributed to

the smaller particle size, hardness, and the surface treatment (details of
this were not provided by the supplier) of the CaCO3 filler [23,24].

3.3. Effect of initial solvent concentration on the curing-induced internal

stress

The rate of solvent evaporation for different initial solvent concen­

trations is shown in Fig. 5. During the first 20 min, the evaporation of
solvent is fast, and then it decreases to a very low value (note that the
evaporated solvent weight percentage in 10 and 20 % volume solvent
samples are only 30 and 52 %, respectively).
Transients of coating formulations with different initial solvent
concentrations during curing are shown in Fig. 6. The presence of re­
sidual solvent in 10 and 20 % volume solvent samples can enhance the
flexibility after vitrification. Therefore, the final conversion of 20 %
volume solvent is the largest and the solvent-free coating shows the
smallest.
For solvent-containing samples, the elastic modulus is smaller than
for solvent-free coatings; however, the elastic modulus at 20 % volume
solvent is a little bit larger than 10 % volume solvent, which can be
explained by a slightly higher final conversion in the 20 % volume
solvent coating. On the other hand, the volumetric shrinkage of solvent-
containing samples is much larger than solvent-free coating because of
extra shrinkage resulting from solvent evaporation and the volumetric
shrinkage increases with increasing initial solvent concentration.
A measurable internal stress begins to build later in the solvent-
containing than in the solvent-free coating and the internal stress in
solvent-containing coatings decreases with increasing initial solvent
concentration. In addition, larger uncertainties can be seen in the 10 %
volume solvent coating and this can be explained by the competition
between the internal stress development induced by the crosslinking
reaction and the plasticizing effect from the residual solvent. For the 20
% volume solvent coating, the plasticizing effect of solvent becomes
more dominant and leads to the smallest internal stress. Oppositely, for
the 10 % volume solvent coating, the plasticizing effect of solvent is
weaker than that of the 20 % volume solvent coating and results in
larger uncertainties. However, a much longer experimentation time is
needed to evaluate the long term influence of solvent on curing-induced
internal stress (see for instance [8]), but this was outside the scope of the

60
Evaporated solvent weight (%)

10% volume solvent

40 20% volume solvent

60

20 40

20

0
0.0 0.5 1.0 1.5 2.0
0
0 20 40 60 80 100 120 140
Time (hours) Fig. 6. Transients of the 300 μm BPF-MX coatings with different initial solvent
concentrations cured at 23 ± 0.5 ◦ C and 35 % RH. Note that in this case, the
Fig. 5. Solvent evaporation behavior of the 300 μm BPF-MX coatings with
epoxy conversion represents the coating-substrate interface conversion. In all
different initial solvent concentrations. Cured at 23 ± 0.5 ◦ C and 35 % RH.
four plots, standard deviations with errors bars are shown.
Standard deviations with errors bars are shown in the plot. The insert in the
figure is a magnification of the first 2 h.

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Q. Li et al. Progress in Organic Coatings 173 (2022) 107175

present work.

3.4. Effects of curing temperature on the curing-induced internal stress

The coating transients, under different curing temperatures, are

shown in Fig. 7. A faster reaction rate and a higher final conversion can
be seen (top plot) at an elevated curing temperature. At 45 ◦ C, the
conversion increases fast during the first 2 h to 0.77 and then converges
to a plateau around 0.85 after 10 h. Similarly, at 35 ◦ C, the conversion
increases fast during the first 4 h to 0.73 and then slowly reaches a
plateau around 0.79 after 24 h. For ambient curing (23 ◦ C), the con­
version increases fast during the first 6 h to 0.66, and then slowly rea­
ches a plateau around 0.7 after 24 h.
The elastic modulus at an elevated curing temperature, due to the
accelerated crosslinking reaction, is larger and develops earlier than
ambient curing coatings during the first 24 h.
After 3 h at 35 ◦ C, a measurable elastic modulus around 1.12 GPa is
seen, and after that the elastic modulus slowly increases. When 24 h has
passed, it comes to a plateau value around 1.6 GPa. At 45 ◦ C, a
measurable elastic modulus around 1.07 GPa after 2 h is observed, and it
then converges to a plateau value around 1.7 GPa after 120 h. Although
the elastic modulus develops earlier at an elevated curing temperature,
the final elastic moduli of the samples cured at 35 and 45 ◦ C are smaller
than for samples cured at 23 ◦ C, and little difference only can be seen in
samples cured at 35 and 45 ◦ C.
During the first 6 h, the rate of relative volumetric shrinkage is faster
in samples cured at 35 and 45 ◦ C. In the case of the BPF-MX coating,
cured at 35 ◦ C, the relative volumetric shrinkage changes from zero to
− 0.023 after 6 h, and at 45 ◦ C it varies from zero to − 0.025 after 6 h.
Following this, the relative volumetric shrinkage shows a downward
tendency and the final relative volumetric shrinkage values at 23, 35,
and 45 ◦ C is − 0.028, − 0.029, and − 0.033, respectively. This can be
attributed to a combined effect of the higher conversion and an
enhanced material expansion at elevated curing temperatures [25]. The
internal stress of the BPF-MX coating cured at 35 ◦ C increased from zero
MPa at 3 h to 1.3 MPa after 20 h and at 45 ◦ C, it increased from zero at 2
h to 1.5 MPa after 20 h. When exceeding 60 h, the internal stress from
samples cured at 35 and 45 ◦ C shows little difference. The final internal
stress in samples cured at 35 and 45 ◦ C is slightly larger than that at
23 ◦ C, indicating that it is possible to use elevated curing temperature
(35 or 45 ◦ C) to achieve a faster curing process and very little internal
stress.

3.5. Effect of relative humidity on the curing-induced internal stress

The transients under different values of relative humidity are shown

in Fig. 8. A faster reaction rate and a higher final epoxy conversion, due
to hydroxyl group catalysis in the epoxy amine reaction process, can be
seen at a higher relative humidity.
For the elastic modulus, slightly higher values are observed for
samples cured during the first 24 h at 60 and 90 % RH than those at 35 %
RH, which can be attributed to a higher conversion at a higher relative
humidity. After 24 h, the elastic modulus at 60 % RH shows a limited
increase and the coating ends up with a smaller modulus (1.9 GPa)
compared to the one at 35 % RH (2.1 GPa). However, the elastic
modulus at 90 % RH shows a slight decrease because the swelling effect
exceeds the effect of the slightly higher conversion and ends up with a
smaller modulus (1.6 GPa).
The rate of volumetric shrinkage exhibits little difference in samples
cured at 35, 60 and 90 % RH during the first 24 h. At later times, the
volumetric shrinkage at 35 % RH shows a slow change, and the volu­
metric shrinkage at 60 and 90 % RH, due to a swelling effect, stays
almost the same. The final value of the relative volumetric shrinkage at Fig. 7. Transients of the 300 μm solvent-free BPF-MX coating, cured under
different temperatures (23, 35, and 45 ◦ C) at 35 % RH. Note that in this case,
60 % RH is − 0.022 and at 90 % it is − 0.020. At 35 % RH, the most
the epoxy conversion represents the coating-substrate interface conversion. In
significant volumetric shrinkage was seen (− 0.028).
all four plots, standard deviations with errors bars are shown.
A measurable internal stress begins to build after 4 h for all three

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Q. Li et al. Progress in Organic Coatings 173 (2022) 107175

conditions (35, 60, and 90 % RH) and comes to a maximum value for 60
and 90 % RH around 10 h. Later, the internal stress at 35 % RH shows a
slow increase and ends up at the largest value (1.2 MPa), while at 60 %
RH and 90 % RH, the stress shows a slight decrease. The final internal
stress of 60 % RH is the smallest (0.1 MPa), and at 90 % RH the internal
stress is around 0.7 MPa. A higher internal stress at 90 % RH can be
attributed to a higher conversion, although stress relaxation induced by
swelling occurred; only 30 % internal stress is relaxed. While for 60 %
RH, almost 80 % of the internal stress relaxed. In contrast to previous
research [14], compressive internal stress was not observed in this work.
Furthermore, when the relative humidity increased from 60 to 90 %, a
slight increase in the measured tensile internal stress was recorded.

4. Conclusions

A comprehensive analysis of the simultaneous conversion, coating

elastic modulus evolution, volumetric shrinkage, and internal stress for a
series of coatings under different curing temperatures and relative hu­
midities was conducted.
Due to a reduced volumetric shrinkage, epoxy resins and hardeners
with molecular structures that provide lower functionality or a reduced
reaction rate are helpful in achieving lower curing-induced internal
stress. On the other hand, stress can also be reduced, as a result of a
smaller elastic modulus, by raising the volume solvent to around 20 %.
In addition, to strengthen the coating, fillers (CaCO3 in particular) with
smaller volumetric shrinkage and internal stress sensitivity can be
introduced.
For the curing conditions, an elevated curing temperature (35 or
45 ◦ C) can deliver faster curing and an acceptable increase in the in­
ternal stress. Furthermore, a medium to high relative humidity (60 %)
provides less internal stress.
Overall, the curing-induced internal stress is highly influenced by the
coupling of curing reactions and mechanical property evolutions,
including elastic modulus and volumetric shrinkage. The experimental
approach in this work can optimize coating formulations and curing
conditions in the pursuit of a low internal stress.

CRediT authorship contribution statement

Qiong Li: Conceptualization, Methodology, Formal analysis, Inves­

tigation, Data curation, Writing – original draft. Claus Erik Weinell:
Supervision, Writing – review & editing. Søren Kiil: Conceptualization,
Supervision, Writing – review & editing.

Declaration of competing interest

The authors declare that they have no known competing financial

interests or personal relationships that could have appeared to influence
the work reported in this paper.

Data availability

Data will be made available on request.

Acknowledgements

Financial support from The Hempel Foundation to CoaST (The

Hempel Foundation Coating Science and Technology Centre) is grate­
fully acknowledged.

Fig. 8. Transients of the 300 μm solvent-free BPF-MX coating when cured

under different relative humidities (35, 60, and 90 %) at 23 ± 0.5 ◦ C. Note that
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