Construction and Building Materials 30 (2012) 753–760

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Construction and Building Materials

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Effects of humid environment on thermal and mechanical properties

of a cold-curing structural epoxy adhesive
Mariateresa Lettieri a,⇑, Mariaenrica Frigione b
a
Institute of Archaeological Heritage, Monuments and Sites, CNR–IBAM, Provinciale Lecce-Monteroni, 73100 Lecce, Italy
b
Department of Innovation Engineering, University of Salento, Via Arnesano, 73100 Lecce, Italy

a r t i c l e i n f o a b s t r a c t

Article history: The effects of exposure to different humid environments in a commercial cold-cured epoxy adhesive
Received 2 September 2011 were investigated. Samples were exposed up to one month to 55%, 75% and 100% relative humidity
Received in revised form 15 December 2011 (RH) or immersed in liquid water, at a constant temperature (23 °C). Weight changes, thermal and
Accepted 23 December 2011
mechanical properties before and at different stages of the aging, were discussed.
Available online 17 January 2012
In the examined aging conditions, absorbed water remained below 1% and saturation level was not
achieved. Plasticization, reactivation of curing reactions and erasure of physical aging were observed in
Keywords:
the specimens subjected to the different humidity regimes, all affecting both the thermal and the
Cold-curing adhesives
Durability
mechanical properties of the aged samples: while the Tg was influenced by plasticization mainly at
Hygrometric aging shorter times of exposure and by post-curing at longer treatment times, the mechanical characteristics
Water sorption were less affected by these phenomena. These effects were found more pronounced at humidity levels
DSC analysis higher than 75% RH. Doubly hydrogen-bonded water molecules linked to the network also influenced
Flexural mechanical properties the Tg of the system, while they did not affect noticeably their flexural properties. Finally, the effects
of water exposure can be regarded as equivalent to those of a thermal treatment at temperature around
the Tg, i.e. both leading to an erasure of the physical aging.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction conditions has detrimental effects on the epoxies, leading to prop-

In recent years, epoxy resins have received considerable atten-
tion and they are commonly used as adhesives, coatings and matri-
ces for composites, due to their advanced chemical and mechanical
properties. They found employment in civil engineering for struc-
tural applications and in cultural heritage conservation, as well. In
these fields, practical and economical reasons force to use ‘‘cold-
curing’’ resins, that is epoxy systems able to achieve a suitable
degree of cure and acceptable mechanical properties at ambient
temperature. Aliphatic amines are usually used as curing agents
for this purpose, since they are able to react with epoxies also at
low temperature. However, many weeks of cure, if compared to
the few hours curing times required by the epoxy cured with a
source of heat, are necessary to provide a material with a reason-
ably high degree of cross-linking, even though the conversion of
epoxy groups is never complete, and a moderate glass transition
temperatures (Tg), which generally does not exceed 60 °C [1–3].
The excellent properties of epoxy adhesives may be modified
by the environment which often acts as a degrading agent. Of
particular relevance is the ambient humidity that in actual service
⇑ Corresponding author. Tel./fax: +39 0832 422219.
E-mail addresses: mt.lettieri@ibam.cnr.it (M. Lettieri), mariaenrica.frigione@
unisalento.it (M. Frigione).
erty changes as a consequence of physical and/or chemical transfor-
mations. Actually, epoxy adhesives exposed to a wet environment
absorb water because they possess polar groups attracting water
molecules. Once inside, water may alter the properties of the poly-
mer both in a reversible manner, through plasticization, and in an
irreversible manner, if hydrolysis, cracking or crazing occur.
The lowering of the Tg due to water ingress into epoxy resins
[4–11] can be particularly harmful for cold-curing epoxies whose
typical Tg, as already underlined, is not much higher than the ser-
vice temperature. Therefore, if the service temperature approaches
the Tg of the system, a lowering of the adhesion strength and of the
mechanical properties of the adhesive could occur.
Both the kinetics and the effects of water absorption in epoxy sys-
tems have been deeply investigated by means of various analytical
techniques [4,5,12–23], the most of studies in literature report the
results of immersion treatments; minor attention has been given
to the action of the atmospheric vapor of varying relative humidity.
Furthermore, whereas the exposure of epoxy resins cured at ele-
vated temperatures has been widely studied, the sorption process
in epoxy systems cured under ambient conditions has been scarcely
investigated. Starting from this lack of information, an experimental
study was devoted to the effects of water absorption in a cold-cured
epoxy adhesive either exposed to different levels of relative humid-
ity or immersed in actual water. In order to better understand the

0950-0618/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.conbuildmat.2011.12.077
754 M. Lettieri, M. Frigione / Construction and Building Materials 30 (2012) 753–760
independent effects of water on the studied resin, synergistic influ-
ence of moisture and temperature was avoided. To this aim, any
treatment was performed in isothermal conditions (i.e. at the tem-
perature of 23 ± 2 °C). In fact, a synergistic effect of the different
environmental agents cannot be excluded, thus their combined ef-
fects can result larger than the sum of their separate effects.
The research was aimed at investigating the behavior of the
adhesive in a real service condition, rather than in the saturation
stage, which can require years of exposure to be achieved [24].
The changes, promoted by the absorption of water, on the proper-
ties of the adhesive has been evaluated, while the kinetic aspects of
the process have been discussed in a previous work [24]. The expo-
sures have been prolonged up to one month of treatment. This time
of exposure was, in fact, expected to yield amounts of water uptake
very small (lower than 1%) and far from the saturation level (found
to be around 1.8% of absorbed water, in the previous study [24]);
however, this limited water content can be more significant from
the application point of view because closer to that measured in
true environmental conditions, as experienced in a recent study
on weathering of cold-curing epoxy adhesives [25].
In a previous research, the same epoxy adhesive taken into ac-
count in this study was investigated after 10 and 30 thermo
-hygrometric cycles [3,24]. In addition, 10-day and 28-day isothermal
treatments (50 °C) were used to examine the effects of temperature in
isolation [3]. For comparative purposes, the same time spans, i.e. 10-
day and 28-day, were chosen to analyze the effects of water in order to
complete the pattern of behavior.
The thermal and the mechanical properties measured before
and at different stages of the hygrometric treatments, are dis-
cussed. The changes in weight were also evaluated throughout
the exposure to water.
2. Materials and methods
2.1. Materials and curing conditions
The material object of this study is a commercial epoxy adhesive produced and
supplied by MAPEI S.p.A. (Italy). The system is representative of epoxy resins used
for rehabilitation procedures as adhesive and it has been already employed for res-
toration of both civil and monumental buildings [26].
The epoxy resin is based on diglycidylether of bisphenol-A; the curing agent is a
mixture of aliphatic and aromatic amines, i.e. polyethylenimine – m-xylenediamine
– nonylphenol, provided ready-to-use. Nonylphenol is usually added to hardener
mixtures to increase the rate of curing due to the presence of phenolic OH group;
the nonyl group, as aliphatic chain, can reduce the evaporation during the applica-
tion procedure, and have plasticizing effects, as well.
Samples of the adhesive were prepared using the mixing ratio suggested by
suppliers, that is resin:hardener = 4:1 by weight. The exact amount of each compo-
nent was weighed with an analytical balance (Sartorius, Mod. BP 221S) with an
accuracy of ±0.1 mg. The hardener was poured into the base resin and they were
gently stirred, avoiding the formation of air bubbles, until the mix was perfectly
homogeneous. Specimens of standard rectangular form (dimensions: 90  10 
4 mm) were obtained by pouring the mix into Teflon moulds of apposite shape.
The samples were cured at a temperature of 23 ± 2 °C and a relative humidity
(RH) of 50 ± 5%. They were removed from the moulds after 26 h and maintained un-
der the same controlled conditions of temperature and humidity (i.e. T = 23 ± 2 °C
and RH = 50 ± 5%) for further 9 days. In fact, the curing time reported on the product
data sheet is 7 days; however, in previous studies it has been found that curing
times higher than those suggested by the suppliers are necessary to reach the max-
imum state of cure achievable by the epoxy adhesive cured at ambient temperature.
In particular, calorimetric and spectroscopic analyses revealed that, for the system
object of this study, 3.5 months of cure are required to reach the maximum cross-
linking degree of the resin at ambient temperature [3], that does not correspond the
complete cure of the same system, i.e. the conversion of epoxy groups was not com-
plete. The specimens were, then, moved in a desiccator with silica gel and stored at
room temperature for further 3 months before expose them to moisture or water.
During both the preparation of the specimens and the curing stage, the environ-
mental conditions were monitored by means of a humidity–temperature logger. A
Digitron MonoLog (Mod. MLH) was used; it can collect temperature data in a range
from 20 °C to 50 °C (with an accuracy of ± 2 °C) and relative humidity data in a
range from 5% to 100% (with a precision of ±5%).
The specimens’ shape and dimensions were chosen on the basis of ASTM
standard for flexural mechanical tests [27].
2.2. Exposure procedures
In order to examine the effects of water ingress on the properties of the adhe-
sive, samples of resin were exposed to controlled humidity level (55% and 75% RH),
kept in saturated water vapor atmosphere (100% RH) or immersed in distilled
water, at a constant temperature (23 ± 2 °C).
The samples were treated after the maximum state of cure achievable at ambi-
ent temperature was reached, that is, as previously stated, the treatments were per-
formed on samples cured for 3.5 months at 23 °C.
In Table 1, the curing procedure and the treatments performed on all the sam-
ples before the tests, were summarized.
The exposure to moisture was realized in a desiccator: the ambient at 55% RH
was attained through the water vapor evaporated from a saturated solution of
Mg(NO3)2; the conditions of 75% RH was obtained by means of a saturated solution
of NH4Cl, while 100% RH was reached using ultrapure water (conductiv-
ity = 0.06 lS/cm at 25 °C, produced using a Milli-Q (Millipore S.p.A.) water system).
The immersion treatment was performed placing the specimens into liquid ultra-
pure water. Each treatment was carried out up to 28 days.
Control samples were left in a dry atmosphere (in a desiccators with silica gel, at
15% RH) to monitor the evolution of the properties of the epoxy system not exposed
to water.
2.3. Test methods
2.3.1. Gravimetric measurements
The weight variations measured on both the samples exposed to moisture and
those immersed in water were used to assess the amount of water absorbed during
any treatment. In all cases, the samples were periodically removed from the storage
box, wiped with a dry cloth and weighed in order to calculate the percentage of ab-
sorbed water. The analytical balance, described in Section 2.1, was used.
After the measurements the samples were replaced in the container as soon as
possible. Throughout any treatment performed, the environmental parameters
were controlled by the humidity–temperature logger described in Section 2.1;
the reported data were calculated as the mean value of measurements performed
on five samples.
2.3.2. Calorimetric analyses
Differential scanning calorimetry (DSC) was performed on untreated samples
just before the exposure/immersion treatments. The thermal dynamic scans were
carried out between 5 °C and 210 °C with a heating rate of 10 °C/min, under nitro-
gen atmosphere (flow rate = 80 mL/min); a DSC 822, Mettler Toledo, calorimeter
was used. The glass transition temperature was determined as the transition mid-
point; the relaxation enthalpy and the residual heat of cross-linking reactions were
evaluated from the peak area delimited by the tangent line to DSC curve. In order to
prove the repeatability of results, the calorimetric experiments were repeated at
least three times and the results averaged.
Epoxy resins held below their Tg are subjected to ‘‘physical aging’’, that reflect
the tendency of the system to approach the equilibrium state [28–30]. At each tem-
perature below its Tg, polymers are in the glassy state and they are frozen in a non-
equilibrium condition. However, a slow structural relaxation toward the final ther-
modynamic equilibrium state at that temperature occurs. The presence of physical
aging in a polymer isothermally aged can be measured in a dynamic calorimetric
experiment. An endothermic peak in the glass-transition region, whose position
and intensity depends on temperature and time of aging, is observed. The area of
this peak is related to the relaxation enthalpy (DHrel) and it increases with the aging
time, becoming constant when the equilibrium is achieved.
Table 1
Curing and drying conditions before the treatments and procedures of exposure to
water.
System Curing Drying procedure Exposure to water
conditions
H55 50% RH and 15% RH (silica gel) and 55% RH and 23 C° up to
23 C° for 23 C° for 3 months 28 days
10 days
H75 50% RH and 15% RH (silica gel) and 75% RH and 23 C° up to
23 C° for 23 C° for 3 months 28 days
10 days
H100 50% RH and 15% RH (silica gel) and 100% RH and 23 C° up to
23 C° for 23 C° for 3 months 28 days
10 days
WL 50% RH and 15% RH (silica gel) and Immersion in liquid water
23 C° for 23 C° for 3 months at 23 C° up to 28 days
10 days
Control 50% RH and 15% RH (silica gel) and –
23 C° for 23 C° for 4,5 months
10 days
 M. Lettieri, M. Frigione / Construction and Building Materials 30 (2012) 753–760 755

The calorimetric tests were repeated after a 12-day treatment on the H55 sys- Table 2
tem, and 10 days of exposure on the systems H75, H100 and WL. The thermal prop- Water uptake amount and thermal properties measured on epoxy adhesive before
erties were also measured after 28 days of exposure to water vapor or immersion and during the exposure to humidity or immersion in water.
in liquid water.
All tests were performed immediately after the end of any treatment, to mini- System Treatment time [days] WAa [%] Tgb [°C] DHresc [J/g] DHreld [J/g]
mize the desorption of water from the exposed samples. H55 0 0 57.1 ± 0.3 9.2 ± 0.3 8.7 ± 0.3
12 0.12 ± 0.01 53.9 ± 0.2 6.1 ± 1.7 10.0 ± 0.3
28 0.17 ± 0.01 51.9 ± 0.2 5.8 ± 1.3 6.6 ± 0.5
2.3.3. Flexural mechanical tests
H75 0 0 57.1 ± 0.3 9.2 ± 0.3 8.7 ± 0.3
Flexural mechanical tests were carried out in three points bending, using a
10 0.15 ± 0.04 51.8 ± 1.1 6.5 ± 1.8 6.8 ± 0.4
Lloyd LR-MK4 Dynamometer (load capacity of the testing rig 1 kN, class of the ma-
28 0.27 ± 0.04 51.5 ± 1.8 5.0 ± 1.9 7.7 ± 0.3
chine 1, maximum accuracy 0.54%, maximum repeatability 0.38%), following the
H100 0 0 57.1 ± 0.3 9.2 ± 0.3 8.7 ± 0.3
ASTM D 790-10 standard [27]; the experiments were performed at room tempera-
10 0.32 ± 0.01 52.8 ± 1.1 5.2 ± 0.8 3.9 ± 0.7
ture, with a support span of 60 ± 0.1 mm and a crosshead rate of 2 mm/min; flex-
28 0.59 ± 0.03 49.4 ± 1.6 3.9 ± 0.1 0.9 ± 0.6
ural mechanical properties (i.e. flexural modulus and maximum flexural strength)
WL 0 0 57.1 ± 0.3 9.2 ± 0.3 8.7 ± 0.3
were calculated as the average of five measurements. The mechanical tests were
10 0.24 ± 0.02 48.7 ± 2.5 5.1 ± 0.3 4.7 ± 1.6
performed at start of the exposure/immersion procedures and they were repeated
28 0.49 ± 0.03 51.7 ± 2.4 4.0 ± 0.1 3.5 ± 1.7
after the same treatment times used to monitor the thermal properties: 12-day
and 28-day treatments for the H55 system, and 10-day and 28-day treatments for a
Absorbed water amount.
the systems H75, H100 and WL. b
Glass transition temperature.
Also in this case, each experiment on aged samples was carried out immediately c
Residual heat of reaction.
at the end of the treatment. d
Relaxation enthalpy.

3. Results and discussion

Table 3
3.1. Un-exposed epoxy system Flexural mechanical properties measured in three point bending on epoxy adhesive
before and during the exposure to humidity or immersion in water.

The thermal and mechanical properties of the specimens iso- System Treatment time [days] Eflexa [GPa] rmaxb [MPa]
thermally cured for 3.5 months in a dry environment, were first H55 0 3.45 ± 0.66 93.4 ± 12.0
measured. 12 3.17 ± 0.17 97.8 ± 6.5
The un-exposed samples showed a Tg of 57.1 ± 0.4 °C; a relaxa- 28 3.16 ± 0.34 97.9 ± 15.7
H75 0 3.45 ± 0.66 93.4 ± 12.0
tion peak was noticed in the DSC thermogram and the correspond-
10 3.72 ± 0.20 92.1 ± 16.8
ing enthalpy was calculated to be 8.7 ± 0.3 J/g. A residual heat of 28 3.27 ± 0.21 105.7 ± 13.6
reaction was also observed and its average value was equal to H100 0 3.45 ± 0.66 93.4 ± 12.0
9.2 ± 0.3 J/g. A measurable residual heat of reaction indicates that, 10 3.59 ± 0.15 105.6 ± 15.7
even after long time of cure, that is 3.5 months, the cross-linking 28 3.00 ± 0.28 93.9 ± 11.0
WL 0 3.45 ± 0.66 93.4 ± 12.0
process carried out at ambient temperature did not reach the
10 3.75 ± 0.30 107.2 ± 13.4
completion. 28 2.94 ± 0.44 91.4 ± 13.2
The results of mechanical tests performed on the un-exposed a
Flexural modulus of elasticity.
samples are: a flexural modulus of elasticity of 3.45 ± 0.66 GPa, b
Maximum flexural strength.
an average maximum flexural strength of 93.4 ± 12.0 MPa.
The thermal and mechanical properties of the un-exposed sam-
ples are reported in Table 2 and Table 3, respectively, with the indi-
cation of the maximum deviation.
Both the calorimetric and mechanical tests were also performed
on the adhesive samples cured for 5 months and stored at 23 °C in
a dry atmosphere (i.e. 15% RH).

3.2. Weight variations

The percentage of absorbed water (WA) in any sample was cal-

culated from the equation:

WA ¼ ½ðM t  M 0 Þ=M 0   100

where Mt and M0 are the weights of the specimen after and before
the treatment, respectively.
In Fig. 1, the values of WA for the four treated epoxy systems as
a function of the exposure time, up to 28 days, are reported.
The sorption rate was very high during the first days of treat-
ment and the process resulted faster as the humidity level in- Fig. 1. Water absorption percentage (WA) as a function of the exposure/immersion
creased. Other authors found a similar trend [15]. The higher time.
sorption rate observed during the first day of treatment could ac-
count for stronger interactions between water and the polymer
network. In the dry resin, the hydrophilic sites are unoccupied and they
The research dealing with the sorption mechanism has sug- easily link the water, involving singly or doubly hydrogen-bonded
gested that the water molecules into the polymer have a double molecules [17,32], that is water molecules forming one or two
nature: unbound molecules confined into the free volume of the hydrogen bonds, respectively. In the absorption process into epoxy
system and molecules bound to hydrophilic sites along the poly- networks, water molecules firstly bind with the hydrophilic
mer [6,12,16,31–33]. groups, then diffuse into free volume elements as unbound water
756 M. Lettieri, M. Frigione / Construction and Building Materials 30 (2012) 753–760
[13,20,34]. Therefore, the hydrogen-bonds, which are energetic
favorable, appears earlier in the water absorption process and are
produced prior to the free water molecules [35]. As the water con-
centration increases, the number of polar groups on the network
available for hydrogen bonding remains unvaried, but they result
saturated by water and additional water molecules prefer to form
hydrogen bonds with other water molecules whereas with the po-
lar groups in the polymer [33,36,37].
A slower water uptake was measured for few days of exposure
suggesting that the absorption was retarded since several polar
sites were previously involved in the aforementioned hydrogen
bonds. At this stage, the entering water molecules have a higher
possibility to remain inside the epoxy network as unbound water.
The investigated exposure time (i.e. 28 days) was not sufficient
to achieve the saturation level in any of the examined conditions.
In an earlier study performed on the same epoxy adhesive cured
at ambient temperature and subjected to either immersion or
exposure to 100% RH, in fact, 60 weeks were necessary to reach
the saturation condition [24].
The highest amount of absorbed water was measured for the
system H100, that is the system exposed to 100% RH. The increase
in weight over the time of the system WL, immersed in liquid
water, was comparable to that of samples H100, even if the im-
mersed samples showed lower amounts of absorbed water
throughout the whole treatment time.
At 100% RH the chemical potential of the water vapor is the
same as that of the liquid, hence sorption, diffusion and equilib-
rium moisture uptake should be the same as in the liquid phase
[34,38]. However, differences between water content in specimens
exposed to environment with 100% RH and those immersed have
been already observed and attributed to the formation of micro-
cracks or to reactions occurring between the liquid water and the
polymer [34], phenomena that are reported to be more pro-
nounced in systems immersed into water. The initial difference
in the sorption curves of immersed and 100% RH exposed speci-
mens was found to be erased after about 12 weeks of aging [24].
In addition, both aging treatments led to very close diffusion coef-
ficients (1.19  109 for immersed specimens and 1.98  109 for
samples exposed to 100% RH) and water content profiles [24].
Similar water sorption profiles were observed for samples H55
and H75, in particular during the early stage of the absorption pro-
cess. Slightly different amounts of absorbed water were measured
in the same specimens just after several days of exposure (i.e.
20 days), coherent with the different levels of humidity exposure.
When the relative humidity is lower than 100%, fewer water
molecules are in the air than there would be over a pure water sur-
face. Therefore, progressively less marked effects in terms of water
absorbed are expected after exposure to 75% and 55% RH. In fact, in
our case, the lower the humidity level, the lower the amount of ab-
sorbed water. In order to illustrate the different behavior of the
specimens at high humidity levels, in Fig. 2 the absorbed water
amounts vs. the relative humidity of treatment, are reported. A lin-
ear trend can be observed for exposure environments up to 75%
RH, while larger increases in absorbed water were measured as
the humidity level increased. An additional 25% increase in humid-
ity level of exposure, up to 100% RH, produced, in fact, a doubled
water absorption. Other authors have experienced a threshold in
the water uptake process at relative humidity higher than 80%
[34,39].
Finally, no change in weight was measured on control samples
kept in dry atmosphere.
3.3. Thermal properties
The thermal properties of the epoxy adhesive under study, sub-
jected to the hygrometric treatments, are listed in Table 2. In the
Fig. 2. Water absorption percentage (WA) as a function of the relative humidity
level.
same table, the amounts of water absorbed by the specimens after
different exposure to moisture or immersion times, are also
reported.
As expected, the exposure to moisture, as well as the immersion
treatment, decreased the Tg of the epoxy resin, since the absorption
of water molecules gives rise to plasticizing effects.
Whereas the unbound water molecules are characterized by a
higher mobility, due to the low interaction with the polymer net-
work, the bound molecules are immobilized, since an high energy
barrier have to be overcome [15,40] and are expected to be respon-
sible for the plasticization [16,32,41,42]. These effects are mainly
attributed to the water forming single hydrogen bonds; on the
other hand, doubly hydrogen-bonded molecules do not signifi-
cantly contribute to plasticization, whereas produce opposite ef-
fects as a consequence of pseudo-crosslinking resulting from the
secondary bridging they form between the chain segments [9,17].
A general reduction in Tg was observed after each 10-day treat-
ment: H55, H75 and H100 exhibited very similar Tg, being the differ-
ences within the experimental error; on the other hand, the Tg
value measured for WL was even slightly lower.
Different trends were observed as the treatment time increased.
At 28 days of exposure, only the systems H55 and H100 showed an
additional decrease in Tg with respect to the 10-day treatment;
similar values of glass transition temperature were measured for
H75 samples treated for either 10 or 28 days. An appreciable in-
crease in Tg was found only in immersed specimens. The latter re-
sult could be related to a post-curing process promoted by the
decrease in Tg upon moisture ingress in the partially cured resin.
It is reported that the lower Tg allows the polymer chains to be-
come mobile, increasing the probability of a contact between the
groups that have not reacted, thus promoting additional cross-link-
ing reactions and making possible the completion of the curing
process [43–45]. In that case, an increase in Tg is expected.
The changes in thermal properties, as a consequence of water
ingress, are manifest in DSC traces drawn in Fig. 3. In this figure
the glass transition region, the endothermic peak related to the
physical aging and the exothermic peak due to the residual heat
of reaction, are evidenced.
In Fig. 4 the Tg is reported as a function of the percentage of
water uptake for the specimens exposed to different levels of
humidity or immersed in water. Within the early stage of the
absorption process, even low amounts of water gain were able to
produce an appreciable reduction in Tg. Closer Tg values were mea-
sured at larger weight gain. The behavior of Tg measured on speci-
mens immersed is somehow different from that of samples exposed
 M. Lettieri, M. Frigione / Construction and Building Materials 30 (2012) 753–760
Fig. 3. DSC traces of the 28-day aged samples.
Fig. 4. Glass transition temperature (Tg) as a function of absorbed water amount
(WA).
to different levels of RH, in particular for low amounts of absorbed
water. In the same Fig. 4, the curve used to fit the experimental Tg
data of specimens exposed to different levels of humidity is also
shown. It is confirmed that the curve is able to fit also the Tg value
of the immersed specimens only at the longest immersion time.
The reductions in Tg observed at low amounts of sorbed water
can be ascribed to the prevailing of plasticization effects on the
post-curing. At low amount of sorbed water, in fact, strong
water–resin interactions are more likely to occur: in this case,
bound molecules, which are responsible of Tg decrease, prevail
[13,33,36,46]. On the other hand, as the water content increases,
the occurrence of a more rigid molecular structure, caused by both
the post-curing process and doubly hydrogen-bonded water mole-
cules, is able to counteract the decrease in Tg due to the plasticiza-
tion. Absorbed water molecules forming two hydrogen bonds
cause, in fact, an increase in Tg [9,35].
The Tg of the control samples, kept for 4.5 months at 15% RH
(equivalent to a 28-day treatment), remained unchanged (Tg =
56.9 ± 0.4 °C) with respect to the same parameter measured after
3.5 months of cure (i.e. before the treatments). Therefore the varia-
tions in Tg measured on the treated epoxy resin can be ascribed just
to the water action.
In examining the residual heat of reaction, it is worth noting that
all samples showed a reduction in DHres (Table 2 and Fig. 3). A
757
dependence on the humidity level of treatment was noticed: the
higher the percentage of relative humidity of exposure, the lower
the residual heat of reaction. The values found for H100 and WL coin-
cide in the whole range of observation. The same values of DHres
measured for H100 and WL would suggest comparable degrees of
cross-linking for these two systems. This result indicates that the
increase in Tg observed for the immersed samples between 10
and 28 days of exposure cannot be simply related to the post-curing
process. It can be hypothesized that the resumption of curing reac-
tions along with pseudo cross-linking brought about by the water
molecules forming bridging between chain segments, produce less
mobile polymer chains due to constrains into the structure.
Despite the fact that a reduction of the residual heat of reaction
was observed throughout each treatment, the Tg values were al-
ways lower than those measured on the untreated resin. This result
suggests that the plasticization undoubtedly prevailed, while the
post-cure produced minor effects on the thermal properties of this
epoxy adhesive.
In Fig. 5, the residual heat of reaction as a function of the water
gain, is reported. The DHres decreased as the amount of absorbed
water increased. As previously stated, the more mobile chains,
due to the platicization effect, allow to post-cure and increase
the cross-linking density of the systems. The ingress of few water
molecules during the first stage of the absorption process were
able to reduce roughly by half the residual heat of reaction. Then,
little additional decreases of DHres were measured even at much
greater amounts of sorbed water. In the latter case, a less mobile
polymer structure can be suggested once again: the bridging
formed between the water molecules and the polar sites in the re-
sin slow the motion of the polymer chains thus reducing the prob-
ability of a contact between the un-reacted groups. The total
disappearance of the peak due to residual curing reactions was
not experienced, proving that un-reacted groups are still present
in the treated resin samples.
By comparing the fitting curves for Tg and DHres vs. amount of
absorbed water reported in Figs. 4 and 5, respectively, a very sim-
ilar trend is observed. This to confirm that the calorimetric proper-
ties of cold-curing epoxy adhesive under study are significantly
affected by small quantities of sorbed water, while greater
amounts do not appreciably influence these properties, at least
for the investigated range of exposures.
The residual heat of reaction (DHres) on control samples, kept
for 4.5 months at 15% RH, was still measured, being around
7.7 ± 2.4 J/g. This value is comparable with that found before the
treatments, since the difference is within the experimental error.
Fig. 5. Residual heat of reaction (DHres) vs. absorbed water amount (WA).
758 M. Lettieri, M. Frigione / Construction and Building Materials 30 (2012) 753–760
In thermosetting resins, the increased segmental mobility, in-
duced by water ingress, can be the consequence of the motions
of both segments of unreacted molecules, which can be still pres-
ent in the cured system, and chain segment in cross-linked regions
of network [28]; hence, the erasure of physical aging can be also
observed [10,37,47] not only by heating the system above its Tg
[29,48,49], but also by the action of other factors, including tem-
perature, moisture and stress [50–52].
The relaxation enthalpy (DHrel), as a measure of the physical
aging phenomenon, is reported in Table 2 at different exposure/
immersion times. The immersed samples and the specimens ex-
posed to the highest humidity level exhibited similar trend of DHrel
vs. immersion/exposure time, that is a continuous decrease. How-
ever, the lowest relaxation enthalpy was measured on the systems
H100.
In the systems exposed to 75% and 55% RH, the exposure to
moisture produced no appreciable variations in DHrel. From data
in Table 2, the small differences in DHrel can be, in fact, attributed
to inevitable inaccuracy in the calculation of the small areas repre-
sentative of the relaxation enthalpy released during DSC scans, as
already reported elsewhere [53].
In Fig. 6 the DHrel as a function of the absorbed water amount, is
reported. The trend to decrease can be observed, confirming the
partial erasure of physical aging occurring as a consequence of
water ingress.
The relaxation enthalpy (DHrel) in function of the residual heat
of reaction (DHres) is reported in Fig. 7. Increasing the immersion/
exposure time, both DHrel and DHres decreased. In fact, water in-
gress promoted the resumption of curing reactions (producing a
DHres decrease) and made the system less ‘‘dense’’ in terms of
physical aging (as a consequence DHrel decrease). The data are
not on a straight line, but they exhibit a similar trend, irrespective
to the exposure regime used.
The value of relaxation enthalpy (i.e. 9.4 ± 0.2 J/g) of the control
samples (kept for 4.5 months at 15% RH) is close to that measured
on un-exposed specimens.
In conclusion, the variations in relaxation enthalpy as conse-
quence of de-aging process are almost insignificant for the speci-
mens exposed to intermediate levels of humidity, while they
become appreciable starting from the exposure to 100% RH The re-
sults observed for H100 and WL specimens testify the equivalence of
a low amount of water ingress and a moderate temperature, not
exceeding the Tg of the resin, in the de-aging process of these res-
ins. In a previous research, similar results were found, confirming
that, during a hygrometric treatment, a de-aging process took place
[3]. The influence on mechanical properties of de-aging, achieved
Fig. 6. Relaxation enthalpy (DHrel) as a function of absorbed water amount (WA).
Fig. 7. Relaxation enthalpy (DHrel), in logarithmic scale, vs. residual heat of reaction
(DHres).
as consequence of water ingress, is likely to be measurable only
for immersed and 100% RH exposed specimens, as discussed next.
3.4. Mechanical properties
In literature, studies dealing with the effect of the immersion in
water on the mechanical properties of epoxy resins in bulk are re-
ported. This treatment yields an initial increase in ultimate tensile
strength, followed, at longer immersion times, by a decrease to val-
ues similar to that of the unaged polymer [42,43]. The initial in-
crease in the ultimate tensile strength was explained in terms of
an increase in cross-link density [42,54]. Later reductions in
strength, finally, were the result of degradation due to the presence
of water. From the same studies, the Young’s modulus of the aged
epoxy resulted slightly lower than that of the control samples,
increasing the reduction in modulus by increasing the immersion
time [39,55,56]. The physical aging gives rise to continuous
changes of the material properties, with reduction in creep compli-
ance, stiffening, reduction of ultimate elongation, increase in yield
strength [57–59].
The mechanical properties of the epoxy adhesive under study
are listed in Table 3.
The flexural modulus of elasticity (Eflex) was calculated as
follow:
3
Eflex ¼ ðL3 mÞ=4bd Þ
where L is the support span in mm, m is the slope of the initial
straight-line portion of the load–deflection curve in N/mm, b is
the width in mm of the tested specimen, and d is the sample thick-
ness in mm.
Comparing first the Eflex data as a function of exposure/immer-
sion time, the systems H75, H100 and WL exhibited a slight increase
in flexural modulus at shorter times, up to 9%. However, the differ-
ences in Eflex calculated on treated and untreated samples fell with-
in the range of the experimental error. A subsequent appreciable
decrease of this parameter was verified at longer exposure/immer-
sion times, the highest the humidity level the greater the reduction
in stiffness. The behavior observed after few days of exposure
could be ascribed to a more marked influence on the flexural mod-
ulus of the effects due to the reactivation of the curing reactions,
already witnessed by the decreased residual heat of reaction mea-
sured through the DSC analyses. Similar results were found by
other researchers in mechanical tensile tests: the exposure to
 M. Lettieri, M. Frigione / Construction and Building Materials 30 (2012) 753–760
water yielded an initial slight increase in the elastic modulus, fol-
lowed by more marked plasticization effects (that is, elastic mod-
ulus decrease) at larger water uptake [42]. The samples exposed
to 55% RH exhibited values of flexural modulus Eflex slightly lower
than those calculated on the untreated system, irrespective to the
exposure time. It must be noted, however, that the std. deviation in
mechanical data, reported in Table 3, are in the order of 20%, but
only for un-exposed specimens.
In Fig. 8 the flexural modulus as a function of water absorbed
for any humidity regime used, is reported.
At lower water contents, i.e. up to 0.32%, Eflex fluctuated around
a mean value (3.46 GPa) very close to that calculated before the
treatments (3.45 GPa). The decrease of Eflex expected as a conse-
quence of the plasticization was most likely balanced by the in-
crease due to the post-curing process, resulting in not dissimilar
values of flexural modulus. At higher water uptake, a decrease up
to 15% was observed with respect to Eflex calculated on un-exposed
material. In this case, the cross-linking reactions were almost com-
pleted (minor changes were detected in DHres), then the plasticiz-
ing effect prevailed.
The maximum flexural strength (rmax) was calculated using the
following equation:
rmax ¼ ð3PLÞ=ð2bd2 Þ
where P is the load (in N) at a given point on the load–deflection
plot, L is the support span in mm, b is the width of the tested spec-
imen expressed in mm, and d is the sample thickness in mm.
Average stress–strain curves found for the resin exposed to the
different regimes of moisture or immersed in water for 28 days, are
shown in Fig. 9. A linear relationship was observed in all cases, irre-
spective to the treatment performed. The yield point was never ob-
served and the maximum flexural strength coincided with the
stress at break. A similar trend was found by other authors [42].
The values of rmax for the systems analyzed, reported in Table 3,
reveal a certain increase in strength at the lowest exposure/immer-
sion time, again ascribed to a post-curing process, even though
high values of maximum deviations in results can be noticed. At
the longest time, no difference is measured as a consequence of
the different regimes of exposure. It can be concluded that the ef-
fect of short term (up to one month) exposure to water had an
insignificant effect on the strength of specimens.
As previously stated, mechanical properties can be also influ-
enced by the erasure of physical aging especially in the epoxy
adhesives exposed to the highest levels of water. A reduction in
both the elastic modulus and the maximum strength is expected
Fig. 8. Flexural modulus of elasticity (Eflex) as a function of the absorbed water
amount (WA).
759
Fig. 9. Stress–strain curves of the 28-day aged samples.
as a consequence of de-aging process. At short immersion/expo-
sure times its effects could have been counteracted by those pro-
duced by the reactivation of cross-linking reactions while they
are likely to result more marked at higher amounts of water up-
take, where the lowest values of DHrel along with the greatest
reductions in elastic modulus were measured.
The flexural modulus of the control samples left for 4.5 months
at low relative humidity (at 15% RH) was measured to be
3.48 ± 0.67 GPa, the maximum flexural strength 95.0 ± 19.9 MPa.
These results confirmed that steady values of the properties of
the epoxy resin were already attained before the exposure to water.
4. Conclusion
In the present study, the effect of the immersion of liquid water
or the exposure to different levels of relative humidity on the ther-
mal and mechanical properties of a commercial cold-cured epoxy
adhesive was analyzed and discussed. The observed changes were
undoubtedly due to water action since the aged specimens were
exposed after a curing time suitable to stop, not necessarily to
complete, the cure at ambient temperature. In fact, no significant
variations in properties of the control samples left for 4.5 months
at 15% RH were measured.
All the examined aging conditions were not able to give rise to
the saturation level in the investigated exposure time (i.e.
4 weeks). However, a short period of exposure was chosen in order
to be more similar to that experienced in true service conditions.
The amounts of absorbed water depended on humidity level of
exposure. Generally, the higher the relative humidity, the higher
the water uptake; however, larger increases in absorbed water
were measured above 75% RH.
The water ingress led to the plasticization of the adhesive, en-
hanced the reactivation of cross-linking reactions, as well as the
erasure of physical aging. In the latter case, the consequence of
water exposure was equivalent to the effects of a thermal treat-
ment at temperature around the Tg. This process was appreciable
again at regimes of humidity higher than 75%.
Plasticization influenced the Tg particularly at shorter times of
exposure; at longer treatment times, the same parameter was
more influenced by the effects of both the reactivation of curing
reactions and the doubly hydrogen-bonded water molecules.
Regarding the mechanical properties, at lower amounts of
water absorption, the action of the post-cure balanced the effects
760 M. Lettieri, M. Frigione / Construction and Building Materials 30 (2012) 753–760
of the plasticization and, possibly, of de-aging. As a consequence,
the mechanical properties appear to be scarcely influenced by
the exposure to humidity/immersion in water. However, at higher
water uptake values, i.e. in correspondence of humidity levels
higher than 75%, the effects of the de-aging process coupled with
those of the plasticization led to a certainly reduction in the stiff-
ness. A linear relationship in stress and strain curves was observed
in all cases, irrespective to the treatment performed.
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