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Effects of environmental factors on the adhesion and durability

characteristics of epoxy-bonded concrete prisms

Article  in  Construction and Building Materials · February 2009

DOI: 10.1016/j.conbuildmat.2008.02.013

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 Construction and Building Materials 23 (2009) 758–767

Contents lists available at ScienceDirect

Construction and Building Materials

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

Effects of environmental factors on the adhesion and durability characteristics

of epoxy-bonded concrete prisms
Adnan Çolak a,*, Turgay Çosßgun a, Ahmet E. Bakırcı b
a_ _
Istanbul University, Faculty of Engineering, Department of Civil Engineering, 34320 Avcılar, Istanbul, Turkey
b_ _
Istanbul University, Vocational College of Technical Science, Fire Fighting and Safety Program, 34320 Avcılar, Istanbul, Turkey

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

Article history: This work is concerned with the effects of environmental factors on the adhesion and durability charac-
Received 26 September 2007 teristics of epoxy-bonded concrete prisms. The results indicate that the presence of liquid water at the
Received in revised form 22 February 2008 interfacial zone during the epoxy injection process disrupts the initial bond configurations. The freezing
Accepted 25 February 2008
and thawing up to about 40 cycles do not have a significant effect on the bond stability. An adequate
Available online 23 April 2008
degree of chemical stability is maintained in the bond line by the epoxy adhesives after 120 days of expo-
sure to corrosive environments such as MgSO4 and MgCl2. However, there is a pronounced effect of these
Keywords:
chemical substances on the concrete strength. The load-bearing capacity of epoxy-bonded concrete
Epoxy adhesives
Concrete
prisms decreases with increasing temperature. Despite this fact, the EP3-bonded concrete prisms give
Bond stability relatively high joint strengths at temperatures up to 100 °C.
Environmental factors Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction ularly distilled water, alkaline and acid cleaning agents (NaOH and
HCl) may also affect the joint performance [32–35]. Indeed, a study
The moisture stability of adhesive joints depends on the con- [36] conducted on concrete–methylmethacrylate bonded joints
centration of liquid water at the interfacial zone between adhesive has shown that distilled water has a detrimental effect on the joint
and adherend. A few monolayer of water absorbed on the adher- strength. On the other hand, many joints appear to be able to with-
end would be expected to have little effect on the adhesion, be- stand exposure to NaOH and HCl for 30 days. However, this im-
cause they are readily displaced by the adhesive. However, bulk proved stability can be related to the decrease in concrete
water cannot be tolerated because of its adverse effect on the strength. For this reason, both qualitative and quantitative infor-
spreading of the adhesive at the time of application [1]. Some mea- mation are necessary to characterize the behaviour and perfor-
sures can be taken to prevent the ingress of water to the interfacial mance of well-prepared joints in these chemical environments.
regions in high concentrations. A more conservative and preferable Still another phenomenon that has been observed to reduce the
approach would be to enhance the hydrophobic characteristics of strength of joints is warm/moist environment. Hockney [37], Butt
epoxy resins [2–8]. This approach, based on experimental investi- and Cotter [38] have demonstrated the potential magnitude of this
gations, is described by Shaw et al. [9–11]. These studies have effect. At warm/moist environments, the extent and rate of damage
shown that the application of fluoroepoxies to the substrate sur- are found to be related to the chemical nature of the adhesive. For
face can result in substantial improvements in adhesive-substrate example, both vinyl-phenolic and nitrile-phenolic adhesives gen-
interfacial stability in the presence of moisture. The other approach erally exhibit optimum performance [39–45]. Nylon-modified
has been to use pre-bond primers such as silane coupling agents or epoxies, on the other hand, display a marked decrease in strength
otherwise chemically altering the adherend surface and bonding [46–48].
with epoxy adhesives [12–23]. The influence of peel stresses less than the ultimate strength of
There are several additional harsh environmental conditions. the joints combined with moisture attack has also been investi-
These are liquid contaminants, stress, temperature and freezing gated. In these studies, the wedge test was employed as a compar-
and thawing action. Liquid contaminants such as fuels and de-icing ative test technique [49]. In this test, the sample is simply stressed
fluids tend to attack the adhesive-adherend bond and destroy the by inserting a wedge into the bondline. Failure is believed to occur
integrity of the joint [24–31]. Other chemical environments partic- as a result of the slow extension of crack probably aided by mois-
ture until they reach a critical severity.
* Corresponding author. The stress responsible for failure is generally the resultant of a
E-mail address: [email protected] (A. Çolak). combination of externally applied stresses acting with internal

0950-0618/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.conbuildmat.2008.02.013
 A. Çolak et al. / Construction and Building Materials 23 (2009) 758–767 759

stresses arising from freezing and thawing, swelling, shrinkage, technique was applied to the concrete prisms, and their flexural
temperature, radiation and salt crystallization [50–60]. The contri- strengths were measured as 7.5 MPa. The compressive strength
bution of each of these can vary considerably. In freezing and was determined on 4  4  4 cm concrete samples. These samples
thawing, the de-icing fluids may aggregate the problem by chang- exhibited compressive strength values between 35 and 45 MPa for
ing the structures of adhesive and concrete. In this case, internal 28 days. The injection technique was used for bonding the broken
stresses are large enough to produce failure at the interfacial zone parts of concrete prisms that were previously subjected to the flex-
or through the weakened concrete. This phenomenon is generally ural test. The epoxy adhesive formulations used in the injection
observed in repaired concrete structures such as bridge and road process are given in Table 3. The preparation of EP1 and EP3 adhe-
[61–70]. Thus, the effect of de-icing fluids on the joint performance sive formulations is a two-step process in which a linear, process-
must be considered when attempting to repair this type of struc- able, low molecular weight epoxy resin is first made, and then
tures. In some cases, salt solutions may crystallize in capillaries mixed with a curing agent to produce a tough, intractable resin
or voids in the concrete, leading to pressure. In the wetting and of complex structure. The EP2 and EP4 adhesive formulations were
drying cycles, the internal stresses of such magnitude may build achieved solely by adding a filler such as quartz sand to the EP1
up that adhesional failure can occur in the absence of externally and EP3 adhesive formulations. The size and gradation of quartz
applied forces. Another factor which must be considered is temper- sand are given in Table 4. For EP1 and EP2 and EP3 and EP4 adhe-
ature; higher temperature generally increases the rate and magni- sive formulations, glass transition temperature ranged from 80 to
tude of corrosive attack [71–73]. The joints should be made to have 75 °C and from 100 to 90 °C, respectively. These values are charac-
high resistance to failure under these harsh environmental condi- teristic of epoxy adhesives. The compressive strength of these
tions [74–98]. adhesive formulations was generally of the order of 70–80 MPa.
In this work, the adhesion and durability characteristics of con- The flexural strengths were found to be 27 MPa for EP1 and
crete prisms bonded with epoxy resin are discussed with reference 20 MPa for EP2. Similarly for EP3 and EP4, the flexural strengths
to some of the most functionally significant variables, such as varied from 35 to 24 MPa, respectively. Gaps which were narrower
moisture, freezing and thawing, temperature and chemicals. These than 1, 1 and 5 mm were initially left between the broken parts of
variables, which affect the adhesion properties, are defined in EN concrete prisms to represent cracks. The sealing of the cracks on
1504. In addition, consideration is given to the properties of epoxy the surface of a prism was made by using an epoxy sealant to pre-
resin determining the adhesion characteristics of joints. vent the low viscosity adhesive from escaping during the injection
process. This treatment was applied to three surfaces of the prism.
2. Experimental After this treatment, the moisture content of the prism was chan-
ged to investigate the effect of different moisture conditions during
2.1. Materials and method injection process on the bond stability. The samples were sub-
jected to two different moisture conditions during injection. The
Ordinary Portland cement was used in the production of con- former moisture condition was obtained by completely immersing
crete prisms of dimensions 4  4  16 cm. Natural river sand and the concrete prisms in water for 24 h and the latter at the labora-
crushed limestone were used as fine and coarse aggregate, respec- tory conditions. A properly moistured sample by the conditions
tively. The sieve analysis results for the aggregates and their mix mentioned above were subjected to the injection process. The
proportions are given in Table 1. As noted in Table 1, the particle crack on the open face of the prism was used for this purpose. After
size distribution of the crushed limestones I and II ranges from the injection process, the prisms were kept for one week under the
8 mm to 0.5 mm. The sand was very fine. The water to cement ratio laboratory conditions for the polymerization of epoxy adhesives,
was 55%. This ratio is adjusted by a naphthalene-based superplast- and then they were examined under four-point flexural test. The
icizer in a proportion of 1% by the weight of cement. The slump va- samples for the durability tests were moistured at the laboratory
lue of the concrete was 11 ± 1 cm. The composition of concrete is conditions. The moisture content of these samples during injection
given in Table 2. All concrete prisms were cured for one day in process and cure is about 5%. This low amount of moisture has no
the mould, covered at 20 ± 1 °C with a plastic sheet, followed by negative effect on the formation of a good bond between the adhe-
27 days under water at 20 ± 1 °C. After curing, the prisms were sive and the concrete. In this case, the change in the adhesion char-
dried in the laboratory conditions of 65% RH and 20 ± 1 °C until
they attain constant weight. The flexural test with three points
Table 3
Epoxy adhesive formulations

Epoxy Epoxy resin Diluent Curing agent Filler

Table 1
system
Properties and particle size distribution of aggregates
EP1 Diglycidyl ether Diglycidyl Triethylenetetramine
Materials Sieve opening (mm) Mix proportion Specific of bisphenol A ether
(%) weight EP2 Diglycidyl ether Diglycidyl Triethylenetetramine Quartz
8 4 2 1 0.5 0.25
(kg/dm3) of bisphenol A ether
Sand 100 95 85 76 55 14 60 2.61 EP3 Diglycidyl ether Diglycidyl Trimethylhexamethylenediamine
Crushed limestone I 100 53 7 2 0 0 15 2.70 of bisphenol A ether
Crushed limestone II 100 22 2 1 0 0 25 2.71 EP4 Diglycidyl ether Diglycidyl Trimethylhexamethylenediamine Quartz
of bisphenol A ether

Table 2
Table 4
Composition of concrete
Size and gradation of quartz sand
Cement Sand Crushed Crushed Water Superplasticizer
Sieve opening (mm)
(kg/m3) (kg/ limestone I limestone II (kg/ (kg/m3)
m3) (kg/m3) (kg/m3) m3) 2 1.5 1 0.5 0.1
400 937 405 240 221 4 Percent passed 100 93 75 47 15
760 A. Çolak et al. / Construction and Building Materials 23 (2009) 758–767

acteristics of epoxy-bonded concrete prisms will be undoubtedly Table 6

due to the durability tests. The samples prepared by this way were Effect of freezing and thawing in the presence of NaCl on the strength retention of
epoxy-bonded concrete prisms
subjected to the durability tests. These tests are
Epoxy system Adhesive thickness Number of cycles Sd/Sc Mode of failure
1. Freezing and thawing: In this test, the alternate freezing and (mm)

thawing cycles were applied to the samples. For practical pur- <1 1 5 20 40 60 80
poses, a finite number of cycles, namely 80, was used. A cycle EP1 + + 0.93 Concrete
consists of thawing the samples for 8 h in de-icing fluid at EP1 + + 0.88 Concrete
20 ± 1 °C followed by 16 h freezing at 20 °C in air. The de-icing EP1 + + 0.89 Concrete
EP2 + + 0.91 Concrete
fluid is a mixture of water and NaCl. This fluid contains 2.5%
EP3 + + 0.92 Concrete
NaCl. After every 20 cycles, the samples were removed from EP3 + + 0.94 Concrete
the de-icing fluid and allowed to dry in the laboratory condi- EP3 + + 0.91 Concrete
tions for 30 days, and then were examined under four-point EP4 + + 0.93 Concrete
EP1 + + 0.87 Concrete
flexural test.
EP1 + + 0.80 Concrete
2. Test temperature: The flexural strength of epoxy-bonded con- EP1 + + 0.81 Concrete
crete prisms were measured for the test temperatures between EP2 + + 0.79 Concrete
20 and 100 °C. In this case, the test temperature interval was EP3 + + 0.85 Concrete
taken as 20 °C. The samples were heated in an oven at a rate EP3 + + 0.82 Concrete
EP3 + + 0.85 Concrete
of 20 °C per hour. The change in temperature was carefully con-
EP4 + + 0.83 Concrete
trolled so as to provide a uniform temperature distribution EP1 + + 0.72 Concrete
throughout the adhesive joint. After a certain period of expo- EP1 + + 0.74 Concrete
sure to the test temperature, the samples were taken out from EP1 + + 0.51 Interface
the oven and they were immediately examined under four- EP2 + + 0.75 Concrete
EP3 + + 0.76 Concrete
point flexural test. EP3 + + 0.71 Concrete
3. Corrosive environment: For these tests, the samples were placed EP3 + + 0.72 Concrete
in pans containing the following corrosive solutions. EP4 + + 0.73 Concrete
a. Two concentrations of MgCl2 (10% and 15%), EP1 + + 0.63 Concrete
EP1 + + 0.62 Concrete
b. Two concentrations of MgSO4 (1.5% and 3%),
EP1 + + 0.38 Interface
EP2 + + 0.35 Interface
The samples were exposed to these corrosive solutions EP3 + + 0.65 Concrete
for 120 days. At the end of this period, the samples were removed EP3 + + 0.61 Concrete
from the solutions and allowed to dry in the laboratory condi- EP3 + + 0.58 Interface
EP4 + + 0.57 Interface
tions. The drying process continued for 30 days. The samples were
examined under four-point flexural test. For comparison purposes,
three concrete prisms were stored in laboratory conditions and
tested by using the aforementioned test set up at the same time
as the epoxy-bonded concrete prisms were exposed to tests 1, 2 relative values (Sd/Sc) in these tables express the ratio of flexural
and 3. strength of epoxy-bonded concrete prisms to that of concrete
prisms stored in the laboratory conditions. These tables also pres-
3. Results and discussion ent the modes of failure of the samples. Each of the results given in
Tables 5–8 represent an average of three relative values. For each
The effects of environmental factors on the adhesion and dura- case, the dominant failure mode is determined on the basis of vi-
bility characteristics of concrete prisms bonded with varying epoxy sual examination of fracture surfaces of the three samples.
systems at different bond thickness are given in Tables 5–8. The
3.1. Effect of moisture during injection process

Moisture affects the joint strength in a variety of ways depend-

Table 5
ing on the mechanism of absorption. Comyn [99] has found an
Effect of moisture on the strength retention of epoxy-bonded concrete prisms
essentialy linear relationship between joint strength and the total
Epoxy system Adhesive Moisture content Sd/Sc Mode of failure quantity of moisture absorbed by the adhesive. The data given in
thickness (mm)
Table 5 appear to be in general agreement with this theory. The
<1 1 5 About 5% Saturated concrete prisms absorb a relatively small amount of moisture to
EP1 + + 1.08 Concrete reach equilibrium in the laboratory conditions. These samples con-
EP1 + + 1.01 Concrete tain 5% moisture or less. It is clearly seen from Table 5 that the low
EP1 + + 1.02 Concrete values of moisture have no effect on the adhesion characteristics of
EP2 + + 1.12 Concrete
EP3 + + 1.23 Concrete
EP1, EP2, EP3 and EP4 adhesive formulations. The samples break by
EP3 + + 1.05 Concrete failure in concrete rather than at the interface of adhesive and con-
EP3 + + 1.10 Concrete crete. However, epoxy-concrete bond failure occurs when the sam-
EP4 + + 1.03 Concrete ples are joined in the saturated condition. Liquid water on the
EP1 + + 0.49 Interface
surface or within the voids in the concrete can become attached
EP1 + + 0.53 Interface
EP1 + + 0.51 Interface to the resin molecule itself, thereby generating swelling stresses
EP2 + + 0.58 Interface [100–104]. In this case, the bonds’ linking chain atoms are
EP3 + + 0.65 Interface stretched or twisted, and the stability of the bond is correspond-
EP3 + + 0.68 Interface ingly diminished [105–116]. This effect becomes more pronounced
EP3 + + 0.69 Interface
in the concrete prisms bonded using EP1 adhesive formulation. The
EP4 + + 0.73 Interface
flexural strength of the concrete prisms bonded with this adhesive
 A. Çolak et al. / Construction and Building Materials 23 (2009) 758–767 761

Table 7 Table 8
Effect of test temperature on the strength retention of epoxy-bonded concrete prisms Effect of corrosive environments on the strength retention of epoxy-bonded concrete
prisms
Epoxy system Adhesive Test temperature (°C) Sd/Sc Mode of failure
thickness Epoxy Adhesive MgCl2 MgSO4 Sd/ Mode of
(mm) system thickness concentration concentration Sc failure
(mm) (%) (%)
<1 1 5 20 40 60 80 100
<1 1 5 10 15 1.5 3
EP1 + + 1.05 Concrete
EP1 + + 1.01 Concrete EP1 + + 0.77 Concrete
EP1 + + 1.12 Concrete EP1 + + 0.84 Concrete
EP2 + + 1.08 Concrete EP1 + + 0.71 Concrete
EP3 + + 0.98 Concrete EP2 + + 0.88 Concrete
EP3 + + 0.99 Concrete EP3 + + 0.76 Concrete
EP3 + + 1.22 Concrete EP3 + + 0.78 Concrete
EP4 + + 1.03 Concrete EP3 + + 0.80 Concrete
EP1 + + 0.89 Concrete EP4 + + 0.73 Concrete
EP1 + + 0.87 Concrete EP1 + + 0.58 Concrete
EP1 + + 0.85 Concrete EP1 + + 0.64 Concrete
EP2 + + 0.88 Concrete EP1 + + 0.63 Concrete
EP3 + + 0.92 Concrete EP2 + + 0.67 Concrete
EP3 + + 0.93 Concrete EP3 + + 0.59 Concrete
EP3 + + 0.87 Concrete EP3 + + 0.55 Concrete
EP4 + + 0.81 Concrete EP3 + + 0.61 Concrete
EP1 + + 0.85 Concrete EP4 + + 0.57 Concrete
EP1 + + 0.83 Concrete EP1 + + 1.12 Concrete
EP1 + + 0.60 Polymer EP1 + + 1.06 Concrete
EP2 + + 0.55 Polymer EP1 + + 1.22 Concrete
EP3 + + 0.83 Concrete EP2 + + 1.05 Concrete
EP3 + + 0.80 Concrete EP3 + + 1.15 Concrete
EP3 + + 0.74 Polymer EP3 + + 1.17 Concrete
EP4 + + 0.60 Polymer EP3 + + 1.26 Concrete
EP1 + + 0.35 Polymer EP4 + + 1.16 Concrete
EP1 + + 0.27 Polymer EP1 + + 1.21 Concrete
EP1 + + 0.20 Polymer EP1 + + 1.05 Concrete
EP2 + + 0.12 Polymer EP1 + + 1.09 Concrete
EP3 + + 0.79 Concrete EP2 + + 1.11 Concrete
EP3 + + 0.70 Polymer EP3 + + 1.18 Concrete
EP3 + + 0.62 Polymer EP3 + + 1.03 Concrete
EP4 + + 0.53 Polymer EP3 + + 1.14 Concrete
EP1 + + 0.22 Polymer EP4 + + 1.07 Concrete
EP1 + + 0.17 Polymer
EP1 + + 0.11 Polymer
EP2 + + 0.05 Polymer
EP3 + + 0.61 Polymer
difference in behaviour produced by adhesive thickness can ade-
EP3 + + 0.52 Polymer
EP3 + + 0.45 Polymer quately be accounted for on the basis of cracks at the bondline
EP4 + + 0.37 Polymer developed during the solidification of the adhesive [1]. These
cracks serve to penetrate the de-icing fluid into the interface be-
tween the adhesive and the concrete. Absorption of the de-icing
is reduced to approximately 50% of its original strength obtained at fluid on the interfaces of a microcrack and of freezing and thawing
the laboratory conditions. On the other hand, significantly higher cycles would presumably result in a local lowering of bond
strength retention can be obtained at the saturated condition for strengths and institute a spreading pressure at the apex of the fis-
the EP3 adhesive formulation. This adhesive retains an excess of sure, with the resultant propagation of a crack along the lines of
65% of its original strength. The EP3 system can, therefore, be con- least resistance [122–138]. On the EP2-bonded concrete prism,
sidered to have an improvement over the EP1 system with regard 5 mm adhesive thickness does not have any pronounced effect
to hydrophobic character. The addition of filler to the EP1 and EP3 on the bond stability. This sample maintains a relatively constant
adhesive formulations produces a modest increase in flexural and high flexural strength at 60 cycles. This increase in bond stabil-
strength of concrete prisms bonded with this adhesive. This ity appears to be directly attributable to the influence of filler in
improvement appears to be due to the decrease in swelling stres- adhesive formulation. The addition of 74% by volume of quartz fil-
ses generated within the sample during the absorption of liquid ler to the EP1 adhesive formulation can reduce the magnitude of
water on the surface or within the voids in the concrete [117–121]. stresses developed on the solidification of the adhesive, and result
in a substantial increase in bond stability during freezing and
3.2. Effect of freezing and thawing thawing cycles [139–145]. After 80 cycles at 5 mm adhesive thick-
ness, similar effects are noted for the EP3-bonded concrete prisms.
The effects of freezing and thawing in the presence of NaCl on Despite this fact, the EP3-bonded concrete prism retains apprecia-
the bond stability of epoxy-bonded concrete prisms are listed in ble strength at 80 cycles. In contrast, the EP1-bonded concrete
Table 6. The results indicate that the transitions from cohesive fail- prism has very low flexural strength at 80 cycles. This result is to
ure mode in concrete to adhesional failure mode typically occur as be expected because the properties of the DGEBA adhesive cured
the number of cycle increases. The epoxy adhesives tested in this with TMHMD are different from that cured with TETA.
work continue to maintain the bond stability up to about 40 cycles. The bond stability after 80 cycles is maintained at adhesive
However, the adhesional failure is attained at 5 mm adhesive thicknesses up to 1 mm. In this case, the samples fail outside the
thickness for the concrete prism bonded with the EP1 adhesive for- joint area at a load less than the strength of the original concrete.
mulation as the number of cycles is increased from 40 to 60 cycles. As can be seen in Table 6, a decrease in the flexural strength of
The 49% decrease in flexural strength of this prism is observed. This epoxy-bonded concrete prisms from 12% to 39% is observed as
762 A. Çolak et al. / Construction and Building Materials 23 (2009) 758–767

the number of cycles is increased from 20 to 80 cycles. The rapid mately 5% of its original strength at 100 °C. The decrease in
rise in strength loss of the concrete with freezing and thawing cy- strength retention under high temperature is due to the vibration
cles can be explained by depending on a number of factors. The of chain segments of the epoxy adhesives. This motion weakens
stresses and strains generated within the samples are the result the cohesive forces between the molecules and thereby causes a
of hydraulic pressure developed during the freezing of de-icing softening of the material [160]. On the other hand, the EP3 and
fluid. However, this does not appear to be the only cause of con- EP4-bonded concrete prisms are less affected by such tempera-
crete deterioration. The osmotic pressure can be another source tures. They offer relatively high joint strengths at temperatures
of concrete deterioration. In addition, the chemical interactions be- up to 80 °C. This advantage is due to a decrease in the polymer seg-
tween the salt and the hydration products of the concrete may ment mobility [161].The introduction of methyl groups onto epoxy
have a drastic effect on the strength of concrete [146–159]. chains increases the cohesive energy and imposes a restraint on
the amount of softening [162–174]. A simultaneous decrease in
3.3. Effect of test temperature the strength retention capability at the short-term high tempera-
ture is also related to the adhesive thickness. The results listed in
Table 7 lists the modes of failure and the ratios of reduction in Table 7 clearly indicate that the strength retention for EP3-bonded
flexural strength of epoxy-bonded concrete prisms at a different concrete prisms in the temperature range of 80–100 °C decreases
test temperature. Figs. 1 and 2 show the retention of original approximately linearly with adhesive thickness as the adhesive
strength achieved at the laboratory conditions as a function of test thickness changes from less than 1–5 mm [175–180]. The same
temperature for epoxy adhesives. From these data, it is entirely is also valid for the EP1 adhesive formulation. The strength reten-
clear that the load-bearing capacity of the samples is greatly de- tion capability varies with adhesive formulation [181–186]. For
creased with increasing temperature. For example, the concrete example, the strength retention ability of EP4 at temperatures up
prism bonded with EP2 adhesive formulation retains approxi- to 100 °C is lower than that of EP3. When the EP3 and EP4 are com-

1.2

EP1 <1

1
EP1 1
Strength retention (Sd/Sc)

0.8 EP1 5

EP2 5
0.6

0.4

0.2

0
20 30 40 50 60 70 80 90 100
Test temperature (°C)

Fig. 1. Strength retention capability of EP1 and EP2-bonded concrete prisms at high temperature.

1.2

1
Strength retention (Sd/Sc)

0.8

0.6

EP3 <1
0.4
EP3 1

0.2 EP3 5

EP4 5

0
20 40 60 80 100
Test temperature (°C)

Fig. 2. Strength retention capability of EP3 and EP4-bonded concrete prisms at high temperature.
 A. Çolak et al. / Construction and Building Materials 23 (2009) 758–767 763

pared, this reduction may be attributed to the presence of filler in erties of concrete are quite different because large amounts of Mg
the EP4 system. The cause of this difference is the reduction in the atoms are present in the final structure of concrete. This leads to
resin content. The presence of high amount of filler in the resin the disruption of interfacial transitional zones between aggregate
may weaken the structure and adversely affect the adhesion char- and cement paste [213–218]. Therefore, the flexural strengths of
acteristics of the adhesive at high temperature [187–205]. the samples measured after 120 days of immersion in 15% MgCl2
The flexural strength of epoxy-bonded concrete prisms is inde- solution decrease sharply. The decrease in the strength due to
pendent of adhesive thickness up to about 40 °C. However, the MgCl2 is attributed primarily to the formation of magnesium–sili-
adhesion is adversely influenced by 5 mm adhesive thickness as cate–hydrate (M–S–H) within the concrete [219,220]. In the alka-
the test temperature is increased from 40 to 60 °C. On these sam- line concrete environment, the reaction of MgCl2 with Ca(OH)2
ples, where failure occurs in polymer, similar results are obtained takes place and gives rise to Mg(OH)2 and CaCl2 [221]. The
with EP1 and EP4 adhesive formulations. The flexural strengths Mg(OH)2 precipitated in the concrete structure probably contrib-
of these samples are found to be only to 60% of the original utes to the decrease in strength with increase in crystal growth
strength obtained at the laboratory conditions. On the other hand, pressure [222], but in this case the strength loses due to CaCl2
the flexural strength of EP3-bonded concrete prism is relatively are also involved. The CaCl2 affects the solubility of Ca(OH)2 and
less affected by 60 °C as compared to the effects shown for EP1, can accordingly exert a profound influence on the growth mecha-
EP2 and EP4. This sample having an adhesive thickness of 5 mm re- nism [223]. The CaCl2 can also form double salt such as Ca(OH)2-
tains an excess of 70% of its original strength obtained at the labo- CaCl2H2O [223–229]. An alternative is the reaction between C3A
ratory conditions. and CaCl2. The CaCl2 may react with C3A to form C3ACaCl2H2O,
At 80 °C test temperature, the load-bearing capacity of epoxy- which is an expansive salt [230].
bonded concrete prisms is governed by the epoxy adhesives, The damage mechanism is somewhat different for the concretes
increasing with a decrease in adhesive thickness. Indeed, under exposed to MgSO4. The flexural strengths of the epoxy-bonded
these conditions, a satisfactory result is only obtained by EP3 sys- concrete prisms measured after 120 days of immersion in MgSO4
tem having an adhesive thickness less than 1mm. The strength solution exhibit either a slight increase or no significant change.
retention capability of this system at temperatures up to about At 1.5% concentration of MgSO4 solution, the range of Sd/Sc values
80 °C is remarkably high. Even at 100 °C , Sd/Sc values as high as is approximately 1.05–1.26, while at 3% concentration of MgSO4
61% are observed for this system. Failure mode of these samples solution, values as low as 1.21 are observed. The increase in the
at high temperature is usually cohesive within the adhesive layer. strength of concrete due to MgSO4 is related to the formation of Ca-
This type of failure indicate that the adhesion strengths of epoxy SO42H2O and Mg(OH)2 in the hardened cement phase [231–237].
adhesives to concrete are higher than their cohesive strength. However, crystallization pressure of the newly-formed salts will
Figs. 1 and 2 show the strength retention of epoxy-bonded con- eventually reduce the strength of concrete to a level incapable of
crete prisms at high temperature. These figures are presented only sustaining even the mildest stresses.
for the purpose of giving a general picture of the direction and The crystallization pressure appears to concentrate in the bulk
magnitude of the property changes. The relative values in Figs. 1 phase of the concrete rather than at the concrete-adhesive inter-
and 2 may vary depending on the test method used, the test con- face. Since the voids in the regions near the crack surface are filled
ditions, and the specific composition of the adhesives. The strength with the polymer, the growth of crystals is substantially impeded
retention capabilities of these samples in the temperature range of and the interface retains its adhesion properties. In other words,
20–100 °C can be represented to a good approximation using a sec- the disruptive dislocations in these sites are held to a minimum.
ond or higher order polynomial. The constants could be deter- For this reason, failure occurs through the concrete rather than at
mined by using the relative values in Figs. 1 and 2, writing the the interface [60,74,75].
proposed equation using these values, and then solving the result-
ing equations simultaneously. However, it is important that equa- 4. Conclusions
tions be developed which can be used to predict adhesion
behaviour using a limited number of test data [206]. Therefore, 1. The decrease in flexural strength of epoxy-bonded concrete
the procedure for obtaining a solution consists of reducing the prisms is directly proportional to the sorbed water content,
number of constants in the equation and of formulating the desired with the greatest effect occurring at the saturated conditions.
solution in terms of adhesive properties [207,208]. 2. In freezing and thawing, the magnitude of the observed effects
It is seen from the above discussion that the strength retention generally increases proportionally with the number of cycles.
capabilities of epoxy adhesives tested in this study are quite low. Particularly at high cycles, the concrete prisms bonded with
This depends largely upon the molecular structure of adhesives EP2 and EP4 have much higher flexural strength than those
[209]. Attempts have been made to overcome the limitation caused bonded with EP1 and EP3.
by high temperature by reacting a high molecular weight epoxy 3. The strength retention capability of the epoxy-bonded concrete
with a phenolic resin. This type of adhesive is shown to retain in prisms at high temperatures depends on the adhesive formula-
excess of 50% of its room temperature strength at about 250– tions. Here, softening of the polymer determines the limit of its
300 °C [210–212]. use before any decomposition occurs. This limit for EP3 is some-
where in the range of 80–100 °C. The decrease in the load-bear-
3.4. Effect of corrosive environments ing capacity of EP2 and EP4-bonded concrete prisms at high
temperature is a result of the combined effects of the test tem-
The test results listed in Table 8 clearly indicate that an ade- perature and the stress concentrations around the inclusions
quate degree of chemical stability is obtained in the bondline by [97,238–291]. However, more important for the present discus-
the epoxy adhesives to corrosive environments such as MgCl2 sion are the adhesive thickness. In the case of samples tested at
and MgSO4. These chemical substances cause a change in the high temperature, it is found that as the adhesive thickness
strength of concrete. For example, 120 days of immersion in 10% increases, the load-bearing capacity decreases.
concentration of MgCl2 solution causes a reduction of about 12– 4. No deterioration is observed at the interface between epoxy
29% in the flexural strength of epoxy-bonded concrete prisms. adhesives and concrete after 120 days of immersion in 10%
The increase in the concentration of MgCl2 generally results in an and 15% concentration of Mg(Cl)2 solutions. This phenomenon
increased degree of damage in the concrete. In this case, the prop- only occurs in concrete. This is reflected by the observed
764 A. Çolak et al. / Construction and Building Materials 23 (2009) 758–767

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