Strength Developments and Deformation Characteristics of MMA-Modified Vinyl Ester Polymer Concrete
International Journal of Concrete Structures and Materials
Strength Developments and Deformation Characteristics of MMA-Modified Vinyl Ester Polymer Concrete
Nan Ji Jin
This study investigated the strength developments and deformation characteristics of methyl methacrylate (MMA)modified vinyl ester polymer concrete, with MMA contents and curing temperatures as test variables. To lower the viscosity of the vinyl ester resin applied as a binder, an MMA monomer was added. In this study, the developed 168-h compressive and flexural strengths were 43.8-77.2 and 18.2-21.8 MPa, respectively. Also, these values decreased as MMA contents increased and curing temperatures decreased. The coefficient of thermal expansion ranged from 10.82 9 10-6 to 14.23 9 10-6/ C, and it decreased as an MMA content increased. The ultimate compressive strain ranged from 0.00391 to 0.00494, which decreased with an increase in MMA contents and notably decreased with a decrease in curing temperatures. The modulus of elasticity tended to decrease as MMA contents increased and curing temperatures decreased.
polymer concrete; vinyl ester resin; compressive strength; flexural strength; thermal expansion coefficient; modulus of elasticity
Concrete-polymer composites are generally one of three
classifications, i.e., polymer-modified (or cement) concrete
(PCC), polymer concrete (PC), or polymer-impregnated
(Chandra and Ohama 1994)
. Both PCC and
PC have been in commercial use since the 1950s and PIC has
been in use since the 1970s
(Mehta and Monteiro 2006)
representative characteristic of polymer concrete is rapid
hardening. The hardening time of polymer concrete is much
faster than the hardening time of ordinary portland cement
concrete. Therefore, by applying polymer concrete, the curing
time of cast-in-place applications can be reduced and the
productivity of precast construction products can be
enhanced. Hence, it is applied for cast-in-place applications
and precast construction applications such as building panels,
utility boxes, and underground junction boxes. Also, polymer
concrete is employed mainly as a patching material to fill
minor damages and to overlay damaged concrete bridge
(Chandra and Ohama 1994; Fowler 1989)
The binder principally used to produce polymer concrete
is a thermosetting resin (e.g., unsaturated polyester, epoxy,
acrylic, and vinyl ester). Also, apparent differences existed
in the physical and mechanical properties depending on the
type of binder
(Haddad et al. 1983; Hyun and Yeon 2012;
. In addition, studies to improve the properties
of these binders have been actively conducted
Yeon 2012; Son and Yeon 2012)
In this study, vinyl ester resin was chosen as a binder. Due
to its excellent chemical and corrosion resistances coupled
with outstanding heat resistance, it is suitable for practical
applications, such as in swimming pools, sewer pipes, and
solvent storage tanks
(Cao and Lee 2003; Cook et al. 1997)
An MMA monomer used in this study as a reforming
agent has low viscosity, and thus is effective in lowering the
viscosity of generally high viscosity resins. Also, it not only
has excellent chemical and corrosion resistances but also
high bond strengths
(Hyun and Yeon 2012)
. By taking the
advantages of vinyl ester resin and an MMA monomer, it is
possible to lower the viscosity of the binder, as well as
improve workability and various properties of polymer
concrete. However, despite these advantages of MMA
monomer-modified vinyl ester resin, there are few existing
studies except for research on evaluating the setting
shrinkage characteristics of MMA-modified vinyl ester
(Choi et al. 2016)
Thus, in this study, polymer concrete using MMA
monomer-modified vinyl ester resin is applied as a binder to
examine the effects of MMA contents and curing
temperatures on compressive strengths, flexural strengths, the
Fig. 1 Flow and viscosity characteristics with respect to
binder and MMA contents.
coefficient of thermal expansion, and the modulus of
elasticity. The ultimate purpose of this study is to examine the
strength developments and deformation characteristics at
various MMA contents and curing temperatures. Hence, the
fundamental material properties determined in this study can
be referred to by designers or contractors who have decided
to apply vinyl ester polymer concrete in both cast-in-place
and precast construction applications.
2.1 Vinyl Ester Resin
Vinyl ester (VE) resin is an adduct of epoxy resin and an
unsaturated carboxylic acid such as acrylic or methacrylic
(Martin et al. 2000)
. This vinyl ester resin can be cured
at room temperature and its curing time can be easily
controlled by the amounts of initiator and promoter. The vinyl
ester resin applied as the main binder in this study was a
bisphenol A epoxy-based vinyl ester resin, and its properties
are listed in Table 1.
Density (25 C)
Density (25 C)
Density (25 C)
Styrene content (%)
Bulk density (kg/m3)
Moisture content (%)
2.2 MMA Monomer
Methyl methacrylate (MMA) is a colorless liquid, made by
producing methacrylic acid through the oxidization of C4
raffinate-extracted isobutylene in a gaseous state and then
esterifying the methacrylic acid with methanol. In general,
the characteristics of MMA include excellent transparency,
strong weather resistance, and good colorability. MMA was
applied as a modifier of vinyl ester resin in this study, the
properties of which are shown in Table 2.
An initiator and a promoter should be added to harden the
vinyl ester resin. A dimethyl phthalate (DMP) solution with
55% methyl ethyl ketone peroxide (MEKPO) was applied as
Fig. 4 Curing age versus compressive strength with MMA
content. a 20 C, b 10 C, c 0 C.
an initiator for vinyl ester resin. The properties of the
initiator are listed in Table 3.
Vinyl ester resin and MMA do not react with each other in
a copolymerization state when only an initiator is added.
Accordingly, to initiate a quick curing reaction, a promoter is
required. In this study, cobalt naphthenate, which enables
polymerization at both room temperatures and low
temperatures, was used as a promoter. The properties of the
promoter are presented in Table 4.
2.5 Aggregate and Filler
For this study, silica sand was applied as an aggregate. The
physical properties of the aggregate used are shown in
3.1 Determination of Mixture Proportions
In this study, optimum mixture proportions were selected
based on a series of trial tests on slump loss and strength.
The optimum mixture proportions can be achieved when
maximizing the amount of aggregate, while minimizing the
amount of polymer binder, as long as a certain degree of
workability and strength is respectively ensured. The binder
content was determined according to ASTM C1437-15
(Standard Test Method for Flow Cement Mortar). Figure 1
shows the changes in mortar flow for different amounts of
binder and the changes in viscosity for MMA contents
simultaneously. Based on these test results, the polymeric
binder formulations and the mixture proportions of the
polymer concrete were determined, as shown in Table 8.
3.2 Strength Test
The compressive strength test was conducted according to
ASTM C 579 (Standard test Method for the Compressive
Strength of Chemical-Resistant Mortars, Grouts, Monolithic
Surfacings, and Polymer Concretes), and the flexural
strength test was conducted pursuant to ASTM C 293
(Standard Test Method for the Flexural Strength of
Concrete). In this study, [5 9 10 cm cylindrical specimens
were used for the compressive strength test, and
4 9 4 9 16 cm prism specimens were used for the flexural
strength test. The strength test was conducted using a 20-t
universal testing machine (Instron 8502).
3.3 Coefficient of the Thermal Expansion Test
The coefficient of the thermal expansion test was
conducted referring to RILEM TC 113-CPT (PC-13 Method to
Test for the Coefficient of Thermal Expansion of Polymer
Concrete and Mortar). Each specimen was
100 9 100 9 400 mm, and three parallel specimens were
made under identical conditions for each batch and were
cured for 7 days at the room temperature (20 ± 5 C). The
thermal expansion test setup is shown in Fig. 2. The TC
113CPT proposes the following formula for the thermal
where L is the thermal expansion rate, lo is the length before
heating, and l is the length measured at each temperature.
Furthermore, the TC 133-CPT proposed the following
formula for calculating the coefficient of thermal expansion.
L ¼ ðl loÞ=lo
a ¼ De=Dt
where a is the coefficient of thermal expansion, De is the
thermal expansion rate according to the temperature
difference, and Dt is the temperature difference.
3.4 Modulus of Elasticity Test
The modulus of elasticity test was conducted as per ASTM
C 469M (Standard Test Method for the Static Modulus of
Elasticity and Poisson’s Ratio of Concrete in Compression),
and the strain was measured with a Data Logger (Tokyo
Sokki, TDS-602) by attaching a wire strain gauge (30 mm).
The compressive strength test was executed with
[5 9 10 cm cylindrical specimens to determine the
modulus of elasticity, as shown in Fig. 3.
The modulus of elasticity was calculated as follows:
E ¼ ðS2
where E is the modulus of elasticity (MPa), S1 is the stress
for longitudinal strain of 0.00005 (MPa), S2 is the stress
corresponding to 40% of ultimate stress (MPa), and e2 is the
longitudinal strain caused by the stress.
4. Results and Discussion
4.1 Compressive Strength
The compressive strength developments according to
MMA contents and curing temperatures are shown in Figs. 4
and 5, respectively. As seen in the results, the compressive
strength tended to rapidly increase until 24 h but increased
slowly thereafter until 168 h. This tendency varied
depending on MMA contents and curing temperatures, with 168-h
compressive strength of 43.8–77.2 MPa. These compressive
strength values are lower than those of other types of
(Haddad et al. 1983; Hyun and Yeon 2012;
Son and Yeon 2012)
As shown in Fig. 4, the compressive strengths tended to
decrease as MMA contents increased from 0–2.5 and 5 wt%.
As a result, the range of the decreased compressive strength
at the age of 168 h was 2.4–6.2 MPa. This compressive
strength decreased with an increase of an MMA content
appears to be due to the phase separation phenomenon (the
repulsive force occurring between the interfaces of different
materials and preventing complete synthesis)
In previous studies,
Hyun and Yeon (2012)
stated that in
UP-MMA polymer concrete, an increase in an UP-MMA
ratio (ratio of UP to MMA) to 8:2, 7:3, and 6:4 led to a
decrease in the compressive strength.
Patel et al. (1990)
stated that an increase in the styrene monomer content of
vinyl ester resin resulted in larger strength reductions,
similar to the results of this study.
Figure 5 shows the compressive strength changes
according to the curing temperatures (20, 10, 0, and
- 10 C). According to Fig. 5, lower curing temperature led
to a notable decrease in the compressive strength. The extent
of the compressive strength reduction according to the
curing temperature was greatest at 3 h, and gradually decreased
over time. The notable characteristics of the compressive
strength development were that a lower curing temperature
led to a sharp increase in compressive strength at an early
age whereas it led to a lower compressive strength at 3 h.
At 168 h, the compressive strengths (at curing temperature
of 20 and - 10 C) were 77.2 and 49.7, 76.0 and 48.8, and
74.8 and 43.8 MPa with MMA contents of 0, 2.5, and
5 wt%, respectively, indicating a 28.5 MPa reduction on
average. These results show that the curing temperature had
a significant effect on the strength development of
MMAmodified vinyl ester polymer concrete. In particular, at the
age of 168 h, the measured compressive strength was lowest
at 43.8 MPa with an MMA content of 5 wt% and a curing
temperature of - 10 C, which was much higher than the
28-day compressive strength for portland cement concrete
(4.8 MPa) and high-performance concrete (30.6 MPa) at
- 5 C curing temperature
(Cook et al. 1997)
. This study
Fig. 9 Curing age versus flexural strength with curing
temperature. a MMA 0 wt%, b MMA 2.5 wt%, and c MMA 5
result shows that MMA-modified vinyl ester polymer
concrete develops the high strength (even at a low temperature).
To obtain more detailed information on the effects of
MMA contents on the compressive strength, Fig. 6 shows
that each relative gain of compressive strength was
determined after comparing with 0 wt% MMA content as criteria
of an MMA content. Also, Fig. 7 shows that each relative
gain of compressive strength was determined after
comparing with 20 C curing temperature as criteria to investigate
more specific information on the compressive strength
relating the effects of curing temperatures. Figure 6 shows
that the relative gains of the compressive strengths were
compared with criteria of an MMA content (0 wt% MMA
content) from the age of 3 h to the age of 168 h. The results
show that the relative gains of the compressive strengths
regarding 5 wt% MMA content were from 74.8 to 93.5%.
Meanwhile, the relative gains of the compressive strengths
regarding 2.5 wt% MMA content were from 91.4 to 97.4%.
These results show a lower relative gain with an increase in
In addition, Fig. 7 shows that the relative gains of the
compressive strengths were compared with criteria of a
curing temperature (20 C) from the age of 3 h to the age of
168 h. The results show that the relative gains of the
compressive strengths regarding 10 C curing temperature were
from 40.6 to 86.4%. Plus, the relative gains of the
compressive strengths regarding 0 C curing temperature were
from 10.6 to 75.3%. Moreover, the relative gains of the
compressive strengths for - 10 C curing temperature were
from 5.8 to 62.5%. Thus, these results show a notably lower
relative gain with a decrease in curing temperatures.
Thus, compared to ordinary portland cement concrete
(with a water/cement ratio of 0.6), whose compressive
strength development was 11, 41, and 68% at 1, 3, and
7 days, respectively
, polymer concrete had
the high compressive strength even at a very early age.
According to the previously mentioned results, the relative
gains of compressive strengths of MMA-modified vinyl ester
polymer concrete decreased with an increase of MMA
contents and a decrease in curing temperatures, and curing
temperatures had a more sensitive effect than MMA contents
on strength developments.
4.2 Flexural Strength
The results by ages of the flexural strength test according
to MMA contents and curing temperatures are shown in
Figs. 8 and 9, respectively. In these figures, the development
of the flexural strength tends to rapidly increase until the age
Fig. 11 Relationship between temperature and thermal
expansion. a MMA 0 wt%, b MMA 2.5 wt%, and
c MMA 5 wt%.
of 24 h. But it slowly increases until the age of 168 h. The
168-h flexural strength was affected by both MMA contents
and curing temperatures. According to MMA contents, the
changes of the flexural strength developments are shown in
Fig. 8. The development of the flexural strength decreased
when an MMA content was increased to from 2.5 to 5 wt%,
compared to an MMA content of 0 wt%. As a result, the
magnitude of the decreased flexural strength was from 0.9 to
2.2 MPa at the age of 168 h. According to the flexural strength
test results regarding the curing temperatures (20, 10, 0, and
- 10 C) applied in this study, the flexural strengths were
notably decreased as the curing temperature is decreased as
shown in Fig. 9. According to the curing temperature, the
decreased magnitude of the flexural strength was greatest at
the age of 3 h and gradually became weaker over time. At
168 h, the developed flexural strengths at curing temperatures
of 20 and - 10 C were 21.8 and 19.4 MPa for 0 wt% MMA,
20.9 and 18.4 MPa for 2.5 wt% MMA, 19.6 and 18.2 MPa
for 5 wt% MMA, respectively. Based on these investigations,
the identified reduction of the flexural strength was 2.1 MPa
on average. According to these results, it was determined that
the effects of MMA contents and curing temperatures on the
flexural strength developments are very similar to the results
regarding the effects of MMA contents and curing
temperatures on the compressive strength results.
The data obtained by compressive and flexural strength
tests were applied to a regression analysis to define their
relations and the results of a regression analysis are shown in
Fig. 10. The compressive strength-flexural strength
regression equation, obtained by analyzing the data, was
y = 10.778x - 143.89 with a coefficient of determination
R2 of 0.8961. Thus, once either the compressive strength or
the flexural strength is determined, this equation can be
applied to estimate a corresponding value of the compressive
strength or a corresponding value of the flexural strength.
4.3 Coefficient of Thermal Expansion
The thermal expansion rates of vinyl ester polymer
concrete according to MMA contents are shown in Fig. 11.
Also, the coefficients of thermal expansion calculated based
on Fig. 11 is shown in Table 9. In Fig. 11, the maximum
thermal expansion rates were 890 9 10-6, 821 9 10-6, and
672 9 10-6 at MMA contents of 0, 2.5, and 5 wt%,
respectively. The relation between the test temperature and
the coefficient of thermal expansion can be defined as a
linear regression equation, and the coefficient of
determination R2 was 0.9 or higher, showing a high correlation. As
shown in Table 9, the coefficients of thermal expansion were
14.23 9 10-6, 13.25 9 10-6, and 10.82 9 10-6/ C for
MMA contents of 0, 2.5, and 5 wt%, respectively, thus
showing a decreasing trend as MMA contents increased.
This shows that adding MMA is effective in reducing the
coefficient of thermal expansion. The coefficients of thermal
expansion were measured under the temperature range from
20 to 80 C for this study. But the coefficients of thermal
expansion could be increased if more practical temperature
range from 20 to 60 C was applied.
The thermal expansion coefficient test results from this
study were lower than those of previous studies (UP-MMA
polymer concrete’s coefficient of thermal expansion was
21.6 9 10-6 to 31.2 9 10-6/ C, epoxy polymer mortar was
28.60 9 10-6/ C, unsaturated polyester polymer mortar was
23.00 9 10-6/ C, and PMMA polymer mortar was
21.50 9 10-6/ C)
(Omata et al. 1995; Yeon and Yeon 2012)
and were similar to the results for ordinary portland cement
concrete (11.1 9 10-6/ C) (Omata et al. 1995).
MMA content (wt%)
4.4 Modulus of Elasticity
The static modulus of elasticity for a material under
tension or compression is given by the slope of the stress–strain
curve for concrete under uniaxial loading. Since the stress–
strain curve for portland cement concrete is nonlinear, three
types of elastic modulus existed: tangent modulus, secant
modulus, and chord modulus. In this study, compressive
loading was applied, and the secant modulus, among those
three types, was defined. The secant modulus is given by the
slope of a line drawn from the origin to a point on the curve
corresponding to a 40% stress of the failure load
The effects of curing temperatures on the compressive
stress–strain curves according to MMA contents are shown
in Fig. 12. Also, the modulus of elasticity was calculated,
and the results are shown in Table 10. The ultimate strains,
being 0.00406–0.00494, 0.00401–0.00481, and
0.00391–0.00485 at MMA contents of 0, 2.5, and 5 wt%,
respectively, tended to decrease with an increase in MMA
contents and to notably decrease with a decrease in curing
temperatures. These determined ultimate strains in this study
are similar to UP-MMA polymer concrete’s ultimate strains
(Yeon and Yeon 2012)
. However, those
values are lower than the ultimate strains of PMMA polymer
(Son and Yeon 2012)
Lastly, Table 10 shows that the modulus of elasticity
ranged from 2.24 9 104 to 2.90 9 104 MPa. The elastic
modulus values tended to decrease as MMA contents
increased and curing temperatures decreased. These elastic
modulus values are lower than that of portland cement
concrete (3.6 9 104 MPa) when the development of a
compressive strength is 60 MPa
and that of
UP-MMA polymer concrete (2.8 9 104 to 3.3 9 104 MPa)
(Yeon and Yeon 2012)
This study investigated the strength developments and
deformation characteristics of MMA-modified vinyl ester
polymer concrete with different MMA contents (0, 2.5, and
5 wt%) and curing temperatures (- 10, 0, 10, and 20 C).
The results of this study can be summarized as follows:
According to the results of compressive strength tests,
the range of the compressive strength was between
43.8 and 77.2 MPa at the age of 168 h. The identified
range of the compressive strength of MMA-modified
vinyl ester polymer concrete was lower than the
compressive strength range of other types of polymer
concrete. Also, the compressive strength tended to
decrease with an increase in MMA contents and a
decrease in curing temperatures.
The flexural strength test results showed that the range
of flexural strength was between 18.2 and 21.8 MPa at
the age of 168 h. The flexural strengths also decreased
when MMA contents were increased and the curing
temperatures were decreased.
The coefficients of thermal expansion were
14.23 9 10-6, 13.25 9 10-6, and 10.82 9 10-6/ C
for 0, 2.5, and 5 wt% MMA contents, respectively,
showing a decrease with an increase in MMA contents.
According to the results of strain measurements, the
ultimate strain varied between 0.00391 and 0.00494.
The measured strains tended to decrease with an
increase in MMA contents and to notably decrease
with a decrease in curing temperatures. The values
were similar to or slightly lower than those of other
types of polymer concrete.
The range of the elastic modulus was between
2.24 9 104 and 2.90 9 104 MPa. It was found that
the modulus of elasticity decreased with an increase in
MMA contents and a decrease in curing temperatures.
The values were lower than those of ordinary portland
cement concrete or other types of polymer concrete.
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