Article

Effect of Epoxy Latexes on the Mechanical Behavior and

Porosity Property of Cement Mortar with Different Degrees of
Hydration and Polymerization
Pengfei Li 1, Wei Lu 1, Xuehui An 2,*, Li Zhou 2 and Sanlin Du 3

1 Harbor, Waterway and Coastal Engineering, Chongqing Jiaotong University, Chongqing 400074, China;
[email protected] (P.L.); [email protected] (W.L.)
2 State Key Laboratory of Hydroscience and Engineering, Tsinghua University, Beijing 100084, China;

[email protected]
3 Huaneng Tibet Hydropower Safety Engineering Technology Research Center, Tibet 860000, China;

[email protected]
* Correspondence: [email protected]

Abstract: In this study, an analysis of the influence of polymer modification on the mechanical be-
havior, porosity, and microstructure of mortar is carried out. Epoxy latexes contents of 5%, 10%,
15%, and 20% of cement were employed in the preparation of cement mortars based on the same
workability. The specimens were subjected to dry, wet, and wet–dry curing regimes. Compressive
strength, flexural strength, Mercury intrusion porosimetry (MIP), and scanning electronic micro-
scope (SEM) tests were conducted to analyze the effect of epoxy latexes on the mechanical property
and porosity of modified mortars. Based on the compressive strength test results, a quantitative
method was established to calculated the degree of hydration and polymerization. The results show
that the mechanical behavior and porosity property of epoxy latexes modified mortar are influenced
by the degree of hydration, the degree of polymerization, and the volume changing effect of mortar.
The polymerization of epoxy latexes could improve the flexural strength of the mortar. The
Citation: Li, P.; Lu, W.; An, X.; Zhou,
macropores of specimens tended to decrease with the increase of the degree of epoxy latexes
L.; Du, S. Effect of Epoxy Latexes on
polymerization and cement hydration. In practical engineering, it is necessary to ensure the degree
the Mechanical Behavior and
of hydration and increase the polymerization rate. Thus, the wet–dry curing regime is recom-
Porosity Property of Cement Mortar
mended.
with Different Degree of Hydration
and Polymerization. Materials 2021,
14, 517. https://doi.org/10.3390/
Keywords: epoxy latexes modified mortar; mechanical property; porosity; degree of hydration; de-
ma14030517 gree of polymerization

Received: 09 December 2020

Accepted: 18 January 2021
Published: 21 January 2021 1. Introduction
Concrete is the most widely used material in China's hydropower construction
Publisher’s Note: MDPI stays neu-
thanks to its low cost and relatively good strength in compression. Concrete structures
tral with regard to jurisdictional
often suffer various deteriorations caused by the ambient environment, such as frost dam-
claims in published maps and insti-
age, carbonation, corrosion, alkali–aggregate reaction, and so on [1]. In the construction
tutional affiliations.
of hydropower, the extreme environmental conditions put forward higher requirements
for the properties of concrete materials. Polymer latexes modified mortar (PMM) and con-
crete (PMC) have been widely used as construction materials in the past decades to over-
Copyright: © 2021 by the authors. come some disadvantages of conventional cement-based materials, such as brittleness and
Licensee MDPI, Basel, Switzerland. deformation property [2,3]. As the composite material combines the advantages of poly-
This article is an open access article mer and concrete, PMM and PMC can effectively improve the properties of concrete struc-
distributed under the terms and con- tures.
ditions of the Creative Commons At- With the recent development in the polymer material technologies fields, applica-
tribution (CC BY) license (http://cre- tions of polymer are more and more extensive. Innovative strengthening strategies have
ativecommons.org/licenses/by/4.0/). been developed, based on externally bonded fiber-reinforced polymer and fiber-

Materials 2021, 14, 517. https://doi.org/10.3390/ma14030517 www.mdpi.com/journal/materials

Materials 2021, 14, 517 2 of 23

reinforced cementitious matrix systems, to improve the capacity of existing structures in

order to guarantee the safety of masonry structures [4–6]. Furthermore, organic–inorganic
nanocomposite materials possess unique properties as new materials and compounds for
academic research as well as for the development of innovative industrial applications
[7,8]. In classical nanocomposites, the addition of nanofillers to a polymer matrix allows,
in principle, the tailoring of physical properties. The resulting composite might exhibit
improved thermal, mechanical, rheological, electrical, catalytic, fire retardancy, and opti-
cal properties [9–15]. The basic multifunctional feature of these nanocomposite materials
makes them potentially applicable in various areas in high added-value applications such
as adsorbents of toxic metal ions, smart coatings for corrosion protection, nanoscopic re-
actors, and so on.
In general, polymer latexes were used as a cement modifier and will form flexible
polymer films in polymer-modified cement-based material [16,17]. The polymer–cement
co-matrix consists of polymer films, hydration products, and cement particles, which can
significantly improve the tensile strength, flexural strength, impermeability, and chemical
resistance of cement-based material [18–20]. Various types of polymer latexes such as sty-
rene-butadiene rubber (SBR) latex, ethylene-vinyl acetate (EVA) latex, and styrene-acry-
late copolymer (SA) latex have been tested to assess their effect on the material properties
at the macro-scale and micro-scale [21–25]. Among these polymer latexes, epoxy latexes
are widely used in PMC and PMM thanks to their excellent mechanical properties, dura-
bility, and the controllable process of polymerization [26–28].
Numerous test programs have been conducted to study the effect of epoxy latexes on
the properties of cement-based materials. The test results show that the flexural strengths
and ductility of PMM and PMC are increasing significantly, while the compressive
strengths are quite discrete. Aggarwal et al. [26] pointed out that the compressive
strengths of the mortar increase with the epoxy–cement ratio. Ariffin et al. [29] found that,
when the epoxy latexes content increased beyond 10%, the compressive strength declined.
Jo [30] pointed out, in contrary reports, that the compressive strengths of the mortar de-
crease with the increase of epoxy latexes. Therefore, it is difficult to directly predict the
modification effect of epoxy latexes from macroscopic indicators. The properties of PMM
are governed by both the process of cement hydration and the epoxy polymerization
[31,32]. The properties of PMM should be analyzed based on the coupled effect of hydra-
tion and polymerization. It has been reported that the addition of polymer latexes has a
significant retardation effect on the cement hydration process [33–35]. Kong et al. [31,33]
conducted experiments to investigate the effect of copolymer latexes on cement hydration
and proposed the retardation mechanism of polymer latexes as two modes: chemical re-
tardation and physical retardation. Zhang and Yan [34] investigated the retardation effect
of epoxy resin on hydration kinetics at different temperatures. The test results show that
the cumulative hydration heat of epoxy modified cement was relatively smaller than that
of conventional cement. The retardation effect of epoxy latexes may be the reason for the
scattering of the compressive strength results. Tian et al. [35] examined the microstructure
formation of polyacrylate latex modified mortars and confirmed that polymer latexes will
introduce big pores to cement mortars, which will increase the total porosity of PMM. The
higher total porosity will lead to a decrease in the compressive strength [36]. Ma and Li
pointed out that the contrary reports may be caused by the different manners in which
the polymer latexes were added [37].
In general, the tensile strength, flexural strength, and deformation properties of PMM
and PMC are relatively higher compared with the conventional cement-based materials
[38,39]. It has been reported that the improvement of the tensile and flexural strength de-
pends mainly on the polymer content rather than the water–cement ratio [40]. This phe-
nomenon could be explained by the excellent tensile properties of polymer films and the
forming of the polymer–cement co-matrix [17]. Polymer film will be formed within its
applicable temperature and physical–chemical conditions. Some models have been pro-
posed to illustrate the modification mechanism of the phenomenon. Ohama’s three-step
Materials 2021, 14, 517 3 of 23

model is the most widely accepted method in describing the formation process of the pol-
ymer–cement co-matrix [41]. As the model illustrated, polymer particles will be close-
packed on the surfaces of cement and then coalesce into a continuous film. Several inte-
grated models were established based on the three-step model to consider the chemical
interaction between polymer and cement [42,43]. For the PMM and PMC, polymer latexes
were usually used in combination with harder ones to achieve a higher rate of polymeri-
zation. Numerous studies also show that epoxy resin can be polymerized in the presence
of hydroxyl ions without hardener [44,45]. The polymerization degree of epoxy has a sig-
nificant influence on the mechanical properties of modified cement-based materials.
Therefore, it is important to quantify the process of cement hydration and epoxy resin
polymerization and clarify the effect of the coupled process on the properties of epoxy
modified mortar.
In this research, polymer-modified mortars using epoxy latexes with hardener were
prepared with various epoxy latexes contents and curing conditions. Compressive and
flexural strength were tested to evaluate the effectiveness of modification. Mercury intru-
sion porosimetry (MIP) tests were conducted to analyze the effect of epoxy latexes on the
porosity of modified mortar. Scanning electronic microscope (SEM) tests were used to
evaluate the influence of epoxy latexes on the morphologies of the co-matrix. Based on the
experimental results, a quantitative method was established to clarify the degree of ce-
ment hydration and epoxy resin polymerization. The effects of these two parameters on
the properties of modified mortars were analyzed and discussed.

2. Materials and Methods

2.1. Materials
2.1.1. Raw Materials
Type PO42.5 ordinary Portland cement with a relative density of 3080 kg/m3 was
adopted in this research. The specific area of the cement was 390 m2/kg. Well-graded man-
ufactured quartz sand with a specific gravity of 2700 kg/m3 was employed as fine aggre-
gates. The particle sizes of manufactured sand range from 0.075 mm to 4.75 mm. The par-
ticle size distribution curves of manufactured sand are shown in Figure 1.

Figure 1. Particle size distribution curves of manufactured sand.

2.1.2. Epoxy Latexes

Epoxy latexes were prepared by emulsifying epoxy resin, based on bisphenol A-type
epoxy resin and curing agent in water using an emulsifier. As shown in Figure 2, the
epoxy latexes material was a three-part based mixture, which consists of part A: an epoxy
resin, part B: an epoxy resin hardener (composed of curing agent and emulsifier), and part
C: water. In addition, the epoxy resin hardener is a self-emulsifying epoxy curing agent
Materials 2021, 14, 517 4 of 23

with the model QS-R06, which is a water-soluble curing agent formed from a variety of
modified amines. The prepared epoxy resin had a density of 1.00–1.05 g/cm3, epoxide
equivalent value of 200–300 g eq, and total solids of 99.9%. The epoxy resin hardener had
a density of 1.00–1.05 g/cm3 and total solids of 50%.

Figure 2. The images of epoxy latexes material of the unmixed stage and mixed stage and the
high-speed shear dispersing emulsification tools.

In this investigation, a high-speed shear dispersing emulsification tool was used for
mixing the epoxy latexes, as shown in Figure 2. The shearing speed of the tool was 3500
r/min during mixing. As mentioned, the epoxy latexes were composed of three parts (part
A, part B, and part C). Before mixing, all components were accurately weighed according
to the mix proportion, as listed in Table 1. The epoxy resin and hardener were mixed to-
gether in advance for 3 min, and then water was added for shear for another 3 min to
obtain epoxy latexes. The mix proportions of epoxy latexes obtained in this research are
shown in Table 1. The total solid content ratio was set and maintained at 50%.

Table 1. Mix proportions of epoxy latexes (wt %).

Mix Label Epoxy Resin Hardener Water

epoxy emulsion 28.57 42.86 28.57

2.1.3. Mixture Proportions and Specimen Preparation

The mix proportions of epoxy latexes modified mortar were designed based on that
of a self-compacting mortar. The mix proportions of self-compacting mortar were selected
based on our previous research [46–50], which has been used in Chinese engineering. For
all the mortars, the volume water/cement ratio (Vw/Vc) was set and maintained at 1.The
volume ratio of sand to cement was kept constant at 1.The epoxy resin to cement (P/C)
ratios of 0, 5%, 10%, 15%, and 20% were chosen to investigate the effect of various contents
of epoxy latexes. In addition, a kind of polycarboxylate-based superplasticizer (SP) was
used with density of 1.20 g/cm3 based on Chinese standard CECS 203:2006 [51], which
consists of air entraining agents, water reducing agents, viscosity modifiers, and so on.
The superplasticizer was the same as in the previous research [46–50]. With reference to
JC/T 986-2018 [52], the superplasticizer was added to ensure mortars have a flowability of
200 mm. The mix proportions of epoxy latexes modified mortars are listed in Table 2. It is
should be noted that the volume of water, cement, and sand was kept constant in the
experiment. With the mixing of epoxy latexes, the volume of modified mortar will in-
crease. The influence of volume increase on modified mortar is discussed in Results sec-
tion. Furthermore, P/C and L/C for the modified mortar consider the ratio of dry epoxy
resin to cement and epoxy latexes to cement, respectively. The hardener is incorporated
to ensure that the epoxy resin is fully hardened. AD is the quality of the superplasticizer
Materials 2021, 14, 517 5 of 23

mixed in the mortar to ensure the fluidity of the self-compacting mortar. The effect of the
hardener on the properties of mortar with epoxy latexes modification will be investigated
in the future.

Table 2. Mix proportions of epoxy latexes modified mortar (kg).

Mix Label Vw/Vc SP% P/C L/C C S W AD ER H

Control 1.1 1.4 0% 0% 832.69 1199.80 281.46 11.66 0 0
Latex 1 1.1 1.4 5% 8.7% 832.69 1199.80 281.46 11.66 41.63 31.23
Latex 2 1.1 1.4 10% 17.4% 832.69 1199.80 281.46 11.66 83.27 62.45
Latex 3 1.1 1.4 15% 26.1% 832.69 1199.80 281.46 11.66 124.90 93.68
Latex 4 1.1 1.4 20% 34.8% 832.69 1199.80 281.46 11.66 166.54 124.90
Notes: SP% is the superplasticizer dosage, and C, S, W, AD, ER, and H are the quality of cement,
sand, water, superplasticizer, dry epoxy resin, and dry hardener, respectively.

With reference to ISO 679:2009 [53], a standard laboratory mortar mixer was used to
prepare the mortars. All components were accurately weighed before mixing. The fine
aggregates and cement were initially blended and mixed for 1 min for all mixtures. Then,
the prepared epoxy latexes, water, and superplasticizer were added slowly into the mix-
tures and mixed for another 2 min.
Mortar cube specimens with the size of 70.7 mm × 70.7 mm × 70.7 mm were cast for
the compressive strength test and mortar prism specimens with the size of 40 mm × 40
mm × 160 mm were cast for the flexural test. After casting, the mixtures were covered with
plastic sheets to avoid water evaporation. After 2 days, all specimens were demoulded
and cured according to three different curing regimes.

2.1.4. Curing Regimes

To investigate the coupled effect of cement hydration and epoxy resin polymeriza-
tion on the properties of epoxy latexes modified mortar, dry curing, wet curing, and wet–
dry curing regimes were applied for all the mortar specimens.
Dry curing: after de-moulding, the mortar specimens were transferred into a stand-
ard curing chamber and cured under the standard environmental condition at a temper-
ature of 20 ± 1 °C and relative humidity of 60 ± 5% until the test age;
Wet curing: after de-moulding, the mortar specimens were immediately immersed
in a water chamber with a temperature of 20 ± 1 °C until the test age;
Wet–dry curing: after de-moulding, the mortar specimens were immediately im-
mersed in a water chamber with a temperature of 20 ± 1 °C for 5 d. Then, the mortar spec-
imens were transferred into a standard curing chamber and cured under the standard
environmental condition at a temperature of 20 ± 1 °C and relative humidity of 60 ± 5%
until the test age.

2.2. Testing Procedures

2.2.1. Compressive Strength
The compressive strength tests of mortar cube specimens were carried out at the ages
of 7 d, 14 d, 28 d, 45 d, 60 d, and 90 d with a standard compression test machine, according
to BS EN 12390 [54]. All the mortar specimens were tested up to failure with a constant
load rate of 1500 ± 200 N/s. For each parameter, three specimens were prepared and the
compressive strength of mortar cube specimens was calculated by the average of three
specimens, as shown in Equation (1):

Fc
fcm  (1)
A,
Materials 2021, 14, 517 6 of 23

where fcm represents compressive strength, Fc is the total maximum load, and A is the area
of the loaded surface (70.7 mm × 70.7 mm = 4998.49 mm2).

2.2.2. Flexural Strength

The flexural strength tests of mortar prism specimens were carried out using a uni-
versal test machine at the ages of 7 d, 14 d, 28 d, 45 d, 60 d, and 90 d, according to standard
ISO 679:2009 [53]. The tests were conducted under a load control mode with a constant
loading rate of 50 N/s. For each parameter, three specimens were loaded up to failure. The
average flexural strength of mortar prism specimens can be calculated by Equation (2):

1 .5 F f L
f fm  2
(2)
bt ,
where ffm represents flexural strength; Ff is the peak load; L (100 mm) is the distance be-
tween the support points; and b (40 mm) and t (40 mm) are the width and height of the
cross-section of the specimens, respectively.

2.2.3. MIP
The porosity and pore size distribution of mortar specimens were measured by the
mercury intrusion test using a Micromeritics Poresizer model AutoPore IV 9500 (Mi-
cromeritics Instrument Corporation, Norcross, GA, USA). The mortar specimens were col-
lected from the crushed specimens in compressive tests at the ages of 7 d, 14 d, 28 d, 45 d,
60 d, and 90 d.

2.2.4. SEM
SEM tests were carried out to clarify the morphologies of epoxy latexes modified
mortars. Test specimens were also collected from the crushed specimens in compressive
tests at the ages of 7 d, 14 d, 28 d, 45 d, 60 d, and 90 d. All the specimens were etched with
ethanol for 24 h and coated with a plastic film before the test. Magnifications ranged be-
tween 5000× and 20,000×.

3. Results
3.1. Compressive Strength
The P/C ratios varied from 0 to 20%. The relationship between the epoxy latexes con-
tent and the compressive strength of mortar specimens with different curing regimes at
the ages of 7 d, 14 d, 28 d, 45 d, 60 d, and 90 d is shown in Figure 3. In general, the com-
pressive strength of epoxy modified mortars tended to decrease with the increase of the
P/C ratios. In the case of dry curing, the compressive strengths of mortars with different
P/C ratios had a reduction of 30–45% compared with control mortars without epoxy la-
texes at the age of 90 d. A similar tendency could be observed in the wet curing and wet–
dry curing regimes. The result is consistent with the literature [55,56] inclusion of polymer
latexes in cement mortar and concrete decreases compressive strength. The reduction in
compressive strength may be caused by both the retardation effect of epoxy latexes on
cement hydration and the change of the volume of mortar in unit volume, which will be
discussed in the next section.
Materials 2021, 14, 517 7 of 23

(a) (b)

(c)
Figure 3. Compressive strength of epoxy latexes modified mortar: (a) dry curing, (b) wet curing,
and (c) wet–dry curing.

Figure 4 shows the development paths of compressive strength under different cur-
ing regimes. As shown in Figure 4, the compressive strength of specimens under wet–dry
and dry curing regimes was higher than that of specimens under wet curing, except the
control specimens. The tendency was much different from the control specimens. The dis-
tinction could be caused by the effect of epoxy resin polymerization. The epoxy resin had
a much higher polymerization rate under the wet–dry and dry curing regimes. The poly-
mer–cement co-matrix formed in mortar has a restraint effect on the expansion of mortars
and has a beneficial impact on the compressive strength. The result is consistent with lit-
erature [29] showing that the wet–dry curing regime provided the optimum condition for
Materials 2021, 14, 517 8 of 23

both hydration and polymerization processes. Meanwhile, for the control specimens, wet
curing regimes provide adequate water for the cement hydration and lead to a higher
compressive strength.

(a) (b)
Materials 2021, 14, 517 9 of 23

(c) (d)

(e)
Figure 4. Compressive strength of epoxy latexes modified mortar under three curing regimes: (a)
0%, (b) 5%, (c) 10%, (d) 15%, and (e) 20%.

3.2. Integrated Model for the Degree of Cement Hydration and Epoxy Latexes Polymerization
As mentioned, the properties of epoxy latexes modified mortar were significantly
governed by both the process of cement hydration and the epoxy resin polymerization
[31,32]. It is important to quantify the coupled effect and clarify the relationship between
the coupled process and the mechanical properties of epoxy latexes modified mortars. In
this research, the degrees of hydration and polymerization were selected as the quantita-
tive indexes to represent the process of cement hydration and the epoxy resin polymeri-
zation, respectively. An integrated model for the degree of cement hydration and epoxy
latexes polymerization was established based on the test results of compressive strength.
Materials 2021, 14, 517 10 of 23

Neville [57] developed a simplified model regardless of the age and mix proportions
to describe the relationship between the compressive strength of mortars and the cube of
the gel/space ratio, as shown in Equation (3):
3
fc  234  r (3)
,
where fc is the compressive strength in MPa, 234 MPa represents the intrinsic strength of
the hydrates gel for the type of cement, and the gel/space ratio r is defined as the ratio of
the volume of gel and the total space available to the gel:

k h vc
r (4)
vc  w c
0

,
where kh is the hydrate volume expansion coefficient of ordinary Portland cement, which
indicates that the products of complete hydration of 1 mL of cement will be assumed to
occupy 2.06 mL gel. vc is the specific volume of cement, which denotes the volume of unit
mass with a value of 0.317 cm3/g. α is the degree of hydration of cement. w0 is the volume
of mixing water. Finally, c is the mass of cement.
The validity of the model was verified by plenty of tests in the cement paste and
mortar scale without polymer. In this research, new parameters will be introduced to rep-
resent the interaction between cement hydration and epoxy resin polymerization based
on the model.
The degree of cement hydration is calculated by Equations (3) and (4), based on the
experimentally determined compressive strengths of the control mortars. The hydration
degree of cement under dry curing, wet curing, and wet–dry curing regimes was calcu-
lated by fitting the experimental results with Equations (3) and (4). Moreover, the calcu-
lated results of the degree of hydration for all specimens are listed in Table 3.

Table 3. The degree of hydration calculated by Equations (3) and (4).

Curing Regimes 7d 14 d 28 d 45 d 60 d 90 d
Wet 0.405 0.425 0.435 0.447 0.462 0.502
α Dry 0.400 0.413 0.423 0.436 0.451 0.485
Wet–dry 0.405 0.420 0.426 0.453 0.458 0.493

It should be noted that, in this research, the mixture proportions of epoxy modified
mortar were designed with a constant volume water/cement ratio (Vw/Vc). As shown in
Figure 5, the addition of epoxy latexes will decrease the volume of mortar in unit volume.
As the compressive strength of mortar specimens was affected by the volume of mortar
in unit volume, the volume changing effect should be considered and the volume chang-
ing index i was first introduced as shown in Equation (5):

f c  1  i   r
3

, (5)

where i is the volume changing index and can be calculated according to Table 4.
Materials 2021, 14, 517 11 of 23

Figure 5. The proportion of cement mortar in the unit volume of epoxy latexes modified mortar.

Table 4. Reduction of cement paste in the unit volume of mortar (i).

P/C 5% 10% 15% 20%

i 6.791% 12.719% 17.937% 22.567%

3.2.1. Retardation Effects of Epoxy Latexes

It has been reported that the addition of polymer latexes has a significant retardation
effect on the cement hydration process [33]. The degree of cement hydration will decrease
with the retardation effect. In this research, the effects of both the chemical retardation
and the physical retardation were combined by a retardation coefficient ξ. The gel/space
ratio in epoxy latexes modified mortar could be modified as Equations (6) and (7):

kh vc 
r (6)
vc   w0 c ,

    , (7)

where α' a is the actual hydration degree of epoxy latexes modified cement mortars. ξ is
the retardation coefficient, which indicates the retardation effect of epoxy latexes on the
degree of cement hydration. For the series of control cement mortars, ξ = 1.
As reported before, Ohama proposed a simplified model of polymer–cement co-ma-
trix formation wherein, with water withdrawal by cement hydration, the close-packed
polymer particles on the cement hydrates coalesce into continuous films or membranes
[2,58]. In the case of the wet curing regime, epoxy latexes will fail to form a continuous
close-packed layer owing to the adequate capillary water. Thus, an assumption was made
in this research that no polymerization reaction was produced in the case of the wet curing
regime. Based on the assumption, the retardation effect coefficient of specimens under the
wet curing regime could be calculated by fitting the test data by Equations (5)–(7), as listed
in Table 5. The retardation effect coefficients of specimens with P/C ratios of 5%, 10%, 15%,
and 20% were 0.880, 0.870, 0.865, and 0.855, respectively.
Materials 2021, 14, 517 12 of 23

Table 5. Experimentally determined compressive strength of specimens under the wet curing regime and the predicted
results by Equations (5)–(7).

P/C ξ 7d 14 d 28 d 45 d 60 d 90 d
0% 1.000 α 0.405 0.425 0.435 0.447 0.462 0.502
α'=ξα 0.356 0.374 0.383 0.393 0.407 0.442
Predicted (MPa) 28.10 31.21 32.82 34.79 37.31 44.37
5% 0.880
Experimental (MPa) 28.36 30.80 32.45 34.50 36.23 43.51
Model absolute error 0.92% 1.33% 1.14% 0.84% 2.98% 1.98%
α'=ξα 0.352 0.370 0.378 0.389 0.402 0.437
Predicted (MPa) 26.25 29.16 30.66 32.50 34.85 41.45
10% 0.870
Experimental (MPa) 26.84 28.25 31.68 32.87 35.69 40.59
Model absolute error 2.20% 3.22% 3.22% 1.13% 2.35% 2.12%
α'=ξα 0.350 0.368 0.376 0.387 0.400 0.434
Predicted (MPa) 24.31 27.00 28.39 30.09 32.28 38.38
15% 0.865
Experimental (MPa) 23.91 26.33 29.36 30.75 33.57 37.74
Model absolute error 1.67% 2.54% 3.30% 2.15% 3.84% 1.70%
α'=ξα 0.346 0.363 0.372 0.382 0.395 0.429
Predicted (MPa) 21.82 24.23 25.48 27.01 28.97 34.45
20% 0.855
Experimental (MPa) 21.50 23.71 24.51 27.16 29.19 34.98
Model absolute error 1.49% 2.19% 3.96% 0.55% 0.75% 1.52%

3.2.2. Polymerization Effects of Epoxy Latexes

It can be seen from the test results that the polymerization of epoxy resin has a bene-
ficial effect on the compressive strength of mortar specimens. To represent the beneficial
effect, the degree of epoxy resin polymerization is introduced into the model, as shown in
Equation (8):
f c  234 1  i   r
3

, (8)
 Vp

 e 2 Vc
(9)
,
where φ is defined as the beneficial effect of epoxy resin polymerization on the compres-
sive strength; η is the degree of polymerization; and Vp and Vc are the volume of polymer
and cement, respectively.
It has been reported that the degree of polymerization of epoxy resin has little influ-
ence on the hydration kinetics of epoxy resin-modified cement at normal temperatures
[34]. Thus, the retardation effect coefficient of specimens under the dry and wet–dry cur-
ing regimes was assumed to be the same as that under wet curing regimes. Based on the
calculated ξ, the degree of polymerization (η) can be calculated by fitting the experimental
results through Equations (6) and (8).
The calculated results of polymerization for all of the specimens are listed in Table 6.
The comparison of the hydration degree of specimens with different P/C ratios under the
dry, wet, and wet–dry curing regimes is shown in Figure 6. There is a nearly logarithmic
relationship between the degree of polymerization and curing age. Both the degree of hy-
dration and the degree of polymerization of specimens under wet–dry curing regimes
were highest at later ages of 45 d, 60 d, and 90 d. The results were consistent with previous
conclusions. In general, the degree of hydration decreases with the increase of the P/C
ratio, and the hydration rate tends to decrease as the curing ages increase.
Materials 2021, 14, 517 13 of 23

Table 6. The degree of polymerization calculated by Equations (6) and (8).

Curing Regimes 7d 14 d 28 d 45 d 60 d 90 d
Wet 0 0 0 0 0 0
η Dry 0.450 0.500 0.650 0.700 0.720 0.760
Wet–dry 0 0.300 0.550 0.750 0.790 0.810

(a) (b).

(c)
Figure 6. Degrees of hydration and polymerization under different curing regimes: (a) dry curing,
(b) wet curing, and (c) wet–dry curing.
Materials 2021, 14, 517 14 of 23

3.3. Flexural Strength

3.3.1. Effect of Epoxy Latexes Modification
An investigation of the material’s ability to resist deformation under load was done
through the flexural test. Figure 7 shows the relationship between the epoxy latexes con-
tent and the flexural strength of mortar specimens with different curing regimes at the
ages of 7 d, 14 d, 28 d, 45 d, 60 d, and 90 d. As shown in Figure 7a, in general, the flexural
strength of epoxy modified mortars under dry curing regime tended to increase with the
increase of the P/C ratios and curing ages. The flexural strength of mortar specimens with
15% and 20% epoxy content increased by approximately 30% compared with control mor-
tars at the age of 90 d. The improvement of flexural strength could be caused by the film
formation, which will increase the flexural strength of the binder matrix between the ag-
gregate and cement hydrates. Meanwhile, for the case of wet curing, the flexural strength
of epoxy latexes modified mortars was smaller than that of control mortars, as shown in
Figure 7b The reduction of the flexural strength could be the low polymerization rate un-
der the wet curing regime. Figure 7c shows the flexural strength of mortar specimens un-
der the wet–dry curing regime; it can be seen that, at the age of 7 d and 14 d, the flexural
strength of control mortars was much higher than that of epoxy latexes modified mortars.
It should be noted that, for the wet–dry curing regime, mortar specimens were first im-
mersed in a water chamber for 5 d. The low polymerization rate in the first 5 d may lead
to a reduction in flexural strength. The flexural strength of epoxy latexes modified mortars
increased at a relatively higher rate from 28 d until 90 d, which is consistent with literature
[59] stating that the wet–dry curing regime benefited in the long term. At the age of 90 d,
the flexural strength of mortars with 15% and 20% epoxy content was 28% and 23% higher,
respectively, than the control mortars. It can be seen that the polymer–cement co-matrix
formed in mortar has a restraint effect on the crack development of mortars and has a
beneficial impact on the flexural strength.

(a) (b)
Materials 2021, 14, 517 15 of 23

(c)
Figure 7. Flexural strength of epoxy latexes modified mortar: (a) dry curing, (b) wet curing, and (c)
wet–dry curing.

3.3.2. Effect of Hydration and Polymerization

It has been reported that the polymer–cement co-matrix formed in PMM can signifi-
cantly improve the flexural strength of mortar and concrete [38,39]. It is important to clar-
ify the relationship between the flexural and the coupled effect of cement hydration and
epoxy resin polymerization. The calculated degrees of hydration and polymerization
(listed in Tables 3 and 6) were used to analyze the quantitative relation with different
curing regimes. As discussed before, the compressive strength of epoxy modified mortars
was influenced by the degree of hydration, the degree of polymerization, and the volume
changing effect of mortar. Similarly, two influence factors were defined:

1  1  i    , (10)

Vp
2  V   1  i    (11)
c
,
where λ1 is the influence factor representing both the effect of cement hydration and the
volume of mortar. λ2 is used to represent the coupled effect of the degree of hydration, the
degree of polymerization, and the volume changing effect of mortar.
The relationship between the flexural strength of specimens under the wet curing
regime and λ1 is shown in Figure 8a. An obvious logarithmic relationship could be found.
Because of the relatively lower rate of epoxy resin polymerization, the flexural strength of
specimens under the wet curing regime was mainly determined by the degree of hydra-
tion. The relationship between the flexural strength of specimens under the dry and wet–
dry curing regimes and λ2 is shown in Figure 8 b,c, respectively. The flexural strength
increased approximately linearly with the increase of λIt can be concluded that the flex-
ural strength of epoxy latexes modified mortar was also influenced by the degree of hy-
dration, the degree of polymerization, and the volume changing effect of mortar. Mean-
while, the improvement of the flexural strength depends mainly on the degree of epoxy
resin polymerization. It can be speculated that, for the engineering application of epoxy
latexes modified mortar, the dry and wet–dry curing regimes are suitable for the devel-
opment of the mechanical properties.
Materials 2021, 14, 517 16 of 23

(a) (b)

(c)
Figure 8. Relationship between flexural strength and λ1 and λ2: (a) wet curing, (b) dry curing, and
(c) wet–dry curing.

3.4. Porosity
The effects of epoxy latexes modifications on pore size distributions of cement mor-
tars determined from MIP are discussed in this section. In general, the pores in concrete
can be classified as gel (d < 10 nm), transition (10 nm ≤ d < 100 nm), capillary (100 nm ≤ d
< 1000 nm), and large (d ≥ 1000 nm) pores [60]. Capillary voids larger than 50 nm are
referred to as macropores, whereas voids smaller than 50 nm are referred to as micropores
[61]. Figure 9 shows the pore-size distributions of the mortar specimens at 90 d under the
three curing regimes. As seen in Figure 9, under the dry and wet–dry curing regimes, the
Materials 2021, 14, 517 17 of 23

micropores of mortar specimens tended to increase with the increase of the P/C ratios.
This tendency agrees with the results of many previous studies on polymer cement mortar
[62]. Meanwhile, the peak of the curve for the epoxy latexes modified mortar specimens
shifted upwards and was broader with the increase of the P/C ratio, which indicates that
the capillary pores of specimens tended to increase. The increase of micropores could be
caused by the retardation effect of epoxy latexes on cement hydration and the volume
changing effect of mortar. Compared with the pore-size distribution under the dry and
wet–dry curing regimes, the micropores of mortar specimens under wet curing regimes
rapidly increased. Furthermore, the peak of the specimens shifted upwards rapidly and
rapidly became broader after adding epoxy resin. It could be attributed to no polymeriza-
tion reaction being produced in the case of the wet curing regime, and a large amount of
free epoxy adsorbed on the surface of cement particles enhances the retardation effect of
epoxy latexes on cement hydration.

Figure 9. The pore structure of epoxy latexes modified mortars at 90 d under three curing regimes.

Similarly, an influencing factor was defined:

3  , (12)

where λ3 is the influence factor to represent both the coupled effect of the degree of hy-
dration and polymerization. Figure 10 shows the relationship between λ3 and the
Materials 2021, 14, 517 18 of 23

macropores under the dry and wet–dry curing regimes. As seen in Figure 10, the
macropores of epoxy latexes modified mortar specimens tended to decrease with the in-
crease of the hydration products, and the polymerization of epoxy latex will also fill part
of the pores. The result is consistent with literature [35] stating that more and more
macropores are refined as medium capillary pores with the increase of curing ages in
modified mortars. It can be concluded that the retardation effect of epoxy latexes on ce-
ment hydration leads to increased micropores, whereas macropores gradually trans-
formed into micropores with the increase of hydration degree. The porosity reduction of
the macropores is mainly determined by the cement hydrates and the filling effect of the
film structure formed after epoxy latexes polymerization.

(a) (b)
Figure 10. Relationship between the degree of λ3 and the macropores: (a) dry curing and (b) wet–
dry curing.

3.5. SEM Investigation

To understand the modification mechanism of epoxy latexes more clearly, the
microstructure of the fracture surfaces of the 45 d cured modified mortar specimens under
different curing regimes with the addition of 15% epoxy resin was observed by SEM. As
seen in Figure 11, needle products and other cement hydrate mixtures were found in the
specimens. These needle-like products are called ettringite, which is the main hydration
product of cement, and it is woven together to form dense structure, which ultimately
helps the high strength of cement composites [63]. At high magnifications, the
polymerized epoxy resin formed as polymer films is seen in the mortar specimens, and it
connects cement hydration products to enhance the interaction between crystals. As
shown in Figure 12, the plate-like Ca(OH)2 crystals and ettringite needles produced by
Materials 2021, 14, 517 19 of 23

cement hydration could be found. However, contrary to the mortar specimens under dry
curing regimes, the polymer films could not be observed clearly from the mortar
specimens under wet curing regimes. It is interesting to note a large amount of
unhardened epoxy resin in the mortar aggregates, which proves that no polymerization
reaction was produced in the case of the wet curing regime. Meanwhile, as seen in Figure
13, the polymer network film was found in the mortar under wet–dry curing regimes, and
its benefits enhance the properties of cement mortar of flexural strength. Though adding
the epoxy resin leads to a decrease of the compressive strength, the polymerized epoxy
resin formed as polymer films can enhance the compressive and flexural strength of the
modified mortar to some degree. It could be attributed to the polymer film increasing the
adhesion and bond strength of the epoxy latexes modified mortar, which heightens the
ability to undergo shear forces, and reducing the risk of structural fracture.

Figure 11. Scanning electronic microscope (SEM) image of fractured sections of epoxy latexes modified cement mortar
under dry curing regimes with the addition of 15% epoxy resin at 45 d: (a) 5000× and (b) 20,000×.

Figure 12. SEM image of fractured sections of epoxy latexes modified cement mortar under wet curing regimes with the
addition of 15% epoxy resin at 45 d: (a) 5000× and (b) 20,000×.
Materials 2021, 14, 517 20 of 23

Figure 13. SEM image of fractured sections of epoxy latexes modified cement mortar under wet–dry curing regimes with
the addition of 15% epoxy resin at 45 d: (a) 5000× and (b) 20,000×.

4. Conclusions
In this research, polymer-modified mortars using epoxy latexes were prepared with
various epoxy latexes contents and curing conditions. Compressive, flexural strength,
MIP, and SEM were conducted to analyze the effect of epoxy latexes on the mechanical
behavior and porosity property of cement mortar. Based on the experimental results, an
integrated model for the degree of cement hydration and epoxy latexes polymerization
was established. The following conclusions can be drawn from the present study:
1. The compressive strength of epoxy modified mortars tends to decrease with the in-
crease of the P/C ratios. The compressive strength of specimens under wet–dry and
dry curing regimes is higher than that of specimens under wet curing.
2. Based on the proposed model, the degree of hydration and polymerization of mortar
specimens under different curing regimes can be calculated. The degree of hydration
decrease with the increase of the P/C ratio, and the hydration rate tends to decrease
as the curing ages increase. The compressive strength of epoxy latexes modified mor-
tar was mainly governed by the cement hydration.
3. Epoxy latexes provide a considerable increase in the flexural strength under the dry
and wet–dry curing regimes. Meanwhile, for the case of wet curing, the flexural
strength of epoxy latexes modified mortars is less than that of than control mortars.
The reduction of the flexural strength is caused by the low polymerization rate under
the wet curing regime.
4. The flexural strength of epoxy latexes modified mortar is influenced by the degree of
hydration, the degree of polymerization, and the volume changing effect of mortar.
Meanwhile, the improvement of the flexural strength depends mainly on the degree
of epoxy resin polymerization.
5. According to the findings of the study, the strength of epoxy latexes modified con-
crete is related to hydration and polymerization. In practical engineering, it is neces-
sary to ensure the degree of hydration and increase the polymerization rate, thus the
wet–dry curing regime is recommended.
6. The micropores of epoxy latexes modified mortars tend to increase with the increase
of the P/C ratios. The macropores of epoxy latexes modified mortar specimens tended
to decrease with the increase of the degree of epoxy latexes polymerization and ce-
ment hydration.
7. The addition of epoxy latexes is helpful to improve microstructures by forming the
continuous films in cement mortar under dry and wet–dry curing regimes. Mean-
while, little continuous films can be founded under the wet curing regime owing to
no polymerization of epoxy resin.
Materials 2021, 14, 517 21 of 23

Author Contributions: Conceptualization, P.L. and X.A.; Data curation, L.Z and S.D.; Funding
acquisition, P.L.; Investigation, P.L and W.L.; Methodology, X.A.; Validation, W.L. and L.Z.;
Visualization, W.L. and S.D.; Writing—original draft, P.L. and W.L.; Writing—review & editing,
P.L. and X.A.
Funding: This research was funded by the National Natural Science Foundation of China (Grant
No. 51709026), the Foundation of Chongqing Education Commission (Grant No. KJQN201800741),
and the Foundation of Chian Huaneng Research Project (Grant No. HNKJ19-H13).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study are available on request from
corresponding author.

Conflicts of Interest: The authors declare no conflict of interest.

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