materials

Article
Effect of Polymer Addition on Performance of
Portland Cement Mortar Exposed to Sulphate Attack
Paweł Łukowski 1, * and Dominika D˛ebska 2
1 Department of Building Materials Engineering, Faculty of Civil Engineering, Warsaw University of
Technology, 00-637 Warsaw, Poland
2 Chair of Building Materials Engineering, Faculty of Civil Engineering, Cracow University of Technology,
31-155 Cracow, Poland; ddebska@pk.edu.pl
* Correspondence: P.Lukowski@il.pw.edu.pl




Received: 19 November 2019; Accepted: 18 December 2019; Published: 22 December 2019


Abstract: Resistance to degradation contributes greatly to the durability of materials. The chemical
resistance of polymer-cement composites is not yet fully recognized. The goal of the research presented
in this paper was to assess the performance of polymer-cement mortars under sulphate aggression,
as compared to unmodified cement mortar. Mortars with polymer-to-cement ratios from 0 to 0.20
were stored in either a 5% MgSO4 solution or distilled water for 42 months. During this time, changes
in elongation, mass, and compressive strength were determined. The results of these investigations,
together with the visual and microscopic observations, allowed us to conclude that polymer–cement
composites demonstrated better resistance to the attack of sulphate ions than unmodified cement
mortar, even when using Portland cement with enhanced sulphate resistance.

Keywords: durability; polymer-cement composite; sulphate aggression

1. Introduction
Cement composites, such as mortar and concrete, are relatively cheap but not very durable
materials. The repair or replacement of these composites during exploitation of the building structure
is technically difficult and usually expensive [1]. The durability of the building objects and materials,
defined as the ability of the product to maintain its required performance over time [2], is an important
element of sustainable development in construction [1].
One of the main reasons for the insufficient durability of concrete or mortar is degradation
caused by chemical, physical, or biological factors. A durability assessment is possible using tests and
observations of the material being exposed to the corrosive environment for a long time. Due to the
lack of such data for the relatively recently introduced materials, various procedures are employed
to accelerate ageing, compensating for the shorter time of investigation by the intensity of the
corrosive factors.
Sulphate ions SO4 2– can cause substantial damages in the concrete. Sulphate corrosion is a
complex process. First, a gypsum dihydrate is formed:

−
Ca(OH)2 + SO2−
4 → CaSO4 + 2OH (1)

CaSO4 + 2H2 O → CaSO4 ·2H2 O (2)

Then trisulphate (AFt, ettringite) is created from unreacted tricalcium aluminate:

3CaO·Al2 O3 + 3(CaSO4 ·2H2 O) + 26H2 O → 6CaO·Al2 O3 ·3SO3 ·32H2 O (3)

Materials 2020, 13, 71; doi:10.3390/ma13010071 www.mdpi.com/journal/materials

Materials 2020, 13, 71 2 of 12

or from monosulphate (AFm):

4CaO·Al2 O3 ·SO3 ·12H2 O + 3(CaSO4 ·2H2 O) + 14H2 O → 6CaO·Al2 O3 ·3SO3 ·32H2 O. (4)

These reactions are accompanied by significant stresses, leading to the weakening and damage to
the structure of the material [3]. Sulphate corrosion of cement concrete has been a subject of many
studies. According to Heinz and Ludwig [4], the main reason for the excessive internal stresses is the
creation of the shells made from large, densely packed ettringite crystals around the aggregate grains.
According to Brown and Taylor [5], the source of these stresses is the formation of nanometric ettringite
crystals during the C-S-H phase [5]. Yu et al. [6] reported that in some cases gypsum is formed in
the later stages of deterioration and thus its presence does not necessarily mean the beginning of
the concrete degradation. The pressure caused by the growth of the ettringite crystals is commonly
accepted as the most probable mechanism of concrete microstructure deterioration [7,8].
However, not all of the questions have already been answered. For instance, the effects of the
simultaneous attack of sulphate ions and other corrosive factors (e.g., freezing and thawing cycles [9] or
mechanical loading [10]) need to be considered. A model of the concrete deterioration under sulphate
attack has been developed [11], as has a model of sulphate ion transport in concrete [12]. Another
field of research in this area is the impact of various modifiers on the concrete’s resistance to sulphate
aggression. In this context, the results of nanomodification [13] and the effects of industrial wastes in
the concrete are studied [14].
Polymers are one widely used modifiers of contemporary concrete. By adding polymers to
the cement concrete or mortar mix, polymer-cement composites (PCCs) are created. PCC materials
belong to the group of building polymer composites, together with resin concretes and mortars
and polymer-impregnated concretes [15,16]. The polymer in such a composite is a co-binder [17],
creating an interpenetrating network with Portland cement. Polymer-cement concretes and mortars
are successfully used in construction; one example of their application is the repair and protection of
concrete structures, making pavements (including industrial floors), and the production of pre-cast
elements [18]. Polymer-cement composites demonstrate substantial advantages over ordinary concrete
and mortar regarding properties such as tensile and flexural strength, adhesion to various substrates,
and tightness [19–21]. They also have a significant potential for efficient utilization of burdensome
industrial wastes since it has been demonstrated that such materials as various types of fly ashes and
waste perlite powder can be successfully used as components of polymer-cement composites [22].
However, the question of PCC durability has not yet been fully resolved. The majority of published
papers show a rather optimistic view of this problem, based on the published test results [23–25].
However, there are other issues that need to be considered. One of these is the resistance of
polymer–cement composites to chemical attacks.
This paper presents our investigation of the impact of polymer addition on PCC resistance to
sulphate attack. The experiment compared the behaviour of polymer-cement and ordinary cement
mortars exposed to sulphate aggression. Polyacrylic ester (PAE) in the form of water dispersion (solid
content 54% ± 1%) was used as a polymer co-binder.
The improvement of Portland cement composite performance by polymers is a result of two basic
mechanisms [15]. The first is the strengthening of the aggregate-paste interfacial transition zone, which
is the most porous and weakest place in ordinary concrete or mortar. In PCCs, however, the voids
are filled with polymer particles that also increase the adhesion between the aggregate grains and
the cement matrix. The second mechanism is the crack-bridging ability of the polymer. Generally,
since polymers are commonly used as modifiers for the cement composites (i.e., PAEs, styrene-acrylic
copolymers, styrene-butadiene rubber, ethylene-vinyl acetate copolymer, polyvinyl alcohol, and epoxy
resins), these mechanisms do not depend on the chemical nature of the polymer [21]. Therefore, the
choice of the polymer modifier is based mainly on the technological ease of its application, availability,
and economic rationality. The PAEs are disperse well in water and have a favourable low minimum
film-forming temperature of about 0 ◦ C [18]. For this reason, they are one of the most often used
Materials 2020, 13, 71 3 of 12

polymer modifiers and, simultaneously, their effect on the performance of cement composites is
representative of the wide group of polymer modifiers.

2. Materials and Methods

The following materials were used to prepare the tested mortars:

• Portland cement CEM I 42.5 N according to European Standard EN 197-1 [26], with enhanced
resistance to sulphate corrosion (medium sulphate resistance, MSR). The chemical composition of
the cement is presented in Table 1.
• CEN standard sand 0-2 mm according to European Standard EN 196-1 [27].
• Tap water, conforming to European Standard EN 1008:2004 [28].
• A commercially available polymer modifier: a PAE in the form of water dispersion (solid content
54%) (MC-Bauchemie, Sroda Wlkp., Poland). The basic properties of the polymer are presented in
Table 2.

Table 1. Chemical composition of cement.

Component Content, in mass %

CaO 64.89
SiO2 21.60
MgO 0.76
Al2 O3 3.44
Fe2 O3 3.50
SO3 2.71
Na2 Oeq 0.32
Cl 0.018
Insoluble part 0.38
Loss on ignition 1.43
C3 A 3.20
C3 S 59.9

Table 2. Basic properties of polyacrylic ester (PAE).

Property Unit Value

Form of delivery - Water dispersion
Solid content % 54 ± 1
Density of dispersion kg/m3 1270 ± 10
Minimum film-forming temperature ◦C ~0

The use of sulphate-resistant cement was chosen based on the main aim of the research, which
was the verification of the hypothesis that the polymer addition can further improve the sulphate
resistance of the composite, even if it already contains sulphate-resistant cement.
The reference material was not modified (polymer-to-cement ratio, p/c = 0): standard Portland
cement mortar according to European Standard EN 196-1 [27] (the cement-to-sand ratio was 1:3 and
water-to-cement ratio was 1:2). The polymer-cement ratio in polymer-cement mortars was 1:20, 1:10,
and 1:5 (by mass). The mix compositions are presented in Table 3.
Materials 2020, 13, 71 4 of 12

Table 3. Mixture compositions (in g).

Series Cement Water 1 Sand Polymer

p/c = 0 450 225 1350 0
p/c = 0.05 450 225 1350 22.5
p/c = 0.10 450 225 1350 45.0
p/c = 0.20 450 225 1350 90.0
1 Including that contained in the polymer dispersion.

The beam specimens with dimensions 2 cm × 2 cm × 16 cm were cast for all proposed mixes,
according to the European Prestandard ENV 196-X [29]. All specimens were cured for 28 days. The
cement mortar specimens were stored in water, while polymer-cement mortar specimens were stored
for 7 days in water and later kept in standard laboratory conditions (temperature 20 ± 2 ◦ C and relative
humidity 60% ± 10%, according to the Warsaw University of Technology procedure for PCC curing [30]).
Half of the specimens were placed in a 5% MgSO4 solution (the solution was replaced every 28 days to
keep the concentration constant), and the second half were stored in distilled water. The temperature
of both media was 20 ± 2 ◦ C. The tested properties included elongation and mass changes as well as
compressive strength. The measurements were performed after 28 days of curing (i.e., immediately
before placing the specimens in the sulphate solution or distilled water) and then after 6, 12, 18, 30,
and 42 months of storing the specimens in the sulphate solution or distilled water. Specimens of each
mortar type, stored in both media, were measured with the accuracy of 0.01 mm (with a Graf-Kaufman
apparatus, EMEL, Warsaw, Poland, according to the prENV 196-X [29]) and weighed (after 24 h of
drying in standard laboratory conditions) with the accuracy of 0.01 g. The specimens were cut in half
and used for the compressive strength determination (according to EN 197-1 [26], with only deviation
referring to the size of specimens). The length and mass of the specimens were controlled during each
replacement of the sulphate solution. Some visual and microscopic observations were also conducted.
Magnesium sulphate(VI) solution was selected as the corrosive medium because MgSO4 is
harmful to all cement minerals, including the C-S-H phase, while sodium sulphate, according to some
studies [31], attacks mainly portlandite and tricalcium aluminate. Thus, strength reduction can be
determined earlier when magnesium sulphate(VI) is used as the aggressive factor.

3. Results and Discussion

This investigation covered the determination of elongation and mass changes, as well as the
compressive strength of the specimens made of Portland cement mortars which contained different
amounts of a polymer modifier, PAE (polymer-to-cement ratio 0–0.20 by mass) after various times of
exposure to either a 5% MgSO4 solution or distilled water (0–42 months).

3.1. Elongation
The elongation of the specimens is presented in Figure 1.
The changes in length of the specimens stored in water were almost negligible, independent of the
level of polymer addition. However, when exposed to the 5% MgSO4 solution, the mortar specimens
showed elongation that increased with the time of exposure. The changes were significant in spite of
using Portland cement with enhanced sulphate resistance (MSR). The polymer addition improved
mortar performance in such circumstances. The analysis of the results showed that the elongation
diminished with increasing polymer content.
 Materials 2019, 12, x FOR PEER REVIEW 5 of 13
Materials 2020, 13, 71 5 of 12

H2O MgSO4 H2O MgSO4

1.2 1.2
p/c=0 p/c=0.05
1.0 1.0
Linear changes, mm/m

Linear changes, mm/m

0.8 0.8

0.6 0.6

0.4 0.4

0.2 0.2

0.0 0.0
0 6 12 18 24 30 36 42 0 6 12 18 24 30 36 42
Time, months Time, months

H2O MgSO4 H2O MgSO4

1.2 1.2
p/c=0.10 p/c=0.20
1.0 1.0
Linear changes, mm/m

Linear changes, mm/m

0.8 0.8

0.6 0.6

0.4 0.4

0.2 0.2

0.0 0.0
0 6 12 18 24 30 36 42 0 6 12 18 24 30 36 42
Time, months Time, months

Figure 1. Elongation
Figure ofof
1. Elongation mortar
mortarspecimens
specimens exposed to5%
exposed to 5%MgSO
MgSO 4 solution
4 solution and
and distilled
distilled water.
water.

TheThe
relative
changesdifferences
in lengthin
ofelongation between
the specimens stored the mortar
in water with
were the polymer-cement
almost ratio of
negligible, independent of0.20
and the
thatlevel
containing no polymer
of polymer were
addition. similar when
However, for various times
exposed of exposure,
to the 5% MgSOand were roughly
4 solution, close to
the mortar
50%.specimens
For instance,
showedafter 6 monthsthat
elongation of exposure, the absolute
increased with difference
the time of exposure.was
The equal
changesto were
0.23 mm/m, which
significant
in spite
meant of usingbyPortland
a decrease cement
53%, while with
after 42enhanced
months, sulphate resistance
the absolute (MSR).was
difference The equal
polymer
to addition
0.45 mm/m,
improved
which meant
Materials amortar
2019, 12, decreaseperformance
x FOR PEER by 45.5% in
REVIEW such circumstances.
(Figure 2). The analysis of the results showed that the 6 of 13
elongation diminished with increasing polymer content.
The relative differences in elongation
after 6 between
months theafter
mortar with the polymer-cement ratio of 0.20
42 months
and that containing
1.2 no polymer were similar for various times of exposure, and were roughly close
to 50%. For instance, after 6 months of exposure, the absolute difference was equal to 0.23 mm/m,
which meant a decrease by 53%, while after 42 months, the absolute difference was equal to 0.45
1
mm/m, which meant a decrease by 45.5% (Figure 2).
Linear changes, mm/m

0.8

0.6

0.4

0.2

0
0 0.05 0.1 0.15 0.2
Polymer/cement ratio

Figure 2. Elongation of mortar specimens with various content of polymer modifier after 6 and
Figure 2. Elongation of mortar specimens with various content of polymer modifier after 6 and 42
42 months of exposure to the 5% MgSO4 solution.
months of exposure to the 5% MgSO4 solution.

3.2. Mass Changes

The results of the mass change determination are presented in Figure 3. The mass changes of the
specimens stored in water were caused by water absorbance. After a significant increase within the
first 6 months, it stabilized to some extent. The addition of polymer diminished the water
absorbability of the mortars to a greater degree as the polymer content increased. This was due to the
changes in the porosity structure: at a similar level of the total pores volume, the presence of polymer
led to the domination of finer and closed pores. Additionally, the formed polymer film is an obstacle
for the moisture transport inside the polymer-cement composite. The behaviour of the specimens
exposed to the 5% MgSO4 solution was different. The initial increase of the mass was higher than that
Materials 2020, 13, 71 6 of 12

3.2. Mass Changes

The results of the mass change determination are presented in Figure 3. The mass changes of the
specimens stored in water were caused by water absorbance. After a significant increase within the
first 6 months, it stabilized to some extent. The addition of polymer diminished the water absorbability
of the mortars to a greater degree as the polymer content increased. This was due to the changes in
the porosity structure: at a similar level of the total pores volume, the presence of polymer led to the
domination of finer and closed pores. Additionally, the formed polymer film is an obstacle for the
moisture transport inside the polymer-cement composite. The behaviour of the specimens exposed
to the 5% MgSO4 solution was different. The initial increase of the mass was higher than that in
water as it was caused not only by water absorbance but also by forming additional substances inside
the specimens—gypsum and ettringite, the products of sulphate corrosion of the cement composites.
However, after a longer exposure time, the mass of the specimens began to decrease. This was a result
of damage to the specimens caused by the deterioration of the internal structure of the mortar by the
corrosion products. The damage could be observed mainly in the form of corners and edges spalling
(see the observations presented in Section 3.4.). This negative effect was mitigated by the polymer
and the degree of this improvement increased with the polymer content. This phenomenon can be
explained by the fact that the water is necessary for the chemical reactions causing deterioration of the
composite, and because the presence of polymer reduces the water absorbability, as mentioned above.
In a few cases, the values of mass changes presented in Figure 4 for the specimens stored in water and
in the sulphate solution seem to be close, but the standard deviations of the average values are low
enough (below
Materials 1%x FOR
2019, 12, in either case) to confirm the reliability of the observed tendencies.
PEER REVIEW 7 of 13

H2O MgSO4 H2O MgSO4

12 12
p/c=0 p/c=0.05
10 10
Mass change, %

Mass change, %

8 8

6 6

4 4

2 2

0 0
0 6 12 18 24 30 36 42 0 6 12 18 24 30 36 42
Time, months Time, months

H2O MgSO4 H2O MgSO4

12 12
p/c=0.10 p/c=0.20
10 10
Mass change, %

Mass change, %

8 8

6 6

4 4

2 2

0 0
0 6 12 18 24 30 36 42 0 6 12 18 24 30 36 42
Time, months Time, months

Figure 3. Mass
Figure changes
3. Mass of of
changes mortar
mortarspecimens
specimensexposed to the
exposed to the5%
5%MgSO
MgSO 4 solution
4 solution andand distilled
distilled water.
water.

3.3. Compressive Strength

The results of the compressive strength investigation are presented in Figure 4.

H2O MgSO4 H2O MgSO4

80 80
p/c=0 p/c=0.05
Compressive strength, MPa

Compressive strength, MPa

70 70

60 60

50 50

40 40

30 30

20 20

10 10
 Time, months Time, months

Figure 3. Mass changes of mortar specimens exposed to the 5% MgSO4 solution and distilled water.

3.3. Compressive Strength

Materials 2020, 13, 71 7 of 12
The results of the compressive strength investigation are presented in Figure 4.

H2O MgSO4 H2O MgSO4

80 80
p/c=0 p/c=0.05
Compressive strength, MPa

Compressive strength, MPa

70 70

60 60

50 50

40 40

30 30

20 20

10 10

0 0
0 6 12 18 24 30 36 42 0 6 12 18 24 30 36 42
Time, months Time, months

H2O MgSO4 H2O MgSO4

80 80
p/c=0.10 p/c=0.20
Compressive strength, MPa

Compressive strength, MPa

70 70

60 60

50 50

40 40

30 30

20 20

10 10

0 0
0 6 12 18 24 30 36 42 0 6 12 18 24 30 36 42
Time, months Time, months

Figure 4. Compressive strength of mortars exposed to 5% MgSO4 solution and distilled water.
Figure 4. Compressive strength of mortars exposed to 5% MgSO4 solution and distilled water.
3.3. Compressive Strength
The results of the compressive strength investigation are presented in Figure 4.
The development of the strength of the mortars stored in water was typical for cement composites.
The compressive strength increased for the first 6 months of storage, then stabilized at a relatively
high level. The compressive strength of polymer-cement mortars increased for a longer period of
time but remained lower in value than that of the unmodified composite. This is a well-known
phenomenon, caused by disruption of the cement hydration by an otherwise advantageous polymer
film [15]. The continuous polymer film hinders the moisture transport inside the composite. This
leads to a deficiency of the water necessary for the cement hydration process and thus reduces the rate
of hydration. For this reason, the strength development in PCCs is usually delayed as compared to
unmodified composites [17,21].
Corrosion processes in the mortar attacked by sulphate ions led to a deterioration of the strength.
The compressive strength of the unmodified mortar exposed to the 5% MgSO4 solution developed
until the sixth month of storage, then began to decrease; the decrease was particularly noticeable after
30 months of exposure. The compressive strength decreased from almost 70 MPa after 6 months to less
than 40 MPa after 42 months of storage.
The polymer addition improved the performance of the cement mortar exposed to the sulphate
solution. At the polymer-cement ratio of 0.05, the decrease of the strength was much milder than in the
case of the unmodified mortar. At higher contents of the polymer modifier, the compressive strength
did not decrease after 6 months of exposure, and only after the 30th month could some diminishment
of the strength be observed.
Figure 5 presents the ratio of the compressive strength of the mortars exposed to the 5% MgSO4
solution to that of the mortars stored in pure water, for the range of exposure times. It clearly
demonstrates that an increase in the polymer content led to a better performance of the composite.
For the unmodified mortar, the loss of the compressive strength after 42 months of exposure to the
sulphate solution was 44% compared to that determined for the mortar stored in water. For the mortar
with the polymer-cement ratio of 0.20 it was only 18%.
 Figure 5 presents the ratio of the compressive strength of the mortars exposed to the 5% MgSO4
solution to that of the mortars stored in pure water, for the range of exposure times. It clearly
demonstrates that an increase in the polymer content led to a better performance of the composite.
For the unmodified mortar, the loss of the compressive strength after 42 months of exposure to the
sulphate solution was 44% compared to that determined for the mortar stored in water. For the
Materials 2020, 13, 71 8 of 12
mortar with the polymer-cement ratio of 0.20 it was only 18%.

p/c=0 p/c=0.05 p/c=0.10 p/c=0.20

120

100
fc(MgSO4) to fc(H2O) ratio, %

80

60

40

20

0
0 6 12 18 24 30 36 42
Time, months
Figure 5. The ratio of compressive strength of mortars stored in 5% MgSO4 solution to those stored in
Figure 5. The ratio of compressive strength of mortars stored in 5% MgSO4 solution to those stored in
distilled water after different exposure times, for various polymer contents.
distilled water after different exposure times, for various polymer contents.
3.4. Visual and Microscopic Observations
3.4. Visual and Microscopic Observations
The visual observations generally corresponded with the results of the technical
The visual
properties observations generally corresponded with the results of the technical properties
investigations.
Materials 2019, 12, x FOR PEER REVIEW 9 of 13
investigations.
The unmodified Portland cement mortar began to demonstrate clear signs of corrosion after
12 months Theofunmodified
exposure to the 5%
Portland MgSO
cement 4 solution
mortar began (Figure 6a). After
to demonstrate clear 42 months
signs of exposure,
of corrosion after 12 the
months
specimens of exposure
were seriouslyto damaged,
the 5% MgSO 4 solution
which is in (Figure 6a). After 42with
good correlation months
the of exposure,
results the specimens
of previously reported
were seriously damaged, which is in good correlation with the results of previously
test results (Figure 6b). In addition, the structure of the mortar was damaged in a manner corresponding reported test
results (Figure 6b). In addition, the structure of the mortar was damaged in a manner
to the above observations. Needle-like ettringite crystals were present after 12 months (Figure 7a), corresponding
to the above observations. Needle-like ettringite crystals were present after 12 months (Figure 7a),
while—as described in the Introduction—massive ettringite forming the shells around the aggregate
while—as described in the Introduction—massive ettringite forming the shells around the aggregate
grains, dominated after 42 months of exposure (Figure 7b).
grains, dominated after 42 months of exposure (Figure 7b).

(a) (b)
Figure
Figure 6. Cement
6. Cement mortar
mortar without
without polymerstored
polymer stored in
in 5% MgSO
MgSO4 4solution:
solution:(a)(a)
after 12 months;
after (b) after
12 months; (b) after
42 months.
42 months.
 (a) (b)
Materials 2020, 13, 71
Figure 6. Cement mortar without polymer stored in 5% MgSO4 solution: (a) after 12 months; (b) after 9 of 12
42 months.

(a) (b)
Figure
Figure 7. Microscopic
7. Microscopic images
images of cement
of cement mortar
mortar without
without polymer
polymer storedinin
stored 5%5% MgSO
MgSO solution: (a)
4 4solution: (a) after
after 12 months; (b) after 42 months;
12 months; (b) after 42 months; magn. 50×. magn. 50×.

AddingAdding polymer
polymer to to
thethePortland
Portlandcement
cement mortar
mortar led
ledtotoananimprovement
improvement in the composite
in the composite
performance subjected to the sulphate aggression. Even a small content of the polymer modifier
performance subjected to the sulphate aggression. Even a small content of the polymer modifier
(polymer-cement ratio 0.05) delayed the beginning of corrosion (Figure 8a). However, after a longer
(polymer-cement ratio 0.05) delayed the beginning of corrosion (Figure 8a). However, after a longer
exposure, this composite showed a similar degradation as that without modification (Figure 8b). Due
exposure, this composite showed a similar degradation as that without modification (Figure 8b). Due to
to the action of the polymer, the structure of the composite was more homogeneous and compacted,
the action of the
thus less polymer, the structure
water-permeable of the
(Figure 9a). composite
However, after was more homogeneous
42 months, and compacted,
clear signs of weakening of the thus
less water-permeable (Figure 9a). However, after 42 months, clear signs of weakening of
structure could be seen, namely microcracks and delaminations in the aggregate-paste contact zonethe structure
could(Figure
be seen,
9b).namely microcracks and delaminations in the aggregate-paste contact zone (Figure 9b).
Materials
Materials2019,
2019,12,
12,xxFOR
FORPEER
PEER REVIEW
REVIEW 1010ofof1313

(a)
(a) (b)
(b)
FigureFigure
Figure 8.8. Polymer-cement
Polymer-cement
8. Polymer-cement mortar, p/c =
mortar,
mortar, p/c0.05,
p/c == 0.05, stored
stored
0.05, in
in 5%
in 5%
stored MgSO
MgSO
5% 4 solution: (a)
4 solution:
MgSO (a) after
4 solution: (a)after
12
after12 months;
months;(b)
12months; (b)
(b) after
after
42 months. 42 months.
after 42 months.

(a) (b)
(a) (b)
Figure 9. Microscopic images of polymer-cement mortar, p/c = 0.05, stored in 5% MgSO4 solution: (a)
Figure Figure 129.months;
Microscopic
9. Microscopic
after images
(b)images
after 42 ofofpolymer-cement
polymer-cement mortar,
months. mortar,p/cp/c = 0.05,
= 0.05, stored in 5%in
stored MgSO 4 solution:
5% MgSO (a)
4 solution:
after 12 months; (b) after 42 months.
(a) after 12 months; (b) after 42 months.
Higher polymer content brought more substantial enhancement in the mortars’ behaviour. After
Higher of
12 months polymer
exposurecontent
to thebrought
5% MgSO more substantial enhancement in the mortars’ behaviour. After
4 solution, only efflorescence without advanced corrosion
12
symptoms could be found on the specimens’ surfacesonly
months of exposure to the 5% MgSO 4 solution, efflorescence
(Figure 10a), while without advanced
after 42 months corrosion
of exposure,
symptoms could be found on the specimens’ surfaces (Figure 10a), while after 42 months
the specimens were still in satisfactory shape, with only moderate visible signs of corrosion (Figure of exposure,
the specimens
10b). were stillobservations
The microscopic in satisfactoryof shape, with only
the structure moderate
of the visible signs
polymer-cement of corrosion
mortars were in(Figure
good
10b). The microscopic
correlation observations
to these findings. of the structure
The structure of the polymer-cement
of the composite mortars were
with a polymer-cement in 0.20
ratio of good
Materials 2020, 13, 71 10 of 12

Higher polymer content brought more substantial enhancement in the mortars’ behaviour. After
12 months of exposure to the 5% MgSO4 solution, only efflorescence without advanced corrosion
symptoms could be found on the specimens’ surfaces (Figure 10a), while after 42 months of exposure,
the specimens were still in satisfactory shape, with only moderate visible signs of corrosion (Figure 10b).
The microscopic observations of the structure of the polymer-cement mortars were in good correlation
to these findings. The structure of the composite with a polymer-cement ratio of 0.20 looked sound
after 12 months of exposure to the sulphate solution (Figure 11a), while after 42 months of exposure, it
showed only slight microcracks and deformations (Figure 11b). The action of the polymer content was
sufficient to ensure not only a tighter structure but also better adhesion between aggregate grains and
hardened cement paste.
Materials 2019, 12, x FOR PEER REVIEW 11 of 13
Materials 2019, 12, x FOR PEER REVIEW 11 of 13

(a)
(a) (b)
(b)
Figure
Figure Polymer-cement
10.10. Polymer-cementmortar,
Polymer-cement mortar, p/c===0.20,
mortar,p/c
p/c 0.20,stored
0.20, inin
stored
in 5%
5% MgSO
5% MgSO
MgSO solution: (a)after
4 solution:
4 4solution: (a) after
(a) 1212
after months;
(b)(b)
12 months;
months;
after
(b) 4242
after
after months.
42months.
months.

(a) (b)
(a) (b)
Figure
Figure 11.11. Microscopicimages
Microscopic images of polymer-cement
polymer-cementmortar,
mortar,p/c
p/c = 0.20,
= 0.20, stored in 5%
stored in MgSO 4 solution:
5% MgSO (a)
4 solution:
Figure
(a) after11.
after 12 Microscopic
12months;
months;(b) images
(b)after
after4242 of polymer-cement mortar, p/c = 0.20, stored in 5% MgSO4 solution: (a)
months.
months.
after 12 months; (b) after 42 months.
4. Conclusions
4. Conclusions
4. Conclusions
The results
The resultsofofinvestigations
investigationspresented
presentedin inthis
this paper allow
allow usustotoconclude
concludethat thatthe
theaddition
addition of of
thethe
Themodifier
polymer
polymer results oftoinvestigations
modifier to Portland
the presented
the Portland cement
cement inmortar
mortar this paper
could could allow
greatly us toimprove
greatly
improve conclude itsthat the addition
performance
its performance of the
when
when exposed
to exposedmodifier
polymer
sulphate to sulphate
aggression.to aggression.
the
ThePortlandThecement
measurements
measurements mortarofcould
of elongation elongation
massand
and greatly mass changes
improve
changes of the specimens,
itsspecimens,
of the performance when
as well as
theasdetermination
welltoas
exposed the determination
sulphate of aggression. of
The
the compressive themeasurements
compressive
strength, showedstrength, showed
of elongation
a significant and amass
significant
advantage changes advantage
of the of of the
the specimens,
polymer-cement
as polymer-cement
well as over
composite thecomposite
the determination
unmodified over the regarding
of one
the unmodified
compressive one
their regarding
strength,
behaviour their
showed behaviour
during a long-term during
significant long-term
advantage
(up (upthe
of
to 42 months)
to 42 months)
polymer-cement
storage storage in a
composite over
in a 5% magnesium 5% magnesium sulphate(VI)
the unmodified
sulphate(VI) solution.one solution.
In regarding In these conditions,
their behaviour
these conditions, the elongation
duringoflong-term
the elongation PCCs with (up
a
to of
42PCCs withstorage
months)
polymer-cement a ratio
polymer-cement
in 0.20
of a 5%was ratio
magnesium
aboutof 50%
0.20 was about
sulphate(VI)
of that 50% of that
solution.
measured measured
forIn
thethese for the mortar
conditions,
mortar without the without
elongation
polymer. The
of polymer.
PCCs with The mass of the tested
a polymer-cement mortar
ratio specimens
of 0.20 was aboutstored
50%inofwater stabilized for
that measured when
thethey
mortar achieved
without
polymer. The mass of the tested mortar specimens stored in water stabilized when theydecrease
saturation, however, the mass of the specimens stored in the sulphate solution started to achieved
after 12 to 18 months due to damage to the specimens. The polymer mitigated this effect, reducing
saturation, however, the mass of the specimens stored in the sulphate solution started to decrease
the absorbability of the water necessary for the reactions that lead to damage. For PCCs with a
after 12 to 18 months due to damage to the specimens. The polymer mitigated this effect, reducing
polymer-cement ratio of 0.20, the mass increase after 42 months of storage in the sulphate solution
the absorbability of the water necessary for the reactions that lead to damage. For PCCs with a
was very close to that in water and did not exceed 5%. Determination of the compressive strength
Materials 2020, 13, 71 11 of 12

mass of the tested mortar specimens stored in water stabilized when they achieved saturation, however,
the mass of the specimens stored in the sulphate solution started to decrease after 12 to 18 months due
to damage to the specimens. The polymer mitigated this effect, reducing the absorbability of the water
necessary for the reactions that lead to damage. For PCCs with a polymer-cement ratio of 0.20, the
mass increase after 42 months of storage in the sulphate solution was very close to that in water and
did not exceed 5%. Determination of the compressive strength also showed a significant advantage of
the polymer-cement composite over the unmodified one. The compressive strength of the unmodified
mortar exposed to the 5% MgSO4 solution decreased from almost 70 MPa after 6 months to less than
40 MPa after 42 months of storage. The compressive strength of PCCs with a polymer-cement ratio of
0.20 after 6 months of storage was about 50 MPa, but after 42 months it still exceeded 45 MPa. For
the unmodified mortar, the loss of the compressive strength after 42 months of exposure to sulphate
solution was 44% compared to that determined for the mortar stored in water, while for the mortar
with the polymer-cement ratio of 0.20 it was only 18%. Within the polymer-cement ratio range from 0
to 0.20, the resistance of the material to sulphate aggression improved as the polymer content increased.
These findings are in good correlation with the results of the visual inspection of the tested specimens
and microscopic observations.

Author Contributions: Conceptualization, formal analysis, writing-original draft, supervision, P.Ł.; methodology,
investigation, D.D.; writing-review and editing, P.Ł. and D.D. All authors have read and agreed to the published
version of the manuscript.
Funding: This research was supported by the Faculty of Civil Engineering, Warsaw University of Technology and
Faculty of Civil Engineering, Cracow University of Technology, as a part of their „Statutory Research Activity
2016-2019”.
Conflicts of Interest: The authors declare no conflicts of interest.

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