materials

Article
Durability of Concrete with Partial Replacement of Portland
Cement by Incorporating Reactive Magnesium Oxide
and Fly Ash
Lucas Sequeira 1 , Javier Forero 2 , Miguel Bravo 1, * , Luís Evangelista 3 and Jorge de Brito 1, *

1 CERIS—Civil Engineering Research and Innovation for Sustainability, Department of Civil Engineering,
Architecture and Georesources, Instituto Superior Técnico (IST), University of Lisbon,
1049-001 Lisbon, Portugal
2 Postgraduate Program in Structural Engineering and Construction (PECC), Predio SG-12 Campus Darcy
Ribeiro, University of Brasília, Brasilia 70910-900, Brazil
3 CERIS—Civil Engineering Research and Innovation for Sustainability, Lisbon’s Polytechnic Engineering
Institute (ISEL-IPL), 1959-007 Lisbon, Portugal
* Correspondence: [email protected] (M.B.); [email protected] (J.d.B.)

Abstract: In this research, the durability performance of sustainable concrete with the incorporation of
reactive magnesium oxide (MgO) and fly ash (FA) was evaluated. The partial replacement of cement
with these two materials is an appealing solution for the construction sector due to sustainability
benefits and shrinkage reduction. The incorporation of FA by partial replacement of cement was
carried out at 0%, 15% and 30%. The incorporation of MgO in concrete was carried out at 0%, 5%,
10% and 20%. Two types of MgO were used, one from Australia and another of Spanish origin. These
two materials were evaluated in terms of their individual incorporation, and then an evaluation
was carried out when the two were simultaneously used. In terms of durability, performance losses
between 3% and 95% were obtained in all tests (water absorption by capillarity and immersion,
carbonation depth and resistance to chloride penetration). However, over time, the difference in
performance relative to the reference concrete tends to decrease due to the slow hydration that
characterizes these two alternative materials. It was found that, in most of the tests, no overlapping of
Citation: Sequeira, L.; Forero, J.; the negative effects occurred. In other words, the simultaneous incorporation of MgO and FA caused
Bravo, M.; Evangelista, L.; de Brito, J. performance losses lower than the sum of the losses of their individual incorporation.
Durability of Concrete with Partial
Replacement of Portland Cement by Keywords: concrete; MgO; fly ash; durability properties
Incorporating Reactive Magnesium
Oxide and Fly Ash. Materials 2023, 16,
2670. https://doi.org/10.3390/
ma16072670 1. Introduction
Academic Editor: Carlos Leiva The world population has been increasing exponentially in recent decades. One of the
consequences of this population increase will be an increase in the number of dwellings
Received: 27 February 2023
and infrastructures, especially in large cities.
Revised: 24 March 2023
Accepted: 26 March 2023
The construction industry will play a fundamental role in allowing the correct ac-
Published: 27 March 2023
commodation of this large number of human beings. The same industry is responsible
for the emission of 10% of the CO2 produced worldwide. More specifically, 7.4% of CO2
comes from cement production. Based on these facts, it is clear that concrete production
has a high ecological footprint [1]. The use of special mortars is a way of mitigating the
Copyright: © 2023 by the authors. impact of climate change by using them as a carbon dioxide capture, utilization and storage
Licensee MDPI, Basel, Switzerland. technology [2]. With the aim of reducing this footprint, several alternatives have been
This article is an open access article proposed, among which comes the one that will be presented in this paper [3]. The use of
distributed under the terms and mineral admixtures in concrete production can help in the resolution of this problem. In
conditions of the Creative Commons
this research, the use of MgO and fly ash was studied.
Attribution (CC BY) license (https://
The cracking of concrete can lead to a reduction in its durability and can also compro-
creativecommons.org/licenses/by/
mise the safety of structures. This can be particularly problematic in regions with harsh
4.0/).

Materials 2023, 16, 2670. https://doi.org/10.3390/ma16072670 https://www.mdpi.com/journal/materials

Materials 2023, 16, 2670 2 of 19

weather conditions or high-traffic areas where constant exposure to environmental stressors

can weaken concrete. Another problem with Portland cement concrete is the high alkalinity
of the mix, which can cause the corrosion of reinforcing steel, leading to potential structural
damage. This issue has been of concern in the construction industry for several decades, as
the reinforcement is essential for the structural stability of concrete structures. To address
these problems, researchers have been studying the use of active magnesium oxide and fly
ash as partial replacements for Portland cement.
Regarding MgO, it is possible to produce concrete with its incorporation, reducing
CO2 emissions [4]. The use of reactive MgO as a partial replacement for Portland cement
in concrete can reduce the amount of CO2 emitted for two major reasons. The first one
is the lower calcination temperature, since the production of Portland cement involves
heating raw materials, such as limestone and clay, to temperatures of around 1450 ◦ C. This
process releases large amounts of CO2 into the atmosphere. In contrast, reactive MgO
can be produced at much lower temperatures, typically around 750 ◦ C, which results in
much lower CO2 emissions [5–7]. That reduction may be explained by carbonation; i.e.,
when concrete is exposed to the atmosphere, it naturally absorbs CO2 over time. The use
of reactive MgO can accelerate this process, as MgO reacts with CO2 to form magnesium
carbonate. This reaction helps to offset the carbon emissions associated with the production
of Portland cement. In this investigation, light-burned MgO was used, characterized by
high reactivity, caused by its calcination temperature between 700 ◦ C and 1000 ◦ C [5]. These
temperatures are relatively low compared to that needed for the production of Portland
cement, which is 1450 ◦ C [6,7].
Jin and AL-Tabbaa [5], citing Kramer and Shand [8,9], stated that much of the MgO
used in industry is produced through the calcination of MgCO3 , as seen in Equation (1).

MgCO3 + heat ⇒ MgO + CO2 (1)

Mo et al. [10] stated that in the hydration reaction of MgO brucite, Mg(OH)2 , is
obtained as the end product (Equation (2)).

MgO + H2 O ⇒ Mg(OH)2 (2)

Du [11] presented more information on the hydration of magnesium oxide. The author
states that the formation of brucite causes expansion in concrete because the hydration
products of MgO have a larger volume than the reactants. One of the most important
characteristics in the use of MgO is its reactivity. This property is evaluated through the
reaction of MgO with water and dilute acids, and the reactivity depends mainly on the
physical characteristics and purity of the material. The reactivity of MgO tends to increase
with the reduction in its particle size and with the increase in its specific surface area. These
two parameters are controlled by the production conditions, i.e., raw material purity and
calcination temperature [12].
The lower the reactivity of a MgO sample, the slower its hydration. The smaller
specific surface area causes more clumping of the particles in a sample, which leads to
lower hydration. Jin and Al-Tabba and Mo et al. [5,10] reached the same conclusions.
One of the most important concrete characteristics is porosity. Given its relevance,
several studies have already been conducted. Mo and Panesar [13] studied the porosity
in cement pastes with MgO. The amount of MgO present was 0%, 10%, 20% and 40%.
The researchers found that incorporating 20% MgO could lead to a 32% decrease in pore
volume at 28 days when compared to that of the reference cement paste under accelerated
carbonation. On the contrary, a 6–10% increase in pore volume was found in pastes with
10–40% MgO under non-carbonation conditions, indicating that the higher the amount of
MgO used, the higher the porosity of concrete, impairing some of its properties in terms of
durability [14].
Materials 2023, 16, 2670 3 of 19

Liu et al. [15] reached the same conclusions, where the use of 5% MgO as a substitute
for OPC, in mortar production, led to a 19% increase in porosity, compared to the reference
mortar, at 91 days.
Several studies have been conducted on cementitious materials with the incorporation
of MgO. In terms of durability, the conclusions obtained by the different authors were clear.
Bravo et al. [16] analyzed the water absorption by capillarity in mortars with the
presence of 5%, 10%, 15%, 20% and 25% MgO in their constitution. The authors stated
that the greater the amount of MgO present, the greater the water absorption by capillarity
relative to the reference mortar. In fact, when adding 25% MgO, the worst results were
obtained, with an increase of about 44% in absorption.
On the other hand, Mavroulidou et al. [17] studied the water absorption capacity in
concrete with the incorporation of 5% and 10% MgO, together with FA and metakaolin, as a
substitute for OPC, at 28 days of age. It was found that the incorporation of 5% MgO caused
a decrease in water absorption capacity, which was attributed to the better compaction of
mixes with higher levels of MgO and metakaolin, due to the greater water requirements in
its composition to maintain consistency. However, with the presence of 10% MgO, better
results were obtained than those observed for the reference concrete, but worse results
were obtained than those observed for concrete with 5% MgO.
Pu and Unluer [18] analyzed the carbonation capacity of concrete with the incorpora-
tion of 10% MgO, at 14 days. The authors observed that the carbonation depth in specimens
with MgO was twice that obtained in the reference concrete. Gonçalves et al. [19] reached
the same conclusions, observing an increase in the carbonation depth in mortars as the
percentage of MgO increased. In fact, the presence of 20% MgO in the produced mortars
increased the carbonation depth by between 139% and 483% at 91 days, depending on the
reactivity of MgO used.
In summary, the use of MgO in cementitious materials leads to worse characteristics
in terms of its durability. Analyzing the studies presented, it is clear that the presence of
MgO causes an increase in water absorption by capillarity and immersion. The presence of
this oxide also causes a greater depth of carbonation in specimens with MgO. Regarding
the resistance of chloride penetration, taking into account the variation in the properties
mentioned, it is expected that the presence of MgO causes a decrease in this capacity.
The use of fly ash is interesting because it allows for its recycling. This material
is mainly composed of SiO2 and Al2 O3 . According to the American Society for Test-
ing Materials [20], the fly ash used in this investigation is class F since the amount of
SiO2 + Al2 O3 + Fe2 O3 (silicate + alumina + iron oxide) is higher than 70%. Physically, it is
possible to observe a filler effect, which consists in filling the voids between particles of
Portland cement with fly ash particles, because these have smaller dimensions [4]. Due
to the presence of siliceous compounds, which in the presence of water can be related
to calcium hydroxide, there is an increase in calcium silicate hydrate (C-S-H), leading to
advantages in terms of durability [21,22].
During the first 24 h, fly ash has a retarding impact on concrete hydration. This
phenomenon is because the ash needs the glassy fraction to solubilize in order to interact
with the calcium hydroxide. After 28 days of age, hydrate growth occurs on the surface of
the fly ash particles. The degree of hydration can increase up to 16%, in order to compensate
for the lower degree of hydration at the beginning of curing [23].
Saha [24] demonstrated that the capillary water absorption in concrete with 10%, 20%,
30% and 40% FA was decreased by 4%, 13%, 29% and 32%, respectively, relative to the
reference concrete at 28 days of age. The study noted that FA concrete lost capillary water
absorption for two distinct reasons. The first is that FA has a greater specific surface area
than cement, and the second is that FA reduces the thickness of the interfacial transition zone
(ITZ) between aggregates and binders. Nayak et al. [25] concluded that water absorption by
immersion and capillarity in concrete with 40% FA was 26% lower than that in the reference
concrete, which is probably due to its improved reaction with the products released during
the hydration process. The secondary gel or extra C-S-H produced in the presence of fine
Materials 2023, 16, 2670 4 of 19

FA particles filled some pores inside the concrete, making it denser and more compact.
Consequently, the permeability coefficient was reduced as the FA content increased to a
given level [26].
Again, Saha [24] concluded that the chloride penetration at 28 days in concrete with
10%, 20%, 30% and 40% FA was reduced by 3%, 27%, 48% and 53%, respectively, relative to
the reference concrete. The study suggested that this decrease is due to the fineness of fly
ash. However, the lower concentration of alkali ions (Na+ and K+ ) and associated hydroxyl
ions (OH− ) in the pore solution is mentioned as another reason for this better behavior [27].
Sadrmomtazi et al. [28] reported an increase in chloride penetration at 28 days in concrete
with FA compared to control concrete. On the other hand, at the age of 90 days, the chloride
penetration decreased by up to 30% with the use of FA, due to the progress of pozzolanic
reactions.
An experimental study by Turk et al. [29] showed that as the FA content in self-
compacting concrete increases, the carbonation resistance decreases [30]. This is because
the use of FA reduces the concentration of carbonation-prone products (calcium hydroxide
and C-S-H). As a result, total CaO decreases due to higher carbonation rates [31].
With an increasing amount of FA in concrete, it is expected that water absorption by
capillarity and immersion will show lower values than those of the reference concrete. The
same happens for chloride penetration resistance and carbonation depth, as found in the
studies presented above.
Analyzing the combination of fly ash with MgO, it was possible to conclude that MgO
is insoluble with C-S-H from the hydration of Portland cement and fly ash. Thus, brucite
will react with the silica from fly ash, forming a compound called hydrated magnesium
silicate (M-S-H) [32]. Depending on the amount of silica present, the hydration of MgO
may give rise to two products that may or may not coexist: brucite and M-S-H.
Choi et al. [33] focused their study on concrete with partial incorporation of FA
and MgO. For the experimental campaign, they incorporated 20% FA in all mixes, while
the amount of MgO varied between 0% and 5%. The specimens were water cured for
28 and 360 days. The authors used different water/binder ratios of 0.65 and 0.48. From the
chloride ion migration test results, 65-M0-28 had a 1.1% lower coefficient than 65-M5-28,
but 65-M0-360, with a longer curing period, had a 20% higher coefficient compared to
65-M5-360. In addition, MgO worked similarly in concrete with w/b = 0.48.
In the same study, the authors also analyzed the carbonation capacity of the different
mixes produced at 28, 90 and 180 days of age. The carbonation depths of 65-M0-28 and
65-M5-28 were almost identical up to 180 days of exposure, with a difference of only 4%. On
the other hand, 65-M5-360, having been cured for a longer duration, produced a shallower
depth of carbonation (15%) than 65-M0-360 from the start. It is then possible to conclude
that the carbonation depth at early ages is little affected by the presence of MgO and FA,
showing better results at later ages. It is known that an increase in porosity promotes
concrete carbonation since it facilitates the influx of CO2 [27,30,31].
In this experimental campaign, concrete with 0%, 5%, 10% and 20% MgO and 0%, 15%
and 30% fly ash was produced. It should be noted that the percentages of incorporation are
defined in terms of mass. Furthermore, the study focused mainly on the simultaneous use
of these two materials, but this replacement will also be analyzed individually to better
understand their combined action.
Two different types of MgO were studied, one of Australian origin (MgO-A) and the
other from Spain (MgO-S), in order to obtain conclusions on how some specific characteris-
tics of MgO influence the future performance of concrete. Durability-related characteristics
were analyzed. An analysis of the concrete in its fresh state was also performed, by study-
ing its workability. In terms of durability, the tests performed were water absorption by
capillarity and immersion, carbonation depth and resistance to chloride penetration.
Nowadays there is not enough literature to allow the characterization of concrete with
MgO and FA in terms of durability. It is important to fill this gap in order to be able to
advance in the research of more sustainable concrete. Therefore, this is the main objective
Materials 2023, 16, 2670 5 of 19

of this study. In fact, the scarce research conducted on the combined use of these two
materials does not comprehensively assess the durability of these mixes. On the other
hand, the evaluation of the use of MgO’s with different reactivity (a low-reactivity MgO
and a high-reactivity MgO were used) in these concrete mixes with MgO and FA is also
completely innovative.

2. Materials and Methods

2.1. Materials
For this investigation, the following materials were used: fine aggregates, coarse
aggregates, cement CEM I 42.5R, tap water, MgO and fly ash. No additives were used in
this experimental campaign.
Portland cement CEM I 42.5R was produced by Secil (Lisbon, Portugal). In terms
of natural aggregates, two types were used: coarse aggregates (with commercial grading
conforming to the designations 2/6, 6/12 and 12/20 of EN 12620 [34]) and siliceous
sands (0/2 and 0/4). A class F fly ash was obtained from EDP-Gestão da Produção de
Energia, S.A., at the Sines Power Plant, in Portugal (with 58% SiO2 and 24% Al2 O3 ). Two
different types of MgO were used, Spanish and Australian, with purities of 85.0% and
98.8%, respectively. In terms of specific surface area, MgO-S had 4.9 m2 /g, while MgO-A
had 51.2 m2 /g. The reactivity was 3544 s and 14 s for the Spanish and Australian MgO’s,
respectively. Liska et al. [12] also demonstrated that the reactivity of MgO tends to increase
with the increase in the specific surface area. The fly ash used to produce concrete was
also supplied by Secil. In Table 1, the particle size of the different binders is provided.
Table 1 shows that particles of MgO-A clearly have a smaller size than particles of MgO-S.

Table 1. Particle size of the different binders.

Material <3 µm (%) Between 3 and 32 µm (%) >32 µm (%)

OPC 25.9 56.2 17.9
FA 21.3 55.9 22.8
MgO-S 12.1 15.3 72.6
MgO-A 40.1 56.0 3.9

2.2. Composition of the Mixes

In Table 2, the composition of the reference concrete is provided. Only the composition
of the RM mix is provided because the others are the same.
Following a methodology presented by Nepomuceno et al. [35], the composition of
each mix was determined. In order to characterize the reference concrete, a strength class
C30/37 and a consistency class S2 were defined. Different water/binder ratios were used
in order to maintain the S2 consistency class in all the mixes.
The only change in the composition of the other mixes is the amount of each binder,
according to defined and explained percentages. In total, 21 concrete mixes were produced:
reference concrete (RC); mixes with replacement ratios of 5%, 10% and 20% MgO-A and
MgO-S, by mass; mixes with incorporations of 15% and 30% fly ash, by mass (with or
without MgO). Each mix is identified as Cx/y:FA/MgO-A or Cx/y:FA/MgO-S, where x is
the amount of FA and y is the amount of Australian or Spanish MgO, respectively.
Materials 2023, 16, 2670 6 of 19

Table 2. Composition of the reference concrete (RC).

Binder 0.098
0–0.063 0.001
0.063–0.125 0.004
0.125–0.25 0.030
Fine aggregates
0.25–0.5 0.079
0.5–1 0.097
1–2 0.085
2–4 0.036
4–5.6 0.012
5.6–8 0.050
Coarse aggregates
8–11.2 0.072
11.2–16 0.153
16–22.4 0.092
Water 0.174
Voids 0.017
Total 1.000

2.3. Tests
It was decided to divide the experimental campaign into three phases. Firstly, the
different materials that constituted concrete were evaluated. Then, the concrete mixes were
analyzed in their fresh and hardened states.
In order to classify the different mixes in terms of durability, the tests previously men-
tioned were performed. The water absorption by capillarity was evaluated at 28 and 91 days,
in 3 specimens, according to LNEC E-393 (1993) [36]. Water absorption by immersion was
measured at 28 days, in 3 specimens, based on LNEC E-394 (1993) [37]. For chloride
penetration resistance, the diffusion coefficient test was performed at 28 and 91 days, in
3 specimens for each age, according to NT BUILD 492 (1999-11) [38]. Finally, the carbona-
tion depth was measured at 7, 28, 56 and 91 days of age, based on LNEC E391 (1993) [39].
All specimens were placed in a humid chamber for 28 or 91 days.

3. Results and Discussion

3.1. Consistency
By increasing the incorporation ratio of reactive MgO, the consistency of the mixes
tended to decrease. Therefore, it was necessary to increase the water/binder ratio in the
mixes as reactive MgO increased to maintain the target consistency, as observed in Figure 1.
Figure 2 shows that all mixes are within the S2 consistency (50–100 mm) class. Comparing
the two different MgO’s (from Spain and Australia), a higher amount of water was required
in the mix with MgO from Australia. This is due to the higher fineness and specific surface
area of the MgO-A particles, since the greater their specific surface area, the greater the
amount of water required absorbed by their surface. On the other hand, there was a slight
decrease in the amount of water required in concrete with FA.
 mixes as reactive MgO increased to maintain the target consistency, as observed in Figure
1. Figure 2 shows that all mixes are within the S2 consistency (50–100 mm) class. Compar-
ing the two different MgO’s (from Spain and Australia), a higher amount of water was
required in the mix with MgO from Australia. This is due to the higher fineness and spe-
cific surface area of the MgO-A particles, since the greater their specific surface area, the
Materials 2023, 16, 2670 greater the amount of water required absorbed by their surface. On the other hand, there7 of 19
was a slight decrease in the amount of water required in concrete with FA.

Materials 2023, 16, x FOR PEER REVIEW 7 of 19

Figure 1. Abrams cone slump.

Materials 2023, 16, x FOR PEER REVIEW 7 of 19

0.62
Figure
0.61 1.1.Abrams
Figure Abramscone slump.
cone slump.
Water/binder ratio

0.6
0.62
0.59
0.61
0.58
Water/binder ratio

0.6
0.57
0.59
0.56
0.58
0.55
0.57
0 5 10 15 20
0.56
MgO ratio (%)
0.55 MgO-A MgO-S
0 5 10 15 20
C15FA:MgO-A C15FA:MgO-S
MgO ratio (%)
C30FA:MgO-A
MgO-A C30FA:MgO-S
MgO-S

C15FA:MgO-A C15FA:MgO-S
Figure 2. Water/binder ratio.
C30FA:MgO-A C30FA:MgO-S

3.2.Figure
Water2.Absorption by Capillarity
Water/binder ratio.
Figure 2. Water/binder ratio.
Firstly, the results of water absorption by capillarity at 28 and 91 days for concrete
3.2. Water Absorption by Capillarity
with
3.2.the
Waterincorporation
Absorption byofCapillarity
MgO are presented in Figures 3 and 4, respectively. With the
presence Firstly,
of the the
MgO, results of water
water absorption
absorption by capillarity
by capillarity tends at increase
to 28 and 91considerably.
days for concrete
Firstly, the results of water absorption by capillarity at 28 and 91 days for concrete In
with
fact, the incorporation of MgO are presented in Figures 3 and 4, respectively. With
wasthe
with the incorporation of MgO are presented in Figures 3 and 4, respectively. With Itthe
the greater the amount of MgO incorporated, the greater the water absorption.
presence
possible of
to of MgO,
obtain, the water absorption by capillarity tends to increase considerably. In fact,
presence MgO,especially
the water at 91 days, better
absorption results tends
by capillarity when toMgO-A
increasewas used. This phe-
considerably. In
the greater the
nomenon amount of MgO incorporated, the greater ofthe water absorption. It was possible
fact, the can be due
greater to the
the amount smaller
of MgOspecific surface
incorporated, area
the greaterthe
theparticles of MgO-S
water absorption. Itleading
was
to obtain, especially at 91 days, better results when MgO-A was used. This phenomenon can
to possible
greater porosity.
to obtain, especially at 91 days, better results when MgO-A was used. This phe-
be due to the smaller specific surface area of the particles of MgO-S leading to greater porosity.
nomenon can be due to the smaller specific surface area of the particles of MgO-S leading
to greater porosity.
MgO-A MgO-S RC
Capillarity absorption at 72

0.0019 MgO-A MgO-S RC

0.0017
at 72

0.0019
hours (g/mm²)
Capillarity absorption

0.0015
0.0017
hours (g/mm²)

0.0015
0.0013

0.0013
0.0011
RC C5:MgO C10:MgOC20:MgO
0.0011
3. Water RC C5:MgO
absorption C10:MgOC20:MgO
Figure
Figure 3. Water absorption by by capillarity
capillarity at h
at 72 72versus
h versus
MgOMgO content,
content, at 28
at 28 days.
days.
Figure 3. Water absorption by capillarity at 72 h versus MgO content, at 28 days.
Materials 2023, 16, x FOR PEER REVIEW 8 of 19
Materials 2023, 16, x FOR PEER REVIEW 8 of 19
Materials 2023, 16, 2670 8 of 19

MgO-A MgO-S RC
0.0018
MgO-A MgO-S RC
0.0017

Capillarity absorption at 72
0.0018
0.0016
0.0017

Capillarity absorption at 72
hours (g/mm²)
0.0015
0.0016

hours (g/mm²)
0.0014
0.0015
0.0013
0.0014
0.0012
0.0013
0.0011
0.0012
0.0010
0.0011
0.0010 RC C5:MgO C10:MgO C20:MgO

Figure 4. Water absorptionC5:MgO C10:MgO C20:MgO

by capillarity RC
at 72 h versus MgO content, at 91 days.
Figure
Figure4.4.Water
Waterabsorption
absorptionby
bycapillarity
capillarityat
at72
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versusMgO
MgOcontent,
content,at
at91
91days.
days.
As expected, the capillarity values at 28 days are higher than those at 91 days. An
increase Asof
As 37% is observed
expected,
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capillarity valuesatat28
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91 days. in in
Choi C20:MgO-A,
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of Again,
these at 28materials
two days, increases,
thisin-
creases, the capillary absorption capacity also tends to increase. Again, at 28 days, same
the
same capillary
capacity absorption
shows higher capacity
values also
than tends
the tests to increase.
performed Again,
at 91 at
days. 28 days,
The best this
results
this
capacity
were
same obtainedshows
capacity in higher
the
shows mix values than than
C15/5:FA/MgO,
higher values the tests with
the performed
an performed
tests increase at 91
of atdays.
about
91 days.The
4%, best
The results
relative
besttoresultswere
RC,
obtained
both
were in
at obtained the
28 and 91in mix
days. C15/5:FA/MgO,
the Again, with
MgO-A seems with
mix C15/5:FA/MgO, an increase
to show an better of
increase about
results 4%, relative
than 4%,
of about to
the Spanish RC,
relative coun-to RC,at
both
28 and
terpart. 91 days.
both atObserving
28 and 91 days.Again, MgO-A
TableAgain,
3, it is MgO-Aseems
noticeable to
seems show
that,towhen better
showthese results
bettertwo than the
materials
results Spanish
than the counterpart.
areSpanish
used simul- coun-
Observing
taneously, Table
the 3, itobtained
results is noticeable were that, whenbetter
always these than
two materials
the expected are used simultaneously,
theoretical values
terpart. Observing Table 3, it is noticeable that, when these two materials are used simul-
the results
(sum of the the obtained
effects were
of the always better
individual than the of expected theoretical Thisvalues (sum oftothe
taneously, results obtained wereplacement
always better these
thanelements).
the expected is quite
theoretical easyvalues
effects of the at
observe individual placement of mix
thesepresents
elements). Thisvalues
is quitewhen easy MgO
to observe when,
(sum ofwhen,the effects 91 days,
of thethe RC:15FA
individual placement similar
of these elements). This is quite is added.
easy to
at
Thus, 91 days,
in terms the RC:15FA mix presents similar values when MgO is added. Thus, in terms of of
observe when,ofatthis 91 property, the simultaneous
days, the RC:15FA mix presents use ofsimilar
MgO and valuesFA whenin the MgO
productionis added.
this
concreteproperty, the simultaneous use of MgO and FA in the production of concrete seems to
Thus, inseems
termsto ofbethisinteresting.
property, the simultaneous use of MgO and FA in the production of
be interesting.
concrete seems to be interesting.
MgO-A MgO-S RC
MgO-A MgO-S RC
Capillarity absorption at 72 hours

0.0016
Capillarity absorption at 72 hours

0.0016
0.0015
0.0015
0.0014
(g/mm²)

0.0014
0.0013
(g/mm²)

0.0013
0.0012
0.0012
0.0011
0.0011
0.0010
0.0010

Figure 5. Capillarity absorption at 72 h in mixes with MgO and FA at 28 days.

Figure 5. Capillarity absorption at 72 h in mixes with MgO and FA at 28 days.
Figure 5. Capillarity absorption at 72 h in mixes with MgO and FA at 28 days.
Materials 2023, 16, x FOR PEER REVIEW 9 of 19
Materials 2023, 16, 2670 9 of 19

RC MgO-A MgO-S

Capillarity absorption at 72 hours

0.0016
0.0015
0.0014

(g/mm²)
0.0013
0.0012
0.0011
0.0010

Figure 6. Capillarity absorption at 72 h in mixes with MgO and FA at 91 days.

Figure 6. Capillarity absorption at 72 h in mixes with MgO and FA at 91 days.
Table 3. Real values obtained in the laboratory and theoretical expected values at 28 and 91 days.
Table 3. Real values obtained in the laboratory and theoretical expected values at 28 and 91 days.
28 Days 91 Days
28 Days 91 Days
Mix ∆ Expected ∆ Expected
Mix ∆ Real (%) Δ Expected ∆ Real (%) Δ Expected
Δ Real (%) Theoretical (%) Δ Real (%) Theoretical (%)
Theoretical (%) Theoretical (%)
C15/5:FA/MgO-A
C15/5:FA/MgO-A +4.1+4.1 +17.4
+17.4 +4.4
+4.4 +8.9+8.9
C15/5:FA/MgO-S
C15/5:FA/MgO-S +3.7+3.7 +20.7
+20.7 +3.4
+3.4 +10.8
+10.8
C15/10:FA/MgO-A
C15/10:FA/MgO-A +13.0
+13.0 +36.2
+36.2 +5.7
+5.7 +15.5
+15.5
C15/10:FA/MgO-S
C15/10:FA/MgO-S +11.5
+11.5 +29.7
+29.7 +6.5
+6.5 +17.4
+17.4
C15/20:FA/MgO-A
C15/20:FA/MgO-A +16.0
+16.0 +42.8
+42.8 +9.0
+9.0 +21.2
+21.2
C15/20:FA/MgO-S
C15/20:FA/MgO-S
+23.5
+23.5
+41.9
+41.9
+3.4
+3.4
+24.9
+24.9
C30/5:FA/MgO-A +12.0 +23.4 +7.3 +13.6
C30/5:FA/MgO-A +12.0 +23.4 +7.3 +13.6
C30/5:FA/MgO-S +23.5 +26.7 +3.3 +15.5
C30/5:FA/MgO-S +23.5 +26.7 +3.3 +15.5
C30/10:FA/MgO-A +18.0 +42.2 +12.8 +20.2
C30/10:FA/MgO-A
C30/10:FA/MgO-S +18.0
+24.3 +42.2
+35.7 +12.8
+16.4 +20.2
+22.1
C30/10:FA/MgO-S
C30/20:FA/MgO-A +24.3
+19.3 +35.7
+48.8 +16.4
+17.1 +22.1
+25.8
C30/20:FA/MgO-S
C30/20:FA/MgO-A +22.3
+19.3 +47.9
+48.8 +20.1
+17.1 +29.6
+25.8
Note: Δ expected theoretical of mix
C30/20:FA/MgO-S CX/Y:FA/MgO +47.9
+22.3 corresponds to the +20.1
sum of Δ real of mix RCX:FA
+29.6
and Δ real of mix CY:MgO.
Note: ∆ expected theoretical of mix CX/Y:FA/MgO corresponds to the sum of ∆ real of mix RCX:FA and ∆ real of
mix CY:MgO.
3.3. Water Absorption by Immersion
3.3.Figure
Water 7Absorption
shows thatbythe
Immersion
water absorption by immersion at 28 days tends to increase
as the Figure 7 showsratio
incorporation that the waterand
of MgO absorption by immersion
FA increases. at 28 MgO-A,
Using only days tends thetovariation
increase as
the incorporation
varies ratio of
between increases ofMgO and FA
54% and 65%increases.
with respectUsing to only
RC forMgO-A,
the use theofvariation
5% and 20%varies
between increases of 54% and 65% with respect to RC for the use of
MgO-A, respectively. Similar values were obtained for the Spanish counterpart. The worst5% and 20% MgO-A,
respectively.
results were seen Similar
in thevalues were obtained
C30:FA/MgO mixes, asforexpected,
the Spanish withcounterpart.
an absorption Theofworst
about results
16%
for both MgO’s, almost doubling the RC value. However, it should be noted that16%
were seen in the C30:FA/MgO mixes, as expected, with an absorption of about thefor both
com-
MgO’s, almost doubling the RC value. However, it should be noted
bined use of these materials (MgO and FA) shows an improvement relative to the ex- that the combined use
of thesetheoretical
pected materials (MgO
value.andThis
FA) shows
can be an improvement
proved by relativeanalyzing,to thefor
expected theoretical
example, the
value. This can be proved by analyzing, for example, the C15/10:FA/MgO-A
C15/10:FA/MgO-A mix. The RC15:FA mix shows an increase in the water absorption of mix. The
RC15:FA mix shows an increase in the water absorption of 26.5%,
26.5%, in relation to RC. The C10:MgO-A mix presents an increase of 51%. It would thenin relation to RC. The
beC10:MgO-A
expected that mixthe
presents an would
joint use increasecause
of 51%. It would
a 77.5% then be
increase in expected that the
the absorption joint use
capacity
would cause a 77.5% increase in the absorption capacity compared
compared to RC. However, this increase was only 57%. When MgO is mixed with water, to RC. However, this
increase was only 57%. When MgO is mixed with water, it undergoes
it undergoes a chemical reaction to form magnesium hydroxide, which can fill the pore a chemical reaction
to form magnesium hydroxide, which can fill the pore spaces in the concrete and reduce
spaces in the concrete and reduce water absorption. Physically, the use of FA can originate
water absorption. Physically, the use of FA can originate a filler effect, which consists in
a filler effect, which consists in filling the voids between particles of Portland cement with
filling the voids between particles of Portland cement with fly ash particles, because these
Materials 2023, 16, x FOR PEER REVIEW 10 of 19

Materials 2023, 16, x FOR PEER REVIEW 10 of 19

Materials 2023, 16, 2670 10 of 19

fly ash particles, because these have smaller dimensions [4]. When MgO and fly ash are
used simultaneously in concrete, they complement each other’s properties. MgO fills the
flyhave
ash particles,
smaller because these
dimensions have smaller
[4]. When MgO and dimensions are[4].
fly ashgel When
used MgO and flyinash
simultaneously are
pore spaces, while fly ash produces additional C-S-H and improves durability.concrete,
As a
used simultaneously
they the
complement in concrete,
eachofother’s they complement each other’s properties. MgO fills the
result, combination these properties. MgO
two materials fills the pore
provides betterspaces,
resultswhile fly ash
in terms of produces
water
pore spaces,
additional while fly ash produces additional C-S-H gel and improves durability. As a
absorption byC-S-H gel and
immersion than improves
the sumdurability. As a result,
of the individual effectsthe combination of these two
[32].
result, the combination of these two materials provides better results in terms
materials provides better results in terms of water absorption by immersion than the sum of water
absorption
of the by immersion than the sum of the individual effects [32].
18 individual effects [32].

(%) (%)
by immersion 18
16
by immersion

16
14

14
12
absorption

12
10
absorption

10
8
WaterWater

8
6
0 5 10 15 20
6
MgO ratio (%)
0 5 10 15 20
MgO-S MgO-A
MgO ratio (%)
C15:FA/MgO-S C15:FA/MgO-A
MgO-S MgO-A
C30:FA/MgO-S C30:FA/MgO-A
C15:FA/MgO-S C15:FA/MgO-A
C30:FA/MgO-S C30:FA/MgO-A
Figure 7. Water absorption by immersion at 28 days.
Figure
Figure 7. 7. Water
Water absorption
absorption byby immersion
immersion at at
2828 days.
days.
3.4. Carbonation
3.4. Carbonation
In Figures 8–10, the carbonation depth at 7, 28, 56 and 91 days of concrete mixes that
3.4. Carbonation
In Figures
were cured 8–10, the
in a chamber carbonation
with 5% CO2, depth
60% RH at 7,
and28,2356°C
and 91 days of concrete
temperature mixes
is provided. that
It is
wereIn Figures
cured in8–10,
a the carbonation
chamber with 5% depth
CO , at 7,RH
60% 28, 56
and and
23 91
◦ Cdays of concrete
temperature is mixes that It
provided.
2
immediately clear that with the incorporation of MgO and FA, the carbonation depth in-
were cured in a chamber
is immediately clear with
that with5%the
COincorporation
2, 60% RH and 23 °C temperature is provided. It is
of in
MgO
creases. In fact, when the ratio of these materials used the and
mixesFA, the carbonation
increases, the carbon-depth
immediately
increases. clear
In that
fact, with
when the
the incorporation
ratio of these of MgO andused
materials FA, inthethe
carbonation
mixes depth in-the
increases,
ation tends to present higher values. This phenomenon was expected due to several rea-
creases. In fact,tends
carbonation whentothe ratio higher
present of thesevalues.
materialsThis used in the mixes increases, the carbon-
sons. First, the increase in the water/binder ratio in phenomenon
the mixes with was
MgO expected
and/ordueFA to several
causes
ation tends
reasons. to present
First, higher values. This phenomenon was expected
the increase in the water/binder ratio in the mixes with MgO and/or due to several rea-FA
a more porous matrix.
sons. First, the increase
causes a more porous matrix.in the water/binder ratio in the mixes with MgO and/or FA causes
a more porous matrix.
20
(mm)(mm)

20
15
depthdepth

15
10
Carbonation

10
Carbonation

5
0
0 20 40 60 80 100
0 Time (days)
0 20 40 60 80 100
RC Time (days) C5:MgO-A
C10:MgO-A
RC C20:MgO-A
C5:MgO-A
C5:MgO-S
C10:MgO-A C10:MgO-S
C20:MgO-A
C20:MgO-S
C5:MgO-S C10:MgO-S

Figure
Figure C20:MgO-S
8. Carbonation
8. Carbonation depth
depth in mixes
in mixes with
with MgO.
MgO.

Figure 8. Carbonation depth in mixes with MgO.

Materials 2023, 16, x FOR PEER REVIEW 11 of 19
Materials 2023, 16, x FOR PEER REVIEW 11 of 19
Materials 2023, 16, 2670 11 of 19

20
20

(mm)
depth(mm)
15
15

Carbonationdepth
10
10
Carbonation
5
5

0
0
0 20 40 60 80 100
0 20 40 60 80 100
Time (days)
Time (days)
RC15:CV C15/5:FA/MgO-A
RC15:CV C15/5:FA/MgO-A
C15/10:FA/MgO-A C15/20:FA/MgO-A
C15/10:FA/MgO-A C15/20:FA/MgO-A
C15/5:FA/MgO-S C15/10:FA/MgO-S
C15/5:FA/MgO-S C15/10:FA/MgO-S
C15/20:FA/MgO-S
C15/20:FA/MgO-S
Figure 9. Carbonation
Figure
Figure 9. Carbonation depth
9. Carbonation
depth in mixes
depth
in mixes with
in mixes MgO
with
with MgO and
MgO 15%
and
and FA.FA.
15%
15% FA.

20
20
18
18
(mm)

16
depth(mm)

16
14
14
Carbonationdepth

12
12
10
10
Carbonation

8
8
6
6
4
4
2
2
0
0
0 20 40 60 80 100
0 20 40 Time (days) 60 80 100
Time (days)
RC30:FA C30/5:FA/MgO-A C30/10:FA/MgO-A
RC30:FA C30/5:FA/MgO-A C30/10:FA/MgO-A
C30/20:FA/MgO-A C30/5:FA/MgO-S C30/10:FA/MgO-S
C30/20:FA/MgO-A C30/5:FA/MgO-S C30/10:FA/MgO-S
C30/20:FA/MgO-S
C30/20:FA/MgO-S
Figure 10. Carbonation depth in mixes with MgO and 30% FA.
Figure 10.
Figure 10. Carbonation
Carbonation depth
depth in
in mixes
mixes with
with MgO
MgO and
and 30%
30% FA.
FA.
On the other hand, the partial replacement of Portland cement causes lower production
On thethe other hand,hand, the partial
partial replacement
replacement of of Portland
Portland cement
cement causes
causes lower
lower produc-
produc-
of On
C-S-H otherand Ca(OH)the 2 , in which interaction between them would lead to a decrease in
tion
tion of C-S-H
ofprogress
C-S-H and and Ca(OH) 2, in which interaction between them would lead to a decrease
Ca(OH)2, in which interaction between them would lead tothe
a decrease
the of carbonation. In addition, according to Gonçalves et al. [19], decreased
in quantity
in the progress
the progress of carbonation.
of
of Ca(OH) carbonation. In addition,
In addition, according
according toand
to Gonçalves
Gonçalves
a higheret et al. [19],
al. [19], the de-
of the de- ,
2 , which exhibits a pH level of ~12.5, amount Mg(OH) 2
creased
creased quantity
with aquantity
pH of ~10.5, of Ca(OH)
of Ca(OH) 2, which exhibits a pH level of ~12.5, and a higher amount of
means2,that whichtheexhibits
overall pH a pH level
level of ~12.5,
lowers, and ashowing
thereby higher amount of
an increased
Mg(OH) , with
with aa pH
rate of22,carbonation
Mg(OH) pH ofof ~10.5, means
~10.5,
according means that
to thethat the overall
the overall pH
phenolphthalein pHtest.
level
level lowers,
lowers,
This, thereby
thereby
together showing
withshowing an
an
the existence
increased
of a more
increased rate of carbonation
porous
rate of carbonation
microstructure, according to the
relative
according to the phenolphthalein
to RC, test. This,
will be quite coherent
phenolphthalein test. This, together with
justifications.
together with
the existence
The MgO
the existence of a more
of a from
moreSpain porous
porous microstructure,
shows worse results
microstructure, relative
than the
relative to RC,
to RC, will
one will be quite
frombeAustralia. coherent
quite coherent justi-
As previously
justi-
fications.
mentioned, this is because the lower specific surface area of the MgO-S particles causes
fications.
The MgO
greater
The MgO fromfacilitating
porosity,
from Spain shows
Spain shows worse
theworse results than
progression
results than
of the one
one from
carbonation
the from Australia.
to greater
Australia. As previously
depths.
As previously
This can be
mentioned,
seen in this
Figure is
8, because
as the usethe oflower
20% specific
MgO-A surface
increases area
the of
mentioned, this is because the lower specific surface area of the MgO-S particles91causes the MgO-S
carbonation particles
depth at causes
days by
greater
114% porosity,
relative tofacilitating
RC, while the
in progression
MgO-S, this of carbonation
increase exceeds to greater
160%.
greater porosity, facilitating the progression of carbonation to greater depths. This can be depths. This can be
seen in Figure
Table 4 8, as
shows the
the use of
results 20% forMgO-A
the mixes increases
with the
MgO carbonation
and
seen in Figure 8, as the use of 20% MgO-A increases the carbonation depth at 91 days by FA. Once depth
again, atit91is days by
important
114%
114% relative
to note thatto
relative tothe
RC,
RC, while in
simultaneous
while in MgO-S,
MgO-S,
use ofthis
this increase
these exceeds
two exceeds
increase materials 160%.
presents very good results, in
160%.
Table
comparison 4 shows
Table 4 shows withthethe results
theresults
summed for the mixes
for effects
the mixes with
of their MgO
withindividual and
MgO and FA. FA. Once again,
again,Itit
incorporation.
Once itwas
is important
is important
possible to
to note that the simultaneous use of these two materials
to note that the simultaneous use of these two materials presents very good results, inpresents very good results, in
 Materials 2023, 16, 2670 12 of 19

observe that in 11 of the 12 concrete mixes produced with MgO and FA, better values of
this property than the expected theoretical values were obtained.

Table 4. Real values obtained in the laboratory and theoretical expected values, at 91 days.

91 Days
Mix
∆ Real (%) ∆ Expected Theoretical (%)
C15/5:FA/MgO-A 39.6 65.5
C15/5:FA/MgO-S 46.0 44.9
C15/10:FA/MgO-A 75.5 90.4
C15/10:FA/MgO-S 72.7 110.9
C15/20:FA/MgO-A 90.1 121.6
C15/20:FA/MgO-S 94.9 167.2
C30/5:FA/MgO-A 5.4 37.1
C30/5:FA/MgO-S 5.4 35.2
C30/10:FA/MgO-A 42.4 80.8
C30/10:FA/MgO-S 52.4 101.3
C30/20:FA/MgO-A 54.0 111.9
C30/20:FA/MgO-S 72.5 157.6
Note: ∆ expected theoretical of mix CX/Y:FA/MgO corresponds to the sum of ∆ real of mix RCX:FA and ∆ real of
mix CY:MgO.

Knowing that the presence of FA leads to an improvement in carbonation capacity [24,30],

it should be noted that the best results were obtained when a mixture of 30% FA with
MgO was used (a decrease in carbonation depth of 2.5% appears in RC30:FA, compared
to RC). This is because the fly ash particles seem to be able to fill the interstitial pores
(filler effect), halting the advance of carbonation depth. In addition, the use of FA reduces
the concentration of carbonation-prone products (CH and CSH). As a result, total CaO
decreases due to higher carbonation rates [31].

3.5. Resistance to Chloride Penetration

Materials 2023, 16, x FOR PEER REVIEW Figures 11–13 summarize the chloride penetrability test results at 28 and 9113days.
of 19
As expected, it is evident that with the incorporation of MgO and FA, the chloride ion
migration coefficient increases.

30.0
Migration coefficient (x10−12 m2/s)

25.0

20.0

15.0

10.0

5.0

0.0

28 days 91 days

Figure 11. Chloride ion migration coefficient in mixes with MgO.

Figure 11. Chloride ion migration coefficient in mixes with MgO.

30
(x10−12 m2/s)

25

20
 Migr
0.0

Migratio
28 days 91 days
Materials 2023, 16, 2670 28 days 91 days 13 of 19
 
Figure 11. Chloride ion migration coefficient in mixes with MgO.
Figure 11. Chloride ion migration coefficient in mixes with MgO. 
30

Migration coefficient (x10−12 m2/s)

30

Migration coefficient (x10−12 m2/s)
25
25
20
20
15
15
10
10
5
5
0
0

28 days
28 days 91 days
91 days
 
Figure 12. Chloride ion migration coefficient in mixes with MgO and 15% FA. 
Figure 12.12.
Figure Chloride ion
Chloride migration
ion coefficient
migration coefficientinin
mixes with
mixes MgO
with MgOand
and15%
15%FA.FA.

3030
m /s)
m22/s)

2828 days
days 9191 days
days
2525
−12
Migration coefficient (x10−12

2020
Migration coefficient (x10

1515

1010

55

00

 
Figure 13. Chloride ion migration coefficient in mixes with MgO and 30% FA. 
Chloride ion migration coefficient
Figure
Figure 13.13.
Chloride ion migration coefficient inin mixes
mixes with
with MgOand
MgO and30%
30%FA.FA.

    The worst results were obtained when 20% MgO was used, with an increase of 100% in
the chloride ion penetration coefficient relative to RC. As with the previous properties, the
theoretical value expected for the combination of MgO and FA is substantially higher than
the value obtained in the laboratory, as shown in Table 5. This means that the simultaneous
use of MgO and FA in concrete also has positive consequences on these concrete properties.
As expected, the coefficients at 91 days present lower values than those at 28 days. This
means that there is a small improvement in the resistance to chloride penetration over time.
  Several studies have been carried out comparing chloride ion penetration with water
absorption by capillarity. Ferreira [40] concluded that the chloride ion diffusion coefficient
and the water absorption by capillarity have a linear relationship. As seen in Figure 14,
the coefficient of determination at 28 days was 0.74, which shows a reasonable linear
relationship between both properties in the concrete mixes evaluated in this investigation.
The linear relationship between the carbonation depth and the chloride diffusion
coefficient was also analyzed, at 28 days, and it can be observed in Figure 15. In this case,
the linear regression coefficient was 0.79, also indicating a reasonable linear relationship
between the mentioned properties in mixes with MgO and FA. The linear relationships
observed allow demonstrating that the mentioned properties are influenced by identical
factors, both in conventional concrete and in concrete with partial incorporation of MgO
and/or FA.
 91 Days
Mix
Δ Real (%) Δ Expected Theoretical (%)
C15/5:FA/MgO-A 35.4 77.2
C15/5:FA/MgO-S 48.6 84.8
C15/10:FA/MgO-A 53.9 127.2
Materials 2023, 16, 2670 14 of 19
C15/10:FA/MgO-S 65.7 114.6
C15/20:FA/MgO-A 66.0 140.4
C15/20:FA/MgO-S 74.1 139.8
Table 5. Real values obtained in the laboratory
C30/5:FA/MgO-A 38.1 and theoretical expected
78.3 values, at 91 days.
C30/5:FA/MgO-S 35.4 85.9
91 Days
C30/10:FA/MgO-AMix 67.7 128.3
∆ Real (%) ∆ Expected Theoretical (%)
C30/10:FA/MgO-S 70.5 115.8
C15/5:FA/MgO-A
C30/20:FA/MgO-A 76.0 35.4 141.5 77.2
C15/5:FA/MgO-S
C30/20:FA/MgO-S 78.2 48.6 140.9 84.8
Note: Δ expected theoretical of mix CX/Y:FA/MgO corresponds
C15/10:FA/MgO-A 53.9 to the sum of Δ real of mix RCX:FA
127.2
and Δ real of mix CY:MgO.
C15/10:FA/MgO-S 65.7 114.6
C15/20:FA/MgO-A
Several studies have been carried out comparing 66.0chloride ion penetration with 140.4water
absorptionC15/20:FA/MgO-S
by capillarity. Ferreira [40] concluded that74.1the chloride ion diffusion coefficient
139.8
and the water absorption by capillarity have a linear relationship. As seen in Figure 14,
C30/5:FA/MgO-A 38.1 78.3
the coefficient of determination at 28 days was 0.74, which shows a reasonable linear re-
C30/5:FA/MgO-S
lationship between both properties in the concrete35.4 85.9
mixes evaluated in this investigation.
The linear relationship between the carbonation
C30/10:FA/MgO-A 67.7depth and the chloride diffusion
128.3 co-
efficient was also analyzed, at 28 days, and it can be observed in Figure 15. In this case,
C30/10:FA/MgO-S 70.5 115.8
the linear regression coefficient was 0.79, also indicating a reasonable linear relationship
between the C30/20:FA/MgO-A
mentioned properties in mixes with 76.0 141.5
MgO and FA. The linear relationships
observed allow demonstrating that the mentioned78.2
C30/20:FA/MgO-S properties are influenced by140.9 identical
Note: ∆
factors, both in conventional
expected concrete
theoretical of mix and in concrete
CX/Y:FA/MgO with
corresponds partial
to the ∆ real of mix RCX:FA
sum ofincorporation and ∆ real of
of MgO
mix CY:MgO.
and/or FA.

31.0
Chloride ion migration coefficient (x10-12

29.0
R² = 0.74
27.0

25.0
m2/s)

23.0

21.0

19.0

17.0

15.0
0.0010 0.0015 0.0020
Materials 2023, 16, x FOR PEER REVIEW Water absorption by capillarity (g/mm2) 15 of 19

Figure
Figure 14. 14. Relationship
Relationship between
between chloride
chloride ion ion migration
migration coefficient
coefficient andand water
water absorption
absorption by by capillarity.
capil-
larity.
31.0
Chloride ion migration coefficient (x10-12

29.0
R² = 0.79
27.0

25.0
m2/s)

23.0

21.0

19.0

17.0

15.0
0.0 5.0 10.0 15.0
Carbonation depth (mm)

Figure
Figure 15.15. Relationship
Relationship between
between chloride
chloride ion migration
ion migration coefficient
coefficient and carbonation
and carbonation depth.depth.

3.6. Comparative Analysis between Concrete Durability and Compressive Strength

It is important to compare the compressive strength with the different durability
properties analyzed in order to understand whether there is a relationship between the
Materials 2023, 16, 2670 15 of 19

3.6. Comparative Analysis between Concrete Durability and Compressive Strength

It is important to compare the compressive strength with the different durability
properties analyzed in order to understand whether there is a relationship between the
different properties. For the reference concrete, a compressive strength of 44.2 MPa was
obtained at 28 days, and a compressive strength of 48.3 MPa was obtained at 91 days. In
Table 6, the variation in the properties mentioned in the ternary mixes (OPC, MgO, FA),
relative to the reference concrete, is provided.

Table 6. Mechanical and durability behavior of the different mixes.

Variation Relative to RC (%)

Water Absorption Water Absorption Carbonation Chloride
Compressive Strength
Mix by Capillarity by Immersion Depth Penetration
28 Days 91 Days 91 Days 28 Days 91 Days 91 Days
C15/5:FA/MgO-A −26.9 −15.5 +4.40 +42.7 +39.6 +35.4
C15/5:FA/MgO-S −23.1 −13.7 +3.43 +39.5 +46.0 +48.6
C15/10:FA/MgO-A −29.3 −15.5 +5.65 +57.0 +75.5 +53.9
C15/10:FA/MgO-S −30.5 −17.3 +6.54 +65.4 +72.7 +65.7
C15/20:FA/MgO-A −41.1 −34.5 +9.03 +75.3 +90.1 +66.0
C15/20:FA/MgO-S −44.8 −36.8 +3.38 +82.1 +94.9 +74.1
C30/5:FA/MgO-A −34.6 −15.0 +7.30 +54.4 +5.4 +38.1
C30/5:FA/MgO-S −34.1 −18.9 +3.34 +51.7 +5.4 +35.4
C30/10:FA/MgO-A −46.9 −29.1 +12.77 +82.8 +42.4 +67.7
C30/10:FA/MgO-S −42.6 −26.2 +16.41 +79.9 +52.4 +70.5
C30/20:FA/MgO-A −58.2 −39.5 +17.13 +95.3 +54.0 +76.0
C30/20:FA/MgO-S −59.1 −38.5 +20.11 +91.9 +72.5 +78.2

Regarding compressive strength, it is clear that there is a decrease in strength capacity

in concrete with partial incorporation of MgO and FA. In fact, the greater the amount of
MgO and FA incorporated, the greater the observed reduction in this capacity compared to
the reference concrete. At 28 days, there were decreases of between 23% and 60% in the
compressive strength of ternary mixes compared to RC. However, at 91 days of age, this
decrease ranged only between 13% and 40%, proving the better behavior of these concrete
mixes with the progress of curing time.
It is clear that the decay in the mechanical capacity of concrete is accompanied by
worse results in terms of durability. The simultaneous presence of MgO and FA in concrete
composition leads to worse results in all durability properties studied. As the amount of
these materials increases, a worse behavior of ternary mixes is also observed.
It is concluded that the mechanical and durability properties present similar behavior
in concrete with MgO and FA. This phenomenon is proved by verifying that with increasing
amounts of MgO and FA in the cement matrix of concrete, worse compressive strength
results are obtained. The same was found for durability.

4. Conclusions
This research served to study the influence, in terms of durability, of concrete with
partial incorporation of MgO and fly ash. It was possible to analyze the corresponding
variations when Portland cement was replaced with 5%, 10% and 20% MgO and/or 15%
and 30% fly ash. In almost all the properties, worse results were obtained with the presence
of one of these materials, or both, relative to the reference concrete.
It was also found that Spanish MgO generally presents worse results when compared
to the Australian counterpart. This was due to its lower specific surface area and, conse-
Materials 2023, 16, 2670 16 of 19

quently, to its lower reactivity. These characteristics increase the porosity of the cement
paste. It is well known that the porosity of the cement paste is of vital importance in
determining the durability behavior of concrete.
By incorporating MgO and FA in the constitution of concrete, it is concluded that
as the amount of these two materials increases, the capillary absorption capacity also
tends to increase. For mixes with simultaneous incorporation of MgO and FA, there
was an increase in all mixes produced, ranging from 3.7% (C15/5:FA/MgO-S) to 24.3%
(C30/10:FA/MgO-S), at 28 days of curing age.
A similar behavior was detected in the water absorption by immersion capacity at
28 days. The combined incorporation of the two materials caused worse results. In individ-
ual terms, the presence of only 15% FA causes a 26.5% increase in water absorption capacity.
Concrete with 30% FA and 20% MgO-A shows very similar results, with an increase of 64%
and 65% in this property, respectively, compared to conventional concrete. In the combined
use of MgO and FA, the best result was obtained for the mix C15/5:FA/MgO-S, with an
increase of 39.5% relative to RC.
Observing the results obtained for carbonation depth, similar results were obtained.
The worst result was observed for C20:MgO-S, with an increase of 160% in carbonation
depth at 91 days. However, the use of FA originated an improvement in comparison to RC.
The lowest carbonation depth value was obtained for the mix RC30:FA.
As expected, with the incorporation of MgO and FA, the chloride ion migration
coefficient increases. The worst results were obtained when 20% MgO was used, with an
increase of 100% in the chloride ion penetration coefficient relative to RC. As previously
mentioned, with the increase in the amount of MgO and FA in the cement matrix of concrete,
there is an increase in the penetration of chloride ions, for all mixes, with the best value
being reached when using 30% FA and 5% MgO, causing an increase of 35.4% in this
property relative to RC.
By studying the compressive strength at 28 and 91 days, trends similar to those
observed in the durability properties were found. The partial replacement of OPC causes
a decrease in the mechanical capacity. Accompanying this decrease is a worse durability
behavior of the non-conventional concrete. It is thus concluded that the presence of MgO
and FA in concrete negatively affects the mechanical and durability characteristics of
concrete.
Finally, one of the most important conclusions was that in none of these properties
was there total overlapping of the negative effects. In the results obtained, an improvement
is obtained when FA and MgO are combined, relative to the expected theoretical result.
The theoretical value corresponds to the sum of the individual effects of each material. It
was observed that in all the analyzed properties, the results obtained in ternary mixes were
better than the expected theoretical results. This improvement was especially observed in
the carbonation depth and resistance to chloride ion penetration.
Comparing the ratio of OPC replaced with the increase in the studied properties, it is
possible to draw some conclusions. Only in the water absorption by capillarity, decreases
with the use of MgO and FA, relative to RC, lower than the ratio of incorporation of these
materials in the different mixes were observed. For example, in the mix C30/20:FA/MgO-S,
the simultaneous incorporation of MgO and FA (in a total of 50%), originated an increase of
only 20% in the water absorption by capillarity relative to RC. In the remaining properties,
the opposite phenomenon was found. The exception is the mix C30/5:FA/MgO, where
low values of carbonation depth were obtained.
In conclusion, it is clear that the combined use of MgO and FA shows better results than
would be theoretically expected. However, except for water absorption by capillarity, the
OPC replacement ratio is higher than the observed variation. The simultaneous use of these
materials seems to work better, but more studies are needed to find the ideal incorporation
ratio that could lead to better results. In this research, the incorporation of 15% FA and 5%
MgO in concrete seems to be interesting. On the other hand, the replacement of 50% OPC
seems excessive.
Materials 2023, 16, 2670 17 of 19

The practical benefits of using reactive magnesium oxide and fly ash as partial re-
placements for Portland cement in concrete production are significant. First and foremost,
these materials are cost-effective and readily available, making them an attractive option
for builders and engineers seeking to improve the sustainability and durability of their
structures. Additionally, the use of active magnesium oxide and fly ash can improve the
workability of concrete, making it easier to pour, mold and shape into the desired form.
This can be particularly beneficial in construction projects where intricate or complex de-
signs are required, such as in the construction of high-rise buildings, bridges and other
infrastructure. From a maintenance perspective, the use of reactive magnesium oxide and
fly ash can also improve the longevity and safety of concrete structures. By improving the
resistance of concrete to cracking, structures can be expected to last longer and require less
frequent repairs and maintenance.
The use of reactive magnesium oxide and fly ash as partial replacements for Portland
cement in concrete production shows promising results. However, further research is
needed to fully explore and optimize the potential of these alternative materials.
One area of further research is to investigate the performance of concrete mixes
containing different ratios of reactive magnesium oxide and fly ash. This would help to
identify the optimal mixture for achieving maximum performance and sustainability while
maintaining cost-effectiveness. In addition, the long-term durability of concrete structures
containing reactive magnesium oxide and fly ash should be studied. This would involve
testing the performance of these structures under different environmental conditions over
an extended period of time. This information would be valuable in determining the
maintenance requirements of concrete structures containing these alternative materials.
Another area of further research is to study the effects of using reactive magnesium oxide
and fly ash in combination with other sustainable construction materials, such as recycled
aggregates, in order to further reduce the environmental impact of concrete production.
These research topics will be crucial to optimize the use of these materials in concrete
structures with maximum performance, sustainability and cost-effectiveness for growing
cities and communities.

Author Contributions: Conceptualization, L.S., J.F. and M.B.; methodology, L.S., J.F., M.B., L.E. and
J.d.B.; data curation, L.S., J.F. and M.B.; writing—original draft, L.S.; writing—review and editing,
M.B., L.E. and J.d.B.; supervision, M.B., L.E. and J.d.B. All authors have read and agreed to the
published version of the manuscript.
Funding: This research was funded by the Portuguese Foundation for Science and Technology (FCT)
through project PTDC/ECI-COM-31138/2017 (DecarbonCrete).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: The authors wish to thank Civil Engineering Research and Innovation for
Sustainability (CERIS), IST and Foundation for Science and Technology (FCT).
Conflicts of Interest: The authors declare no conflict of interest.

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