Article
Impact of Combined Action of Chloride and Carbonation on
Cement-Based Materials with Fly Ash
Raphaele Malheiro 1, * , Aires Camões 1 , Gibson Meira 2 , Rui Reis 1 and Aline Nóbrega 3
Citation: Malheiro, R.; Camões, A.;
Meira, G.; Reis, R.; Nóbrega, A.
Impact of Combined Action of
Chloride and Carbonation on
Cement-Based Materials with Fly Ash.
Sci 2024, 6, 13. https://doi.org/
10.3390/sci6010013
Academic Editor: Francesco
Bencardino
Received: 15 January 2024
Revised: 12 February 2024
Accepted: 23 February 2024
Published: 28 February 2024
Copyright: © 2024 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Sci 2024, 6, 13. https://doi.org/10.3390/sci6010013
1 Centre for Territory, Environment and Construction (CTAC), University of Minho,
4800-058 Guimarães, Portugal; aires@civil.uminho.pt (A.C.); ruicunhareis@gmail.com (R.R.)
2 Federal Institute of Education, Science and Technology of Paraíba, Rua Deputado Balduíno Minervino de
Carvalho, 155/1104, João Pessoa 58036-860, Brazil; gibson.meira@ifpb.edu.br
3 Department of Civil and Environmental Engineering, Federal University of Campina Grande,
Campina Grande 58429-900, Brazil; aline.figueiredo@professor.ufcg.edu.br
* Correspondence: raphaelemalheiro@civil.uminho.pt
Abstract: Integrating waste and industrial by-products into concrete is an alternative way to reduce
global cement consumption, enhancing its eco-friendliness. In this context, residues with fly ash
have been increasingly utilised. Considering the vulnerability of concrete with fly ash to carbonation
and, at the same time, its high resistance to chlorides, it is important to investigate the behaviour of
these concretes under their combined actions. For this purpose, an experimental investigation was
conducted, studying mortar and concrete specimens with 40% replacement of cement with fly ash.
These specimens were subjected to a combination of actions (Cl− and CO2 ) in two phases: initially
through immersion and drying tests, and subsequently through a combination of accelerated tests.
Concerning the chloride impact study, free and total chloride profiles were studied. Concerning
the impact of carbonation, colourimetric and chemical tests were used. The results demonstrate a
significant influence of combined action not only on chloride penetration in cement-based materials
with fly ash but also on the development of a carbonation front. Exposure of cement-based materials
with fly ash to environments with high Cl− and CO2 content sequentially may lead, on the one hand,
to an increase in carbonation resistance. However, on the other hand, it may result in a substantial
reduction in chloride penetration resistance.
Keywords: concrete; fly ash; chloride; carbonation; combined action; durability
1. Introduction
The utilisation of fly ash (FA) in concrete holds significant importance in the context of
current climate concerns and carbon emissions. FA, a byproduct of coal combustion, has
been used as a sustainable alternative to traditional cement, contributing to a reduction
in carbon dioxide emissions associated with concrete production. In 2022, more than
4100 million tonnes of cement were produced, emitting around 0.58 tonnes of CO2 per
tonne of cement [1]. In this context, FA residues have been increasingly utilised in countries
where they are still available.
In addition to reducing the environmental impact of concrete, FA is also used in
concrete to make it more resistant to the action of chloride ions. The silicon dioxide (SiO2 )
in FA reacts with the calcium hydroxide (Ca(OH)2 ) generated during cement hydration,
forming calcium silicate hydrate (CSH) structures that significantly lower concrete porosity.
Consequently, this inhibits the transportation of harmful agents like chloride ions. More-
over, the aluminates in FA undergo a chemical reaction with free chlorides, binding them
and diminishing the quantity of free chlorides capable of infiltrating the concrete [2]. More-
over, with the inclusion of FA, the formation of Ca(OH)2 is reduced, leading to a lowering
of concrete pH. This reduction in Ca(OH)2 content further decreases the production of
https://www.mdpi.com/journal/sci
Sci 2024, 6, 13 2 of 15

calcium carbonate (CaCO3 ) during carbonation, thereby promoting the advancement of

carbonation [3].
CO2 and chloride ions are the most reported aggressive agents in concrete [4–6]. On the
one hand, CO2 can react with the alkaline components of cement, leading to the formation
of soluble carbonates and compromising the material’s integrity [7]. On the other hand, the
penetration of chloride ions can accelerate the corrosion of steel reinforcements, contributing
to concrete deterioration [8]. When it comes to concretes with FA, the interaction between
aggressive agents and FA adds a layer of complexity. Understanding this interaction is
essential to optimising the performance of these materials in challenging environments.
The impacts of CO2 and chloride ions on concrete structures have traditionally been
studied as separate phenomena. However, research into the combination of these aggressive
agents gained more prominence from the year 2000 onwards. Important examples in this
direction include studies conducted by AL-Ameeri et al. [9], Malheiro et al. [10], Zhang and
Panesar [11], Wang et al. [12], Zhu et al. [13], and Hussain and Ishida [14]. However, even
though the concurrent action of these mechanisms is acknowledged, a consensus regarding
the combined effect of chlorides and carbonation on the durability of concrete, both with
and without FA, remains elusive. According to Wang et al. [12], the exposure of Ordinary
Portland Cement (OPC) concrete to a CO2 environment increases chloride penetration.
In their study, specimens underwent carbonation in a chamber (5% CO2 , 20 ◦ C, and 65%
RH) for 1, 2, and 3 months, followed by total immersion in a solution with 165 g/l NaCl.
Conversely, Holthuizen [15] reported that for OPC mortar, carbonation decreases the
chloride diffusion coefficient. Their specimens were subjected to a carbonation chamber
(3% CO2 , 20 ◦ C, and 65% RH) for 23 weeks, followed by a chloride migration test according
to NT-Built 492.
This paper specifically focuses on studying the combined action of CO2 and chloride
ions in concretes with FA. Our research seeks to fill a significant gap in the literature
because, as in the case of concretes without FA, most studies address these aggressors
in isolation, neglecting the synergistic interactions that may occur in practice. Despite
this, some studies using mortar and concrete with FA were found. Nagataki and Ohga
(1992) [16] studied mortar with FA. Mortars were cured initially in distilled water or NaCl
solution for 7, 28, 56, and 91 days and then exposed to accelerated carbonation. Their
results show that the depth of carbonation of mortar cured initially in NaCl solution is
smaller than of that in distilled water. Xie et al. (2019) [17] studied chloride profiles in
carbonated concretes with FA (15% and 30%). Accelerated carbonation tests and rapid
chloride permeability tests were performed to investigate the distribution and diffusion
of chloride ions in concrete with FA after different carbonation degrees. The findings
revealed that chloride binding capacity is enhanced in early carbonation but drops in late
carbonation stages. Concerning carbonation resistance, it is improved for low water/binder
ratios but reduced for high ones. The differences between the methodologies used by
Nagataki and Ohga (1992) [16] and Xie et al. (2019) [17] make it difficult to compare results
directly, but it is possible to identify some trends. Montemor et al. (2002) [3] wrote that the
type of carbonation exposure is determinant. They studied mortar with 15% and 30% of FA
under CO2 (natural and 5%) and NaCl (15%) contamination. The chloride content in mortar
exposed to accelerated carbonation (5%) increases with the amount of FA. However, under
natural carbonation, it decreases with the addition of FA. Although the use of different
methodologies can provide different dynamics in the laboratory, a convergence of results is
clear concerning the decrease in chloride penetration resistance in carbonated FA concrete
under high CO2 levels.
This gap highlights the importance of the present study, which aims to fill this knowl-
edge void by exploring the interaction between these two aggressive agents in FA concrete.
Understanding this process is crucial for developing effective strategies to mitigate concrete
degradation under adverse environmental conditions. The contribution of this study is
significant as it will provide valuable insights for the construction industry, enabling the
 enabling the development of more effective strategies to improve the durability and
strength of concrete in challenging environments.
Sci 2024, 6, 13 3 of 15
2. Experimental Procedures
Accelerated tests were used to simulate the combined action of chloride and carbon-
development of more effective
ation. The experimental workstrategies to improve
was divided into two theimportant
durabilityparts
and strength of concrete
(Figure 1). In Part I,
inanchallenging
exploratoryenvironments.
study was carried out using mortar specimens to study the influence of
chloride presence on carbonation development. Mortar was used because its high porosity
2.and
Experimental Procedures
absence of coarse aggregate help to reach results faster than concrete. Immersion and
dry Accelerated tests were
cycles were used used to damage.
to accelerate simulate the combined action of chloride and carbona-
tion. TheThe results reached in Part I helped tointo
experimental work was divided twothe
define important partsused
methodology (Figure 1). In
in Part II. Part I,
In Part
anII, exploratory study was
concrete specimens carried
were used out usingtwo
to study mortar specimens
situations: to study the
the influence influence
of chloride of
pres-
chloride
ence on presence
carbonationon carbonation
development development. Mortar
and the influence ofwas used because
carbonation its hightransport.
on chloride porosity
and absence
In this case,ofa coarse aggregate
combination help to reach
of accelerated results
tests faster penetration
(chloride than concrete.byImmersion
immersionand and
dry cycles were used to accelerate damage.
carbonation chamber) was used instead of immersion and dry cycles.

Part I - Mortar study Part II - Concrete study

Characterization

Accelerated Accelerated Porosity

Concrete
Exploratory test: Cycles test: Cl-/CO2 assessment
study:
Mortar Accelerated Porosity
Characterization
test: CO2/Cl- assessment

Figure1.1.Outline
Figure Outlineofofthe
thetesting
testingprocess.
process.

2.1. The
Mortar and Concrete
results reached inSpecimens Production
Part I helped to define the methodology used in Part II. In Part
II, concrete specimens
Ordinary were
Portland used toCEM
Cement, studyI two situations:
42.5R, and FA the influence
were used asofbinder
chloride presencein
materials
on
thecarbonation
mortar anddevelopment and the influence
concrete specimens. of carbonation
Their chemical on chloride
compositions transport.
are presented In this1.
in Table
case, a combination of accelerated tests (chloride penetration by immersion and
The chemical composition of FA was determined using X-ray fluorescence spectroscopy. carbonation
chamber)
These FAwas used
were insteadfrom
obtained of immersion and dry
burning South cycles.
African and Colombian coal in Portuguese
thermoelectric power plants. In specimens with FA, 40% of cement was replaced by FA. A
2.1. Mortar and Concrete Specimens Production
superplasticiser based on polycarboxylic ether was used in the composition of concrete
Ordinary
without FA toPortland
help reachCement,
values CEM I 42.5R,
near the and FAslump,
predefined were used as binder
100 mm ± 5 mm.materials in
Composi-
the mortar
tions withandFA concrete specimens.
have greater Theirthan
workability chemical compositions
compositions are presented
without in Table 1.it
FA and, therefore,
The chemical composition of FA was determined using X-ray fluorescence spectroscopy.
was not necessary to use a superplasticiser. Concerning mortar, flow spread was fixed at
These FA were obtained from burning South African and Colombian coal in Portuguese
190 mm. Granitic crushed sand with a fineness modulus of 2.96 and two types of granitic
thermoelectric power plants. In specimens with FA, 40% of cement was replaced by FA.
crushed coarse aggregate, one with a fineness modulus of 6.07 and the other with 6.94,
A superplasticiser based on polycarboxylic ether was used in the composition of concrete
were used as aggregates. Tap water with a maximum value of 10 mg of chlorides per litre
without FA to help reach values near the predefined slump, 100 mm ± 5 mm. Compositions
of water was used for all the produced mixtures. The mortar and concrete mixtures are
with FA have greater workability than compositions without FA and, therefore, it was not
shown in Table 2. It is important to clarify that the compressive strength of the specimens
necessary to use a superplasticiser. Concerning mortar, flow spread was fixed at 190 mm.
studied is not a central parameter of this study. The focus of this study is on the interaction
Granitic crushed sand with a fineness modulus of 2.96 and two types of granitic crushed
between carbonation and chloride ions. Therefore, the compositions were designed to pro-
coarse aggregate, one with a fineness modulus of 6.07 and the other with 6.94, were used
duce concrete facilitating access for attacking agents.
as aggregates. Tap water with a maximum value of 10 mg of chlorides per litre of water
was used for all the produced mixtures. The mortar and concrete mixtures are shown in
Table 1. Chemical composition of OPC and FA.
Table 2. It is important to clarify that the compressive strength of the specimens studied is
not a central
SiO2parameter
Al2O3 Feof 2Othis study.MgO
3 CaO The focus
SO3 ofKthis
2O study
Na2O is on2 the
TiO Cl−interaction
LI* between
IR* RE
carbonation and
[%] [%] chloride ions. Therefore, the compositions
[%] [%] [%] [%] [%] [%] [%] [%] [%] [%] [%]were designed to produce
concrete facilitating
OPC 20.33 4.59 access
3.06for62.30
attacking
2.12agents.
3.10 0.76 0.19 - 0.07 1.78 1.21 0.49
FA 55.10 26.60 5.70 2.58 1.30 - 1.41 0.26 1.33 - 3.07 - 2.65
Table 1. Chemical composition of OPC and FA.

SiO2 Al2 O3 Fe2 O3 CaO MgO SO3 K2 O Na2 O TiO2 Cl− LI* IR* RE
[%] [%] [%] [%] [%] [%] [%] [%] [%] [%] [%] [%] [%]
OPC 20.33 4.59 3.06 62.30 2.12 3.10 0.76 0.19 - 0.07 1.78 1.21 0.49
FA 55.10 26.60 5.70 2.58 1.30 - 1.41 0.26 1.33 - 3.07 - 2.65
Sci 2024, 6, 13 4 of 15
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Table 2. Mortar and concrete mixtures.

Table 2. Mortar and concrete mixtures.
Mortar Concrete
Materials
M0FAMortar M40FA C0FA ConcreteC40FA
Materials
Cement [kg] M0FA380 M40FA
228 C0FA
380 C40FA
228
Cement [kg] 380 228 380 228
Fly ash [kg] - 152 - 152
Fly ash [kg] - 152 - 152
Water [L] 209 198 190 192
Water [l] 209 198 190 192
Superplasticiser [%] -
Superplasticiser [%] - -- 0.45
0.45 -
-
Sand0/4
Sand 0/4[kg]
[kg] 1140
1140 1140
1140 989.83
989.83 926.18
926.18
Coarseaggregate
Coarse aggregate 4/8 [kg]
4/8 [kg] - - -- 261.30
261.30 281.18
281.18
Coarse
Coarseaggregate
aggregate 6/12 [kg]
[kg] - - -- 492.64
492.64 483.10
483.10

Whenthe
When themortar
mortarandandconcrete
concretespecimens
specimenswere werecast,
cast,they
theywere
werecovered
coveredwith
withplastic
plastic
film and stored in a humid chamber (18 ± 2◦ °C and 93 ± 2% RH) for 24 h. Afterwards,
film and stored in a humid chamber (18 ± 2 C and 93 ± 2% RH) for 24 h. Afterwards, they they
were removed from the moulds and stored in a box with tap water saturated
were removed from the moulds and stored in a box with tap water saturated with lime. with lime.
Sincethe
Since thespecimens
specimenswithwithFA
FA(M40FA
(M40FAand
andC40FA)
C40FA)areareat
atthe
thecentre
centreof
ofthis
thisstudy,
study,the
thecuring
curing
period was fixed at 90 days due to pozzolanic reactions related
period was fixed at 90 days due to pozzolanic reactions related to FA. to FA.

2.2.Accelerated
2.2. AcceleratedTests
Tests
2.2.1.
2.2.1. Immersionand
Immersion andDryDryCycle
CycleTest
Test
Cubic mortar specimens, 50×× 50
Cubic mortar specimens, 50 × 50 mm33,, were used for this test
50 × test in
in Part
Part IIofofthe
the
methodology.
methodology. Since there are no standards to define the methodology of immersionand
Since there are no standards to define the methodology of immersion and
dry
drycycle
cycletests,
tests,these
thesedimensions
dimensions were chosen
were chosen based on previous
based on previous laboratory experience
laboratory and
experience
ease
and of handling
ease samples
of handling duringduring
samples the test.
theThe specimens
test. The specimenswere waterproofed
were waterproofed(with epoxy(with
resin)
epoxyon five out
resin) of six
on five outfaces tofaces
of six allowtofor a unidimensional
allow penetration
for a unidimensional of aggressive
penetration agents.
of aggressive
Immersion and dry cycles were chosen to promote combination
agents. Immersion and dry cycles were chosen to promote combination of a severe envi- of a severe environment
with fast penetration
ronment of aggressive
with fast penetration of agents (Cl−agents
aggressive and CO 2 ).− Regardless
(Cl of its large utilisation,
and CO2). Regardless of its large
there
utilisation, there are no standards to fix the variables involved in the(time
are no standards to fix the variables involved in the procedure to immersion,
procedure (time to
temperature
immersion, and humidityand
temperature of the dry stage.
humidity . .). Thus,
of the the variables
dry stage…). Thus,used here wereused
the variables decided
here
based on previous
were decided based studies [18,19].studies
on previous Figure[18,19].
2 summarises
Figure 2 the test. A complete
summarises the test. A cycle com-
complete
prised seven days.seven
cycle comprised The cycles
days. were carried
The cycles out carried
were for two out
andfor six two
months
and in
sixorder
months to evaluate
in order
sample behaviour over time.
to evaluate sample behaviour over time.

Figure2.2.Immersion
Figure Immersionand
anddry
drycycle
cyclevariables
variablesfor
formortar
mortarspecimens
specimensstudied.
studied.

Once
Oncethethetest
testperiods were
periods finished,
were i.e.,i.e.,
finished, afterafter
two two
and six
andmonths, the specimens
six months, were
the specimens
broken up andup
were broken carbonation depth depth
and carbonation was determined
was determinedusing ausing
colourimetric test (phenolph-
a colourimetric test (phe-
thalein) based on
nolphthalein) RILEM
based specification
on RILEM [20]. [20].
specification
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2.2.2. Combined Test

Considering the difficulty
difficulty experienced in the dry stage of of immersion
immersion and and dry
dry cycles,
cycles,
combined tests were the option chosen for Part II. Other researchers have also used this
methodology [21,22].
methodology [21,22]. We Weused
usedthethechloride
chloridediffusion
diffusionbybyimmersion
immersion test
test based
based onon Por-
Portu-
tuguese
guese Specification
Specification LNECLNEC E390[23]
E390 [23]and
andthetheaccelerated
acceleratedcarbonation
carbonationtest test based
based on on EN
12390-12 [24].
Regarding the theimmersion
immersiontest, test,first,
first,
thethe specimens
specimens underwent
underwent immersion
immersion in lime-
in lime-sat-
saturated distilled water until achieving a consistent mass. Subsequently,
urated distilled water until achieving a consistent mass. Subsequently, these these specimens
were placed in a container with a mixture of lime-saturated distilled water and 15% NaCl
for three
for three months.
months. A A solution-volume-to-specimen-volume
solution-volume-to-specimen-volume ratio ratio of
of two
two waswas employed.
employed.
Throughout
Throughout the thetest,
test,the
thecontainer
container remained
remained sealed, andand
sealed, the chloride solution
the chloride was renewed
solution was re-
on a weekly basis. Upon the completion of the immersion period, the
newed on a weekly basis. Upon the completion of the immersion period, the specimens specimens underwent
a consistentagrinding
underwent consistent process,
grinding gradually
process, transforming into a fineinto
gradually transforming powder.
a fineThis grinding
powder. This
occurred in two consecutive layers, each with a thickness of 5 mm,
grinding occurred in two consecutive layers, each with a thickness of 5 mm, extending extending from the
surface
from thetosurface
a depthto of a30depth
mm. Theof 30powdered
mm. Thesamplespowderedresulting
samples from grinding
resulting weregrinding
from used to
determine
were used tochloride and pH
determine profiles.
chloride andWater-soluble chloride profiles
pH profiles. Water-soluble (Figure
chloride 3a) and
profiles total
(Figure
chloride profiles (Figure 3b) were determined using RILEM TC 178-TMC
3a) and total chloride profiles (Figure 3b) were determined using RILEM TC 178-TMC [25] [25] and RILEM
TC
and178-TMC
RILEM TC [26], respectively.
178-TMC [26], respectively.

(a) (b)
Figure 3. The main steps of chloride content determination: (a) free chloride and (b) total chloride.

Regarding carbonation,
Regarding carbonation,the thesamples
samples underwent
underwent preconditioning
preconditioning before beingbeing
before exposedex-
to this to
posed accelerated test. The
this accelerated test.preconditioning
The preconditioning involved procedures
involved aimedaimed
procedures at achieving
at achiev-an
internal humidity equilibrium, aligning it with the environmental
ing an internal humidity equilibrium, aligning it with the environmental humidity of ap- humidity of approxi-
mately 60%. 60%.
proximately This approach
This approach ensured a more
ensured uniform
a more carbonation
uniform process
carbonation and optimised
process and opti-
its efficiency.
mised The process
its efficiency. comprised
The process two stages.
comprised twoInitially,
stages. the specimens
Initially, were placed
the specimens were in
a chamber ◦ C and 60% RH) until
placed in awith controlled
chamber temperature
with controlled and relative
temperature and humidity
relative (20
humidity (20 °C and 60%
reaching
RH) untilareaching
constantamass (about
constant one(about
mass month). oneInmonth).
the subsequent stage, multiple
In the subsequent stage, layers
multiple of
plastic film shielded the specimens, which were then positioned in a ventilated oven (40 ◦ C)
layers of plastic film shielded the specimens, which were then positioned in a ventilated
for 20(40
oven days °C)to for
evenly distribute
20 days humidity
to evenly within.
distribute The specimens
humidity within. were weighed before
The specimens were
and after oven storage, with water loss limited to 0.10%. Following
weighed before and after oven storage, with water loss limited to 0.10%. Following pre- preconditioning, the
specimens underwent carbonation in a designated chamber (4 ± 0.50% CO , 20 ± 2 ◦ C, and
conditioning, the specimens underwent carbonation in a designated chamber 2 (4 ± 0.50%
55 ±
CO 5% RH) for three or seven months. After the carbonation period, carbonation depth
2, 20 ± 2 °C, and 55 ± 5% RH) for three or seven months. After the carbonation period,
was determined
carbonation depthusing
was adetermined
colourimetric usingtesta (phenolphthalein) based on RILEM specifica-
colourimetric test (phenolphthalein) based on
tion [20]. pH profiles were also determined using McPolin’s
RILEM specification [20]. pH profiles were also determined using McPolin’s method [27]. Each method
sample, with
[27].
a solid-to-liquid
Each sample, with ratio of 1:20, was immersed
a solid-to-liquid in distilled
ratio of 1:20, water, and
was immersed inthe container
distilled wasand
water, sealed
the
to preventwas evaporation. (18.5 ± 2en- ◦C
container sealed to The
preventsamples were stored
evaporation. Theinsamples
a laboratory environment
were stored in a laboratory
and 58 ± 2%
vironment RH)
(18.5 ± 2for
°C 24
andh 58
to ±allow
2% RH)the for
solution
24 h totoallow
reachtheequilibrium. Subsequently,
solution to reach equilibrium.the
alkalinity of the solution was measured by assessing its pH.
Subsequently, the alkalinity of the solution was measured by assessing its pH.
The scheme for combining these tests is shown in Figures 4 and 5. Figure 4 refers to
The scheme for combining these tests is shown in Figures 4 and 5. Figure 4 refers to
the study of the impact of the presence of chlorides on carbonation. The reference test used
the study of the impact of the presence of chlorides on carbonation. The reference test used
Sci 2024,6,
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for
for this
this case
case is
is only
only carbonation.
carbonation. Figure
Figure 55 refers
refers to
to the
the opposite
opposite situation,
situation, the
the study
study ofof the
the
for thisofcase
impact is only carbonation.
carbonation on the Figure 5ofrefers
penetration to theThe
chlorides. opposite situation,
reference test the for
used study
thisofcase
the
impact of carbonation on the penetration of chlorides. The reference test used for this case
impact
is of carbonation on the penetration of chlorides. The reference test used for this case
is only
only chloride
chloride diffusion
diffusion byby immersion.
immersion.
is only chloride diffusion by immersion.

Figure 4.
Figure 4. Scheme
Scheme for
for combining
combining tests
tests to
to study
study the
the effect
effect of
of the
the presence
presence of
of chlorides
chlorides on
on carbonation.
carbonation.
Figure 4. Scheme for combining tests to study the effect of the presence of chlorides on carbonation.

Figure 5. Scheme for combining tests to study the effect of carbonation on the penetration of chlo-
Figure5.5.Scheme
Figure Schemefor
forcombining
combiningtests to to
tests study thethe
study effect of carbonation
effect on the
of carbonation onpenetration of chlorides.
the penetration of chlo-
rides.
rides.
3. Influence of Chloride Presence on Carbonation in Matrixes with FA
3. Influence
3.1. of Chloride
Exploratory Presence on Carbonation in Matrixes with FA
3. Influence of Tests:
ChlorideMortar Specimens
Presence on Carbonation in Matrixes with FA
3.1. Exploratory
3.1.1. Tests: Mortar Specimens
Mortar Characterisation
3.1. Exploratory Tests: Mortar Specimens
3.1.1.Figure
Mortar6 Characterisation
shows the compressive strength evolution of mortars studied before they
3.1.1. Mortar Characterisation
were Figure
submitted to accelerated
6 shows tests. M0FA
the compressive showsevolution
strength better performance
of mortars than M40FA
studied in early
before they
ages. Figure
This 6 shows the
behaviour is compressive
expected, and strength
it is evolution
related to the ofnecessary
mortars studied
period before
to they
develop
were submitted to accelerated tests. M0FA shows better performance than M40FA in early
were
the submittedreactions
pozzolanic to accelerated
in the tests.
M40FA M0FA shows better performance than M40FA in ratio
early
ages. This behaviour is expected, and itspecimens.
is related to Despite the higher
the necessary water/binder
period to develop the
ages.
of This behaviour
M40FA (0.56) when is expected, and it is related to the necessary period to develop the
pozzolanic reactions in compared
the M40FAtospecimens.
M0FA (0.52), the compressive
Despite strengths ofratio
the higher water/binder M0FA of
pozzolanic
(39.07 MPa) reactions
and M40FA in the M40FA
(44.44 MPa) specimens.
are very Despite
similar. the higher water/binder
A reductionstrengths
in connectivity ratio
between of
M40FA (0.56) when compared to M0FA (0.52), the compressive of M0FA (39.07
M40FA
pores (0.56) when compared to M0FA (0.52), the compressive strengths of M0FA (39.07
MPa) produced
and M40FA using
(44.44 FAMPa)
is theare
most
very frequently
similar. Areported
reduction cause [28].
in connectivity between pores
MPa) and M40FA (44.44 MPa) are very similar. A reduction in connectivity between pores
produced using FA is the most frequently reported cause [28].
produced using FA is the most frequently reported cause [28].
 Sci2024,
Sci 2024,6,6,13
x FOR PEER REVIEW 7 of 15
7 of 15

Figure6.6. Compressive
Figure Compressive strength
strengthevolution
evolutionof
ofmortars
mortars(7,
(7,28,
28,and
and90
90days).
days).

3.1.2. Accelerated Test: Immersion and Dry Cycles

3.1.2. Accelerated Test: Immersion and Dry Cycles
The carbonation depths reached after accelerated tests are shown in Figure 7. As
The carbonation depths reached after accelerated tests are shown in Figure 7. As ex-
expected, the specimens with FA have a greater carbonation depth than those without FA,
pected, the specimens with FA have a greater carbonation depth than those without FA,
regardless of the test period. There is a reduction in the Ca(OH)2 content and pH level of the
regardless of the test period. There is a reduction in the Ca(OH)2 content and pH level of
liquid phase of mortars with FA, which facilitates the advancement of carbonation [29]. The
the liquid phase of mortars with FA, which facilitates the advancement of carbonation
evolution of the carbonation depth of the studied specimens over time is residual, regardless
[29]. The evolution of the carbonation depth of the studied specimens over time is resid-
of the presence of FA. For the specimens without FA (M0FA), considering the reference
ual, regardless of the presence of FA. For the specimens without FA (M0FA), considering
situation, there is even a slight reduction (around 2 mm) in the depth of carbonation from
the reference situation, there is even a slight reduction (around 2 mm) in the depth of
2 to 6 months. This reduction is not significant, being within the acceptable error range
carbonation from 2 to 6 months. This reduction is not significant, being within the accepta-
for the colourimetric test. This residual evolution over time may be related to the low
ble error range for the colourimetric test. This residual evolution over time may be related
efficiency of the drying period during the cycles. The drying period and/or conditions
to the low efficiency
(temperature of the
and relative drying may
humidity) period
notduring
have been the cycles.
sufficientThe
to drying
reduce period
humidity and/or
and
conditions (temperature and relative humidity) may not have been
create favourable conditions for the development of the carbonation process inside thesufficient to reduce
humidity and
specimen. create favourable
Therefore, carbonationconditions
was limitedfortothethe
development
surface, neverof the carbonation
reaching 20 mm.process
Thus,
inside the specimen. Therefore, carbonation was limited to the surface, never
it is important to evaluate the limitations of this type of test for situations involving reaching 20 a
mm. Thus, itof
combination is chlorides
importantandto evaluate the limitations
CO2 , regardless of this type
of FA presence. of test for
Malheiro situations
et al. in-
(2021) [10]
volving the
studied a combination
combined actionof chlorides and CO
of chlorides and2, CO
regardless of FA presence. Malheiro et al.
Sci 2024, 6, x FOR PEER REVIEW 2 using three types of tests: immersion 8 of 15
and dry cycles, chloride diffusion by migration, and chlorideCO
(2021) [10] studied the combined action of chlorides and 2 using three types of tests:
diffusion by immersion. They
immersionthat
concluded andthedryimmersion
cycles, chloride
test is diffusion by migration,
more indicated and chloride
for this combined diffusion
action studied.by im-
mersion. They concluded that the immersion test is more indicated for this combined ac-
tion studied.
Regarding the influence of chlorides on carbonation, it is observed that regardless of
the test period and FA presence, chloride influences carbonation depth, decreasing it. This
reduction in carbonation depth was attenuated over time. In specimens without FA, this
reduction trend was more noticeable, with values that went from 53.00% at two months
of testing to 14.00% at six months of testing, while in specimens with FA, these values
were, respectively, 30.00 and 27.00%.

Figure 7.
Figure 7. Carbonation
Carbonation depths
depths in
in mortars
mortars after
after immersion
immersion and
anddry
drycycles:
cycles: 22 months’
months’ test
test (left);
(left); and
and 66
months’ test (right).
months’ test (right).

3.2. Concrete
RegardingSpecimens
the influence of chlorides on carbonation, it is observed that regardless of
the test period
Since and FA presence,
preliminary chloride
tests showed that influences carbonation
chloride influences depth, decreasing
carbonation depth in it. This
mortar
with and without FA, concrete specimens were produced to evaluate this phenomenon.
Considering the limitations of combined cycles, at this stage, were used combined tests as
previously explained in Section 2.2.2.

3.2.1. Concrete Characterisation

Sci 2024, 6, 13 8 of 15

reduction in carbonation depth was attenuated over time. In specimens without FA, this
reduction trend was more noticeable, with values that went from 53.00% at two months of
Figure 7. Carbonation depths in mortars after immersion and dry cycles: 2 months’ test (left); and 6
testing to 14.00% at six months of testing, while in specimens with FA, these values were,
months’ test (right).
respectively, 30.00 and 27.00%.
3.2. Concrete Specimens
3.2. Concrete Specimens
Since preliminary tests showed that chloride influences carbonation depth in mortar
Since preliminary tests showed that chloride influences carbonation depth in mortar
with and without FA, concrete specimens were produced to evaluate this phenomenon.
with and without FA, concrete specimens were produced to evaluate this phenomenon.
Considering the limitations of combined cycles, at this stage, were used combined tests as
Considering the limitations of combined cycles, at this stage, were used combined tests as
previouslyexplained
previously explainedin
inSection
Section2.2.2.
2.2.2.

3.2.1.Concrete
3.2.1. ConcreteCharacterisation
Characterisation
Figure88shows
Figure showsthe thecompressive
compressivestrength
strengthevolution
evolutionof ofconcretes
concretesstudied
studiedbefore
beforethey
they
were submitted to accelerated tests. Similar to the mortars studied,
were submitted to accelerated tests. Similar to the mortars studied, C0FA shows betterC0FA shows better
performancethan
performance thanC40FA
C40FA at early
at early ages.
ages. However,
However, at later
at later ages (after
ages (after 90 C40FA
90 days), days), shows
C40FA
ashows a more pronounced
more pronounced growth
growth than C0FA,thanpresenting
C0FA, presenting verycompressive
very similar similar compressive
strength
strength
values values
at 360 days.at Despite
360 days. Despite
different different
values values of compressive
of compressive strength at 90strength atcapillary
days, the 90 days,
the capillary
absorption absorption
coefficient coefficient
presented presented
similar values. similar values.
C0FA (0.104 kg/m 2 /min)
C0FA (0.104 kg/m2/min)
presents pre-
a slightly
sents value
lower a slightly
when lower value when
compared to C40FAcompared
(0.116 kg/m 2 /min).
to C40FA (0.116
Thiskg/m 2/min). This behaviour
behaviour may be related
may
to thebe related to
reduction in the reductionbetween
connectivity in connectivity betweenusing
pores provided poresFA,
provided using FA,
as previously as pre-
explained
viously
in explained
the mortar case. in the mortar case.

Figure8.8.Compressive
Figure Compressivestrength
strengthevolution
evolutionof
ofconcrete
concrete(7,
(7,28,
28,90,
90,and
and360
360days).
days).

3.2.2.
3.2.2.Accelerated
AcceleratedTest:
Test: Chloride
Chloride Diffusion
Diffusionby byImmersion
ImmersionFollowed
Followedby byCarbonation
Carbonation
The
The effect of chloride presence on the development of carbonation in
effect of chloride presence on the development of carbonation in concretes
concretes sub-
sub-
jected
jected to a combination of tests, chloride diffusion by immersion (three months)followed
to a combination of tests, chloride diffusion by immersion (three months) followed
by
bycarbonation
carbonation(seven
(sevenmonths),
months),can canbe
beassessed
assessedin
inFigure
Figure9.9.
As expected, specimens with FA have a greater carbonation depth than those without
FA. Furthermore, the analysis of Figure 9 corroborates the mortar results (Figure 7) and
makes it clear that chloride presence in the matrix, under the conditions studied, strongly
influences the development of a carbonation front, regardless of FA. However, this influence
is more pronounced in concrete without FA. The reduction in carbonation front is 87%
for C0FA, while in C40FA, it is only 25%. This same trend was verified by mortar results.
Nagataki and Ohga (1992) [16] studied mortars with and without FA cured initially in
distilled water or NaCl solution for 7, 28, 56, and 91 days and then exposed to accelerated
carbonation. They also found that FA mortar shows a higher depth of carbonation than the
reference mortar.
Sci 2024, 6, 13 9 of 15

Figure 9. Carbonation depth of concrete.

In the results in Figure 9, unlike in the case of mortars, internal humidity was not high
because there was a preconditioning process before carbonation. Preconditioning sought
to provide a favourable internal humidity for carbonation (around 60%). Therefore, it is
very likely that this reduction in the depth of carbonation is related to the blocking of the
pores caused by the NaCl (crystallised) remaining from the immersion test. The chloride’s
capacity to physically obstruct the concrete pores results in a reduction in pore size. This,
in turn, impedes the infiltration of CO2 , effectively serving as a “barrier”. While it was
not possible to verify this hypothesis through microstructural analyses within the context
of the present work, results from other authors support it. Leivo et al. [30] suggested in
their findings that salt crystallisation within the pore network could lead to pore blockage.
Malheiro et al. [31] identified a crystalline structure associated with the precipitation of
sodium chloride (NaCl solubility in H2 O at 25 ◦ C is 36.9 g/100 mL), a process occurring
during the drying phase of cycles as water evaporates from the solution.
Since chlorides penetrate more easily into C0FA than into C40FA, the blocking effect
has a greater impact on specimens without FA. In the combined situation, the chloride
penetration depths were 32.76 mm (±0.50) for C0FA and 23.00 mm (±0.15) for C40FA.
The capillary absorption curves presented in Figure 10 corroborate the hypothesis of the
blocking effect as they show a lower capillary water absorption coefficient for C0FA (0.089)
Sci 2024, 6, x FOR PEER REVIEW 10 of 15
instead of C40FA (0.141). It is important to highlight that this test was performed after the
combined tests (chloride diffusion by immersion followed by carbonation).

Figure 10.
Figure 10. Capillary
Capillary water
water absorption
absorption after
after combined
combined tests
tests and
and capillary water absorption
capillary water coefficient
absorption coefficient
(detail in right).
(detail in right).

Despite the effect of chloride action on carbonation development not being given due
attention, some results have been published on this topic, considering concretes without
1FA. In this case, a reduction in carbonation depth or consumption of hydroxyls (OH ) in
−

concrete previously contaminated by chlorides has been found [12,22]. Despite the lack of
results for concrete with FA, the results reached in this study corroborate the results found
for concrete without FA. However, the impact on concrete with FA is lower than the im-
Sci 2024, 6, 13 10 of 15

Despite the effect of chloride action on carbonation development not being given due
attention, some results have been published on this topic, considering concretes without
FA. In this case, a reduction in carbonation depth or consumption of hydroxyls (OH− ) in
concrete previously contaminated by chlorides has been found [12,22]. Despite the lack of
results for concrete with FA, the results reached in this study corroborate the results found
for concrete without FA. However, the impact on concrete with FA is lower than the impact
on concrete with FA.
Considering the results, it is possible to say that, under the conditions studied, the
vulnerability of concrete with FA to the action of carbonation is reduced in environments
where concrete is simultaneously exposed to Cl− and CO2 . Pore blockage is probably the
main cause of this effect.

4. Influence of Carbonation on Chloride Transport in Matrices with FA

The specimens studied at this stage of our work were produced using only concrete.
Concrete characterisation is shown in Section 3.2.1.

4.1. Accelerated Test: Carbonation Chamber Followed by Chloride Immersion

Figures 11 and 12 present the results obtained for concrete with FA (C40FA) subjected
only to a chloride immersion test (reference) (Figures 11 and 12a) and subjected to car-
bonation followed by a chloride immersion test (combined) (Figures 11 and 12b). The
carbonation depth shown for the combined situation was determined using a colourimetric
test (phenolphthalein). The evolution of behaviour over time was evaluated; Figure 11
refers to three months of carbonation, while Figure 12 refers to seven months of carbonation.
After three months of the carbonation test, the data indicate a change in the behaviour
of the chloride profiles and the pH profile related to carbonation. Regarding pH profiles,
the reference profile (Figure 11a) shows a generally stable behaviour, with only one visible
disturbance at around 15 mm, which is most likely associated with deviations occurring
during the experimental determination. In the case of the combined profile (Figure 11b), a
Sci 2024, 6, x FOR PEER REVIEW 11 of 15
continuous reduction in pH value is observed, starting at a depth of 20 mm and remaining
so until the superficial zone, where the value reached is close to 9.

(a) (b)
Figure 11. Chloride and pH profiles for C40FA subjected to (a) reference test (only chloride) and (b)
Figure 11. Chloride and pH profiles for C40FA subjected to (a) reference test (only chloride) and
combined tests (3 months of carbonation followed by chloride).
(b) combined tests (3 months of carbonation followed by chloride).

After three months of the carbonation test, the data indicate a change in the behaviour
of the chloride profiles and the pH profile related to carbonation. Regarding pH profiles,
the reference profile (Figure 11a) shows a generally stable behaviour, with only one visible
disturbance at around 15 mm, which is most likely associated with deviations occurring
during the experimental determination. In the case of the combined profile (Figure 11b),
a continuous reduction in pH value is observed, starting at a depth of 20 mm and remain-
ing so until the superficial zone, where the value reached is close to 9.
Regarding chloride profiles, a reduction in the surface concentration of the combined
profiles (Figure 11b) is observed when compared to the reference profiles (Figure 11a).
This reduction is followed by a significant increase in chloride penetration that remains
up to 20 mm depth. This happens because when not subjected to carbonation (reference
situation), C40FA exhibits high resistance to chlorides. In this way, chlorides are retained
Sci
Sci 2024,
2024, 6,
6, x13FOR PEER REVIEW 12 of 15
11 of 15

(a) (b)
Figure 12. Chloride and pH profiles for C40FA subjected to (a) reference test (only chloride) and (b)
Figure 12. Chloride and pH profiles for C40FA subjected to (a) reference test (only chloride) and (b)
combined tests (7 months of carbonation followed by chloride).
combined tests (7 months of carbonation followed by chloride).

Regarding
Regarding pH profiles,
chloride the values
profiles, of thein
a reduction reference
the surface profile (Figure 12a)
concentration of remain stable
the combined
when
profiles (Figure 11b) is observed when compared to the reference profiles (Figure they
compared to the situation at three months of testing (Figure 11a). However, 11a).
present slightlyishigher
This reduction followed values.
by aFor the combined
significant increase profile (Figurepenetration
in chloride 12b), therethat is a remains
sudden
reduction
up to 20 mm in pH values
depth. This(close to 8) because
happens throughout when thenot
entire carbonated
subjected region which
to carbonation coin-
(reference
cides with the carbonation depth determined by phenolphthalein.
situation), C40FA exhibits high resistance to chlorides. In this way, chlorides are retained on
Regarding
the surface chloride
(weakest profiles,
zone), an enormous
and penetration intoincrease
the interiorin chloride contentisin
of the concrete the com-
reduced. In
bined profiles (Figure 12b), throughout the entire depth, when compared
situations where C40FA is carbonated, resistance to chlorides decreases in the carbonated to the reference
profiles
zone, and (Figure 12a) is clear.
the superficial It is observed
concrete that, for
is no longer able thetoreference situation
retain a large (Figure
portion 12a),
of these
free chlorides
chlorides. are almost
Chlorides thatnon-existent. For theon
are not retained combined
the surface situation, free chloride
penetrate the interior content
of theis
quite highincreasing
concrete, throughout thethe depth (Figure
chloride content.12b). The increase in the amount of free chlorides
couldThus,
be the at cause of this of
three months significant
carbonation increase in carbonation
testing, the penetration of chlorides
increases in C40FA
the penetration of
when subjected to combined action for seven months. To highlight
chlorides in concrete with FA. The increase in the amount of free chlorides resulting from the increase in free
chlorides,
the reductionFigure 13 shows the subtraction
in chloride-binding of the free
capacity verified for chlorides
the specimens present in the
subject to combined
combined
profile
action from
is thethose
mostpresent in thefor
likely cause reference profile.in carbonation depth (superficial in the
the increase
reference situation and increasing to 11 mm in the combined situation).
With the increase in the carbonation test period (from three to seven months) and
the consequent increase in carbonation depth, the increase in the penetration of chlorides
is more evident. It happens throughout the entire depth of the specimens subject to the
combined action (Figure 12).
Regarding pH profiles, the values of the reference profile (Figure 12a) remain stable
when compared to the situation at three months of testing (Figure 11a). However, they
present slightly higher values. For the combined profile (Figure 12b), there is a sudden
reduction in pH values (close to 8) throughout the entire carbonated region which coincides
with the carbonation depth determined by phenolphthalein.
Regarding chloride profiles, an enormous increase in chloride content in the combined
profiles (Figure 12b), throughout the entire depth, when compared to the reference profiles
(Figure 12a) is clear. It is observed that, for the reference situation (Figure 12a), free chlorides
are almost non-existent. For the combined situation, free chloride content is quite high
Figure 13. Freethe
throughout chlorides
depthresulting
(Figure from
12b).theThesubtraction
increaseofin thethe
reference
amount situation
of freefrom the combined
chlorides could
situation.
be the cause of this significant increase in the penetration of chlorides in C40FA when
subjected to combined action for seven months. To highlight the increase in free chlorides,
FigureThe13result
showsofthe thesubtraction
subtractionofbetween
the freefree chloride
chlorides profiles
present is acombined
in the profile with values
profile so
from
high that they far exceed the
those present in the reference profile. chloride threshold (0.5% of the mass of concrete) recom-
mended by Comité Européen du Béton (CEB) for total chlorides in reinforced concrete.
This enormous increase in chloride content can be related to the difficulty of binding
chlorides in a low pH environment. The chemical binding of chloride ions can occur
through Friedel’s salt (3CaO·Al2O3·CaCl2·10H2O) [32]. Friedel’s salt results from reactions
with tricalcium aluminate (C3A), prevalent in concretes with high FA content, and free
 free chlorides are almost non-existent. For the combined situation, free chloride content is
quite high throughout the depth (Figure 12b). The increase in the amount of free chlorides
could be the cause of this significant increase in the penetration of chlorides in C40FA
when subjected to combined action for seven months. To highlight the increase in free
Sci 2024, 6, 13 chlorides, Figure 13 shows the subtraction of the free chlorides present in the combined
12 of 15
profile from those present in the reference profile.

Figure13.
Figure 13. Free
Free chlorides
chloridesresulting
resultingfrom
fromthe subtraction
the of of
subtraction thethe
reference situation
reference fromfrom
situation the combined
the com-
situation.
bined situation.

Theresult
The resultof ofthe
thesubtraction
subtractionbetween
betweenfree freechloride
chlorideprofiles
profilesisisaaprofile
profilewith
withvalues
valuessoso
highthat
high thatthey
theyfarfar exceed
exceed the the chloride
chloride threshold
threshold (0.5%(0.5%
of theof theofmass
mass of concrete)
concrete) recom-
recommended
mended
by Comitéby Comité Européen
Européen du Béton (CEB)du Béton for (CEB) for total in
total chlorides chlorides in reinforced
reinforced concrete. concrete.
Thisenormous
This enormousincrease
increasein inchloride
chloridecontent
contentcancanbe
berelated
relatedtotothe
thedifficulty
difficultyof ofbinding
binding
Sci 2024, 6, x FOR PEER REVIEW 13 of 15
chlorides in
chlorides in aalow
lowpH pHenvironment.
environment. The The chemical
chemical binding
binding of of chloride
chloride ions
ions can
can occur
occur
throughFriedel’s
through Friedel’ssalt
salt(3CaO ·Al2 O
(3CaO·Al 2O3 3··CaCl
CaCl22··10H
10H22O) [32]. Friedel’s salt results
results from
fromreactions
reactions
with
withtricalcium
tricalciumaluminate
aluminate(C (C33A),
A), prevalent
prevalent in in concretes
concretes with
with high
high FAFAcontent,
content, and
andfree
free
chlorides. Nevertheless,
Nevertheless, Friedel’s
Friedel’s saltsalt remains
remains stable
stable at
at a relatively elevated pH [32], a
condition not met in in carbonated
carbonated concrete.
concrete. Some researchers investigated
investigated the combined
combined
effect of chloride presence and carbonation in concrete without FA
effect of chloride presence and carbonation in concrete without FA [13,33,34]. However, [13,33,34]. However,the
the combined
combined effecteffect of chloride
of chloride presencepresence and carbonation
and carbonation in concrete
in concrete with FAwith FA has
has been been
scarcely
scarcely explored
explored to date. to date.

4.2. Accelerated Test:

4.2. Accelerated Test: Comparation
Comparation between
between Concretes
Concretes with
with and
and without
without FA
FA
The
The performance of concrete with and without FA concerning combined
performance of concrete with and without FA concerning combined action
action isis
compared in Figure 14. This figure shows the total chloride profiles achieved
compared in Figure 14. This figure shows the total chloride profiles achieved for the forcom-
the
combined situation
bined situation at three
at three months
months of carbonation
of carbonation (Figure(Figure 14a)
14a) and andmonths
seven seven months
of carbon-of
carbonation (Figure
ation (Figure 14b). 14b).

(a) (b)
Figure 14.
Figure 14. Total
Totalchloride
chlorideprofiles achieved
profiles forfor
achieved C0FA andand
C0FA C40FA afterafter
C40FA the combined situation:
the combined (a) 3
situation:
months of carbonation followed by chloride; and (b) 7 months of carbonation followed by chloride.
(a) 3 months of carbonation followed by chloride; and (b) 7 months of carbonation followed by chloride.

According to
According to Figure
Figure 14,
14, for
for aa short
short period
period of
of carbonation,
carbonation, C40FA
C40FA can
can maintain
maintain its
its
efficiency against
efficiency against the
the penetration
penetration of
of chlorides
chlorides when
when compared
compared toto C0FA.
C0FA. However,
However, when
when
evaluating the results obtained for the combination of tests after seven months of carbon-
ation, an important increase in the chloride content of C40FA is observed, throughout the
entire depth, when comparing its values with those obtained for C0FA. Thus, under the
conditions studied, FA’s resistance to chloride ion penetration is reduced when concrete
structures are in environments which are also subject to high concentrations of CO2.
Sci 2024, 6, 13 13 of 15

evaluating the results obtained for the combination of tests after seven months of carbona-
tion, an important increase in the chloride content of C40FA is observed, throughout the
entire depth, when comparing its values with those obtained for C0FA. Thus, under the
conditions studied, FA’s resistance to chloride ion penetration is reduced when concrete
structures are in environments which are also subject to high concentrations of CO2 .

5. Conclusions
The impact of the combined action of chloride and carbonation on cement-based
materials with fly ash was evaluated for specimens with a 40% replacement of cement
with fly ash. Accelerated tests were conducted to simulate the synergistic effect of Cl− and
CO2 in mortar and concrete specimens. The influence of the carbonation period was also
evaluated. Conclusions are possible based on the results of this study.
Concerning the methodology for combining Cl− and CO2 actions, the combination of
accelerated tests reached better results than immersion and drying cycles in specimens with
fly ash. Since humidity is a crucial factor in carbonation development, the preconditioning
stage before accelerated carbonation was very important to promote representative carbon-
ation depths for this study. This is an important contribution of this study since there is no
consolidated methodology or standards for studying this type of combined action.
The impact of chloride presence on carbonation depth in specimens with fly ash was
verified. There was a reduction in carbonation depth in specimens with and without fly ash.
Although this reduction was significant in specimens with fly ash, it was more pronounced
in specimens without fly ash. The main cause may be related to the hypothesis of reduction
in pores blocked by crystallisation. In this context, the amount of NaCl was greater in
specimens without FA than in specimens with FA because the latter fixed more Cl− and,
therefore, contained less absorbed Cl− . It is important to highlight that cementitious
materials with fly ash have low resistance to carbonation; however, in environments
strongly affected by CO2 and Cl− simultaneously, this resistance is increased.
The impact of carbonation on chloride penetration in concrete with fly ash was more
evident. There was a strong reduction in chloride resistance for carbonated specimens.
This reduction was clearer with greater carbonation depth. The increased aluminates from
substitution of cement with fly ash contributed to lowering free Cl− content in concrete with
fly ash through chemical reactions that bind with Cl− . The enormous increase in chloride
content in the profiles studied can be related to the difficulty of binding chlorides in a low
pH environment. Comparing concretes with and without fly ash in the reference (chloride
presence only) and combined (carbonation followed by chloride presence) situations, under
the conditions studied, it is possible to say that fly ash concrete’s resistance to chloride ion
penetration was reduced when the concrete structure was in an environment that was also
subject to high concentrations of CO2 . Considering the real dynamics of the phenomenon,
in the future, it is also important to study the impact of variables such as the concentration
of CO2 and Cl− on these results.

Author Contributions: R.M.: methodology, investigation, writing—original draft. A.C.: supervi-

sion, writing—original draft. G.M.: supervision. R.R.: writing—review of carbonation analyses.
A.N.: writing—review and editing. All authors have read and agreed to the published version of
the manuscript.
Funding: This work was supported by the Foundation for Science and Technology (FCT) through
a PhD grant with reference number SFRH/BD/90134/2012 and in the scope of the project with
reference 2022.03197.PTDC (https://doi.org/10.54499/2022.03197.PTDC), GlassCON.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Data sharing is not applicable.
Conflicts of Interest: The authors declare that they have no known competing financial interests or
personal relationships that could have appeared to influence the work reported in this paper.
Sci 2024, 6, 13 14 of 15

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1. Cement—Analysis—IEA. Available online: https://www.iea.org/reports/cement (accessed on 8 March 2022).
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de Hormigón Armado. Hormigón Acero 1994, 45, 194.
3. Montemor, M.F.; Cunha, M.P.; Ferreira, M.G.; Simões, A.M. Corrosion Behaviour of Rebars in Fly Ash Mortar Exposed to Carbon
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