materials

Article
Experimental Carbonation Study for a Durability Assessment
of Novel Cementitious Materials
Lucija Hanžič 1, * , Sebastijan Robič 1 , Alisa Machner 2 , Marie Helene Bjørndal 3 , Klaartje De Weerdt 3 ,
Yushan Gu 4 , Benoît Bary 4 , Rosa Maria Lample Carreras 5 and Aljoša Šajna 1

1 Laboratorij za Beton, Zavod za Gradbeništvo, ZAG, Dimičeva Ulica 12, SI-1000 Ljubljana, Slovenia;
sebastijan.robic@zag.si (S.R.); aljosa.sajna@zag.si (A.Š.)
2 Centrum Baustoffe und Materialprüfung, Technische Universität München, TUM, Franz-Langinger-Str. 10,
81245 Munich, Germany; alisa.machner@tum.de
3 Institutt for Konstruksjonsteknikk, Norges Teknisk-Naturvitenskaplige Universitet, NTNU,
Richard Birkelandsvei 1A, 7491 Trondheim, Norway; marie.bjorndal@norconsult.com (M.H.B.);
klaartje.d.weerdt@ntnu.no (K.D.W.)
4 Service d’Étude du Comportement des Radionucléides, Université Paris-Saclay, CEA,
91191 Gif-sur-Yvette, France; yushanjoanna@hotmail.com (Y.G.); benoit.bary@cea.fr (B.B.)
5 Acciona Construction, 28108 Alcobendas, Spain; rosamaria.lample.carreras@acciona.es
* Correspondence: lucija.hanzic@zag.si

Abstract: Durability predictions of concrete structures are derived from experience-based require-
ments and descriptive exposure classes. To support durability predictions, a numerical model related
to the carbonation resistance of concrete was developed. The model couples the rate of carbonation





 with the drying rate. This paper presents the accelerated carbonation and moisture transport exper-
iments performed to calibrate and verify the numerical model. They were conducted on mortars
Citation: Hanžič, L.; Robič, S.;
with a water-cement ratio of either 0.6 or 0.5, incorporating either a novel cement CEM II/C (S-LL)
Machner, A.; Bjørndal, M.H.;
(EnM group) or commercially available CEM II/A-S cement (RefM group). The carbonation rate was
De Weerdt, K.; Gu, Y.; Bary, B.;
Lample Carreras, R.M.; Šajna, A.
determined by visual assessment and thermogravimetric analysis (TGA). Moisture transport experi-
Experimental Carbonation Study for ments, consisting of drying and resaturation, utilized the gravimetric method. Higher carbonation
a Durability Assessment of Novel rates expressed in mm/day−0.5 were found in the EnM group than in the RefM group. However, the
Cementitious Materials. Materials TGA showed that the initial portlandite (CH) content was lower in the EnM than in the RefM, which
2021, 14, 6253. https://doi.org/ could explain the difference in carbonation rates. The resaturation experiments indicate an increase
10.3390/ma14216253 in the suction porosity in the carbonated specimens compared to the non-carbonated specimens. The
study concludes that low clinker content causes lower resistance to carbonation, since less CH is
Academic Editor: Gabriele Milani available in the surface layers; thus, the carbonation front progresses more rapidly towards the core.

Received: 1 September 2021

Keywords: mortar; absorption of water; carbonation; durability assessment; model verification
Accepted: 6 October 2021
Published: 21 October 2021

Publisher’s Note: MDPI stays neutral

1. Introduction
with regard to jurisdictional claims in
published maps and institutional affil- The design process of concrete structures relies on standards such as Eurocode 2 [1,2]
iations. and guidelines such as fib Model Code 2010 [3]. The main focus of the existing codes and
guidelines is on mechanical performance, which is analyzed with advanced structural
design models. In contrast, durability-related phenomena are addressed mainly through
the selection of exposure classes and experience-based requirements. As a result, concrete
Copyright: © 2021 by the authors.
durability forecasts are only crude approximations, which are not supported by the sophis-
Licensee MDPI, Basel, Switzerland.
ticated modelling of concrete degradation over time. The deterioration and maintenance
This article is an open access article
of concrete are having a significant impact on public sector budgets. Maintenance costs
distributed under the terms and and shutdowns of infrastructure, such as tunnels, bridges or power plants, are particularly
conditions of the Creative Commons important, due to their impact on the wider community.
Attribution (CC BY) license (https:// When concrete is exposed to an aggressive environment with an increased concentra-
creativecommons.org/licenses/by/ tion of carbon dioxide in combination with moisture, concrete undergoes a carbonation
4.0/). process. The main process in the carbonation of concrete is the reaction of portlandite,

Materials 2021, 14, 6253. https://doi.org/10.3390/ma14216253 https://www.mdpi.com/journal/materials

Materials 2021, 14, 6253 2 of 17

that is, calcium hydroxide Ca(OH)2 , commonly denoted CH, with carbon dioxide (CO2 ).
The reaction products are calcite, that is, calcium carbonate (CaCO3 ), and water (H2 O).
This reaction leads to a net mass gain, as the uptake of CO2 (44 g mol−1 ) leads to a larger
mass increase compared to the release of water (12 g mol−1 ). While the products of this
chemical reaction are not detrimental to concrete durability per se, the consumption of CH
reduces the pH value of the pore solution, which may lead to the corrosion of reinforcement
steel. The rate of carbonation is influenced by the curing conditions of concrete and by
the climatic and local conditions to which the concrete is exposed. To accurately predict
concrete deterioration, a numerical model for concrete carbonation is being developed [4]
within the Horizon 2020 project, titled EnDurCrete [5]. The model is based on previous
work conducted by Bary et al. [6–8]. It couples the mass conservation equations of water,
CO2 and calcium in pore solution with thermodynamic modelling, which simulates the
phase assemblage of binders upon carbonation. The model is used for the prediction of con-
crete behavior under accelerated carbonation, particularly where novel, more sustainable
cements are used.
The European Commission and the European construction industry push to improve
and develop technologies that reduce CO2 emissions as well as energy and material usage
in the cement production processes [9]. Many studies attempt to develop environmentally-
friendly concrete by reducing Portland clinker content in cement and substituting it with
supplementary cementitious materials. In this manner, the above-mentioned model devel-
opment is also linked to another aim of the EnDurCrete project [5], namely, the development
of low carbon-footprint binders aligned with the new edition of prEN 197-1 [10]. One such
novel cement is CEM II/C (S-LL), a low-clinker cement containing high-value industrial
by-products. The use of this cement is aimed at the creation of cost-effective sustainable
concrete on one hand, and high durability concrete, which can withstand exposure to
aggressive environments, on the other hand. Details of the novel cement CEM II/C (S-LL)
developed by HeidelbergCement are summarized by Bolte et al. [11].
This study aims to present the experimental results of an accelerated carbonation
program conducted on mortar specimens incorporating a novel CEM II/C (S-LL) binder
developed within the EnDurCrete project [5], and to compare it with the performance
of mortars prepared with commercially available cement, CEM II/A-S. The specimens
underwent accelerated carbonation in a conditioning chamber with controlled CO2 con-
centration, temperature, and relative humidity. The carbonation rate was assessed by
measuring the depth of carbonation over time, (i) visually, using a pH indicator, and (ii)
by thermogravimetric analysis (TGA). The impact of carbonation on moisture transport
was evaluated by the gravimetric method on specimens exposed to a specific protocol of
drying and wetting.
The results of the accelerated carbonation tests will serve for the calibration and vali-
dation of the numerical model dealing with carbonation processes in concrete, in particular,
the coupling between saturation degree, water transport and carbonation extent. The
model itself is out of the scope of this paper. Its detailed description, parameter calibra-
tion procedure and results will be comprehensively presented in a separate publication.
In addition, the results aim to further the understanding of concrete deterioration in a
CO2 -rich environment, particularly for concrete made with novel eco-friendly cements.
Consequently, the design of concrete structures in terms of durability will be improved,
resulting in reduced maintenance costs and shutdowns of infrastructure caused by the
deterioration of concrete due to carbonation.

2. Materials and Methods

The concept of the experiment is derived from the requirements of the carbonation
model, where two coupled mass balance equations are considered, one covering the
transport of moisture and the other the migration of CO2 in the interconnected pores. The
carbonation process is simplified into the dissolution of a combined Ca-containing hydrate
phase (mainly CH and C-S-H) and the precipitation of calcite according to thermodynamic
Materials 2021, 14, 6253 3 of 17

modelling. The evolution of their volumes is approximated as a piecewise linear function.

The dissolution rate of the Ca-containing hydrate phase is assumed to depend on the
saturation degree, the partial pressure of CO2 , and the fraction of the current volume
versus the initial volume, from which the precipitation rate of calcite can be predicted.
For these reasons, this experimental study encompassed two test procedures. The
first was the determination of the carbonation rate, which included measurements of
carbonation depth and portlandite profiles, which were subsequently used to verify the
carbonation model and thus estimate the evolution of porosity, saturation degree, and phase
changes. The second test procedure was a moisture transport experiment, from which the
initial porosity and both the initial and relative permeability coefficient were quantified.
Since carbonation leads to microstructure changes and then affects transport properties [12],
tests before and after carbonation in different relative humidity conditions were carried
out. To complement the moisture transport test, the total porosity was also measured.

2.1. Specimen Preparation

Concrete used in applications where carbonation resistance is required is normally
designed with a relatively low water/cement (w/c) ratio and therefore measurable carbon-
ation only occurs during long-term exposure. To accelerate the process, the mixes used in
this study had a higher w/c ratio than is usually applied for such structures, namely 0.50
or 0.60, so that measurable carbonation took place in a reasonable timeframe. Furthermore,
coarse aggregates were excluded to minimize the effects of the interfacial transition zone.
The mortar mix designs are shown in Table 1. The specimens were labelled EnM for
the EnDurCrete mortar using novel CEM II/C (S-LL) cement, and RefM for the reference
mortar using CEM II/A-S cement. The label extension -05 or -06 was used to denote
w/c ratio.

Table 1. Mortar mix design, stating the mass of components needed for 1 m3 of mortar. EnM
and RefM stand for mortar made with EnDurCrete and reference cement respectively, while the
extensions -06 and -05 denote w/c ratios.

Mass of Component per 1 m3 of Mortar (kg)

Components
EnM-06 RefM-06 EnM-05 RefM-05
CEM II/C (S-LL) 487 / 552 /
Cement
CEM II/A-S / 487 / 552
Aggregate Sand 0/4 1524 1524 1498 1496
Admixture Superplasticizer 1.5 1.8 3.2 3.8
Water 292 292 264 263

The two cements were composite blends containing the same types of components,
namely CEM I 52.5 R, ground granulated blast furnace slag (S), and limestone filler (LL).
CEM I 52.5 R consists predominantly of clinker (K), whose content amounts to >95 wt%.
There were, however, two important differences between the two blends. Firstly, the
mass ratio of components was different, as shown in Table 2. The novel CEM II/C (S-LL)
contained significantly less clinker, which was replaced by slag and limestone. The chemical
composition of the two cements is given in Table A1 of the Appendix A. Secondly, the
components of CEM II/C (S-LL) were ground separately to optimize packing and reactivity,
as opposed to the reference cement CEM II/A-S, where the components were inter-ground.
Details on cement development are provided by Bolte et al. [11]. The different composition
and grinding procedures are reflected in the physical properties summarized in Table 2.
Materials 2021, 14, x FOR PEER REVIEW 4 of 17
Materials 2021, 14, 6253 4 of 17

composition and grinding procedures are reflected in the physical properties summarized
inTable
Table2. 2.
Properties of cement. The composition of cement is given as wt% of CEM I 52.5 R, which
contains a minimum of 95 wt% of clinker (K), ground granulated blast-furnace slag (S) and limestone
Table
(LL). 2.
TheProperties
chemicalofcomposition
cement. Theiscomposition of A1
given in Table cement
of theisAppendix.
given as wt% of CEM I 52.5 R, which
contains a minimum of 95 wt% of clinker (K), ground granulated blast-furnace slag (S) and lime-
stone (LL). The chemical composition is given in Table CEM
Property A1 ofII/C
the Appendix.
(S-LL) CEM II/A-S

Property CEM I 52.5 R (K) 50 (S-LL)

CEM II/C 83
CEM II/A-S
Composition (wt%) S 40 13
CEM I 52.5 R (K) 50 83
Composition LL 10 4
S 40 13
(wt%) Density (g cm−3LL) 2.98 3.09
10 4
Specific surface area–Blaine 2 −1 5210 3720
Density (g cm−3) (cm g ) 2.98 3.09
28-day compressive strength (MPa) 62.8 59.7
Specific surface area–Blaine (cm2 g−1) 5210 3720
28-day compressive strength (MPa) 62.8 59.7
The aggregate used for the mortar mixes was limestone/quartz river sand with a
The aggregate used for the mortar mixes was limestone/quartz river sand with a max-
maximum grain size of 4 mm. Its physical properties are summarized in Table 3, while the
imum grain size of 4 mm. Its physical properties are summarized in Table 3, while the
particle size distribution is presented graphically in Figure 1.
particle size distribution is presented graphically in Figure 1.
Table 3. Physical properties of aggregate.
Table 3. Physical properties of aggregate.
Property
Property Sand 0/4
Sand 0/4
Oven-dry (kg m−3(kg
densitydensity
Oven-dry ) m−3) 2730 2730
Saturated surface-dry
Saturated (kg m−3(kg
densitydensity
surface-dry ) m−3) 2765 2765
Apparent density (kg m −3 ) 2830
Apparent density (kg m )−3 2830
Absorption (%)
Absorption (%) 1.3 1.3

Figure 1. Particle size distribution of aggregate.

Figure 1. Particle size distribution of aggregate.
Along with the specimens for other research programs of the EnDurCRete project,
Along with the specimens for other research programs of the EnDurCRete project,
three mortar prisms measuring 10 cm × 10 cm × 40 cm were cast per mix for this car-
three mortar
bonation prisms
study. Themeasuring
processing10ofcm the× prisms
10 cm ×is40graphically
cm were cast per mixinfor
presented this
the carbona-in
flowchart
tion study.
Figure Theprisms
2. The processing
wereofcured
the prisms is graphically
in a humidity chamber presented in thehumidity
with relative flowchart(RH)in Figure
> 95%
2.atThe prisms
◦ were cured in a humidity chamber with relative humidity (RH)
20 ± 2 C for 21 days as per EN 12390-2 [13]. Next, the prisms were wrapped in plastic > 95% at 20
± foil
2 °Cand
for transported
21 days as per EN 12390-2 [13]. Next, the prisms were wrapped in
from the casting to the testing facilities, where they were cured plastic foilat
and transported
◦ from the casting to the testing facilities, where they were
20 C for up to 76 days. The moisture state of the specimens was checked on one prism cured at 20 °C
for up to 76 days. The moisture state of the specimens was checked on one
at this stage using the method described in [14,15] to confirm that the specimens did not prism at this
stage using the method described in [14,15] to confirm that the specimens did not dry out.
dry out.
Materials 2021, 14, 6253 5 of 17
Materials 2021, 14, x FOR PEER REVIEW 5 of 17

Figure 2.
Figure Flowchartshowing
2. Flowchart showingthe
thepreparation,
preparation,conditioning
conditioningand
andtesting
testingofofspecimens.
specimens.
AA detailed
detailed conditioning
conditioning diagram
diagram forfor
the
the moisture
moisture transport
transportexperiment
experimentisisgiven
givenininFigure
Figure3.3.

After curing, the prisms were cut laterally either into thick blocks with dimensions
10 cm × 10 cm × 7 cm or into thin plates with dimensions 10 cm × 10 cm × 2 cm. The end
sections were discarded. This way, either four thick blocks or eight thin plates were ob-
tained from one prism. The thick blocks were used for the carbonation rate measurements,
while the thin plates were used for the moisture transport experiments.
Materials 2021, 14, 6253 6 of 17
Materials 2021, 14, x FOR PEER REVIEW 7 of 17

Figure
Figure 3.
3. Stages
Stagesof
ofthe
the moisture
moisture transport
transport experiment
experiment carried
carried out
out on
on the
the thin
thin plates.
plates.

In stage
After 2, the the
curing, thinprisms
plates were
of thecut“3%” groupeither
laterally were placed in the
into thick carbonation
blocks chamber
with dimensions
10 cma ×
with 10 cm × 7 cm
temperature of 21
or ±into
2 °C,
thinRH 60 ±with
plates 10% dimensions
and 3.1% CO × 10 cmto×EN
according
102,cm 13295
2 cm. The[16].
end
The higher
sections wereCOdiscarded.
2 concentration,
This way, compared to the
either four 1%blocks
thick used on or the
eightthick
thinblocks
plates in chapter
were 2.2,
obtained
fromassumed
was one prism. The thick
to have blocks on
no impact weretheused
typeforof the carbonation
phases that form rate measurements,
during while
the carbonation
the thin plates
process. were used for
This assumption the moisture
is based on findingstransport experiments.
by Revert et al. [20,21], who investigated
the impact of accelerated carbonation on microstructure and phase assemblage and found
2.2. Carbonation
that a concentration Rate of up to 5% is representative of natural carbonation. The thin plates
in the “0%” group wereofstored
Four thick blocks each mix were
in the placed intochamber,
conditioning the carbonation chamber with
with a temperature of a18–25
tem-
perature of 21 ◦
± 2 C, 60 ± 10%
°C and RH 50–65%, atRH
a reduced COand 1% CO2 according
2 concentration. to ENas13295
Soda-lime a CO[16].
2 trap One
wasblock
put
was taken
under out of theto
the specimens carbonation
capture carbon chamber
dioxideafterand14,reduce
28 andits90 days and, depending
concentration in the cham- on
the w/c
ber’s ratio, either
atmosphere. after
Stage 146 (w/c
2 lasted for 0.60) or 167
146 days. Atdays (w/cof0.50)
the end stageof2,exposure.
one plateItfromwas each
split
perpendicularly
group was split intohalftheand
sawn thesurface.
carbonationThe carbonation front wasusing
depth was measured visually determined on
a phenolphthalein
one half with a ruler on a freshly split surface with
pH-indicator solution. The rest of the plates proceeded to stage 3. dimensions 7 cm × 10 cm, which was
sprayed with a thymolphthalein pH-indicator solution. Where
In stage 3, the remaining plates from both groups were re-saturated. The plates the mortar was unaffected
were
by the carbonation (pH above 9.3 to 10.5), the indicator turned
first saturated by capillary absorption. The water level was gradually increased over blue, while the carbon-
sev-
ateddays
eral surface remained
until uncoloured.
the specimens The resultsimmersed.
were completely were plotted against
Again, the square
the mass of theroot
platesof
timemeasured
was and the carbonation rate was When
at regular intervals. calculated
theyas allthe slope aofnear-to-constant
reached the fitted line givenmass,bythey
the
following equation:
were further saturated by vacuum saturation according √ to EN 12390-11 [22]. Stage 3 lasted
for 63 days. dk = a + KAC × t (1)
where In dstage 4, the specimens were kept in normal atmospheric conditions at 20 °C and
k (mm) is the mean carbonation depth at time t (days), a (mm) is a constant
RH 60%. This
representing the stage lasted
y-axis 33 days.
intercept, andOnce
KAC the
(mm day−reached
plates 0.5 ) is thea carbonation
constant mass,
ratethey
[17]. were
furtherForconditioned
the TGA method,at 20 °Cthe
and RH halves
other 30% inof stage 5. blocks were used. The halves were
the split
Upon the completion
profile-ground inwards from of stage 5, thesurface.
the sawn total porosity of the specimens
Approximately was determined
30 g of powder extracted
according to SIA 262-1layers
from the consecutive [23]. This
was is a gravimetric
analyzed using method
a MettlerinToledo
which TGA/DSC3+
the specimen device
is first
weighed after drying
(Mettler-Toledo, at 50 °C,
Kowloon, Hongnext, the specimen
Kong, CHN) in is submerged in
a temperature water
range for several
from 40 to 900 ◦ C,
days
and
at a weighed,
heating rate both 10 ◦ C submerged
of when min−1 . During in water and when above
the measurements, thewater. The specimen
measurement cell was is
dried
purged again
withat50
50mL°C, vacuumed at pressure
N2 per minute. < 1 mbar
The amount of and submerged
CH relative in water
to the and
ignited weighed
mass of the
again
powder under
(CHthe water
ignited and◦ C
) at 900 above the water. as
was calculated Finally, the specimen is weighed after being
dried at 110 °C.
w − w550 M
CHignited = 400 × CH (2)
3. Results and Discussion w900 MH2 O

whereThe results
w400 of the
, w550 and w900accelerated
(g) refer tocarbonation study, at
the mass of powder where theand
400, 550 carbonation rate was
900 ◦ C respectively
measured
and M (g mol ) is the molar mass of either CH or water [18]. The weight loss dueoftoboth
by a−pH-indicator
1 and by TGA, are presented in chapter 3.1. The results the
methods are compared and discussed and are found to have a good correlation.
decomposition of portlandite was determined with the integration method of the derivative The mois-
ture transport results,
thermogravimetric givencurves
(DTG) in chapter 3.2, indicate
described an increase
by Lothenbach in porosity
et al. due
[19]. Since to carbon-
carbonation
ation in specimens with a w/c ratio of 0.6.
consumes CH, its content is a measure of the degree of carbonation. The CH content was

3.1. Carbonation Rate

Materials 2021, 14, 6253 7 of 17

plotted as a function of the depth from the exposed surface. A detailed description of the
experimental setup can be found in [15].

2.3. Moisture Transport

The moisture transport experiment was carried out on the thin plates. It consisted of
several stages of conditioning, as shown in Figure 3, where stage 1 corresponds to curing,
as described in Figure 2 under the “Casting and curing” tab. After 76 days of curing, the
thin plates were sawn and organized into two groups, namely group “0%” and group “3%”,
indicating the CO2 concentration to which groups were exposed in stage 2. Throughout
the experiment, the mass of the plates was measured at regular intervals using a balance
with an accuracy of 0.01 g.
In stage 2, the thin plates of the “3%” group were placed in the carbonation chamber
with a temperature of 21 ± 2 ◦ C, RH 60 ± 10% and 3.1% CO2 , according to EN 13295 [16].
The higher CO2 concentration, compared to the 1% used on the thick blocks in Section 2.2,
was assumed to have no impact on the type of phases that form during the carbonation
process. This assumption is based on findings by Revert et al. [20,21], who investigated
the impact of accelerated carbonation on microstructure and phase assemblage and found
that a concentration of up to 5% is representative of natural carbonation. The thin plates in
the “0%” group were stored in the conditioning chamber, with a temperature of 18–25 ◦ C
and RH 50–65%, at a reduced CO2 concentration. Soda-lime as a CO2 trap was put under
the specimens to capture carbon dioxide and reduce its concentration in the chamber’s
atmosphere. Stage 2 lasted for 146 days. At the end of stage 2, one plate from each group
was split in half and the carbonation depth was measured using a phenolphthalein pH-
indicator solution. The rest of the plates proceeded to stage 3.
In stage 3, the remaining plates from both groups were re-saturated. The plates were
first saturated by capillary absorption. The water level was gradually increased over several
days until the specimens were completely immersed. Again, the mass of the plates was
measured at regular intervals. When they all reached a near-to-constant mass, they were
further saturated by vacuum saturation according to EN 12390-11 [22]. Stage 3 lasted for
63 days.
In stage 4, the specimens were kept in normal atmospheric conditions at 20 ◦ C and
RH 60%. This stage lasted 33 days. Once the plates reached a constant mass, they were
further conditioned at 20 ◦ C and RH 30% in stage 5.
Upon the completion of stage 5, the total porosity of the specimens was determined
according to SIA 262-1 [23]. This is a gravimetric method in which the specimen is first
weighed after drying at 50 ◦ C, next, the specimen is submerged in water for several days
and weighed, both when submerged in water and when above water. The specimen is
dried again at 50 ◦ C, vacuumed at pressure < 1 mbar and submerged in water and weighed
again under the water and above the water. Finally, the specimen is weighed after being
dried at 110 ◦ C.

3. Results and Discussion

The results of the accelerated carbonation study, where the carbonation rate was
measured by a pH-indicator and by TGA, are presented in Section 3.1. The results of both
methods are compared and discussed and are found to have a good correlation. The
moisture transport results, given in Section 3.2, indicate an increase in porosity due to
carbonation in specimens with a w/c ratio of 0.6.
 lution on the freshly split surfaces are given in Figure 4, where carbonation depth is plot-
ted against the square root of time. In general, there is a linear relationship between the
carbonation depth and the square root of time, therefore a straight line (Equation (1)) was
fitted to the results, adopting a confidence level of 95%. The results of the fitting process
are summarized in Table 4. The R2 values ranged from 0.79 to 0.98, indicating a reasona-
Materials 2021, 14, 6253 8 of 17
bly-good-to-excellent fit. In the two cases where the R2 values were less than 0.90, the re-
siduals were evenly distributed.
The results thus show that the carbonation rate of ~1.0 mm day−0.5 found in the EnM-
063.1.
wasCarbonation
the highest, while the RefM-05 had the lowest carbonation rate of ~0.2 mm day−0.5.
Rate
The other
Thetwo mortars, depth
carbonation namely EnM-05
results and Ref-06,
assessed had
visually approximately
after spraying thethe same carbon-
pH-indicator solu-
ation rate of ~0.6 mm day −0.5. Consequently, after 146 days of exposure, the EnM-06
tion on the freshly split surfaces are given in Figure 4, where carbonation depth is plotted
demonstrated a carbonation
against the square depth
root of time. Inof 13 mmthere
general, as opposed to the
is a linear 9 mm measured
relationship betweenon thethe
car-
RefM-06.
bonationSimilarly,
depth andthethe
EnM-05
squaredemonstrated
root of time, atherefore
carbonation depth line
a straight of 8 (Equation
mm while (1)) onlywas4
mm wastomeasured
fitted onadopting
the results, RefM-05.aThe results thus
confidence levelindicate
of 95%. that
The aresults
higherofw/cthe ratio leads
fitting to
process
a higher carbonation
are summarized depth.
in Table 4. This
The Rwas expected,
2 values ranged since
froma higher w/c ratio
0.79 to 0.98, generates
indicating higher
a reasonably-
porosity of the cement matrix, allowing a faster 2
penetration of CO into the sample
good-to-excellent fit. In the two cases where the R values were less than 0.90, the residuals
2 [24–
27].
were evenly distributed.

Figure
Figure 4. 4. Carbonation
Carbonation depth,measured
depth, measuredvisually
visuallyafter
afterspraying
sprayingthe
thesplit
splitsamples
sampleswith
with aa pH
pH indica-
indicator,
plotted
tor, against
plotted thethe
against square root
square of of
root time. “EnM”
time. “EnM” and “RefM”
and “RefM”stand forfor
stand EnDurCrete
EnDurCrete and
andthethe
reference
ref-
mortar
erence respectively,
mortar whilewhile
respectively, the extensions “-06” and
the extensions “-06”“-05”
and refer
“-05”to water/cement
refer ratiosratios
to water/cement of 0.6 of
and0.60.5.
and
The0.5. Thebars
error error bars indicate
indicate the variation
the variation in the carbonation
in the carbonation depth -depth - measured
measured in 10 pointson
in 10 pointson one sample
one
forsample for each
each mortar andmortar and time.
exposure exposure time.

Table
Table4.4.Results
Results ofof
regression analysis
regression based
analysis onon
based thethe
measured values
measured of carbonation
values of carbonationdepth at four
depth at four
different time intervals. As per (Equation (1)), parameter KAC is the carbonation rate and parameter
different time intervals. As per (Equation (1)), parameter K AC is the carbonation rate and parameter a
a is a constant representing the y-axis intercept, while R22 is the coefficient of determination indicat-
is a constant representing the y-axis intercept, while R is the coefficient of determination indicating
ing the quality of fit. “EnM” and “RefM” stand for EnDurCrete and the reference mortar respec-
the quality
tively, while theof fit. “EnM” and
extensions “RefM”
“-06” stand
and “-05” forto
refer EnDurCrete andratios
water/cement the reference mortar
of 0.6 and 0.5. respectively,
while the extensions “-06” and “-05” refer to water/cement ratios of 0.6 and 0.5.
Parameter EnM-06 RefM-06 EnM-05 RefM-05
Parameter
KAC (mm day−0.5) EnM-06 1.03 RefM-06
0.64 EnM-05
0.66 RefM-05
0.23
a (mm)
KAC (mm 0.15 1.22 −0.71 1.47
−
R 0.5
2 1.030.98 0.64
0.92 0.66
0.88 0.23
0.79
day )
Thea (mm)
CH content determined 0.15 by TGA as 1.22
a function of depth −0.71 1.47
for the samples prepared
R 2 0.98 0.92 0.88 0.79
with a w/c ratio of 0.6 is shown in Figure 5. Selected individual TGA results are presented
in Figures A1 and A2 of the Appendix. In general, the CH content decreased towards the
The results thus show that the carbonation rate of ~1.0 mm day−0.5 found in the
EnM-06 was the highest, while the RefM-05 had the lowest carbonation rate of ~0.2 mm
day−0.5 . The other two mortars, namely EnM-05 and Ref-06, had approximately the same
carbonation rate of ~0.6 mm day−0.5 . Consequently, after 146 days of exposure, the EnM-06
demonstrated a carbonation depth of 13 mm as opposed to the 9 mm measured on the
RefM-06. Similarly, the EnM-05 demonstrated a carbonation depth of 8 mm while only
4 mm was measured on RefM-05. The results thus indicate that a higher w/c ratio leads to
a higher carbonation depth. This was expected, since a higher w/c ratio generates higher
porosity of the cement matrix, allowing a faster penetration of CO2 into the sample [24–27].
Materials 2021, 14, 6253 9 of 17

Materials 2021, 14, x FOR PEER REVIEW 9 of 17

The CH content determined by TGA as a function of depth for the samples prepared
with a w/c ratio of 0.6 is shown in Figure 5. Selected individual TGA results are presented
in Figures A1 and A2 of the Appendix A. In general, the CH content decreased towards
surface,
the where
surface, whereno CH could
no CH be detected
could be detected because all of
because allitofwas consumed
it was consumedduring the car-
during the
bonation reaction. The plateau level of the CH content determined
carbonation reaction. The plateau level of the CH content determined on the deeper on the deeper sections
represents
sections the amount
represents initiallyinitially
the amount presentpresent
in the uncarbonated
in the uncarbonated mortars. These These
mortars. resultsresults
show
that CH
show content
that in mortar
CH content made with
in mortar made thewith
novel thecement
novel with
cement lowwith
clinker
lowcontent
clinker(EnM-06)
content
(EnM-06) was about 1.5 wt% compared to the 3 wt% CH present in mortarthe
was about 1.5 wt% compared to the 3 wt% CH present in mortar made with reference
made with
cement
the (RefM-06).
reference cement Since less CH is
(RefM-06). present
Since lessinCH theisEnM-06,
present thein thecarbonation
EnM-06, thefront was found
carbonation
further
front wasfrom thefurther
found top surface;
from thefor top
example,
surface; after
for90 days ofafter
example, carbonation it was
90 days of found ~12
carbonation it
mm from the surface, while in RefM-06 it was found at ~8 mm.
was found ~12 mm from the surface, while in RefM-06 it was found at ~8 mm. A similarA similar occurrence was
observed bywas
occurrence Carneiro
observedet al.
by[28], who used
Carneiro et al.specimens with low
[28], who used and high
specimens Portland
with low and cement
high
content and found the carbonation front significantly deeper in specimens
Portland cement content and found the carbonation front significantly deeper in specimens with low ce-
ment content. The depth of carbonation front measured with TGA
with low cement content. The depth of carbonation front measured with TGA corresponds corresponds well to the
carbonation
well depth measured
to the carbonation depthwith the visual
measured withmethod and,
the visual therefore,
method and,with the results
therefore, with pre-
the
viouslypreviously
results shown in Figure
shown4. in Figure 4.

(a) (b)
Figure 5.
Figure 5. CH
CHcontent
contentmeasured
measuredwith
withthermogravimetric analysis
thermogravimetric (TGA)
analysis (TGA)after 14, 14,
after 28, 90
28,and 146 days
90 and of exposure
146 days to accel-
of exposure to
accelerated carbonation for (a) EnDurCrete mortar (EnM-06); and (b) the reference mortar (RefM-06), Both made with aaw/c
erated carbonation for (a) EnDurCrete mortar (EnM-06); and (b) the reference mortar (RefM-06), Both made with w/c
ratio of 0.6.
ratio of 0.6.

The lower
The lowercarbonation
carbonationresistance
resistanceofof the
the EnDurCrete
EnDurCrete mortars
mortars compared
compared to reference
to the the refer-
mortars (see Figure 4) might therefore be related to the difference in the CH contentcontent
ence mortars (see Figure 4) might therefore be related to the difference in the CH in the
in the uncarbonated
uncarbonated mortarmortar specimens.
specimens. SinceSince lessisCH
less CH is available
available in thein EnDurCrete
the EnDurCrete mor-
mortars
tars compared to the reference mortars, these samples have a lower buffer
compared to the reference mortars, these samples have a lower buffer capacity during capacity during
carbonation (see,
carbonation (see, for
forexample,
example,[29–31]).
[29–31]).Additionally,
Additionally, Revert et al.
Revert et [21] have
al. [21] observed
have that
observed
low clinker
that binders
low clinker develop
binders a coarser
develop porosity
a coarser upon carbonation,
porosity enabling
upon carbonation, faster carbon-
enabling faster
ation rates. rates.
carbonation

3.2.
3.2. Moisture Transport
Transport
The
The mass
mass changes
changes ofof the
the thin
thin plates
plates during
during thethe moisture
moisture transport
transport experiments
experiments are are
shown
shown in in Figure
Figure 66 for
forw/c
w/c ratio 0.6 and and in
in Figure
Figure 77for forw/c
w/c ratio 0.5.
0.5. The
The results
results in
in both
both
figures
figures are
are normalized
normalized to to the
the initial
initial mass
mass of
of each
each plate.
plate. The
The standard
standard sample
sample deviation
deviation of of
mass changes found
mass changes found on a on a set of three specimens
specimens at any given time was between 5 and 10%.
The
The rapid
rapid drop
drop ofof mass
mass at
at the
thebeginning
beginningofofstage
stage22waswasprobably
probablydueduetoto surface
surface drying
drying of
of
thethe freshly
freshly cutcut samples.
samples. TheThe
platesplates in group
in the the group
“0%”“0%” continued
continued to mass
to lose lose mass
until until
equi-
equilibrium
librium was was reached
reached between
between 96 and
96 and 98 wt%
98 wt% of initial
of the the initial
mass.mass.
When When looking
looking at theatdry-
the
ing profiles of the “0%” series, we can see that the RefM-06 seemed to dry faster and to a
larger extent compared to the EnM-06. The plates in the group “3%”, on the other hand,
 point, the net mass gain due to carbonation (see chapter 1) compensates for the mass loss
due to drying. Sanjuán et al. [32] also reported an initial decrease in weight followed by
mass gain, even though their specimens were stabilized at 60% RH before carbonation.
The only exception within the “3%” group, where the mass continues to decrease
Materials 2021, 14, 6253 throughout stage 2, is EnM-06. The decrease or increase in mass in these experiments 10 of
can17

suggest which of the two mechanisms (drying vs carbonation) has the strongest impact
on the weight of the specimen. When CO2 is present, carbonation will cause weight gain
due to the
drying binding
profiles of “0%”
of the CO2 inseries,
the reaction products.
we can see that theThis weight
RefM-06 gain will
seemed partially
to dry coun-
faster and to
teract the mass loss due to the simultaneous drying. According to Table
a larger extent compared to the EnM-06. The plates in the group “3%”, on the other hand, 4, the EnM-06
mortar has a higher
first decrease in mass carbonation
but then start ratetothan the RefM-06;
increase in mass however, dueof
after ~3 days toexposure.
its lower clinker
At this
content,
point, theit had a lower
net mass COdue
gain 2 binding capacity compared
to carbonation (see Sectionto1)the RefM-06. This
compensates formight explain
the mass loss
why
due tothedrying.
EnM-06Sanjuán
mortar etdid al.not gain
[32] alsoany mass during
reported simultaneous
an initial decrease indrying
weightand carbona-
followed by
tion, whereas the RefM-06 mortar did (stage 2 in Figure 6).
mass gain, even though their specimens were stabilized at 60% RH before carbonation.

Materials 2021, 14, x FOR PEER REVIEW 11 of 17

Figure 6. Mass changes during the moisture transport experiment for thin plates with a water/cement ratio of 0.6. In stage
2, group
Figure “3%” changes
6. Mass was exposed tothe
during carbonation in a 3.1% experiment
moisture transport CO2 environment
for thinand group
plates with“0%” to conditioning
a water/cement in0.6.
ratio of a ~0% CO2
In stage
2, group “3%”“EnM”
environment. was exposed to carbonation
and “RefM” in a 3.1% CO
stand for EnDurCrete 2 environment
and and group
reference mortar “0%” to conditioning in a ~0% CO2
respectively.
environment. “EnM” and “RefM” stand for EnDurCrete and reference mortar respectively.

Figure 7. Mass changes during the moisture transport experiment for thin plates with a water/cement ratio of 0.5. In stage
Figure 7. Mass
2, group “3%” changes during
was exposed tothe moisture transport
carbonation in a 3.1%experiment for thinand
CO2 environment plates with“0%”
group a water/cement ratio of
to conditioning in0.5. In stage
a ~0% CO2
2, group “3%” was exposed to carbonation in a 3.1% CO2 environment and group “0%” to conditioning in a ~0% CO2
environment. “EnM” and “RefM” stand for EnDurCrete and the reference mortar, respectively.
environment. “EnM” and “RefM” stand for EnDurCrete and the reference mortar, respectively.

In stage 3, significant differences between groups “0%” and “3%” were observed. The
uncarbonated plates in the former group absorbed significantly less water than the car-
bonated plates in the latter group (normalized to their initial weight). This indicates an
increase in capillary porosity during carbonation compared to the uncarbonated samples.
This assumption was confirmed by the porosity results shown in Figure 8a, where one can
see that in the “-05” specimens porosity, increased by ~2% due to carbonation, which was
not the case for the -06 samples. Although a decrease in porosity upon carbonation is com-
Materials 2021, 14, 6253 11 of 17

The only exception within the “3%” group, where the mass continues to decrease
throughout stage 2, is EnM-06. The decrease or increase in mass in these experiments can
suggest which of the two mechanisms (drying vs carbonation) has the strongest impact on
the weight of the specimen. When CO2 is present, carbonation will cause weight gain due
to the binding of CO2 in the reaction products. This weight gain will partially counteract
the mass loss due to the simultaneous drying. According to Table 4, the EnM-06 mortar
has a higher carbonation rate than the RefM-06; however, due to its lower clinker content,
Figure 7. Mass changes during the moisture
it had a lowertransport
CO2 bindingexperiment for thin
capacity plates with
compared a water/cement
to the RefM-06. This ratiomight
of 0.5. In stage why
explain
2, group “3%” was exposed to carbonation in a 3.1% CO2 environment and group “0%” to conditioning in a ~0% CO2
the EnM-06 mortar did not gain any mass during simultaneous drying and carbonation,
environment. “EnM” and “RefM” stand for EnDurCrete and the reference mortar, respectively.
whereas the RefM-06 mortar did (stage 2 in Figure 6).
In stage 3, significant differences between groups “0%” and “3%” were observed.
In stage 3, significant differences between groups “0%” and “3%” were observed. The
The uncarbonated plates in the former group absorbed significantly less water than the
uncarbonated plates in the former group absorbed significantly less water than the car-
carbonated plates in the latter group (normalized to their initial weight). This indicates an
bonated plates in the latter group (normalized to their initial weight). This indicates an
increase in capillary porosity during carbonation compared to the uncarbonated samples.
increase in capillary porosity during carbonation compared to the uncarbonated samples.
This assumption was confirmed by the porosity results shown in Figure 8a, where one
This assumption was confirmed by the porosity results shown in Figure 8a, where one can
can see that in the “-05” specimens porosity, increased by ~2% due to carbonation, which
see that in the “-05” specimens porosity, increased by ~2% due to carbonation, which was
was not the case for the -06 samples. Although a decrease in porosity upon carbonation is
not the case for the -06 samples. Although a decrease in porosity upon carbonation is com-
commonly observed in Portland Cement-based binders [33,34], some studies reported an
monly
increase observed
in total in Portland
porosity Cement-based
in the case of cement binders
blends[33,34],
utilizingsome studies reported
supplementary an in-
cementitious
crease in total porosity in the case of cement blends utilizing supplementary
materials [33,35,36]. The latter two studies also reported a coarsening of the pore structure. cementitious
materials
Justnes et[33,35,36]. The latter
al. [35] explained two
this bystudies
the factalso
thatreported a coarsening
the reaction of theapore
of C-S-H with structure.
low Ca/Si ratio
Justnes et al. [35] explained this by the fact that the reaction of C-S-H
to CaCO3 causes a reduction in solid volume and, thereby, an increase in porosity [35]. with a low Ca/Si
The
ratio
Ca/Si to ratio
CaCO causes
of3 the a reduction
C-S-H in solid volume
was not determined and, thereby,
experimentally withinanthis
increase
study.in porosityit
However,
[35].
can The Ca/Si ratio
be assumed of due
that, the C-S-H was not
to the high determined
amount experimentally
of slag present within this
in both binders, thestudy.
C-S-H
However, it can be assumed that, due to the high amount
phase formed shows a considerably lower Ca/Si ratio compared to C-S-H formedof slag present in both binders,
during
the
theC-S-H
hydrationphase formed
of CEM shows a considerably lower Ca/Si ratio compared to C-S-H
I cement.
formed during the hydration of CEM I cement.

(a) (b)

Figure 8. Total porosity (a) measured according to SIA 262-1 [23]; and carbonation depth (b) of conditioned specimens
after stage 5. Specimens in the group “3%” were exposed to a 3.1% CO2 atmosphere, while specimens in the group “0%”
were exposed to the atmosphere with reduced CO2 content. “EnM” and “RefM” stand for EnDurCrete and reference
mortar, respectively, while extensions “-06” and “-05” refer to water/cement ratios of 0.6 and 0.5. The error bars indicate the
variation in values measured on the three specimens.
Materials 2021, 14, 6253 12 of 17

Stages 4 and 5 showed a gradual loss of mass. For the specimens in the “0%” group,
the mass at the end of stage 5 (30% RH) was approximately the same as the mass at the end
of stage 2 (60% RH). The normalized mass (to initial mass) of carbonated specimens was
~2% larger than the normalised mass of the uncarbonated specimens.
The fact that the EnM-06 and RefM-06 were fully carbonated corresponds to the
plateauing of the carbonated specimens during stage 2, as shown in Figure 6, confirming
that these specimens reached equilibrium at those conditions. The corresponding curves
for the carbonated EnM-05 and RefM-05 specimens, shown in Figure 7, did not plateau
during stage 2, which reflects the fact that they had not yet been fully carbonated.
The degree of carbonation at the end of stage 2 was checked on one thin plate with
the pH-indicator method. The plates were considered fully carbonated if the depth of
carbonation was equal to half of the plate thickness, that is, 10 mm. The results for the
plates in groups “3%” and “0%” are shown in Figure 8b. The plates in the “3%” group
and with a w/c ratio of 0.6 (EnM-06 and RefM-06) carbonated completely, while those
with a w/c ratio of 0.5 carbonated slightly less than half the depth, in the case of EnM-
05, and about 5 mm, in the case of RefM-05. This is an undesirable outcome, since the
numerical model calibration is to be performed on a fully carbonated material, on one
hand, and on a completely uncarbonated material, on the other. The results show that the
reduced CO2 levels in the conditioning chamber were able to limit the carbonation depth
of the “0%” specimens. No carbonation depth was measured on the “0%” EnM-05 and
RefM-05 specimens.

4. Conclusions
An experimental program was carried out to collect data for the verification of a
numerical model by studying (1) the rate of carbonation, and (2) the impact of carbon-
ation on moisture transport. For the verification of the rate of carbonation model, thick
mortar blocks were exposed to accelerated carbonation conditions and the depth of car-
bonation was measured visually on split samples sprayed with a pH indicator and on
profile-ground specimens using the TGA method. The impact of carbonation on moisture
transport was monitored by measuring the mass of thin mortar plates subjected to a specific
conditioning protocol.
The results obtained in this study indicate that carbonation depth is affected by the
amount of clinker in the cement and by the w/c ratio. The lower the amount of clinker
and/or the higher the w/c ratio, the higher the carbonation rate. Carbonation rates were
found to be ~1.0 mm day−0.5 for the EnM-06 and ~0.6 mm day−0.5 for the Ref-06, while
for the EnM-05 and RefM-05, the carbonation rates were ~0.7 and ~0.2 mm day−0.5 when
exposed to accelerated carbonation in 1% CO2 atmosphere. The results of both methods,
namely the visual and the TGA method, are in fairly good agreement. Additionally, the
TGA showed that the initial CH content was ~1.5 wt% in the EnM-06, as opposed to
~3.0 wt% in the RefM-06. Based on the results of this study, the lower initial CH content of
the EnDurCrete specimens might have been the reason for the higher carbonation rate.
The moisture transport experiments showed that carbonation increases the total
porosity, which can facilitate the transport of deleterious substances, and therefore can
promote other deterioration processes in addition to the corrosion of reinforcement. The
results obtained on the EnM-06 showed that during carbonation at constant RH EnM-
06 performed differently compared to other mortars. Unlike the results obtained in the
carbonation rate experiment, during exposure to the CO2 -rich environment, its mass
continued to drop, while it exhibited the highest carbonation rate. The decrease or increase
in mass shows which of the two mechanisms (drying vs carbonation) has the strongest
impact. As an improvement to the experiment protocol, we recommend conditioning
specimens at 60% RH after stage 1 until a constant mass is achieved, and then exposing
them to carbonation.
The experimental results presented here will be used for the verification of mechanis-
tic/generic models developed within the EnDurCrete project [5,11], which can be applied to
 mass shows which of the two mechanisms (drying vs carbonation) has the strongest im-
pact. As an improvement to the experiment protocol, we recommend conditioning speci-
mens at 60% RH after stage 1 until a constant mass is achieved, and then exposing them
Materials 2021, 14, 6253 13 of 17
to carbonation.
The experimental results presented here will be used for the verification of mecha-
nistic/generic models developed within the EnDurCrete project [5,11], which can be ap-
plied
novel to novel cements
cements with compositions.
with varying varying compositions. Theseaim
These models models aim to improve
to improve the pre-
the prediction of
diction
concreteofdurability
concrete in
durability in environment
a CO2 -rich a CO2-rich environment and,
and, therefore, therefore,
reduce reduce mainte-
maintenance-related
nance-related costs,
costs, particularly inparticularly in the public infrastructure
the public infrastructure sector. sector.

Conceptualization,A.Š.,
Author Contributions: Conceptualization, A.Š.,A.M.,
A.M.,K.D.W.
K.D.W.andandB.B.;
B.B.; methodology,
methodology, A.Š.,
A.Š., A.M.,
A.M., Y.G.
Y.G. and K.D.W.;
and K.D.W.; validation,
validation, B.BY.G.;
B.B. and andformal
Y.G.; formal analysis,
analysis, L.H.,
L.H., A.Š., A.Š.,and
A.M. A.M., and K.D.W.;
K.D.W.; investi-
investigation, S.R.,
gation,
M.H.B. S.R,
and M.H.B.,
R.M.L.C.;and R.M.L.C.;
resources, resources,
S.R., S.R,R.M.L.C.;
M.H.B. and M.H.B., anddataR.M.L.C.;
curation,data
S.R. curation, S.R.writing—
and M.H.B.; and
M.H.B.;
original writing—original
draft preparation, draft
L.H., preparation,
S.R. and A.Š.;L.H., S.R. and A.Š.;and
writing—review writing—review
editing, A.M.,and editing,
K.D.W., Y.G. and
A.M., K.D.W., Y.G.,S.R.
B.B.; visualization, andand
B.B;M.H.B.;
visualization, S.R and
supervision, M.H.B;
A.Š., K.D.W.supervision, A.Š., K.D.W.,
and B.B.; project and B.B.;A.Š.,
administration,
project administration, A.Š., K.D.W., and B.B.; funding acquisition, A.Š., K.D.W., and
K.D.W. and B.B.; funding acquisition, A.Š., K.D.W. and B.B. All authors have read and agreed B.B. All to
au-
the
thors have read and agreed to the
published version of the manuscript. published version of the manuscript.
Funding:
Funding: This
Thisproject
projectreceived
receivedfunding
fundingfrom
fromthethe
European
EuropeanUnion’s Horizon
Union’s 2020
Horizon research
2020 and and
research
innovation
innovation program
program under
under grant
grant agreement
agreementNoNo760639.
760639.This
Thispublication
publicationreflects
reflectsonly
onlythe
theauthors’
authors’
view and
view and the
theCommission
Commissionisisnot responsible
not forfor
responsible anyany
useuse
thatthat
maymay
be made of theofinformation
be made it
the information
contains.
it contains.

Institutional Review Board Statement: Not applicable.

Institutional
Informed Review
Consent Board Statement:
Statement: Not applicable.
Not applicable
Informed
Data ConsentStatement:
Availability Not data
Statement: The applicable.
presented in this study are available on request from the
corresponding author.
Data Availability The data
Statement: aredata
The not presented
publicly available due toare
in this study theavailable
confidentiality conditions
on request of
from the
the grant agreement.
corresponding author. The data are not publicly available due to the confidentiality conditions of the
grant agreement.
Acknowledgments: The authors would like to thank Vladimir Bras and Tomislav Tomše from
Acknowledgments: Thetechnical
ZAG for their valuable authors support in the
would like execution
to thank of experimental
Vladimir work. Besides,
Bras and Tomislav the au-
Tomše from ZAG
thors would like to thank Andreas Markali, Tone H. Nilsen and Caroline Hallerud from NTNU
for their valuable technical support in the execution of experimental work. Besides, the authors for
their help
would likewith the sample
to thank preparation,
Andreas analyses
Markali, Tone and evaluation.
H. Nilsen and Caroline Hallerud from NTNU for their
help with of
Conflicts theInterest:
sample preparation, analysesno
The authors declare and evaluation.
conflict of interest. The funders had no role in the
design of the study; in the collection, analyses, or interpretation
Conflicts of Interest: The authors declare no conflict of interest. The of data; in the
funders hadwriting of the
no role in the design
man-
uscript, or in the decision to publish the results.
of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, or
in the decision to publish the results.

Appendix A

Table A1. Chemical composition of components used in the production of En cement CEM II/C
(S-LL) and Ref cement CEM II/A-S, as measured with X-ray Fluorescence (XRF). The chemical
composition of the products was calculated by taking into account the proportions of the components
shown in Table 2.

Composition of Components (wt%) Composition of Products (wt%)

Title 1 CEM I 52.5 R S LL CEM II/C (S-LL) CEM II/A-S
SiO2 20.35 35.21 0.85 24.34 21.50
Al2 O3 5.46 11.27 0.15 7.25 6.00
TiO2 0.28 1.07 0.01 0.57 0.37
MnO 0.04 0.21 0.06 0.11 0.06
Fe2 O3 2.40 0.26 0.16 1.32 2.03
CaO 62.33 41.64 54.54 53.28 59.33
MgO 1.49 5.96 0.91 3.22 2.05
K2 O 0.89 0.64 0.04 0.71 0.82
Na2 O 0.20 0.22 0.01 0.19 0.20
SO3 3.68 0.00 0.01 1.84 3.05
P2 O5 0.12 0.01 0.01 0.07 0.10
LOI 1 1.87 (+0.16) 43.32 / /
1 Loss on ignition.
 K 2O 0.89 0.64 0.04 0.71 0.82
Na2O 0.20 0.22 0.01 0.19 0.20
SO3 3.68 0.00 0.01 1.84 3.05
P 2O 5 0.12 0.01 0.01 0.07 0.10
LOI 1 1.87 (+0.16) 43.32 / /
Materials 2021, 14, 6253 1 Loss on ignition. 14 of 17

Materials 2021, 14, x FOR PEER REVIEW 15 of 17

(a) (b)

(c) (d)
Figure
FigureA1.
A1. Differential
Differentialthermal
thermalanalysis
analysis(DTG)
(DTG)results
resultsobtained
obtainedon
onEnDurCrete
EnDurCretemortar,
mortar,EnM-06,
EnM-06,after
after(a)
(a)14,
14,(b)
(b)28,
28,(c)
(c)90,
90,
and (d) 146 days of exposure to accelerated carbonation. Extension “-06” refers to the water-cement ratio of 0.6. Each graph
and (d) 146 days of exposure to accelerated carbonation. Extension “-06” refers to the water-cement ratio of 0.6. Each graph
shows the results of the top layer in black, the innermost layer in light grey, and one layer in between, in medium grey.
shows the results of the top layer in black, the innermost layer in light grey, and one layer in between, in medium grey.
 (c) (d)
Figure
Materials 2021,A1.
14, Differential
6253 thermal analysis (DTG) results obtained on EnDurCrete mortar, EnM-06, after (a) 14, (b) 28, (c) 90,15 of 17
and (d) 146 days of exposure to accelerated carbonation. Extension “-06” refers to the water-cement ratio of 0.6. Each graph
shows the results of the top layer in black, the innermost layer in light grey, and one layer in between, in medium grey.

Materials 2021, 14, x FOR PEER REVIEW 16 of 17

(a) (b)

(c) (d)
Figure
Figure A2.
A2. Differential
Differential thermal
thermal analysis
analysis (DTG)
(DTG) results
results obtained
obtained on
on reference
reference mortar
mortar RefM-06
RefM-06 after
after (a)
(a) 14,
14, (b)
(b) 28,
28, (c)
(c) 90,
90, and
and
(d) 146 days of exposure to accelerated carbonation. Extension “-06” refers to the water-cement ratio of 0.6. Each
(d) 146 days of exposure to accelerated carbonation. Extension “-06” refers to the water-cement ratio of 0.6. Each graph graph
shows the results of the top layer in black, the innermost layer in light grey, and one layer in between, in medium grey.
shows the results of the top layer in black, the innermost layer in light grey, and one layer in between, in medium grey.

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