Case Studies in Construction Materials 17 (2022) e01300

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Case Studies in Construction Materials

journal homepage: www.elsevier.com/locate/cscm

Behavior of cementitious mixtures with filler carbonate subjected

to accelerated carbonation
Munique Fante a, Francisco Roger Carneiro Ribeiro b, David Brandão Nunes a,
Regina Célia Espinosa Modolo a, Claudio de Souza Kazmierczak a, Mauricio Mancio a,
Francisco Manoel Wohnrath Tognoli c, Afonso Rangel Garcez de Azevedo d,
Marlova Piva Kulakowski a, *
a
Civil Engineering Graduate Program, Vale do Rio do Sinos University (UNISINOS), Av. Unisinos, 950, Cristo Rei, São Leopoldo, Rio Grande do Sul,
Brazil
b
Graduate Program in Civil Engineering: Construction and Infrastructure, Federal University of Rio Grande do Sul (UFRGS), Av. Osvaldo Aranha,
99, Centro Histórico, Porto Alegre, Rio Grande do Sul, Brazil
c
Graduate Program in Geology, Vale do Rio dos Sinos University (UNISINOS), Av. Unisinos, 950, Cristo Rei, São Leopoldo, Rio Grande do Sul,
Brazil
d
Civil Engineering Laboratory (LECIV), State University of Norte Fluminense Darcy Ribeiro (UENF), Av. Alberto Lamego, 2000 Rio de Janeiro,
Brazil

A R T I C L E I N F O A B S T R A C T

Keywords: Calcium carbonate limestone filler is used as a partial replacement for clinker in cements to
Calcium carbonate limestone reduce carbon dioxide emissions and fill the voids in the cement paste. However, concrete
Carbonation durability conditions depend on the composition and the water/cement ratio, one of the major
Calcium carbonate polymorphs
origin of concrete´s porosity. The objective of this study was to evaluate physical and chemical
Accelerated carbonation
effects of calcium carbonate limestone filler in mortar pastes subjected to accelerated carbon­
ation. Composite formulations were elaborated with three proportions of filler substitution (15%,
25% and 35%) and three water/cement ratios (0.42, 0.50 and 0.58). Physical, chemical and
mineral characterizations were performed on Portland cement PC V and calcium carbonate
limestone. The resulting mortar paste formulations were evaluated with respect to mechanical
strength and capillary water absorption both for samples without carbonation and with accel­
erated exposure conditions. In the latter, carbonation depth penetration was also ascertained.
Carbonation effects were determined from X-ray diffraction and thermogravimetric analysis.
Results on compression strength and water absorption determined that a 25% filler substitution
achieved the best performance with 40.72 MPa and an absorption of up to 7% for the water/
cement ratio of 0.42. The carbonation coefficient was primarily affected by the water/cement
ratio rather than substitution level. Thermal and mineral analysis indicated that carbonation
consumed portlandite and formed calcite. Further calcium carbonate polymorphs were identified
after 28 days of accelerated carbonation as a result so far unreported in studies of Portland
cement.

* Corresponding author.
E-mail addresses: mfante1@edu.unisinos.br (M. Fante), roger.ribeiro@ufrgs.br (F.R.C. Ribeiro), davidbrnunes@edu.unisinos.br (D.B. Nunes),
reginaem@unisinos.br (R.C.E. Modolo), claudiok@unisinos.br (C.S. Kazmierczak), mancio@unisinos.br (M. Mancio), ftognoli@unisinos.br
(F.M.W. Tognoli), afonso@uenf.br (A.R.G. de Azevedo), marlovak@unisinos.br (M.P. Kulakowski).

https://doi.org/10.1016/j.cscm.2022.e01300
Received 13 April 2022; Received in revised form 15 June 2022; Accepted 4 July 2022
Available online 6 July 2022
2214-5095/© 2022 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).
M. Fante et al. Case Studies in Construction Materials 17 (2022) e01300

1. Introduction

Increases in worldwide carbon dioxide (CO2) concentration are a reality according to the Global Monitoring Division of NOAA/
Earth System Research Laboratory [1]. Notably, the average monthly concentration of CO2 increased from 340 ppm in 1980 to 412
ppm in 2020. The cement industry represents a significant contribution to CO2 emissions due to lime decarbonation and fossil fuel use
in the manufacture of Portland cement. Added to this is a growing demand for cement predicted to reach 4.7 billion tons by 2050 [2].
Attempts to curb the negative environmental impact of this sector make use of supplementary cementitious materials (SCMs) added to
mixtures with the goal of reducing cement clinker to 37% by 2050 [3,4]. However, demand for SCMs is forecasted to outstrip local
supply. Alternatively, lime fillers have been used as clinker substitute since the 1980′ s. John et al. [5] reported that lime filler use could
reduce CO2 emissions in proportion to substitution level since lime did not require calcination to be used in cementitious matrices and
energy expenditure was related only to extraction and grinding.
Several studies have been conducted with respect to the use of limestone mixed with cement. Most results confirmed that, when
used as filler, limestone affected clinker reactivity and hydration kinetics but had little effect on mechanical strength over a range of
substitution levels. In fact, cementitious matrices were affected primarily by the quality of the clinker and quality and fineness of
limestone [6–8]. In addition, results were sometimes inconclusive with varying effects resulting from the substitutions. This was
related to clinker, cement and limestone being unique materials with specific characteristics depending on source.
A major cause of decreased durability of reinforced concrete is rebar corrosion. In principle, concrete offers a natural chemical
protection through the formation of a passivation layer on the surface of steel from the alkaline pH solution in the pores [9]. However,
mechanisms such as carbonation can lead to loss of chemical protection and depassivation of steel. This is a consequence of bonds
between hydration compounds in cement and carbon dioxide penetrating into concrete and forming calcium carbonate (CaCO3).
Damaging effects are: decrease in the pH solution in the pores from the consumption of portlandite and loss of the passivation layer,
microstructural changes, dissolution of alkaline compounds and CaCO3 precipitation [10–12]. This result occurs since calcium silicate
hydrate (C-S-H) and portlandite or calcium hydroxide (CH) are related to the amount of cement and SCMs in concrete [13].
Since 2018, a maximum substitution of 25% clinker in cement CP II – F is allowed in accordance with updates to Brazilian standard
NBR 16697 [14]. Other standards allow varying levels of clinker substitution: 35% in EN 197–1 [15], 15% in CSA A3000 [16], 10% in
ASTM C150 [17] and 5% in GB 175 [18]. In addition, EN 197–1 and CSA A3000 recommend a limestone calcium carbonate level of
75% in mass. The allowed high level of limestone clinker substitution instigates further studies on the properties and durability of
composite mixtures so that the resulting characteristics can be equivalent or superior to common Portland cement. A promising
technique to achieve the desired mechanical properties and durability of mixtures is carbonation curing of cement-based compounds
[19–21]. Other advantages of carbonation curing are lower energy consumption when compared to steam curing and shorter hard­
ening time when compared to wet curing [22,23]. While high initial gains in strength and microstructural hardening have been
ascertained, carbonation curing effects on other fundamental mechanisms, durability with respect to different levels of filler substi­
tution and effect of different water/cement ratios are still unclear.
Consequently this study sought to evaluate the physical and chemical changes related to the use of carbonate filler in cement pastes
and mortars subjected to accelerated carbonation. In order to evaluate the carbonation depth in accelerated test, the porosity and
mechanical strength of the matrices, the relationship between carbonation coefficient and compressive strength, as well as the for­
mation of calcium carbonate polymorphs through accelerated carbonation.

Table 1
Physical and chemical characteristics of cement and limestone filler of this study.
Properties CP V Limestone Filler

Chemical Composition (% w.t) Silicon Dioxide (SiO2) 16.51 12.67

Aluminium Oxide (Al2O3) 2.55 3.59
Iron Oxide (Fe2O3) 4.21 1.70
Calcium Oxide (CaO) 60.42 44.13
Magnesium Oxide (MgO) 1.86 1.09
Sulfuric Anhydride (SO3) 2.10 ND
Sodium Oxide (Na2O) 1.20 0.49
Potassium Oxide (K2O) 1.56 0.60
Titanium Oxide (TiO2) 0.51 0.24
Phosphorus Pentoxide (P2O5) 0.92 0.12
Chromium Oxide (Cr2O3) 0.01 ND
Manganese Oxide (MnO) 0.15 0.06
Zinc Oxide (ZnO) 0.04 ND
Strontium Oxide (SrO) 0.36 0.12
Loss on Ignition (LOI) 7.59 35.18
Physical Composition BET Specific Area (cm2/g) 16.464 33.491
Specific Mass (g/cm3) 2.95 2.65
Granulometric Analysis D10 (µm) 3.64 1.81
D50 (µm) 10.26 3.28
D90 (µm) 24.66 5.85
Dm (µm) 11.82 3.51

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Fig. 1. Mineral characteristics of cement and limestone filler of this study.

2. Material and methods

The materials used in this study were: Portland cement CP V, limestone filler (LF), sand, superplasticizer additive and water. The CP
V cement was selected due to its lack of pozzolanic material and 0–10% carbonate content, which was intended to minimize inter­
ference. The limestone filler had a granulometry of less than a 325 Mesh and calcite content of 77.33%, as determined from the integral
method of thermal analysis. The sand was fine quartz from the Jacui River in RS/Brazil. The superplasticizer was policarboxylate-
based and used to adjust the consistency of the mixtures. Physical, chemical and mineral characteristics of the anhydrous cement
and limestone filler are shown in Table 1 and Fig. 1.
For this study, water/cement (w/c) ratio values of 0.42, 0.50, and 0.58 were employed. These parameters aim at a better variation
of the excess water with respect to pore formation in the cement matrix without segregation or exudation. The w/c and not water/
binder ratio was adopted for a better verification of the inert effect of the lime filler. Therefore, the amount of water was kept constant.
The replacement content of cement by lime filler was adopted according to the maximum content of filler allowed by some
countries and calculated by mass. The following were used: 15%, related to China, Canada and the USA, 25%, referring to Brazil and
Argentina, and 35%, allowed in Europe and South Africa [5,14]. This substitution was accomplished by the difference in the calcite
content present in PC V cement. The calcite content in the cement was calculated by thermal analysis and resulted in 7.27%.
Sand granulometry yielded a fineness module of 2.33, apparent density of 1.63 g/cm3 and specific mass of 2.61 g/cm3. These
measurements were obtained following standards NBR NM 248 [24], NBR NM 45 [25] and NBR NM 52 [26], respectively.
Procedures for mortar production, mechanical mixture, consistency index and molding followed standard NBR 7215 [27]. How­
ever, prismatic samples measuring 40 mm × 40 mm x 160 mm were adopted for carbonation tests in order to obtain 40 mm × 40 mm
x 20 mm slices. All test samples (TS) were subjected to wet curing for 24 h, demolded and stored under saturated curing for 28 days.
Furthermore, to ensure the same relative humidity (RH) for accelerated carbonation tests, all TS were aged with the same procedure.
The aging procedure was based on the method of RILEM TC 116-PCD [28] and consisted of storing all TS in a climate-controlled
environment of RH = 60 ± 10% and T = 21 ± 2ºC. Weightings were conducted and interrupted if measurements presented a differ­
ence of less than 0.5 g in a 24 h interval, up to a maximum of 14 days.
Axial compression strength was measured in accordance with standard NBR 7215 [27]. The TS used measured 50 mm in diameter
and 100 mm in height and 6 sample of each formulation were randomly selected from the entire production. Test samples were capped
and tested until rupture after 28 days of curing.
Capillary water absorption tests followed standard RILEM TC 116-PCD [28]. Three slices were taken from the TS of
40 mm × 40 mm x 160 mm with the ends being discarded. The slices were conditioned in an oven at 50 ºC until stabilized and then
kept in driers to prevent contact with humidity and to maintain a constant temperature. The sides were sealed with duct tape and
coated with latex paint. The upper extremity was sealed with a balloon to expel air from water absorption. Weightings were conducted
with the procedures of Werle et al. [29].
Following aging, accelerated carbonation tests were performed in a carbonation chamber. Chamber parameters were based on
Sartori et al. [30] with 3% CO₂ concentration, 60 ± 5% relative humidity and 20 ± 5 ◦ C temperature. Exposure times were of 7 days,
28 days, 63 days and 91 days. Only the TS sides were exposed to CO₂ as the other surfaces were covered in latex paint. A single TS from
each formulation was ruptured at each time interval and sprayed with a 1% phenolphthalein solution in accordance with standard
RILEM CPC-18 [31] to determine the pH of the sample and carbonated zones. Overall, a total of 2 carbonation front measurements
from sides of the samples and 3 further individual measurements on each face were taken to calculate an average value. While standard
RILEM CPC-18 [31] recommended that measurements be taken 24 h after spraying, data for this study were taken after drying and, at

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Fig. 2. Potential axial compression strength and Abrams’ law curves for each mixture at 28 days.

Table 2
Abrams’ law curve characteristics for each mixture.
Mixture W/C Potential Compression strength (MPa) Abrams Curve Equation R2

CP V 0.42 34.69 Log (fc) = 1.71–0.40 × w/c 0.9387

0.50 33.28
0.58 30.02
15% LF 0.42 37.63 Log (fc) = 1.83–0.65 × w/c 0.9394
0.50 33.56
0.58 28.25
25% LF 0.42 40.72 Log (fc) = 1.96–0.84 × w/c 0.9405
0.50 32.54
0.58 29.94
35% LF 0.42 35.77 Log (fc) = 1.85–0.71 × w/c 0.8823
0.50 28.77
0.58 27.59

most, 1 h after spraying. This was chosen since the intensity of pH coloration faded excessively after 24 h and made data acquisition
difficult.
In order to differentiate the amounts of calcium carbonate from the limestone filler and carbonation, specific formulations with
water/cement (w/c) ratios of 0.42 and 0.58 were produced by derivative thermogravimetry (DTG) and X-ray diffraction (XRD) an­
alyses, respectively. The w/c ratios were adjusted with respect to the slump of the reference paste with highest w/c ratio and
superplasticizer with a slump limit of ± 10 mm. Formulations were evaluated both with a Marsh funnel and Kantro mini slump test
and a maximum level of superplasticizer of 0.57% was determined for which the amount of water did not require adjustment.

3. Results and discussion

3.1. Axial compression strength

For the formulations of this study, average values of axial compression strength, Abrams’ law curve and R2 correlation are shown in
Fig. 2 and Table 2. Results were taken at 28 days and presented a maximum standard deviation of 6%.
Primary compression strength developed from C-S-H formation from clinker silicates (alite and belite) and secondary formation
from SCMs [32]. Fig. 2 shows that, for the same strength, a 25% LF substitution had a 6% reduction in cement use with respect to the
reference PC V formulation. Additionally, Table 2 shows that a 25% substitution had higher strengths than the other formulations for
any w/c ratio. However, at long ages, higher LF substitutions resulted in a loss of mechanical performance and decreased strength

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Fig. 3. Water absorption over time for: a) w/c = 0.58; b) w/c = 0.50 and c) w/c = 0.42.

Fig. 4. Water absorption rate with respect to w/c ratio.

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Fig. 5. Water absorption depth with respect to time for: a) w/c = 0.58; b) w/c = 0.50 and c) w/c = 0.42.

[33–35].
Panesar and Zhang [36] compared the performance of cementitious materials with varying degrees of LF substitution. Results
showed that compression strengths of formulations with up to 10% substitution were equivalent or superior to a reference paste with
no filler after 28 days. In contrast, results for this study show that up to 25% LF substitution could be used with no loss in mechanical
properties, which was also the conclusion of Marzouki et al. [37]. Additionally Oey et al. [38] also noted that in mixtures with up to
25% substitution, LF was a more efficient filler and accelerated clinker hydration. For a strength of 32 MPa, Fig. 2 demonstrates that
cement usage increased when no LF was present after accounting for base consumption. Overall, formulations with 15% LF substi­
tution had lower w/c ratio and porosity, 25% LF substitution had the lowest cement usage and 35% LF substitution had a decrease in
mechanical strength – indicating that it exceeded acceptable limits.

3.2. Water absorption

Water absorption results over time are shown in Fig. 3 for the reference CP V concrete and LF substitution formulations for varying
w/c ratios. Results showed that, for high w/c ratios, matrix porosity increased gradually as less LF was used in substitution. Tsivilis
et al. [39] also concluded that when LF was incorporated into a cementitious matrix, pore size decreased. As the w/c ratio decreased,
water absorption also decreased and the water absorption curves merged together over time. This demonstrated that there was no
significant variation between water absorption and degree of LF substitution.
Fig. 4 presents water absorption rate with respect to w/c ratio for all formulations. The trend line reflected the absorption levels of
Fig. 3 and denoted that a 35% LF substitution had decreased water absorption. Marzouki et al. [37] and Elgalhud et al. [40] reported
that LF substitutions above 25% might not affect significantly matrix porosity. However, pore structure became more fragile and
porosity increased for higher substitution levels due to the decrease in the clinker ratio and/or grind quality.
In practical terms, the time taken for water to reach a certain penetration depth could be determined from the absorption rate. This
methodology was described in standard NBR 6118 [41] and used to obtain the results of Fig. 5.

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Table 3
ANOVA for w/c ratio.
ANOVA: Single factor
SUMMARY

Group Count Sum Mean Variance

0.42 4 4.842571 1.210643 0.011087

0.50 4 6.896989 1.724247 0.049255
0.58 4 7.819214 1.954804 0.091483
ANOVA
Source of variance SQ GL MQ F P-value Critical F
Between groups 1.160961 2 0.580481 11.47009 0.003346 4.256495
Within groups 0.455474 9 0.050608
Total 1.616435 11

Significance: YES

Table 4
ANOVA for LF substitution level.
ANOVA: Single factor
SUMMARY

Group Count Sum Mean Variance

CP V 3 5.675797 1.891932 0.280025

15% LF 3 5.017463 1.672488 0.160822
25% LF 3 4.501505 1.500502 0.075564
35% LF 3 4.364009 1.45467 0.11492
ANOVA
Source of variance SQ GL MQ F P-value Critical F
Between groups 0.353773 3 0.117924 0.747146 0.553748 4.066181
Within groups 1.262662 8 0.157833
Total 1.616435 11

Significance: NO

Table 5
Average carbonation depth (mm) for all formulations under accelerated carbonation.
Mixture 7 days 28 days 63 days 91 days

42 / CP V * * 2.94 4.33
42 / 15 * * 2.92 5.08
42 / 25 * * 1.53 4.76
42 / 35 * * 2.17 5.75
50 / CP V * 1.81 4.85 5.98
50 / 15 * 1.73 4.78 6.30
50 / 25 * 1.10 4.71 6.09
50 / 35 * 1.48 4.88 6.21
58 / CP V * 2.54 6.55 7.29
58 / 15 * 2.39 6.00 6.82
58 / 25 * 2.33 6.26 7.93
58 / 35 * 2.54 6.36 8.44
*
less than 0.5 mm penetration

Fig. 5 demonstrates that the time needed to reach a certain penetration depth increased as w/c ratio decreased while porosity
decreased as LF substitution level increased. For example, the time required for water to penetrate a 25 mm layer of reference cement
paste varied between 115 h and 500 h for w/c ratios of 0.58 and 0.42, respectively. In the case of a 25% LF substiution mixture, the
time varied between 202 h and 427 h for the same respective w/c ratios. This change indicated a higher density of the porous
microstructure with this level of substitution.
An ANOVA statistical analysis was applied to the relation between w/c ratio and LF subsitution level and the results are shown in
Tables 3 and 4. The analysis indicated that w/c ratio had a significant relation to absorption and, by extension, pososity. On the other
hand, LF subsitution level did not appear to have a significant relation with w/c ratio.

3.3. Carbonation measurements

Average carbonation depths over time under accelerated carbonation are shown in Table 5. Data showed that 7 days of accelerated
carbonation were insufficient to produce a significant depth in all samples (< 0.5 mm). Even 28 days of exposure did not produce

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Fig. 6. Carbonation depth with respect to w/c ratio for all formulations.

Table 6
Carbonation penetration depth correlation curves with respect to w/c ratio.
Age (days) % LF Correlation curve R2

28 CP V y = 7.9092ln(x) + 7.0023 0.964

15% LF y = 7.4447ln(x) + 6.5996 0.959
25% LF y = 7.1607ln(x) + 6.172 0.993
35% LF y = 7.8546ln(x) + 6.854 0.998
63 CP V y = 11.163ln(x) + 12.612 1.000
15% LF y = 9.574ln(x) + 11.284 0.995
25% LF y = 14.742ln(x) + 14.509 0.978
35% LF y = 13.04ln(x) + 13.62 0.985
91 CP V y = 9.179ln(x) + 12.308 1.000
15% LF y = 5.453ln(x) + 9.8919 0.967
25% LF y = 9.757ln(x) + 13.106 0.980
35% LF y = 8.1696ln(x) + 12.533 0.842

significant differences for the formulations with a w/c ratio of 0.42. However, in the remaining formulations and time scales, calcium
carbonate was formed from carbon dioxide diffusion and substantial carbonation was observed at 91 days. Resistance to carbonation
also did not decrease as LF substitution increased, which was believed to be a consequence of increased matrix density in the
formulations.
The relation between carbonation depth and w/c ratio for all formulations are shown in Fig. 6 and Table 6. Trend lines showed that
carbonation increased with increasing w/c ratio regardless of LF substitution level and exposure time. This presented a caveat in that
while LF substitution could improve properties of both fresh and hardened cement, special attention was needed to check the w/c ratio

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Fig. 7. Carbonation coefficient for the formulations.

Fig. 8. Carbonation coefficient with respect to axial compression strength for all formulations.

of the formulation since filler dilution affected mechanical and durability characteristics of concrete [42,43].
Fig. 6 shows that, after 28 days of accelerated carbonation, all formulations presented very similar carbonation depths at each w/c
ratio. As the exposure time increased, there was a trend of increased variance in penetration depth between formulations. The most
variance was observed with 35% LF substitution while the least variance occurred with 25% LF substitution at 28 days and 63 days. It
should be noted that the shallowest penetration depth at 91 days corresponded to the reference cement paste without substitution.
Carbonation penetration depth data over time allowed the penetration coefficient (k) to be determined as shown in Fig. 7, with each
bar color denoting a specific w/c ratio. The carbonation coefficient was related to the speed of the carbonation front. Consequently,
Fig. 7 denotes that the smallest k occurred for 25% LF substitution and 0.42 w/c ratio while the largest k occurred for 35% LF sub­
stitution and 0.58 w/c ratio. These results were in-line with the conclusions drawn from the previous figures.
The relation between carbonation coefficient and axial compression strength for all formulations is shown in Fig. 8. There was a
direct relation between carbonation level and porosity through the w/c ratio. That meant carbonation was driven by the porosity
obtained in accordance to the w/c ratio and proportion of LF filler in the formulation. Lauch et al. [44] and Dhandapani et al. [45]
determined that carbonation increased as clinker levels of the formulation decreased – a result caused by alkali reduction in the matrix
as reported by Shah et al. [46]. Fig. 8 demonstrates that, at low w/c ratios, LF substitution levels did not affect the carbonation co­
efficient and its value remained within a narrow band despite changes in strength. However, for the same water/cement ratio,
although the LF content notably influences the strength, the carbonation coefficient levels are practically the same. Observing the w/c
ratio 0.48, one realizes that the carbonation coefficient remains between 0.6 and 0.8 mm/√days).
Some authors, when studying carbonation in concretes composed with supplementary cementitious materials, observed that
concretes developed with the same water-cement ratio, even with a variation in strength by increasing the content of SCM’s, the level

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Fig. 9. Hydration and carbonation products determined from DTG. *Ett: Ettringite, Q: Quartz, Hc: Hemi-calcium carboaluminate, V: Vaterite, Mc:
Mono-calcium carboaluminate, A: Aragonite, CH: Portlandite, CC: Calcite.

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Fig. 10. XRD results for all formulations with: a) w/c = 0.42 and b) w/c = 0.58. *Ett: Ettringite, Q: Quartz, Hc: Hemi-calcium carboaluminate, V:
Vaterite, Mc: Mono-calcium carboaluminate, A: Aragonite, CH: Portlandite, CC: Calcite..

Fig. 11. Polymorph formation in: (a) reference paste with CP V and (b) 35% LF substitution.

of carbonation coefficient remains at the same level. Thus, the evidence that the porosity generated by the water/binder ratio seems to
substantiate the considerations made [9,12,47–49].

3.4. Thermal and mineral analysis

For all formulations, portlandite levels decreased and calcium carbonate levels increased as carbonation progressed. This phe­
nomenon was also reported by Soja et al. [50]. Aragonite and vaterite polymorphs were detected after 28 days of accelerated
carbonation in almost all formulations. The exception was the formulation with w/c ratio of 0.42 and 25% LF substitution, in which
these compounds were detected only after 63 days. According to Wu and Ye [51], a calcite peak should be related to aragonite and
vaterite polymorphs. The formation of these compounds might be induced by the clinker since they were related to the presence of
C-S-H in low calcium/silica concentrations or high CO2 concentrations. However, when reference pastes with no LF substitution were
compared, the same compounds were found in larger amounts at a w/c ratio of 0.58 and to a lesser extent with a w/c ratio of 0.42.
While these samples had the same compounds, porosity diverged between them.
Fig. 9 shows that C-S-H and ettringite peaks were significant in formulations with larger amounts of cement due to the larger
presence of clinker. Peaks of hemi and mono-carboaluminate had minor increases with higher levels of LF substitution, which were a
result of the chemical effect of the filler.
Fig. 10 presents XRD of all formulations with w/c ratios of 0.42 and 0.58. The reference paste was subjected to 28 days of curing
while the LF substitution formulations were subjected to accelerated carbonation.
As expected, as the carbonation process progressed, ettringite and portlandite levels present in all formulations decreased while
calcite increased. This indicated that portlandite was consumed in the carbonation process. Consequently, higher LF substitution

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should decrease portlandite formation and increase the initial quantity of calcite present in the formulation.
No mono-sulfoaluminate formation was detected, which could be related to the presence of calcite. According to Ipavec et al. [52],
even small quantities of calcium carbonate could stabilize aluminates as hemi-carbonates instead of mono-sulfates. Even the reference
paste contained a small quantity of calcite from PC V cement, which accounted for the hemi-carbonate detected.
Further observations related to the formation of aragonite and vaterite polymorphs can be obtained from the detail XRD of the
reference paste and 35% LF substitution formulation of with w/c 0.58 in Fig. 11. In Fig. 11(a), polymorph formation was detected in
the reference paste at 28 days of accelerated carbonation and increased further at 63 days. In contrast, the 35% LF substitution
formulation of Fig. 11(b) had considerably less polymorph formation due to the large use of filler. Aragonite is the polymorph with the
lowest molar volume compared to vaterite and calcite. Due to this factor, aragonite precipitation causes higher porosity and easier CO2
ingress [50].

4. Conclusions

Supplementary cementitious materials can improve cement performance. However, it is necessary to determine the performance
characteristics of formulations with different combinations of substitution levels and w/c ratios. The following conclusions were drawn
from the experimental data of this study:

1. Compression strength results after 28 days increased for the formulation with 25% LF substitution, which corresponded to a 6%
decrease in cement consumption. There were no more gains in strength for a higher 35% LF substitution. Therefore a 25% LF
substitution was the best result regardless of w/c ratios.
2. Water absorption tests indicated what lower w/c ratios resulted in less porosity and the level of filler substitution did not affect
substantially pore structure.
3. Carbonation penetration depth was directly related to w/c ratio and porosity but filler substitution level had the greatest effect. The
smallest carbonation coefficient occurred for a 25% LF substitution and 0.42 w/c ratio, which further reinforced this substitution
level as the most adequate for use as recommended in some standards.
4. Resistance to carbonation did not decrease substantially with increased LF substitution in all formulations up to 91 days of curing.
5. Vaterite and aragonite formed after 28 days of accelerated carbonation. These phenomena could be related to the level of filler
substitution and was inversely proportional to the presence of clinker. This result had not been cited in other studies and denoted
the need of careful detection of these calcium carbonate polymorphs in substitution formulations.

Overall it could be recommended that all international standards allow up to 25% LF substitution. The benefits of carbonation were
not only limited to reducing negative environmental effects of the cement industry and global warming but also to positively affect
compression strength and water absorption of matrices cementitious.

Declaration of Competing 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.

Data Availability

Data will be made available on request.

Acknowledgments

The authors acknowledge the support to this investigation by the Brazilian agencies: Coordenação de Aperfeiçoamento de Pessoal
de Nível Superior (CAPES) and Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq). Numbers: 310369/2021-5
(PQ2), 316211/2021-4 (PQ2), 315912/2021-9 (PQ2) and 307592/2021-9 (PQ2).

References

[1] NOAA (National Oceanic and Atmospheric Administration), Trends in atmospheric carbon dioxide, (2021). 〈https://gml.noaa.gov/ccgg/trends/global.html〉.
[2] IEA (International Energy Agency), Energy technology perspectives, 2015, (2015).
[3] M.C.G. Juenger, R. Siddique, Recent advances in understanding the role of supplementary cementitious materials in concrete, Cem. Concr. Res. 78 (2015)
71–80, https://doi.org/10.1016/j.cemconres.2015.03.018.
[4] WBCSD (World Business Council for Sustainable Development), Tecnology roadmap: low-carbon transition in the cement industry, (2018).
[5] V.M. John, B.L. Damineli, M. Quattrone, R.G. Pileggi, Fillers in cementitious materials — experience, recent advances and future potential, Cem. Concr. Res. 114
(2018) 65–78, https://doi.org/10.1016/j.cemconres.2017.09.013.
[6] S. Tsivilis, G. Batis, E. Chaniotakis, G. Grigoriadis, D. Theodossis, Properties and behavior of limestone cement concrete and mortar, Cem. Concr. Res. 30 (2000)
1679–1683, https://doi.org/10.1016/S0008-8846(00)00372-0.
[7] S. Tsivilis, E. Chaniotakis, G. Kakali, G. Batis, An analysis of the properties of Portland limestone cements and concrete, Cem. Concr. Compos. 24 (2002)
371–378, https://doi.org/10.1016/S0958-9465(01)00089-0.
[8] T. Vuk, V. Tinta, R. Gabrovšek, V. Kaučič, The effects of limestone addition, clinker type and fineness on properties of Portland cement, Cem. Concr. Res. 31
(2001) 135–139, https://doi.org/10.1016/S0008-8846(00)00427-0.

12
M. Fante et al. Case Studies in Construction Materials 17 (2022) e01300

[9] M.P. Kulakowski, F.M. Pereira, D.C.C.D. Molin, Carbonation-induced reinforcement corrosion in silica fume concrete, Constr. Build. Mater. 23 (2009)
1189–1195, https://doi.org/10.1016/j.conbuildmat.2008.08.005.
[10] Z. Shi, B. Lothenbach, M.R. Geiker, J. Kaufmann, A. Leemann, S. Ferreiro, J. Skibsted, Experimental studies and thermodynamic modeling of the carbonation of
Portland cement, metakaolin and limestone mortars, Cem. Concr. Res. 88 (2016) 60–72, https://doi.org/10.1016/j.cemconres.2016.06.006.
[11] F. Pacheco Torgal, S. Miraldo, J.A. Labrincha, J. De Brito, An overview on concrete carbonation in the context of eco-efficient construction: evaluation, use of
SCMs and/or RAC, Constr. Build. Mater. 36 (2012) 141–150, https://doi.org/10.1016/j.conbuildmat.2012.04.066.
[12] S. Hussain, D. Bhunia, S.B. Singh, Comparative study of accelerated carbonation of plain cement and fly-ash concrete, J. Build. Eng. 10 (2017) 26–31, https://
doi.org/10.1016/j.jobe.2017.02.001.
[13] S. Demirhan, K. Turk, K. Ulugerger, Fresh and hardened properties of self consolidating Portland limestone cement mortars: effect of high volume limestone
powder replaced by cement, Constr. Build. Mater. 196 (2019) 115–125, https://doi.org/10.1016/j.conbuildmat.2018.11.111.
[14] ABNT (Associação Brasileira de Normas Técnicas), ABNT NBR 16697: cimento Portland – requisitos, (2018).
[15] ECS (European Committee for Standardization), EN-197-1: Cement - composition specifications and conformity criteria for common cements, (2000).
[16] CSA (Canadian Standard Association), CSA A3000: cementitious materials compendium, (2013).
[17] ASTM (American Society for Testing and Materials), ASTM C150: standard specification for Portland cement, (2018).
[18] SAC (Standardization Administration of China), GB-175: common Portland cement, (2007).
[19] W. Ashraf, Carbonation of cement-based materials: challenges and opportunities, Constr. Build. Mater. 120 (2016) 558–570, https://doi.org/10.1016/j.
conbuildmat.2016.05.080.
[20] B. Šavija, M. Luković, Carbonation of cement paste: understanding, challenges, and opportunities, Constr. Build. Mater. 117 (2016) 285–301, https://doi.org/
10.1016/j.conbuildmat.2016.04.138.
[21] T. Chen, X. Gao, Effect of carbonation curing regime on strength and microstructure of Portland cement paste, J. CO2 Util. 34 (2019) 74–86, https://doi.org/
10.1016/j.jcou.2019.05.034.
[22] Z. Liu, W. Meng, Fundamental understanding of carbonation curing and durability of carbonation-cured cement-based composites: a review, J. CO2 Util. 44
(2021), 101428, https://doi.org/10.1016/j.jcou.2020.101428.
[23] D. Zhang, Z. Ghouleh, Y. Shao, Review on carbonation curing of cement-based materials, J. CO2 Util. 21 (2017) 119–131, https://doi.org/10.1016/j.
jcou.2017.07.003.
[24] ABNT (Associação Brasileira de Normas Técnicas), ABNT NBR NM 248: agregados – determinação da composição granulométrica, (2003).
[25] ABNT (Associação Brasileira de Normas Técnicas), ABNT NBR NM 45: agregados – determinação da massa unitária e do volume de vazios, (2006).
[26] ABNT (Associação Brasileira de Normas Técnicas), ABNT NBR NM 52: agregado miúdo – determinação da massa específica e massa específica aparente, (2009).
[27] ABNT (Associação Brasileira de Normas Técnicas), ABNT NBR 7215: cimento Portland – determinação da resistência à compressão, (1996).
[28] RILEM, TC116-PCD, Permeability of concrete as a criterion of its durability, Mater. Struct. 32 (1999) 174–179.
[29] J.A.A. Werle, A.P., Kulakowski, M.P., Kazmierczak, C.S., Sentena, Carbonation in concrete with coarse recycled concrete aggregates, in: Proceedings of the 12th
International Conference on Durability of Building Materials and Components, (2011).
[30] M. Sartori, B., Hentges, T., Kulakowski, M., Kazmierczak, C., Mancio, Natural and accelerated carbonation in concrete with rice husk ash and recycled concrete
aggregate: comparison by water absorption and mechanical strength., in: Proceedings of the 14th International Conference on Durability of Building Materials
and Components, (2017).
[31] C.P.C.-18 RILEM, Measurement of hardned concrete carbonatio depth, Mater. Struct. 21 (1988) 453–455.
[32] B. Lothenbach, K. Scrivener, R.D. Hooton, Supplementary cementitious materials, Cem. Concr. Res. 41 (2011) 1244–1256, https://doi.org/10.1016/j.
cemconres.2010.12.001.
[33] I. Mohammadi, W. South, The influence of the higher limestone content of General Purpose cement according to high-strength concrete test results and
construction field data, Mater. Struct. Mater. Constr. 49 (2016) 4621–4636, https://doi.org/10.1617/s11527-016-0811-y.
[34] J. Gołaszewski, G. Cygan, M. Gołaszewska, Analysis of the effect of various types of limestone as a main constituent of cement on the chosen properties of
cement pastes and mortars, Arch. Civ. Eng. 65 (2019) 75–86, https://doi.org/10.2478/ace-2019-0035.
[35] M. Zajac, J. Skocek, B. Lothenbach, B.H. Mohsen, Late hydration kinetics: indications from thermodynamic analysis of pore solution data, Cem. Concr. Res. 129
(2020) 1–12, https://doi.org/10.1016/j.cemconres.2020.105975.
[36] D.K. Panesar, R. Zhang, Performance comparison of cement replacing materials in concrete: limestone fillers and supplementary cementing materials – a review,
Constr. Build. Mater. 251 (2020), 118866, https://doi.org/10.1016/j.conbuildmat.2020.118866.
[37] A. Marzouki, A. Lecomte, A. Beddey, C. Diliberto, M. Ben Ouezdou, The effects of grinding on the properties of Portland-limestone cement, Constr. Build. Mater.
48 (2013) 1145–1155, https://doi.org/10.1016/j.conbuildmat.2013.07.053.
[38] T. Oey, A. Kumar, J.W. Bullard, N. Neithalath, G. Sant, The filler effect: the influence of filler content and surface area on cementitious reaction rates, J. Am.
Ceram. Soc. 96 (2013) 1978–1990, https://doi.org/10.1111/jace.12264.
[39] S. Tsivilis, J. Tsantilas, G. Kakali, E. Chaniotakis, A. Sakellariou, The permeability of Portland limestone cement concrete, Cem. Concr. Res. 33 (2003)
1465–1471, https://doi.org/10.1016/S0008-8846(03)00092-9.
[40] A.A. Elgalhud, R.K. Dhir, G. Ghataora, Limestone addition effects on concrete porosity, Cem. Concr. Compos. 72 (2016) 222–234, https://doi.org/10.1016/j.
cemconcomp.2016.06.006.
[41] ABNT (Associação Brasileira de Normas Técnicas), ABNT NBR 6118: Projeto de Estrutura de Concreto – Procedimento, (2014).
[42] C.M.V. Garcia, Avaliação do impacto do uso de fíler calcário como substituição ao cimento no comportamento reológico e retração de microconcretos, (2017).
[43] S. Palm, T. Proske, M. Rezvani, S. Hainer, C. Müller, C.A. Graubner, Cements with a high limestone content - mechanical properties, durability and ecological
characteristics of the concrete, Constr. Build. Mater. 119 (2016) 308–318, https://doi.org/10.1016/j.conbuildmat.2016.05.009.
[44] L. Kim-séang, D. Vinciane, V. Géraldine, Influence of ternary cements containing limestone filler on concrete resistance to carbonation, in: Proceedings of the
14th International Conference on Durability of Building Materials and Components, (2017).
[45] Y. Dhandapani, M. Santhanam, G. Kaladharan, S. Ramanathan, Towards ternary binders involving limestone additions — a review, Cem. Concr. Res. 143
(2021), https://doi.org/10.1016/j.cemconres.2021.106396.
[46] V. Shah, K. Scrivener, B. Bhattacharjee, S. Bishnoi, Changes in microstructure characteristics of cement paste on carbonation, Cem. Concr. Res. 109 (2018)
184–197, https://doi.org/10.1016/j.cemconres.2018.04.016.
[47] F. Lollini, E. Redaelli, Carbonation of blended cement concretes after 12 years of natural exposure, Constr. Build. Mater. 276 (2021), 122122, https://doi.org/
10.1016/j.conbuildmat.2020.122122.
[48] S. Rathnarajan, B.S. Dhanya, R.G. Pillai, R. Gettu, M. Santhanam, Carbonation model for concretes with fly ash, slag, and limestone calcined clay - using
accelerated and five - year natural exposure data, Cem. Concr. Compos. 126 (2022), 104329, https://doi.org/10.1016/j.cemconcomp.2021.104329.
[49] A.B. Ribeiro, T. Santos, A. Gonçalves, Performance of concrete exposed to natural carbonation: use of the k -value concept, Constr. Build. Mater. 175 (2018)
360–370, https://doi.org/10.1016/j.conbuildmat.2018.04.206.
[50] W. Soja, H. Maraghechi, F. Georget, K. Scrivener, Changes of microstructure and diffusivity in blended cement pastes exposed to natural carbonation, MATEC
Web Conf. 199 (2018) 10–14, https://doi.org/10.1051/matecconf/201819902009.
[51] B. Wu, G. Ye, Development of porosity of cement paste blended with supplementary cementitious materials after carbonation, Constr. Build. Mater. 145 (2017)
52–61, https://doi.org/10.1016/j.conbuildmat.2017.03.176.
[52] A. Ipavec, R. Gabrovšek, T. Vuk, V. Kaučič, J. MačEk, A. Meden, Carboaluminate phases formation during the hydration of calcite-containing Portland cement,
J. Am. Ceram. Soc. 94 (2011) 1238–1242, https://doi.org/10.1111/j.1551-2916.2010.04201.x.

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