Article
Sustainable Cements Containing Sugarcane Bagasse Ash and
Limestone: Effects on Compressive Strength and
Acid Attack of Mortar
Andréia Arenari de Siqueira 1 and Guilherme Chagas Cordeiro 2,*
Citation: de Siqueira, A.A.;
Cordeiro, G.C. Sustainable Cements
Containing Sugarcane Bagasse Ash
and Limestone: Effects on
Compressive Strength and Acid
Attack of Mortar. Sustainability 2022,
14, 5683. https://doi.org/10.3390/
su14095683
Academic Editors: João Almeida,
Nuno Simões and Julieta António
Received: 13 February 2022
Accepted: 17 March 2022
Published: 8 May 2022
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s/by/4.0/).
Sustainability 2022, 14, 5683. https://doi.org/10.3390/su14095683
1 Department of Civil Engineering/COPPE, Universidade Federal do Rio de Janeiro,
Rio de Janeiro 21941-972, RJ, Brazil; andreia.siqueira@coc.ufrj.br
2 Laboratory of Civil Engineering, Universidade Estadual do Norte Fluminense Darcy Ribeiro,
Campos dos Goytacazes 28013-602, RJ, Brazil
* Correspondence: gcc@uenf.br; Tel.: +55-22-27397373
Abstract: Sustainable cements are an important alternative to reduce the environmental impact of
the cement industry by lowering the clinker-to-cement ratio with supplementary cementitious
materials. In this respect, the present study aimed to evaluate the influence of partial clinker
replacement by sugarcane bagasse ash (SCBA) and limestone filler (LF) on the mechanical and
durability performance of mortars. Four blended Portland cements were produced with binary and
ternary mixes of clinker, SCBA, and LF. An ordinary cement was also produced for comparison
purposes. All five cements were characterized and applied in mortars in order to assess compressive
strength and water absorption. Next, 28-day specimens were immersed in a sulfuric acid solution
for 56 days to investigate deterioration using mass loss, length variation, water absorption, and
compressive strength tests. In general, the combination of SCBA and LF produced more sustainable
cements with suitable properties, as SCBA improved the mechanical behavior, while LF improved
the durability performance of mortars. In this context, ternary mixes with 14% SCBA and 14% LF
are indicated for mechanical uses, while 7% SCBA and 14% LF are recommended for durability
purposes, as both maintained the respective properties of the reference cement.
Keywords: blended cements; sugarcane bagasse ash; limestone; supplementary cementitious
material; sustainability; durability
1. Introduction
Cement is the main building material used worldwide. The scale of cement
production is related to the development and industrialization levels of countries [1].
However, cement manufacturing is responsible for large energy and raw material
consumption, in addition to the high carbon dioxide emissions caused by clinker
production [1–4]. It is estimated that the cement industry is responsible for around 8% of
all anthropogenic carbon dioxide emissions to the atmosphere [5]. Furthermore, cement
production is expected to increase until at least 2050 [3]. As such, sustainable development
of the cement industry has been a topic of growing interest among researchers. In fact,
various wastes have been used in different cement–based building materials [6–15].
Another important alternative used worldwide consists of incorporating supplementary
cementitious materials (SCM) as cement (or clinker) replacements [16–18]. The use of SCM
can reduce CO2 emissions by up to 40% without significantly changing the mechanical
strength, durability, and cost of Portland cement [17].
Traditional SCMs such as fly ash, blast furnace slag, metakaolin, and natural
pozzolans have been used to reduce the clinker-to-cement ratio [3,19]. Recently, studies
have looked to SCMs from agro-industrial wastes with significant pozzolanic potential.
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Sustainability 2022, 14, 5683 2 of 16

In this case, the effective use of these materials in the cement industry could result in a
sustainable method to discard large amounts of waste and minimize the environmental
damage caused by cement production [16]. In this scenario, sugarcane bagasse ash is a
promising and abundant SCM, especially in tropical countries. The main constituent of
bagasse ash is silica, which makes it extensively studied [20,21]. Numerous studies have
shown the positive effects of bagasse ash on different properties of cementitious materials
[22–29]. The use of processing methods such as burning, grinding, and densimetric
fractionation increases the specific surface area, amorphous content, and pozzolanic
activity of ash due to the reduction of contaminants [30–35].
Several studies have recently investigated the incorporation of limestone and a
pozzolanic material into cementitious compounds in order to combine the physical and
chemical effects of these different materials [36–39]. Limestone provides an extra surface
for hydrate precipitation and nucleation [40–43], but high levels of this material can result
in loss of mechanical strength due to the dilution effect, since it behaves like aquasi-inert
material [38,39,44]. Thus, the combination of limestone and pozzolan is an interesting
alternative for the cement industry, given that the latter can enhance the mechanical
performance at later ages [27].
In this respect, the present study aimed at evaluating the influence of partial clinker
replacement by sugarcane bagasse ash and limestone on the mechanical and durability
performance of mortars. To that end, five different cements were produced, characterized,
and applied in mortars with low water-to-cement ratios. The isolated and combined
effects of SCBA and limestone filler were evaluated and compared in terms of
compressive strength, water absorption, and sulfuric acid attack durability tests.

2. Materials and Methods

For cement production, the clinker and gypsum were provided by a cement factory
in Espírito Santo State, Brazil. The oxide composition of these materials was obtained by
X-ray fluorescence spectrometry using an EDX-720 spectrometer (Shimadzu, Kyoto,
Japan), as shown in Table 1.

Table 1. Chemical composition (% mass) and physical properties of raw materials.

Clinker Gypsum SCBA LF

CaO 71.5 52.3 3.4 52.8
SiO2 14.2 4.5 53.8 3.7
Al2O3 5.2 - 18.1 -
Fe2O3 5.7 0.1 10.8 1.8
K 2O 0.6 - 4.3 0.5
SO3 1.7 40.6 2.7 0.6
TiO2 0.3 - 1.0 -
P2O5 - - 1.6 -
MnO 0.1 - 0.2 -
LOI * 0.8 2.6 3.9 40.5
Physical properties
D50 (μm) - - 4.18 4.17
Density (g/cm³) - - 2.61 2.77
BET specific surface
- - 17,000 5000
area (m²/kg)
Pozzolanic activity index
- - 127 -
with cement (%)
* LOI: Loss on Ignition.

Sugarcane bagasse ash (SCBA) was collected from the ash collector in a Brazilian
sugarcane plant in Rio de Janeiro State, Brazil. The ash was obtained from the
uncontrolled burning of sugarcane bagasse (Figure 1a) in boilers at temperatures around
Sustainability 2022, 14, 5683 3 of 16

800 °C. The as-received SCBA was treated with densimetric fractionation [30] (Figure 1b)
and autogenous recalcination [45] processes that reduced the contaminant content,
resulting in ash with good pozzolanic activity, a high specific surface area, and adequate
chemical and mineralogical compositions, as shown in Table 1 and Figure 2, respectively.
Figure 1c shows the SCBA after grinding.

Figure 1. Bagasse storage in a sugarcane plant (a). Bagasse ash after the densimetric fractionation
process (b). SCBA after grinding (c).

quartz
quartz

microcline

hematite

hematite
microcline

microcline
hematite

quartz

quartz
quartz
hematite

hematite
quartz
quartz

quartz

12 22 32 42 52
2θ angle (°)

Figure 2. X-ray diffraction pattern of SCBA (Cu-kα radiation).

Limestone filler (LF), composed of around 94% CaCO3, was obtained from a mining
company in Rio de Janeiro State, Brazil. Its chemical composition and physical properties
are shown in Table 1. Both SCBA and LF were ground in a ball mill to obtain similar
granulometry (see D50 values) in order to minimize different physical effects. Although
the particle distribution of these materials was similar, the specific surface area of SCBA
was larger than that of LF. This was justified by the porous structure of SCBA, which is
responsible for most of the porous volume of the ash, as described in previous studies
[30,35,46,47].
The Portland cement samples were produced at a laboratory scale with the joint
grinding of clinker and gypsum and mixes of SCBA and LF in specific proportions
established for each cement, as presented in Table 2. Five types of cement were produced:
Sustainability 2022, 14, 5683 4 of 16

a reference cement (PC-1, ordinary cement), two blended cements with binary mixes of
clinker-SCBA and clinker-LF (14% of clinker replacement), and two other blended
cements with ternary mixes of clinker, SCBA, and LF (21 and 28% of total clinker
replacement). The grinding parameters and cement production procedures are described
elsewhere [45]. The gypsum content was fixed at 5% to maintain the same cement formu-
lation and avoid the undersulfation phenomenon, which could result in sulfate depletion
before C3S hydration [36,40].

Table 2. Cement mix proportions (% mass).

Cement Clinker SCBA Limestone Gypsum

PC-1 95 - - 5
PC-2 81 14 - 5
PC-3 81 - 14 5
PC-4 74 7 14 5
PC-5 67 14 14 5

After production, all five types of cement were characterized and applied in mortars.
Figure 3 summarizes the methodological procedures. First, the particle size distribution
was determined by laser diffraction (Mastersizer 2000, Malvern Instruments, Malvern,
UK) with dispersion in absolute ethanol for 15 min. Next, the chemical composition, in
terms of oxides, was obtained by semi-quantitative analysis using an X-ray fluorescence
spectrometer (EDX-720, Shimadzu, Kyoto, Japan) and loss on ignition according to Bra-
zilian standard NBR NM 18 [48]. The initial and final setting times were determined using
the Vicat method [49]. Density and Blaine fineness were determined according to ASTM
C188-17 [50] and ASTM C204-18E1 [51], respectively. Finally, the pozzolanic behavior of
the three cements containing SCBA (PC-2, PC-4, and PC-5) was evaluated by the Frattini
test [52] to determine whether the SCBA content was effective in producing pozzolanic
cements.
Sustainability 2022, 14, 5683 5 of 16

Figure 3. Flowchart of methodological procedures employed in the study.

Next, mortars were produced to assess the influence of cement type on compressive
strength and durability to acid attack. In addition to the cements produced, deionized
water and normalized sand [53] were used to produce the mortar specimens, with con-
stant water-to-cement and sand-to-cement ratios of 0.48 and 3.0, respectively. Polycarbox-
ylate-based superplasticizer (Basf Glenium 51, with 28.9% solid content by mass) content
was fixed at 0.012% of cement mass. The mix was prepared in a standard mortar mixer.
First, water and superplasticizer were homogenized, and the cement was then added and
manually mixed with a spatula for 30 s. This was followed by mechanical mixing at low
velocity for 30 s. The sand was added and mixed for 30 s at low velocity and then at high
velocity for an additional 60 s. The mixture was allowed to rest for 90 s, and the last mix
was carried out for 60 s at high velocity. The mortars were designated, according to ce-
ment type, as M-PC-1, M-PC-2, M-PC-3, M-PC-4, and M-PC-5.
The compressive strength tests were performed at 7, 28, and 84 days of curing, in line
with ASTM C109M-16 [54]. For each age, three cubic specimens (50 mm edge) were
molded for each mortar, demolded after 24 h, and kept in a limewater solution until the
testing ages. The ruptures occurred in a UH-F500kNI hydraulic universal testing machine
(Shimadzu, Kyoto, Japan) operating at 0.5 mm/min. Water absorption tests [55] were per-
formed with four cylindrical specimens (25 mm diameter and 50 mm high) of each mortar
at 28 and 84 days of curing. The molding and curing processes were the same as those
described for cubic specimens.
Finally, a durability test was performed with three cubic (50 mm edge), four cylin-
drical (25 mm diameter and 50 mm high), and three prismatic specimens (25 × 25 × 285
mm) of each mortar. After 28 days of limewater curing, the specimens were immersed in
a sulfuric acid solution for 56 days. The procedures developed by Khan et al. [56] were
Sustainability 2022, 14, 5683 6 of 16

adapted, and the mortars were immersed in a solution with 1.5% H2SO4. The specimen-
to-solution volume ratio was kept at 0.25. The pH was measured weekly, and the solution
was completely changed when it reached the established limit of 1.5, which occurred
about every 2 weeks. During the exposure period, mass loss (cubic specimens) and length
variation (prismatic specimens) were measured twice a week and calculated using Equa-
tions (1) and (2), according to ASTM C267-01 [57] and ASTM C1012-18b [58], respectively:
𝑀 −𝑀
∆𝑀 = × 100 (1)
𝑀

𝐿 −𝐿
∆𝐿 = × 100 (2)
𝐿
where ΔMt is mass loss over time (%); Mt is mass at time t (g); Mi is initial mass (g); ΔLt is
length variation over time (%); Lt is specimen length at time t (mm); Li is the initial speci-
men (mm); and Lg is the nominal gauge length (250 mm).
After the exposure period, the cubic and cylindrical specimens (aged 84 days) were
submitted to compressive strength and water absorption tests, respectively, to evaluate
the mortar performance after the attack. The results were compared to those of the same
age specimens not submitted to the attack. A degraded layer formed and adhered to the
specimen surface. The average thickness of this degraded layer was measured using Im-
ageJ software to analyze the images that were taken after the specimen ruptured. One-
way analysis of variance (ANOVA) and Duncan’s multiple-range tests (p ≤ 0.05) were used
to compare the test data.

3. Results and Discussion

3.1. Characterization of Blended Cements
The addition of SCBA and LF slightly changed the physical properties and chemical
compositions of blended cements compared to the reference, as presented in Table 3. As
expected, incorporating SCBA increased the silica content of blended cements but also
raised the cement alkaline equivalent (Na2Oeq), increasing the expansion potential via the
alkali–silica reaction in concretes [59]. Both SCMs increased the loss on ignition of blended
cements, especially LF, due to its carbonate composition. The particle size distribution
(Figure 4) of all the cements was very similar, allowing them to be compared. However,
the incorporation of ultrafine SCBA and LF resulted in lower density and higher Blaine
fineness of blended cements compared to PC-1, especially with SCBA because of its high
BET specific surface area.

Table 3. Chemical composition (% mass) and the main physical properties of cements.
PC-1 PC-2 PC-3 PC-4 PC-5
CaO 69.96 55.89 68.24 61.18 54.53
SiO2 15.72 23.74 12.96 17.46 21.34
Al2O3 4.10 7.59 3.26 5.18 5.94
SO3 3.62 3.77 3.48 3.55 3.63
Fe2O3 4.71 5.62 4.40 4.63 5.12
K2O 0.60 1.32 0.62 0.84 1.21
TiO2 0.28 0.42 0.44 0.30 0.42
MnO 0.08 0.11 0.08 0.09 0.11
Na2Oeq * 0.39 0.87 0.41 0.56 0.80
LOI 0.91 1.55 6.52 6.77 7.68
D50 (μm) 12.8 10.9 11.4 10.5 9.5
Density (g/cm³) 3.07 2.90 3.01 2.90 2.87
Blaine fineness (m²/kg) 325 418 405 527 633
Initial setting time (min) 120 155 120 130 130
Final setting time (min) 180 200 160 180 200
* Na2Oeq = Na2O + 0.658 K2O.
Sustainability 2022, 14, 5683 7 of 16

100
PC-1
PC-2
80
PC-3
PC-4

Volume (%)
60
PC-5

40

20

0
0.1 1.0 10.0 100.0
Particle size (μm)

Figure 4. Particle size distribution of cements.

The setting times of blended cements were also influenced by SCM incorporation
(Table 3). While SCBA increased the initial and final setting times of PC-2 compared to
PC-1, the opposite was observed for PC-3, since LF shortened the final setting time. These
effects were observed in other studies with SCBA and LF, separately. The hydration delay
promoted by SCBA is related to the presence of contaminants [30,34,60], such as carbona-
ceous compounds (3.9% LOI) and SO3 (Table 1) in the ash. On the other hand, the acceler-
ation provided by the ultrafine LF can be attributed to the extra surface area for hydrate
nucleation [40,61]. A combination of these effects was observed in the ternary mixes, with
a slight increase in the initial setting time of both PC-4 and PC-5 compared to the reference,
and the final setting time of PC-5 because of its higher SCBA content compared to PC-4.
Nevertheless, the setting times of all blended cements were in accordance with the Brazil-
ian standard for blended Portland cements [62]. Moreover, Figure 5 shows the results of
the Frattini test, which indicated that all cements with SCBA (PC-2, PC-4, and PC-5) were
classified as pozzolanic Portland cements. This result may be associated with good poz-
zolanic activity and the large specific surface area of SCBA [20,22,23].

15
PC-2
PC-4
12 PC-5
CaO (mmol/L)

9
Non-pozzolanic cement

3 Pozzolanic cement

0
40 50 60 70 80 90 100
OH- (mmol/L)
Figure 5. Frattini test results for PC-2, PC-4, and PC-5.
Sustainability 2022, 14, 5683 8 of 16

3.2. Mechanical Performance of Mortars

Figure 6 presents the average compressive strength for three specimens of each mor-
tar after 7, 28, and 84 days of curing. According to the results, M-PC-2 showed signifi-
cantly higher strength than that of the other mortars at all ages. In the present case, the
heterogeneous nucleation and pozzolanic effects of SCBA were more effective and signif-
icant than the dilution effect of clinker replacement in PC-2, a finding also reported in
previous studies [27,34]. On the other hand, the isolated effect of LF in PC-3 was negative
for mortar mechanical behavior, since M-PC-3 exhibited significantly lower compressive
strength than that of M-PC-1 at all ages and the worst result between all the mortars at 28
and 84 days of curing. The lower compressive strength of M-PC-3 was related to the dilu-
tion effect [40,43,44]. As expected, the ternary mixes (M-PC-4 and M-PC-5) showed inter-
mediate results compared to their binary counterparts. The compressive strength of both
ternary mortars at 7 days was affected by the high clinker replacement content in PC-4
and PC-5 cements. However, increases in strength were observed in these mortars with
long-term curing, especially due to the pozzolanic effect of SCBA. At 28 days, no signifi-
cant difference was observed in the compressive strength of M-PC-5 and M-PC-1. The LF
effect was more pronounced in M-PC-4, which displayed lower strength than M-PC-1 and
M-PC-5.

80
7 days
28 days
Compressive strength (MPa)

84 days
62.1

65
54.7

51.4
50.5
47.9
49.3

50

43.2
40.91
42.0

39.3
37.18

38.4

34.87
34.57

33.01

35

20
M-PC-1 M-PC-2 M-PC-3 M-PC-4 M-PC-5

Figure 6. Average compressive strength of mortars at 7, 28, and 84 days.

Figure 7 presents the results of water absorption (average of four specimens) after 28
and 84 days of curing. An increase in water absorption was observed for all blended ce-
ments compared to the reference at 28 days. However, at 84 days of curing, there was a
significant reduction in the water absorption of all the cements related to the previous age,
especially for the blended varieties. These results indicate a better effect of SCM at later
ages, particularly SCBA because of its pozzolanic activity, which causes gradual pore clos-
ing [63,64]. In our case, M-PC-2 exhibited higher water absorption than that of M-PC-1 at
28 days, but after 84 days the binary mix showed significantly lower absorption. On the
other hand, LF increased the water absorption of M-PC-3 compared to the reference at
both ages because of the ultrafine particles used in the study. The behavior of ternary
mixes was similar to that of the binary mortars. While M-PC-4 obtained an increase in
absorption owing to the higher LF content, M-PC-5 exhibited a decrease, caused by the
higher SCBA content. Furthermore, no significant differences were found between M-PC-
5, M-PC-1, and M-PC-2 at 84 days.
Sustainability 2022, 14, 5683 9 of 16

10
28 days
84 days
8

Water absorption (%)

7.1

6.3
6.3

6.3

6.0
5.7
5.7
6

5.3

5.2
5.0
4

2
M-PC-1 M-PC-2 M-PC-3 M-PC-4 M-PC-5

Figure 7. Average water absorption of mortars at 28 and 84 days.

3.3. Durability to Sulfuric Acid Attack

As expected, sulfuric acid attack degraded all the mortars, as shown in Figure 8. It is
important to emphasize that sulfuric acid consumes the CH from cement pastes, resulting
in the formation of calcium sulfate or even ettringite, which are expansive products. The
expansion of these products in a hardened mortar (or concrete) causes the degradation of
cementitious composites, and C–S–H decalcification caused by acid exposure results in a
loss of strength [44,65]. Visually, M-PC-3 was the least affected by the attack, while M-PC-
2 showed the greatest apparent degradation.

Figure 8. M-PC-1 (a), M-PC-2 (b), M-PC-3 (c), M-PC-4 (d), and M-PC-5 (e) before sulfuric acid expo-
sure; M-PC-1 (f), M-PC-2 (g), M-PC-3 (h), M-PC-4 (i), and M-PC-5 (j) after 56 days of sulfuric acid
exposure.

In this context, the degradation of mortars caused by sulfuric acid attack resulted in
mass loss in all the specimens, as shown in Figure 9. M-PC-3 showed better behavior due
to the presence of LF. The calcite from LF reacted with the sulfuric acid, protecting the
mortar against C–S–H decalcification and enhancing its capacity to neutralize the acid
[66,67]. On the other hand, M-PC-2 exhibited the highest mass loss among the mortars
studied, including the reference, as previously observed in visual inspection. After 56 days
Sustainability 2022, 14, 5683 10 of 16

of exposure, the mass loss for M-PC-2, M-PC-1, and M-PC-3 was 43.9, 33.8, and 20.9%,
respectively. These results suggest that CH consumption by the pozzolanic reaction of
SBCA was not enough to improve the durability of this mortar to sulfuric acid attack,
despite the good mechanical behavior of M-PC-2. Similar findings were reported by Sen-
hadji et al. [44] in mortars containing silica fume. A more in-depth investigation on the
mechanisms of sulfuric acid attack is needed to better understand the influence of SCBA
on the durability properties of cementitious material. Ternary mixes displayed intermedi-
ate behavior compared to their binary counterparts and results very similar to those of the
reference. At the end of the attack, M-PC-4 and M-PC-5 showed 31.8 and 34.3% mass loss,
respectively, which confirmed the positive effect of adding LF to these mortars.

Exposure period (day)

0 10 20 30 40 50 60
0

-10
Mass variation (%)

-20

M-PC-1
-30
M-PC-2
M-PC-3
-40
M-PC-4
M-PC-5
-50

Figure 9. Mass variations of mortars during the sulfuric acid attack exposure period.

As expected, expansion trends were observed in all mortars during 56 days of expo-
sure, as presented in Figure 10. The four mortars with blended cements had significantly
lower expansion than that of the reference, indicating better mortar performance with
SCBA and LF during the sulfuric acid attack. At the end of the exposure period, M-PC-1
showed 0.039% expansion, while M-PC-2, M-PC-3, M-PC-4, and M-PC-5 obtained 0.022,
0.008, 0.008, and 0.006%, respectively. Unlike the mass variation results, the mortars con-
taining SCBA (M-PC-2, M-PC-4, and M-PC-5) showed the best length variation results,
probably due to pozzolanic reactions, and their expansion values were considered non-
significant according to ASTM C1012-18b [58].
Sustainability 2022, 14, 5683 11 of 16

0.05
M-PC-1
M-PC-2
0.04
M-PC-3

Length variation (%)

M-PC-4
0.03 M-PC-5

0.02

0.01

0.00
0 10 20 30 40 50 60
Exposure period (day)

Figure 10. Length variation of mortars during the sulfuric acid attack exposure period.

Figure 11 shows the formation of a degraded layer on the surface of mortar speci-
mens after acid exposure. The photographs were taken after the rupture of cubic speci-
mens. This layer was composed mainly of calcium sulfate, the main product of cementi-
tious degradation caused by sulfuric acid attack [44]. The average thickness of this de-
graded layer was 0.619, 0.817, 1.666, 0.869, and 1.724 mm for M-PC-1, M-PC-2, M-PC-3,
M-PC-4, and M-PC-5, respectively. Mortars containing blended cements were thicker than
the reference, especially mortars containing LF, indicating that blended cements were
more degraded, since more gypsum was formed in the presence of SCM.

Figure 11. Degraded layer on the surface of mortar specimens: M-PC-1 (a), M-PC-2 (b), M-PC-3 (c),
M-PC-4 (d), and M-PC-5 (e).

Figures 12 and 13 present the compressive strength and water absorption results of
mortars, respectively, after 56 days of acid exposure compared to specimens that were not
Sustainability 2022, 14, 5683 12 of 16

attacked. As expected, there was a clear decline in the strength of all the mortars after the
sulfuric acid attack due to C–S–H decalcification [44,67] and a significant increase in water
absorption after the exposure period caused by mortar deterioration in the acid environ-
ment. Figure 12 shows that despite the good performance of M-PC-3 and M-PC-5 in terms
of mass loss, these mortars presented significantly lower strength than that of the refer-
ence after the attack and the greatest decline in strength compared to the specimens cured
in limewater. The loss of strength was 49 and 47% for M-PC-3 and M-PC-5, respectively,
while M-PC-1 lost 31% of its compressive strength compared to the nonattacked mortar.
On the other hand, M-PC-2 and M-PC-4 lost 41 and 31% of their strength, respectively,
albeit with no significant difference compared to the reference mortar after the attack.

Figure 12. Average compressive strength of attacked and nonattacked mortars at 84 days.

Figure 13 shows that the presence of SCBA did not favor water absorption of M-PC-
2 and M-PC-5, which obtained increases of 29 and 32%, respectively, when compared to
mortars of the same age cured in limewater. The rise in water absorption may have caused
mortar deterioration and mass loss during acid exposure. M-PC-1, M-PC-3, and M-PC-4
showed increased water absorption of 12, 7, and 12% respectively, indicating good LF
performance. Calcium sulfate formation due to acid exposure may have caused densifica-
tion of the degraded layer, as observed in Figure 11, enhancing the absorption of LF mor-
tars [68]. After acid exposure, M-PC-1 exhibited the lowest water absorption, but no sig-
nificant difference was observed between this mix, M-PC-2, and M-PC-3. The higher SCM
content influenced ternary mortar absorption, which displayed the highest values after
the attack.
Sustainability 2022, 14, 5683 13 of 16

Figure 13. Average water absorption of attacked and nonattacked mortars at 84 days.

The results showed that adding LF decreased the water absorption and mass varia-
tion of mortars, while SCBA showed good mechanical behavior and reduced expansion
potential during sulfuric acid exposure. The combined effects of these materials resulted
in cements with good durability to sulfuric acid attack. Limestone acted as a sacrificial
medium, causing less deterioration because of its higher calcium content, and SCBA de-
creased the CH content in mortars due to the pozzolanic reaction [44,66,67]. Different con-
tents of these SCMs as clinker replacements should be studied to optimize their effects on
cementitious systems and enable the production of sustainable cements.

4. Conclusions
The present study aimed at evaluating the effects of partial clinker replacement by
SCBA and LF on the compressive strength and durability against a sulfuric acid attack of
mortars. Based on the test results, the following conclusions can be drawn:
• The incorporation of ultrafine SCBA and LF into Portland blended cements signifi-
cantly increased the Blaine fineness of cements, especially those containing ash due
to its higher specific surface area. In addition, the binary clinker–SCBA mix and both
ternary mixes were classified as pozzolanic Portland cements, indicating that the re-
activity of SCBA was more effective than the dilution effect of 28% clinker replace-
ment. However, SCBA increased cement setting times, delaying hydration due to the
presence of contaminants in the ash. On the other hand, LF accelerated hydration
because of the nucleation effect, reducing the final setting time compared to the ref-
erence.
• SCBA had a positive effect on the compressive strength and water absorption of mor-
tars due to its pozzolanic activity, especially at later ages. However, the dilution effect
was more pronounced with the addition of LF, and the binary clinker–LF mortar dis-
played the worst performance among all the mortars after 28 days. In the ternary
mixes, strength was compromised in the early days due to the dilution effect, but the
action of SCBA contributed to the mechanical performance of these mortars after 28
days of curing.
• With respect to durability tests, blended cements showed good performance com-
pared to the reference. Cements containing LF exhibited excellent mass loss and wa-
ter absorption, while SCBA provided lower length variation and good mechanical
behavior after the sulfuric acid attack. The combined effect of these materials was
Sustainability 2022, 14, 5683 14 of 16

evident in ternary mixes, which displayed good durability, with little mass and
length variation, and good mechanical performance after the attack.
The results obtained in this work revealed the significant potential of SBCA and LF
combinations for sustainable cement production with up to 28% clinker replacement. Fu-
ture research should investigate higher clinker replacements with different contents of
SCBA and LF, optimizing the effects of both SCMs. In addition, a life cycle assessment
study could be performed to evaluate the environmental influence of blended cements on
the reduction of CO2 emissions. In addition, the durability of cements in other aggressive
environments should be evaluated.

Author Contributions: A.A.d.S.: Conceptualization, Methodology, Validation, Investigation, Writ-

ing—original draft. G.C.C.: Conceptualization, Resources, Supervision, Visualization, Writing—
original draft, Writing—review and editing. All authors have read and agreed to the published ver-
sion of the manuscript.
Funding: This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoal de
Nível Superior—Brasil (CAPES)—Finance Code 001.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Data sharing was not applicable to this study.
Acknowledgments: The authors would like to thank the Brazilian agencies Conselho Nacional de
Desenvolvimento Científico e Tecnológico (CNPq) and Fundação Carlos Chagas Filho de Amparo
à Pesquisa do Estado do Rio de Janeiro (FAPERJ) for additional funding.
Conflicts of Interest: The authors declare no conflicts of interest. The funders had no role in the
design of the study; in the collection, analyses, or interpretation of data; in the writing of the manu-
script; or in the decision to publish the results.

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