Cleaner Materials 3 (2022) 100034

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Cleaner Materials
journal homepage: www.elsevier.com/locate/clema

Red ceramic and concrete waste as replacement of portland cement:

Microstructure aspect of eco-mortar in external sulfate attack
Fernanda Brekailo a,⇑, Eduardo Pereira a, Elias Pereira b, Marcelo M. Farias c, Ronaldo A. Medeiros-Junior d
a
Department of Civil Engineering, State University of Ponta Grossa, Ponta Grossa, Paraná CEP 84030-900, Brazil
b
Department of Civil Engineering, Graduate Student, Engineering and Materials Science Graduate Department, State University of Ponta Grossa, Ponta Grossa, Paraná CEP 84030-900, Brazil
c
Graduate Student, Engineering and Materials Science Graduate Department, State University of Ponta Grossa, Ponta Grossa, Paraná CEP 84030-900, Brazil
d
Civil Engineering Studies Center (CESEC), Postgraduate Program in Civil Engineering (PPGEC), Federal University of Parana – UFPR, Curitiba, Brazil

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

Keywords: The use of red ceramic and concrete waste as a replacement for cement has great importance from an environ-
Red ceramic waste mental point of view, and it is necessary to understand its influence on the cement matrix's performance. In this
Concrete waste paper, mortar mixtures with partial replacement of the Portland cement by the addition of 3, 5, 12, and 20% of
Sustainable construction limestone filler (as reference), concrete waste, and red ceramic were subjected to sulfate attack. The acceler-
Eco‐mortar production
ated test was monitored until the age of 98 days and microstructure analysis techniques were applied.
Sulfate attack
Mortars with ceramic and concrete waste addition had greater expansion than the reference mortar. The addi-
tion of 12% of limestone filler mitigated the expansive reactions. The mortars with any type of addition had
greater porosities. In this case, the aluminum oxide content in the ceramic and the calcium carbonate and cal-
cium oxide contents in the concrete waste acted as a source for reaction with the sulfate ions. Due to the attack,
the pore size distribution changed, showing that the pores in the band between 0.01 and 1 µm were filled with
ettringite. The microcracks from the attack increased the pores with diameters over 1 µm. This performance
reduction against sulfate attack must be considered for the use of ceramic and concrete residues in eco‐
efficient mortars, especially when it is inserted in environments subjected to this type of degradation.

Introduction lion tons of cement in the next 30 years, implying an increase in

Civil construction is a relevant sector of the economy that grows
with increasing urbanization and cities' new needs. Associated with
this growth, there is an increase in the amount of waste generated
by this sector. This amount reaches 2.36 billion tons per year in China
and 850 million tons in the European Union (Zheng et al., 2017; Sáez
and Osmani, 2019).
The environmental impact generated by the construction industry
is not only related to the waste emitted by it. Each year, over 4 billion
tons of cement are produced. During the process of Portland cement
clinker production, carbon dioxide – CO2 – the gas responsible for
the greenhouse effect, is emitted. The cement production industry is
responsible for 8% of the world's total CO2 emissions. It corresponds
to a production of over 4 billion tons of Portland cement, where each
ton of cement produced emits about 0.83 tons of CO2 (Ali, Saidur and
Hossain, 2011; Teklay, Yin and Rosendahl, 2016; Lehne and Preston,
2018). Recent evidence suggests that the production will reach 5 bil-
CO2 emissions (Lehne and Preston, 2018).
An alternative to reduce the amount of clinker in cement is the use
of mineral additions, whether with filler effect, pozzolanic additions,
or cementing agents. In Brazil, contents of clinker replacement of up
to 25% for fillers, 50% for pozzolans, and 75% for cementitious mate-
rials are allowed (ABNT, 2018). Most of the materials used as addi-
tions are residues from other processes, such as rice husk ash, which
is a residue from the rice processing process, fly ash, which is a residue
from thermoelectric plants, and blast furnace slag, which is a waste
from iron processing.
From an environmental point of view, using these wastes to reduce
the amount of clinker per m3 of cement has a positive impact on at
least two aspects: reducing CO2 emissions and reusing waste or by‐
products. The latter reduces the pressure on natural reserves and land-
fills, enabling the manufacture of more sustainable composites and
meeting the circular economy.
Using red ceramic and concrete waste stands out among the studies
that seek the application of new materials that can be used as mineral

⇑ Corresponding author.
E-mail address: f.brekailo@uepg.br (F. Brekailo).

https://doi.org/10.1016/j.clema.2021.100034
Received 10 August 2021; Revised 11 November 2021; Accepted 5 December 2021

2772-3976/© 2021 The Authors. Published by Elsevier Ltd.

This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
F. Brekailo et al.
additions in concrete. These materials can be found in the composition
of construction and demolition waste (CDW). Although the composi-
tion of CDW varies depending on the place of origin, in some coun-
tries, such as Spain and Brazil, concrete waste represents the largest
portion of CDW, together with ceramic. This gives great importance
to finding correct destinations for these materials (Oliveira et al.,
2011; Zheng et al., 2017). The red ceramic waste might also be origi-
nated from the disposal of ceramics with defects (Pitarch et al., 2021).
Most studies still aim at using CDW as fine and coarse aggregate
and have not dealt with its use as a replacement for Portland cement.
Ulsen et al. (2013) highlight the need for studies of the fine fraction of
these recycled aggregates. Previous researches have established that
red ceramic waste can be used as an addition, as it has also shown poz-
zolanic potential in some reports from 1998 (Winkler and Müeller,
1998) and recent studies (Pitarch et al., 2021). The pozzolanic poten-
tial associated with the red ceramic addition is related to the calcina-
tion temperature during the material production that gave rise to the
residue, as seen in the review by (Pitarch et al., 2021). Without heat
treatment, clay minerals do not have pozzolanic properties (Ay and
Ünal, 2000). Another option would be to perform heat treatment on
the material before using it as an addition, avoiding environmental
issues related to the use of this waste due to the energy demand
(Gobbi, 2014; Brekailo et al., 2019).
Regarding concrete waste, which is another part of the CDW, stud-
ies have shown its use as an inert addition. CDW has similar behavior
to the limestone filler, acting as a filling material and nucleation site
for cement hydration (Florea, Ning and Brouwers, 2014; Barthel
et al., 2016; Oksri‐Nelfia et al., 2016; Oliveira, Dezen and Possan,
2020). As with ceramic addition, its behavior can be improved by heat
treatment. Florea, Ning, and Brouwers (2014) observed for concrete
residue calcined at 800 °C a mechanical behavior similar to fly ash.
The authors found that the calcined material can activate the granu-
lated blast furnace slag, leading to higher strengths than when only
the slag was used. Barthel et al. (2016) state that the effect of this
material, used as an addition, has better results if used together with
a reactive addition. Oksri‐Nelfia et al. (2016) also found that its use
as a replacement for Portland cement can accelerate the cement hydra-
tion process and decrease the total heat emitted.
Even if not used to replace cement, the powdery fraction of CDW
materials is often inevitable and can reduce the performance of cement
composites that use recycled aggregates (Medeiros et al., 2016). Then,
it is fundamental to keep a broader view of the behavior of concrete
and mortars that have fine fractions of red ceramic and concrete waste
in their constitution. Previously published studies are limited to ana-
lyzing mechanical, physical, and microstructural properties of these
cementitious composites in situations where there is no degradation.
However, it is still necessary to understand the impact of the fine frac-
tion of these residues used as a replacement to Portland cement on the
composites' performance.
The durability of concrete and mortar is not only a function of the
material, but it is also affected by the interaction of the material with
the environment where it is inserted. Environments considered highly
aggressive, such as marine regions, and large urban and industrial cen-
ters might cause early degradation of concrete structures. Sulfate
attack outstands among these deterioration processes (Medeiros‐
Junior, 2018; Melara et al., 2020; Wang et al., 2020).
In sulfate attack, sulfate ions (SO‐2
4 ) react with the cement hydrated
phases, such as calcium hydroxide (portlandite), calcium silicate
hydrate (C‐S‐H), and calcium monosulfate. These reactions originate
phases such as gypsum, ettringite, and in specific cases, the thauma-
site, which might cause expansions with consequent concrete cracking.
The reactions might also lead to a progressive reduction in the con-
crete strength and its mass loss (Guo et al., 2019; Qin et al., 2021).
The gypsum and the ettringite formed due to the sulfate attack lead
to expansions and rupture of the concrete. It is caused because the
formed products have a greater volume than the compounds they
2
Cleaner Materials 3 (2022) 100034
replaced. This expansion causes tensile stress inside the porous struc-
ture of the material, which exceeds the stress that the concrete can
support (Wu et al., 2019; Pinto et al., 2020).
In places where it is not possible to interfere in the aggressiveness
of the environment, Portland cement with lower C3A content should
be used. This type of cement reduces the advance of external sulfate
attack (ESA), forming less ettringite during the attack (Mehta and
Monteiro, 2006; Hossack and Thomas, 2015; Tang et al., 2019).
Ikumi et al. (2018) showed that mortar mixtures with air‐entraining
agents have a similar performance to those with sulfate‐resistant
cement when exposed to sulfate attack. Here, the air‐entraining agent
increases the material porosity, allowing the accommodation of the
reaction products without creating expansion. It preserves its durabil-
ity during the initial stages of the attack.
In later stages, the durability is defined by the diffusion of the sul-
fate ion, which is a function of permeability. Here, the flow of fluids
that might transport sulfate ions inside the structure should be reduced
using a low permeability concrete. This is commonly achieved by the
reduction of the water/cement ratio and the use of mineral additions.
Using mineral additions alters the concrete microstructure due to
small particles that might occupy empty spaces. It results in a refine-
ment of pores of the hydrated matrix by the filler effect. Also, the fine
particles act as nucleation sites for cement grain hydration. With reac-
tive mineral additions, there is the effect of pozzolanic reactions,
which originates secondary C‐S‐H. The C‐S‐H precipitates in the larger
empty spaces of the paste, modifying the concrete porous structure.
This process reduces the matrix permeability by filling the pores with
reaction products (pore buffering), which minimizes the diffusion of
sulfate ions inside the concrete (Medeiros‐Junior et al., 2019). Previ-
ous researches about sulfate attacks studied the use of concrete addi-
tions such as silica fume, fly ash, and blast furnace slag. The increase
of the resistance to sulfate attack caused by the additions, mainly of
highly reactive materials, is related to parameters such as alteration
in pore distribution and reduction in the C3A and Ca(OH)2 contents
(Džunuzović et al., 2017; Liu et al., 2018).
Also, incorporating mineral additions in the cement composition
results in economic and environmental benefits, since these additions
are mainly waste from other processes. Natural resources are pre-
served by the reuse of environmental liabilities and the reduction of
the energy consumed for cement production. As the civil construction
industry represents a great environmental impact, these issues are very
relevant (Araújo et al., 2019).
In such a context, to evaluate the performance of mortars with
lower clinker contents due to the replacing of cement by additions
of fine residue fractions, this study provides new insights into the
behavior and microstructure alterations of mortars with the addition
of red ceramic block waste and CDW concrete. Mortars with limestone
filler were also used as a reference. The mineral additions were used as
a partial substitution to the cement (3, 5, 12, and 20%) and evaluated
regarding their effect concerning the sulfate attack in a sodium sulfate
solution. In this sense, the choice to study external sulfate attacks is
due to its high aggressiveness and high influence on the cementitious
materials performance. Thirteen different mortar mixtures were evalu-
ated for length change, XRD, porosimetry, and SEM, over 98 days.
Experimental program
Materials
Red ceramic powder, concrete waste powder, and limestone filler
were analyzed as mineral additions. The ceramic material is originated
from blocks of ceramic waste. The concrete waste powder was chosen
from construction and demolition wastes. Both were previously pro-
cessed in the Los Angeles abrasion machine. A 2 kg load was applied
with the use of 18 steel balls. These materials were processed for
F. Brekailo et al. Cleaner Materials 3 (2022) 100034

30 min at 30 rpm, totaling 90 revolutions. The resulting material was Table 1

sieved, and the final material used was the one that passed through a Characterization of the mineral additions.
0.075 mm sieve. This method was chosen because, among the tested Red ceramic Concrete Limestone filler
milling options, the material processed in the Los Angeles abrasion
SiO2 (%) 55.32 27.41 2.97
equipment showed better particle size distribution homogeneity. It
CaO (%) 0.19 52.23 78.03
also permitted the production of an addition with a similar particle Fe2O3 (%) 5.27 8.60 0.44
size distribution of limestone filler (Fig. 1). The filler was used as a ref- Al2O3 (%) 35.50 7.35 1.73
erence to the analyzes since it is a known inert mineral addition, which K2O (%) 1.28 1.45 0.31
is also used commercially. Fig. 1 shows the particle size distribution of SO3 (%) 1.23 1.15 1.21
TiO2 (%) 1.09 1.33 –
the filler and the Portland cement. The specific mass and the chemical MnO (%) 0.04 0.48 –
characterization of the mineral additions, obtained by X‐ray fluores- MgO (%) – – 15.06
cence (XRF), are shown in Table 1. *Equivalent alkalies (%) 0.84 0.95 0.41
Mineralogical characterization was executed using X‐ray diffrac- Specific mass (g/cm3) 2.53 2.39 2.70
tometry (XRD). The XRD test was performed in a Rigaku Ultima IV Note: *Equivalent alkalies = (%Na2O) + 0.658*(%K2O).
diffractometer. A step of 0.02° and a 1 s time per step, with a scanning
interval between 5° and 55° (2θ), was adopted for the test. The Cu‐Kα
(40 kV, 30 mA) radiation and a 1° divergent slit were used. The min- are shown in Table 3. These substitution values were based on the con-
eral chemical phases were identified through comparison with the tent of powdery material commonly found in aggregates of natural ori-
ICDD (International Center for Diffraction Data) standards. As some gin (3 to 5%), crushed aggregates (12%), and CDW (20%), according
studies show that the red ceramic may have a pozzolanic potentiality, to the Brazilian standards NBR 7211 (ABNT, 2005) and NBR 15116
the reactivity of this material was also examined through the modified (ABNT, 2004). Eight specimens per mix proportion were tested.
Chapelle’s method, according to the Brazilian standard NBR 15895 The procedures adopted for molding, curing, and immersion are
(ABNT, 2010). This test allows determining the amount of calcium under NBR 13583 (ABNT, 2014). The mortar bars were kept in the
hydroxide fixed by the material. molds for 2 days and then immersed in lime‐saturated water (calcium
The CPII F‐40 Portland cement was used, equivalent to CEM II/A‐L hydroxide) for 12 days. They were then submitted to the final expo-
42.5N (according to the European EN 197‐1 standard), which is a sure conditions. In this phase, the samples of each mixture were
cement with 10% addition of filler in its composition. Table 2 shows divided into two groups. Four specimens were immersed in sodium
the cement physicochemical characterization results. The chemical sulfate solution (10% Na2SO4). The other four specimens were
characterization was carried out by XRF. immersed in lime saturated water, at a controlled temperature of
A natural riverbed fine aggregate (quartzous) was used. Its granu- 40 °C. According to NBR 13583 (ABNT, 2014), the resultant expansion
lometric distribution was composed of 4 equal fractions retained in is calculated as a function of the mortar bar expansion immersed in
the 1.20, 0.60, 0.30, and 0.15 mm mesh sieves, as specified in the sodium sulfate, related to the expansion of the same mortar when
Brazilian NBR 7214 (ABNT, 2015) standard. immersed in lime saturated water. The measurements were carried
out in the larger axis of the samples every 7 days until 98 days of
immersion. The measures were taken using an electronic length
Expansion of mortar bars in external sulfate attack
comparator.
The mineral additions were used as a partial substitution to the
cement of the mortar. They were evaluated regarding their effect con- Characterization of mortars after external sulfate attack
cerning the sulfate attack in a sodium sulfate solution, according to
NBR 13583 (ABNT, 2014). The dimensional variations (length change) After the period of exposure to sulfates, physical and microstruc-
of 25 mm × 25 mm × 285 mm mortar bars were evaluated in this tural analyzes were made in the mortars. The specimens were dried
test. A mix proportion of 1: 3.2: 0.60 (cement: fine aggregate: in an oven at a temperature of 40 ± 5 °C for approximately 24 h.
water/binder ratio) was used, as defined in the referred standard. Four The real density of the specimens immersed in lime saturated water
mix proportions of mortars were used for each addition, each one with was determined using the helium pycnometer method in a Quan-
different percentages of substitution: 3, 5, 12, and 20%, keeping a con- tachrome Ultra‐pycnometer 1000 equipment. It aimed to compare
stant water/binder ratio. Besides these mixes, analyzes were also made the packaging of the different mortars with different contents of min-
to a reference (no addition) mix, totaling 13 mixes. These proportions eral addition.
The microstructural analysis was made for the reference mortar
and for the mortars that had maximum mineral addition contents
(20% substitution). For image acquisition, a microscopy FEG SEM, Tes-
can, Mira 3, with SE/BSE detectors, was used. For this test, the speci-
mens were reduced and superficially metalized with gold. Here, the
fracture surface was analyzed. The porosity of the specimens was
determined using a mercury intrusion porosimeter of a Micromeritcs
AutoPore IV 9500 machine.

Results and discussions

Characterization of mineral additions and mortars

Fig. 2 shows the X‐ray diffractograms of the additions. The red

ceramic powder diffractogram showed predominantly quartz peaks
(SiO2), muscovite (KAl2Si3AlO10(OH,F)2), and hematite (Fe2O3). The
concrete powder diffractogram showed predominantly peaks of
Fig. 1. Particle size distribution of the Portland cement and mineral additions. quartz, calcite (CaCO3), and calcium oxide (CaO). In the limestone fil-

3
F. Brekailo et al. Cleaner Materials 3 (2022) 100034

Table 2
Chemical composition of the CEM II/A-L 32.5 N Portland cement.

Chemical composition (%)

CaO SiO2 MgO Al2O3 SO3 Fe2O3 K2O TiO2 Insoluble residue Loss on ignition

74.73 11.31 3.58 3.25 3.01 2.48 1.36 0.27 0.99 4.59

Table 3
Mix proportion of mortars for evaluation of mitigation potential for sulfate attack in a sodium sulfate solution.

Mortar (% of substitution) Porland cement (g) Sand (g) Mineral addition (g) Water (g) Water/binder

0 (Reference) 750 2400 – 450 0.60

3 727.5 22.5
5 712.5 37.5
12 660 90
20 600 150

2017). The pozzolanic properties observed in ceramic additions are

associated with the presence of an unstable and reactive form of meta-
kaolin (Winkler and Müeller, 1998). Their composition and manufac-
turing process is similar, but the ceramic additions have a slighter
amorphous halo, leading to a lower reactivity (Brekailo et al., 2019).
It means that the amorphous ceramic portion would behave similarly
to the metakaolin, while the crystalline portion would have a similar
effect to a filler addition.
When evaluating the red ceramic pozzolanic activity by the modi-
fied Chapelle’s method (ABNT, 2010), it was observed that the fixation
results were lower than the minimum consumption assigned to poz-
zolanic materials. A value of 395 mg Ca(OH)2/g addition was found.
In its turn, a value of 436 mg Ca(OH)2/g pozzolan is the minimum con-
sumption ascribed to these materials (Raverdy et al., 1980). So, the red
ceramic used in this research cannot be classified as a pozzolan. How-
ever, the obtained value is near the established threshold. It shows that
the red ceramic has some reactivity with sodium hydroxide. Previous
research has established that the increase in the milling time in asso-
ciation with the calcination process increases the amount of sodium
hydroxide fixed, leading to a higher reactivity (Mohammed, 2017).
These forms of material processing are beyond the scope of this
research.

Mortar exposed to sodium sulfate

Fig. 3 shows the resultant expansion of the reference mortar bars

Fig. 2. X-ray diffractograms of the mineral additions.
ler sample, the diffractogram exhibited calcite, dolomite (CaCO3.
MgCO3), and quartz peaks.
In the ceramic material, a discrete amorphous halo was identified,
which is characteristic of the glassy fraction between 15 and 40°. This
phenomenon occurs with more evidence between 20 and 40°in the
concrete waste diffractogram. The presence of an amorphous halo
shows a vitreous phase, which is related to the material reactivity with
Portland cement. For red ceramic, Brekailo et al. (2019) found that the
natural material had low reactivity, contrary to what was observed in
concrete waste. The concrete waste had an amorphous halo that can be
attributed to C‐S‐H in the hydrated cement paste, as this compound
has an amorphous formation. The limestone filler did not show an
amorphous halo, confirming the inert character of this mineral
addition.
An amorphous material was identified in the XRD for the ceramic
addition. It shows that this material has low reactivity with the Port-
land cement as it can interact with the calcium hydroxide. It is the
principle of a pozzolanic reaction (ABNT, 2010; Hoppe Filho et al.,
and the mortars with different percentages of red ceramic powder,
concrete waste, and limestone filler. At 98 days, it was not possible
to evaluate the expansion of the mortars with red ceramic substitution.
Except for the 5% mix proportion, the mortar bars immersed in sodium
sulfate solution, with different substitution percentages, were noticed
to have a brittle effect. The bars with this material broke or reached
lengths longer than those possible to fit in the length comparator, mak-
ing readings unfeasible up to 98 days. For this reason, the bar expan-
sion analysis was made up to 70 days, as highlighted in Fig. 3, since
there is data for all mixes at this age.
The real density of the mortars immersed in lime saturated water
(Fig. 4) shows the packing differences, which can help explain the
expansions observed in Fig. 3. According to Fig. 3, only the mortars
with 12 and 20% limestone filler replacement showed shorter expan-
sions than the mortars without substitution at 70 days of immersion.
All the remaining mortar mixtures had greater expansions than the ref-
erence mortar, showing that the partial replacement of Portland
cement for concrete waste and red ceramic addition increased the mor-
tar susceptibility to the sodium sulfate attack. For concrete waste, the
resulting expansions increased with the content of addition. This
behavior can be related to the greater availability of calcium ions that

4
F. Brekailo et al. Cleaner Materials 3 (2022) 100034

Fig. 3. Expansion of the mortar containing different percentages of mineral additions in substitution to Portland cement up to 98 days.

nucleation sites during the paste hydration process (Ouyang et al.,

Fig. 4. Density of the mortar containing different percentages of mineral
additions in the composition of the Portland cement.
2017).
With the ceramic addition, the mortar with 5% content showed bet-
ter packing. This mortar also showed lower aluminum availability than
the higher contents of the same addition, as this material has alu-
minum oxide (Al2O3) in its composition. The aluminum oxide, by its
turn, might act as a source of reactions with sulfate ions. Therefore,
the best packing along with the low aluminum amount allowed the
5% addition to obtaining the lowest expansion between the mortars
with different contents of ceramic addition. When considering the
limestone filler, the availability of calcium as calcite (CaCO3) for the
degradation reactions does not stand out concerning the beneficial
effect of packing, allowing lower expansions even with higher contents
of addition.
For the mortar to be considered resistant to sulfate attack, the
resulting expansion at 42 days is limited to 0.030%, according to the
test conditions used (ABNT, 2018). As evidenced in Fig. 5, the refer-
ence mortar is not resistant to sulfate attack, since expansion values
were greater than 0.030% at 42 days. This expansion limit value also
agrees with its cementitious classification, according to the Brazilian

can react with the sulfate ions when the addition content is increased.
Besides the presence of calcium oxide (CaO) (Fig. 2), considering that
the concrete is a waste and its age is unknown, part of its Ca(OH)2
could have carbonated. So, it would be feasible the presence of cal-
cium as calcite (CaCO3) for the degradation reactions. Costa et al.
(Costa et al., 2018) observed that the cements with lower content of
CaO had better resistance to sulfate attack. In this paper, the cement
was partially replaced with the addition containing CaO, which might
have been the source of calcium ions for the reactions. Although addi-
tions can improve particle packing (Fig. 4), the effect of an additional
load of old concrete compounds outstands.
The expansions did not always increase (Fig. 3) with the content
increment of the ceramic and limestone filler additions. The mortars
containing 5% red ceramic addition had a significantly lower expan-
sion than mortars with 3%. Mortars with 12 and 20% of limestone fil-
ler had lower expansions than those with 3 and 5% of this same
addition. An explanation for this might be that values close to 5% cera-
mic and 12% limestone filler created a better particle packing, as Fig. 5. Expansion of the mortars containing different percentages of mineral
shown in Fig. 4. In this case, the small particles of the additions might additions in the composition of the Portland cement up to 42 days and the
have buffered the pores. Besides that, the additions also promoted limit expansion by NBR 16697 (ABNT, 2018).

5
F. Brekailo et al.
standard (ABNT, 2018). None of the mortar mix proportions with cera-
mic powder or concrete waste showed an expansion lower than the
proposed limit. Both additions increased the resulting expansions to
values even greater from 0.030%. Regarding the limestone filler addi-
tions, the mortars showed expansions either equal or lower than the
reference bars. The mortars containing 12% of this addition reached
a resulting expansion of 0.030% at 42 days, which is the limit pro-
posed by NBR 16697 (ABNT, 2018). Then, the mortars with this addi-
tion proportion were resistant to the sulfate attack. The resistance to
attack refers to the Brazilian standard since it is known that the lime-
stone filler provides the calcium carbonate charge, which at low tem-
peratures allows thaumasite formation. This is not a common
degradation mechanism in Brazil.
A brittle effect was noticed in the mortars with ceramic waste, as
the bars with this material broke or had expansions that made the
measurements after 70 days not possible. This reveals that the poz-
zolanic properties, even being low as expected because of the reactiv-
ity observed in the XRD and modified Chapelle’s tests, were not
effective in preventing the ESA. The partial replacement of cement
by ceramic waste leads to a higher water/cement ratio, implying a
greater porosity. It results in the weakening effect and greater expan-
sions observed in the mortar bars with this type of addition. This also
explains the greater expansions observed in the mortar bars with con-
crete waste addition. It is worth mentioning that just the water/cement
ratio changes when the partial substitution of cement occurs since the
water/binder relation value (Portland cement + addition) is kept con-
stant in this study.
A reduction in porosity was expected in the mortars with mineral
additions. A lower porosity along with lower C3A content (because
of a reduction in cement content) would compensate for the adverse
effects of fewer cement amounts and higher water/cement ratio, mit-
igating the sulfate attack. Yet, such improvements in the mortar behav-
ior were not seen. It is confirmed by the increase in the resulting
expansion of the bars and also by the porosimetry test. Table 4 and
Fig. 6 show the porosity and pore size distribution of the mortars,
respectively. Regarding all mortar samples and concerning the total
number of pores, the bars exposed to the sodium sulfate solution
had a greater number of pores with larger diameters (above to approx-
imately 1 µm) than those mortars immersed in the calcium hydroxide
solution. Smaller pores (0.01 to 1 µm) were seen to be partially filled
by crystals, evidencing that they were occupied by the products
formed from the reactions of the aggressive sulfate ions solution.
The reduction in total porosity is mainly caused because the smaller
pores were filled with crystals. The increase in pores of larger diame-
ters is ascribed to the microcracks from the stress caused by the
expandable crystals. Similar results were observed by Müllauer et al.
(2013).
Fig. 6 and Table 4 show that the replacement of Portland cement by
red ceramic or concrete waste may have contributed to the increase in
porosity and facilitated sulfate diffusion in the cement matrix. It also
leads to the formation of ettringite and gypsum. The pore distribution
of the mortar with ceramic addition showed the lowest quantity of big-
ger pores and the lesser buffering effect of smaller pores. A lesser
reduction of total porosity after the attack was also observed. This
Table 4
Porosities of the mortars after 98 days of immersion in lime saturated solution
and sodium sulfate solutions.
Mortar Immersion solution
Lime-saturated Sodium sulfate
Reference 11.05 2.55
20% Red ceramic 16.25 15.48
20% Concrete 13.56 3.78
20% Limestone filler 13.04 8.29
6
Cleaner Materials 3 (2022) 100034
behavior might be associated with the brittleness observed in this type
of mixture. When the cracking started, the mortar bars broke before
any buffering effect and consequent porosity reduction could have
been observed. This research group has studies to investigate mechan-
ical properties, but those properties are beyond the scope of this paper.
Among the mortars with any addition, the mortars with concrete
waste addition were the ones that showed the greatest expansions.
They also showed the greatest total porosity reductions due to the
attack. In this case, it can be noted the increment in bigger pores
because of cracking. Regarding the mortars containing limestone filler,
a similar pore size distribution was observed, with the buffering of the
smaller pores and the formation of bigger pores.
In addition, the aggressive solution ingress inside the matrix is
facilitated due to the increase of matrix porosity. The reaction of the
sulfate ions solution with the cement hydration phases originates
expansive crystals inside the pores of the composite, such as the ettrin-
gite. This effect results in a reduction of the matrix porosity since the
mortar that was immersed in the aggressive solution had its pores buf-
fered by the ettringite crystals. It consequently increased its resulting
expansion, as the formed crystals had a larger volume than the original
crystals (Santhanam, Cohen and Olek, 2002; Souza et al., 2017).
The microstructural analyzes of the mortars confirmed this hypoth-
esis. Fig. 7 shows a large concentration of acicular ettringite crystals in
the mortar pores, which were originated from the sulfate attack reac-
tions. The reference mortar (Fig. 7a to 7c) shows the crystals occupy-
ing the entire volume of the pore and generating tensile stress inside
the material. This same sequence was observed by Santhanam et al.
(Santhanam, Cohen and Olek, 2002). Here, cracks are generated if
the stress exceeds the mechanical strength of the matrix. The crystals
deposit on the cracks originated by the stress, increasing their size
and allowing the entrance of the sulfate solution to the material inner
regions, advancing the attack.
The formation of expansive crystals is seen in all mortar samples
submitted to the attack (Fig. 7). Regarding the mortar added with
red ceramic, the walls of the pores chipped in a plate shape. This
was caused by the stress derived from the crystals on the pore walls
(Fig. 7e and 7f). The resistance against sulfate attack is related to
the content of expansive hydrated phases formed in the hardened mor-
tar matrix (Souza et al., 2017). The ceramic addition contains 35.5%
aluminum oxide (Al2O3) in its composition, which might have com-
pensated for the reduction in C3A coming from the clinker. So, it acted
as an aluminum source for the reaction with sulfate ions (SO‐2 4 ).
In the mortar samples with concrete powder and limestone filler
addition, the originated ettringite crystals formed crystal agglomerates
(Fig. 7g, 7h, 7j, and 7l). When the cement was partially replaced, there
was a reduction in the amount of portlandite (Ca(OH)2) able to react
with the sulfate ions. However, the additions also showed calcite
(CaCO3) in their composition, which becomes a source of calcium ions
for the reactions and acts as a nucleation site for the ettringite
formation.
Unlike the remaining mortar samples submitted to immersion in
aggressive solution, in mortars containing concrete waste, the ettrin-
gite crystals were not strictly only in the inner of pores. Its microstruc-
ture follows the attack aggressiveness since the ettringite crystals were
distributed inside the pores and on the paste surface (Fig. 7i). This
mortar also outstood the greatest resulting expansion during the
attack. Another factor observed was that the addition already had
formed crystalline phases such as portlandite. The portlandite could
decompose in the pore solution to become reactive and accelerate its
reaction with sulfate, increasing the formation of expansive crystals.
Engineering implications
Using a fine portion of red ceramic and concrete waste as a replace-
ment for Portland cement is of great interest for cleaner production
and circular economy. It has positive impacts on two key points: the
F. Brekailo et al.
Fig. 6. Mortar pore size distribution after 100 days of immersion in lime saturated solution and sodium sulfate solutions: (a) Reference; (b) 20% red ceramic
powder; (c) 20% concrete powder; (d) 20% limestone filler.
reduction of CO2 and the reduction of unused waste. The reduction of
CO2 is possible by replacing part of the clinker with these additions,
with replacement contents ranging from 3 to 20% (adopted in this
research). This replacement could be used in over 4 billion tons of
cement produced annually (Lehne and Preston, 2018).
From the amount of waste point of view, as an example, China gen-
erates 2.36 billion tons of CDW per year. From this amount, 48% is
concrete, and 10% is a ceramic material. It corresponds, respectively,
to 1.13 and 0.24 billion tons of material that could be reused (Zheng
et al., 2017).
Most previous studies have evaluated the use of these materials in
cementitious composites, but not their relationship with the environ-
ment. This research results show that for environments subject to
external sulfate attack, the degradation process of these composites
would be more aggressive than in composites without the presence
of residues in their composition. These data are relevant to delimit
these materials use. It is also noteworthy that, in other types of degra-
dation mechanisms, the effect can be different, as shown by
Higashiyama et al. (2012) with chloride penetration.
In Brazil and other developing countries, the use of construction
waste is still insufficiently explored, with no regulations for its wide
use as cementitious composites. Highlighting the importance of this
study, it provides subsidies for the possibility of exploring these mate-
rials so that the construction industry has financial and environmental
gains. The feasibility of these replacements could also yield carbon
credits as an incentive for countries to change their production pro-
cesses. In countries that still lack CDW processing and disposal proce-
7
Cleaner Materials 3 (2022) 100034
dures, the combination of financial feasibility and technical benefits
could have a significant environmental and economic effect.
Conclusions
The microstructural aspects of mortars containing fine fractions of
ceramic and concrete wastes subjected to external sulfate attack were
studied to assess the microstructure aspect of these eco‐efficient com-
posites. The conclusions of the study are highlighted:
- The partial replacement of Portland cement for different contents
of concrete waste and red ceramic additions provided an increase
in the resulting expansion when compared to the reference mortar.
The concrete waste additions had the greater resulting expansions.
However, the red ceramic added mortar samples became weaker
with the progress of the attack and showed earlier ruptures. In
these samples, the walls of the pores chipped in a plate shape
due to the stress from the crystals on these surfaces. This effect
was not observed in other conditions.
- The limestone filler addition in replacements of 12 and 20% were
the only mixes tested with resulting expansion smaller than the ref-
erence mortar. The mortar sample with 12% limestone filler
reached expansion values below 0.030% and was considered resis-
tant to the sulfate attack.
- The mortar samples exposed to the sodium sulfate solution showed
a greater concentration of ettringite crystals in their pores. It justi-
fies the expansion of the bars. As this interaction consequence, a
F. Brekailo et al. Cleaner Materials 3 (2022) 100034

Fig. 7. Microstructure of the mortar samples after 100 days of immersion in a sodium sulfate solution.

8
F. Brekailo et al.
reduction in the mortar total porosity was observed. With the
advance of the reactions, the samples also showed alteration in
the pore size distribution, showing that pores with smaller diame-
ters were buffered by the formed crystals.
- The greater porosity justifies the greater attack intensity to the
mortars with additions when compared to the reference sample.
Also, the red ceramic addition has greater availability of aluminum
oxide. This oxide became a source for the reactions with the aggres-
sive ions, compensating for the C3A reduction. As for the concrete
waste addition, the source for these reactions was the calcium ions
from calcium oxide and carbonate in its composition. The sum of
these factors made the mortar samples more susceptible to the sul-
fate attack.
- The partial replacement of Portland cement for concrete waste and
red ceramic additions increased the mortar susceptibility to the
sodium sulfate attack. Although the observed results indicate a
reduction in the mortar performance when these additions were
used in external sulfate attacks situations, such additions are under-
stood as inevitable in cement matrices of composites that contain
CDW.
- Further studies about durability should be developed, seeking to
understand the variables that might optimize the use of these addi-
tions and the limitations of their use possibilities.
Data availability
The raw/processed data required to reproduce these findings can-
not be shared at this time due to technical or time limitations. The
raw/processed data required to reproduce these findings will be
shared later.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
The authors would like to thank the State University of Ponta
Grossa for providing the infrastructure for this research, in particular,
the multi‐user laboratories complex (C‐LABMU) and the Araucária
Foundation and CNPq for funding as scholarships.
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