See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/361210495

Effects of TiO2 waste on the formation of clinker phases and mechanical

performance and hydration of Portand cement

Article in Cement · June 2022

DOI: 10.1016/j.cement.2022.100036

CITATIONS READS

3 120

4 authors:

José da Silva Andrade Neto Bruna Bueno Mariani

Universidade do Estado de Santa Catarina Universidade Federal do Rio Grande do Sul
50 PUBLICATIONS 427 CITATIONS 24 PUBLICATIONS 71 CITATIONS

SEE PROFILE SEE PROFILE

Nilson Santana de Amorim Júnior Daniel Véras Ribeiro

Universidade Federal da Bahia Universidade Federal da Bahia
30 PUBLICATIONS 309 CITATIONS 127 PUBLICATIONS 1,798 CITATIONS

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Investigation of the hydration of C3S and C3A polymorphs and their interaction with sulfate ions View project

AVALIAÇÃO E IDENTIFICAÇÃO DE CAUSAS DE PATOLOGIAS ASSOCIADAS AO DESTACAMENTO DE CERÂMICAS CERBRÁS EM OBRAS DO ESTADO DA BAHIA View project

All content following this page was uploaded by Nilson Santana de Amorim Júnior on 13 July 2022.

The user has requested enhancement of the downloaded file.

 Cement 9 (2022) 100036

Contents lists available at ScienceDirect

Cement
journal homepage: www.sciencedirect.com/journal/cement

Effects of TiO2 waste on the formation of clinker phases and mechanical

performance and hydration of Portand cement
José S. Andrade Neto a, *, Bruna B. Mariani a, Nilson S. Amorim Júnior Junior b,
Daniel V. Ribeiro c
a
Laboratory of Testing on Materials Durability (LEDMa) / Federal University of Bahia, Rua Aristides Novis, 02. Federação. 40210-630. Salvador/BA, Brazil
b
Post-Graduate Program in Civil Engineering (PPEC) / Federal University of Bahia, Aristides Novis, 02. Federação. 40210-630. Salvador/BA, Brazil
c
Department of Materials Science and Technology / Federal University of Bahia, Aristides Novis, 02. Federação. 40210-630. Salvador/BA, Brazil

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

Keywords: The incorporation of different levels of UOW into Portland clinker raw meals and its effects on the clinker and
Portland clinker cement properties were evaluated. Clinkers were produced and characterized by X-ray diffractometry (XRD) and
Unreacted ore waste (UOW) optical microscopy; the cements were produced and physically characterized. Finally, pastes were produced and
Mineralizer
analyzed using isothermal calorimetry, thermogravimetry, XRD, and compressive strength tests. UOW, when
Hydration
added up to 1.29% in Portland clinker raw meal, acts as a mineralizer, increasing the content of alite by 6.44%.
The incorporation of UOW reduces the hydration rate in the first days owing to the increase in the size of the alite
crystals and delays the point of sulfate depletion due to the increase in the SO3 content of the clinkers. Owing to
the higher content of alite formed, the cement produced from the raw meal with 1.29% of UOW presents the
highest early mechanical strength (up to 7 days).

1. Introduction
In recent years, the cement industry, the largest consumer of natural
resources globally, has adopted the practice of co-processing, where
wastes are calcined in rotary kilns during the manufacture of Portland
clinker. In addition to contributing to the proper destination of solid
wastes, this practice contributes to the preservation of natural resources
as it partially replaces raw materials and fuels. Co-processing has been
studied using the most diverse residues, including residues from coal
combustion [1], ceramic residues [2,3], civil construction waste [4], pot
furnace slag [5], ladle furnace slag [6], waste gypsum [7], waste fibre
cement [8], fines of granitic rock [9,10], fluorine-containing sludge [11]
and titanium-containing pickling sludge [12] as raw materials for
Portland clinker.
To be used as a raw material for Portland clinker, the residues should
preferably have a chemical composition similar to limestone, clay, or
iron ore and/or have mineralizing chemical components facilitating
clinker synthesis and the formation of alite, in addition to reducing the
amount of free lime [10, 13–15]. As the use of mineralizers accelerates
the formation of alite, these materials can be used to reduce the required
temperature of the cement kiln and decrease CO2 emissions from the
burning of fossil fuels [16–18]. Mineralizing agents can also be used in
cement industries where the raw meal has low reactivity; hence, the
amount of alite formed for the same clinker temperature increases [18].
Among the residues used successively for mineralizing purposes by
the cement industry are residues rich in calcium fluoride and from the
zinc, molybdenum, barium, and phosphogypsum industries [14]. The
use of these residues typically increases the content of alite, a reduction
in free lime, and an increase the initial strength of the cement [14,16,
17].
Unreacted ore waste (UOW) is generated during the production
process of titanium dioxide. The generation of this waste by Tronox
Pigmentos do Brasil, a factory located in the city of Camaçari-Bahia, is
approximately 30,000 tons per year. To date, this residue does not have
an effective plan for reuse and is disposed of in industrial landfills.
UOW has high levels of titanium dioxide (TiO2) in its composition
(approximately 40%) [19–21]. In the Portland clinker manufacturing
process, when added in moderate amounts, TiO2 acts as a mineralizer,
reducing the temperature of formation of the liquid phase and increasing
the amount of molten material [22–24]. Furthermore, TiO2 decreases
the viscosity of the liquid phase, increasing the diffusion of calcium ions
[22]. Consequently, up to an optimum content (typically 1 wt.%), TiO2

* Corresponding author.
E-mail address: josedasilvaandradeneto@gmail.com (J.S. Andrade Neto).

https://doi.org/10.1016/j.cement.2022.100036
Received 17 June 2021; Received in revised form 6 May 2022; Accepted 7 June 2022
Available online 9 June 2022
2666-5492/© 2022 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
J.S. Andrade Neto et al.
Fig. 1. TiO2 production process and generation of unreacted ore (UOW) at Tronox Pigmentos do Brasil S.A.
accelerates the speed of the reactions, contributing to the formation of
alite and consumption of free lime [23–25].
As observed by Mariani et al. [19], the addition of up to 2.6 wt.%
UOW in the clinker raw meal is beneficial for clinker production,
increasing the amount of alite formed at a specific temperature. Thus,
UOW has the potential to be used as an alternative raw material to
produce Portland clinker. However, to make the use of UOW feasible in
the production of Portland clinker, studies on the mechanical perfor­
mance and hydration of cements produced from clinkers with UOW are
necessary.
In the present study, clinkers containing UOW are characterized by
X-ray diffraction analysis (XRD) and optical microscopy (OM), and the
physicochemical characterization of the cements produced is per­
formed. Furthermore, the hydration processes of these cements are
monitored using calorimetry, XRD, and thermal analysis (TGA/DTG) in
addition to compressive strength tests.
2. Experimental program
2.1. Materials
The process of TiO2 production and generation of unreacted ore
(UOW) are displayed in Fig. 1. UOW was generated and supplied by
Tronox Pigmentos do Brasil S.A. and collected according to the waste
sampling procedure specified in Brazilian standard NBR 10007 [26].
UOW is generated from the processing of a mixture of ilmenite (FeO.
TiO2) and titanium slag to produce the TiO2 pigment. In this process, this
mixture goes through two stages: i) the sulfation stage, where the
ilmenite and titanium slag are mixed with sulfuric acid and ii) the
neutralization step, where the mixture is filtered and the unreacted part
(solid material) is neutralized with calcium hydroxide [Ca(OH)2],
resulting in the UOW.
After collecting the UOW, a beneficiation process consisting of dry­
ing in an oven at a temperature of 105 ± 5 ºC for 24 hours, grinding in a
horizontal QUIMIS rotary mill, Model Q298, containing ceramic balls
for 30 minutes, followed by sieving in a mesh with a #75 µm opening
was performed.
In addition, limestone and clay were used for the production of the
clinkers, and gypsum was used for the production of the cement. These
2
Cement 9 (2022) 100036
Table 1
Physical properties of the raw materials used.
Material Density Blaine surface area
(g/cm3) (cm2/g)
Limestone 2.73 ± 0.01 6244 ± 131
Clay 2.67 ± 0.01 6469 ± 637
UOW 3.25 ± 0.01 5856 ± 420
raw materials were supplied by a cement plant located in the State of
Bahia, Brazil, and were ground and sieved according to the procedure
described for the UOW.
2.1.1. Raw material characterization
The Blaine surface area of the raw materials was determined using a
BSA1 Acmel automatic permeabilimeter, following the guidelines of the
Brazilian Standard NBR 16372 [27]. The density was also determined,
using an AccuPyc II 1340 Micromeritics helium pycnometer [28]. The
results are presented in Table 1. The raw materials have a high Blaine
surface area, which indicates that the grinding process was effective in
fragmenting the particles of the material.
Table 2 lists the chemical composition of the limestone, clay, and
UOW obtained by X-ray fluorescence (XRF) using an X-ray fluorescence
spectrometer, FRX S2 Ranger, Bruker. For this test, the samples were
fused to form fused beads, providing a homogeneous representation of
the sample. Table 2 also presents the loss on ignition of the raw mate­
rials, determined after calcination in a muffle furnace at 1000◦ C for 1
hour, following the guidelines of the Brazilian Standard NBR NM 18
[29].
Limestone has mainly calcium oxide in its chemical composition, as
expected, being thus, the main constituent of the raw meal. Regarding
the clay, high levels of silicon and aluminum oxides can be observed,
being the source of these constituents in the raw meal.
UOW presented a high content of titanium dioxide in its composition
owing to the use of the raw materials (ilmenite and titanium slag, FeO.
TiO2) that lead to the waste. Calcium oxide (CaO) results from the
neutralization process performed by the addition of calcium hydroxide
[Ca(OH)2]. The presence of sulfur trioxide (SO3) is undoubtedly caused
J.S. Andrade Neto et al. Cement 9 (2022) 100036

Table 2
Chemical compositions of raw materials in oxides obtained by XRF.
Materials Oxide (%)

CaO SiO2 Al2O3 Fe2O3 MgO K2O Na2O TiO2 SO3 Others LOI*

Limestone 47.09 8.21 2.07 1.19 2.06 0.65 - 0.22 0.49 0.12 37.80
Clay 0.24 60.41 21.51 4.94 1.25 1.57 - 1.08 0.12 - 8.47
UOW 12.12 13.50 2.35 6.99 1.37 0.40 2.79 39.86 9.19 3.02 8.15
*
Loss on ignition (at 1000◦ C).

Fig. 2. X-ray diffractogram of the UOW, with identification of the crystalline phases.

by the sulfation stage, where a chemical attack with sulfuric acid occurs
Table 3
on the mixture of ilmenite and titanium slag. Iron oxide III (Fe2O3) is
Quantification of the crystalline phases and the percentage
derived from the oxidation of the iron present in ilmenite. The other
of non-crystalline phases of the UOW, obtained by the
compounds are likely associated with impurities present in the raw
Rietveld method.
materials.
Crystalline phase UOW (%)
The presence of high amounts of TiO2 (39.9%) is remarkably inter­
esting for the co-processing of UOW in the cement industry, as TiO2 acts Anhydrite (CaSO4) 10.35
as a mineralizer in the clinker process, contributing to the formation of Rutile (TiO2) 27.59
Anatase (TiO2) 12.38
alite and the consumption of free lime [25,30]. In addition, according to Armalcolite (MgTi2O5) 1.18
Ludwig and Zhang [31], any non-hazardous waste from an industrial Zircon (ZrSiO4) 2.06
process that has the same main constituents present in Portland clinker Ilmenite (Fe2TiO5) 1.39
can be used as a substitute for natural materials to produce mineralized Hematite (Fe2O3) 0.68
Quartz (SiO2) 8.54
clinker. In addition to TiO2, UOW has the main constituents of the raw
Calcite (CaCO3) 3.80
materials used to produce Portland clinker (calcium, aluminum, iron, ACn 32.30
and silicon). Rwp 9.42
Also noteworthy is the high concentration of sulfur in the residue,
greater than 9%. The addition of sulfur must be limited as part of the SO3
can be volatilized and, consequently, cause damage to the production Database (COD) were used to identify the mineralogical phases. The
process and environmental problems [22]. In addition, increases in the phases were quantified using the Rietveld method using Bruker’s TOPAS
amount of SO3 in the raw meal are known to reduce the alite content of software and the Crystallography Information File.
the clinker, as it favors the stabilization of belite [22]. As the maximum Fig. 2 displays the X-ray diffractogram of UOW. XRD peaks corre­
content of UOW incorporated in this study was 5.16%, resulting in SO3 sponding to the crystalline phases of titanium dioxide anatase (TiO2)
content of only 0.29% (see Table 4), the amount of sulfur present in the and rutile (TiO2), which originate from the non-dissolution of the raw
residue was not a problem in producing Portland clinker. material (ilmenite and titanium slag) during sulfuric acid, can be
The UOW was mineralogically characterized by XRD using a Bruker observed. Anhydrite (CaSO4) is likely the result of reactions between the
Model D2 Phaser X-ray diffractometer with a copper target tube sulfuric acid, used in the sulfation stage, and calcium hydroxide, which
(wavelength: 0.15406 nm) set at 30 kV and 10 mA, without a secondary is added to the residue to neutralize its pH and thus facilitate its disposal.
monochromator filtration system. The diffraction spectra were obtained Ilmenite (Fe2TiO5) originates from the ilmenite ore. Armalcolite
for a scan range (2θ) between 5◦ and 80◦ , with a continuous velocity of (MgTi2O5) could be associated with the titanium slag. Calcite (CaCO3) is
0.002 ◦ /s. The DifracEva software package and Crystallography Open likely the result of the carbonation reaction between the calcium hy­
droxide [Ca(OH)2] and atmospheric carbon dioxide (CO2). Quartz

3
J.S. Andrade Neto et al. Cement 9 (2022) 100036

Table 4
Raw meal formulations (by weight) and the chemical modules.
Clinker Raw meal (wt.%) Chemical modules TiO2 TiO2 SO3
Added* Total** (wt.%)
Limestone Clay UOW LSF SM AM
(wt.%) (wt.%)

REF 90.08 9.92 0.00 98 2.41 2.56 0.00 0.31 0.45

1.29% UOW 89.10 9.61 1.29 98 2.39 2.43 0.50 0.81 0.57
2.58% UOW 88.13 9.29 2.58 98 2.37 2.30 1.00 1.32 0.68
5.16% UOW 86.18 8.66 5.16 98 2.33 2.08 2.00 2.34 0.91
*
TiO2 from the UOW addition.
**
Total TiO2 content in the raw meal, considering the limestone, clay, and UOW.

Fig. 3. (A) Raw meal pellets before the clinker synthesis. (B) The heating regime used for clinker production.

(SiO2), zircon (ZrSiO4), and hematite (Fe2O3) are present due to impu­
rities in the raw materials.
Using the TOPAS software, the quantification of the crystalline
phases was performed based on the Rietveld method. Table 3 presents
the UOW percentage values of the crystalline and the content of amor­
phous or crystalline non-quantified (ACn) phases.
2.2. Methods
2.2.1. Clinker dosage and production
Four different raw meals were dosed, a reference (REF) and three
others with additions of UOW in contents of 1.29%, 2.58%, and 5.16%,
corresponding to additions of 0.5%, 1.0%, and 2.0% of TiO2 (only
considering the TiO2 from the UOW), respectively. Table 4 shows the
proportions of the raw materials used in addition to the chemical dosing
parameters. Table 4 also presents the added TiO2 (considering only the
TiO2 from the addition of UOW) and total TiO2 (considering the TiO2
from the limestone, clay, and UOW), and the SO3 content present in each
raw meal. These values were obtained based on the formulation of each
raw meal and the chemical composition of each raw material (Table 2).
The lime saturation factor (LSF) was set at 98, as this content allows
for the obtaining of Portland clinkers with high alite and low free lime
contents and is a value widely used in several studies [4,6,8–10,19,32].
The silica module (SM) and alumina module (AM) were not fixed,
varying from 2.33 to 2.41 and from 2.08 to 2.56, respectively. The
chemical modules FSC, MS, and MA are calculated based on Eqs. 1 to 3.
100CaO
LSF =
2, 8SiO2 + 1, 2Al2 O3 + 0, 65Fe2 O3
SiO
SM = (2)
Al2 O3 + Fe2 O3
Al2 O3
AM = (3)
Fe2 O3
The raw materials were homogenized in a QUIMIS horizontal rotary
mill (Model Q298). For the clinker production process, the methodology
proposed by the Brazilian Portland Cement Association (ABCP) and
adopted in Mariani et al. [19], Gomes et al. [9], Santos et al. [10] and
Costa and Ribeiro [4] studies were followed. The methodology simulates
the industrial cement production process following the steps of ho­
mogenization and pre-calcination of the raw meal and sintering and
cooling of the clinker for laboratory production.
Pellets with a mass of approximately 1.5 g and a diameter of 1 cm
were prepared. For the preparation of these pellets, a water content
equal to 20% (by mass) was added to provide workability to the material
and obtain an adequate consistency, as can be observed in Fig. 3A. The
pellets were dried in an oven at 100◦ C for 12 hours, placed in alumina
crucibles, and sintered in a Link Elektro Therm furnace (Model KK-220).
Fig. 3B displays the heating regime used for clinker production. The
mixtures were subjected to a heating rate of 10◦ C/min to a temperature
of 900◦ C, remaining at this temperature for 30 minutes. Then, the
samples went on to a second heating step, at 5◦ C/min, until achieving
the final temperature, 1340◦ C, where they remained for 15 minutes.
Afterward, the samples were immediately removed from the furnace and
abruptly cooled (190◦ C/min) with forced ventilation, resulting in
experimental clinkers. This abruptly cooling procedure is necessary to
stabilize the clinker phases and avoid phase instability [13]. The tem­
(1)
perature of 1340◦ C was chosen based on the results of Mariani et al.
[19], which showed that this temperature proved to be adequate to form

4
J.S. Andrade Neto et al. Cement 9 (2022) 100036

Table 5 regarding this method can be found in the studies by Riello [33] and
Crystallographic information files used for phase identification. Calligaris et al. [34]. A similar approach was also used by Andrade Neto
Phase Chemical ICSD Reference Reference et al. [35] and Costa et al. [36].
formula code In addition, the microstructure of the clinkers was analyzed using
C3S M1 Ca3SiO5 — de Noirfontaine et al. reflected light OM. Polished sections of the clinkers were made. To allow
[37] for differentiation between the main clinker phases, a chemical attack
C2S β Ca2SiO4 81096 Mumme et al. [38] was performed with nitric acid (HNO3, 1% in alcohol), which distinctly
C3A cubic Ca3Al2O6 1841 Mondal and Jeffery colors alite and belite.
[39]
C3A Ca8.5Na1Al6O18 1880 Nishi and Takeuchi
orthorhombic [40] 2.2.3. Obtaining and physical characterization of Portland cement
C4AF Ca2AlFeO5 9197 Colville and Geller The experimental cements were produced by adding 5% gypsum to
[41] each type of clinker, in relation to the cement mass, in a Union Process
Free lime CaO 75785 Huang et al. [42]
vertical rotary mill, Model Szegvari Attritor, with steel balls at 3240
Periclase MgO 104844 Sasaki et al. [43]
rpm. The experimental cements were characterized for specific Blaine
surface area (BSA1 Acmel automatic permeabilimeter, following the
high alite content in clinkers with UOW. guidelines of the Brazilian Standard NBR 16372 [27]), density (helium
gas pycnometer, Micrometrics Accupyc II 1340, following the guidelines
2.2.2. Clinker characterization of the ASTM D4892 [28]), and laser granulometry (CILAS equipment,
The mineralogical composition of the clinkers was obtained using the Model 1180, using isopropanol as the dispersant, and considering Mie
XRD technique, using the same equipment and parameters described in theory [44]).
Section 2.1.1. The diffraction spectra were obtained for a scan range (2θ)
between 10◦ and 70◦ , with a continuous velocity of 0.002 ◦ /s. The 2.2.4. Analysis of the hydration process
crystallographic information files used for Rietveld refinement are listed The heat flow (in mW/g) and cumulative heat (in J/g) released
in Table 5. during the first 80 hours of the hydration of the pastes with a water/
The amorphous content of the clinkers was quantified from XRD data cement ratio of 0.45 were monitored. For this, an eight-channel TAM Air
by calculating the areas regarding the crystalline (sharp XRD peaks) and isothermal conduction microcalorimeter was used. A stabilization tem­
non-crystalline phases (smooth background). The amorphous content perature of 25◦ C was adopted, and an ampoule with deionized water
was fitted by a split pseudo-Voigt peak, using the TOPAS software to was used as a reference.
separate the amorphous contribution from the background. The amor­ Using a Shimadzu thermobalance (Model TGA-51-H), thermogravi­
phous content is given by the related intensity between the area of the metric analysis (TGA/DTG) of the pastes was performed after 63 days of
crystalline and amorphous phases over the whole pattern. Details hydration. The temperature varied from 25◦ C to 1000◦ C at a heating

Fig. 4. X-ray diffractograms of the clinkers produced. A - Alite, B - Belite, C – C3A cubic, O - C3A orthorhombic, F - C4AF, M - Periclase, L - Free lime.

5
J.S. Andrade Neto et al.
Table 6
Content (by wt%) of clinker crystalline phases and ACn, obtained by XRD-Rietveld, as a function of UOW content.
Clinker C3S M1 C2S C3A cubic
REF 42.35 26.45 8.95
1.29% UOW 49.09 22.96 6.24
2.58% UOW 44.74 26.68 3.68
5.16% UOW 40.18 28.67 2.24
*
ACn: the content of amorphous or crystalline non-quantified (ACn) phases
**
Rwp : an indicator of the Rietveld discrepancy values. Values lower than 15 indicates good refinements.
rate of 10◦ C/min. The samples (approximately 10 mg) were placed in
platinum crucibles under a dynamic atmosphere of N2 (50 mL.min− 1).
The pastes’ bound water content (BW) was calculated from the mass
loss between 105◦ C and 550◦ C based on Eq. 4. Despite the thermal
decomposition of the C-S-H starting at 50◦ C, this range of temperatures
was adopted to exclude free water. The portlandite content (TCH) was
obtained by Eq. 5.
M105∘ C − M550∘ C
BW =
M40∘ C
mCa(OH)2
TCH = WLCa(OH)2 ×
m H2 O
Where M40◦ C, M105◦ C, and M550◦ C are the masses of the sample at tem­
peratures of 40ºC, 105◦ C, and 550◦ C, respectively. The WLCa(OH)2 is the
weight loss due to the decomposition of crystalline portlandite obtained
by the integration of DTG peak located in the temperature range from
~450 ºC and ~550 ºC using the tangential method [45], the mCa(OH)2 is
the molecular mass of portlandite (74 g/mol) and mH2 O is the molecular
mass of water (18 g/mol).
Finally, the mineralogical characterization of the pastes was per­
formed after 3, 28 and 63 days of hydration using XRD to monitor the
formation of crystalline phases during the hydration process. For this,
the same equipment and parameters described in Section 2.1.1 were
used.
2.2.5. Compressive strength
To evaluate the mechanical performance of the cements produced,
specimens with dimensions of 13 × 13 × 13 mm3 were molded based on
the methodology adopted by Costa and Ribeiro [4] and Costa et al. [46].
Pastes with a water/cement ratio equal to 0.45, the same ratio used for
the hydration analysis, were analyzed. The pastes remained in the molds
for the first 24 hours and then immersed in water saturated with lime
until the analysis. The compressive strength of the pastes was deter­
mined at 1, 3, 7, 28, and 63 days using an Instron 23-10 universal testing
machine with a 10 kN load cell and loading speed of 0.2 N/mm2.s.
3. Results and discussion
3.1. Mineralogical characterization of clinkers
Fig. 4 displays the diffractograms obtained for the clinkers. The
corresponding peaks of the main crystalline phases of Portland clinker
(alite, belite, C3A, and C4AF), in addition to peaks of periclase and free
lime, are present in all diffractograms. No different diffraction peaks
were identified when UOW was incorporated. This behavior is in line
with the results observed by Katyal et al. [53]. They observed that when
added to levels less than 5.0%, titanium is incorporated into the main
clinker phases with no formation of new phases.
Analyzing the characteristic peak of alite (approximately 51.7 ◦ 2θ), it
can be observed that the addition of UOW to the raw meal did not alter
the peak profile, and all clinkers appear to have only the M1 polymorph
[47]. However, there is a difference in the peak intensity depending on
the TiO2 content of the raw meal, indicating that the UOW influences the
formation of alite. Furthermore, analyzing the characteristic peaks of the
Cement 9 (2022) 100036
C3A orthor. C4AF MgO Free lime ACn* Rwp**
2.58 2.39 1.77 0.62 14.90 7.38
4.79 2.82 1.71 0.57 11.82 11.89
7.65 2.51 2.08 0.58 12.08 12.58
9.94 2.28 2.02 1.02 13.67 13.72
C3A (two peaks at approximately 33 ◦ 2θ), the addition of UOW to the
raw meal appears to stabilize the orthorhombic polymorph in relation to
cubic C3A.
Table 6 presents the concentrations of the clinker crystalline phases
determined by the Rietveld method and the content of amorphous or
crystalline non-quantified (ACn) phases. The accuracy of Rietveld
refinement for anhydrous Portland cement is usually between 0.5%-
2.0% [48,49].
(4) The clinkers presented ACn values between 11.82-14.90%. These
values are within the ACn range (6-16%) observed by Suherman et al.
[50] when analyzing commercial and NIST standard Portland clinkers.
(5)
According to Suherman et al. [50], this ACn corresponds to the melt
residue that has failed to crystallize. In addition, the absence of por­
tlandite and ettringite confirms that this ACn does not come from
pre-hydration.
Comparing the phase content determined by XRD-Rietveld with the
calculated phase content by Bogue Equations (see Table S1 in the Sup­
plementary Materials), one can note that C3S content obtained by Bogue
calculation was higher than the observed by XRD-Rietveld (64.41% vs.
42.35% for the reference clinker). On the other hand, the C2S calculated
with Bogue Equations was lower than the content obtained by XRD-
Rietveld (10.36% vs. 26.45% for the reference clinker). These differ­
ences are probably due to the temperature used to produce the clinkers
(1340◦ C), which is lower than the usual (1450◦ C).
Regarding the C3A, the calculated content by the Bogue equations
was very close to the one determined by Rietveld refinement (12.21% vs.
11.53% for the reference clinker). However, the C4AF content deter­
mined by Bogue Equation was much higher than the one obtained by
XRD-Rietveld (7.30% vs. 2.39% for the reference clinker). This indicates
that the iron-containing phases (such as C4AF) failed to crystallize
during the cooling, contributing to the ACn content of the clinkers.
Regarding the role of UOW on the clinker composition, one can note
that it did not influence the C3S polymorph, and only the C3S-M1
polymorph was presented in the evaluated clinkers. This was expected
as all clinker raw meals had low amounts of MgO, which is known to
stabilize the M3 polymorph [31]. Titanium and sulfur (presented in
higher contents in UOW) incorporation typically favor the formation of
M1 polymorph [31]. In this case, as the reference clinker already con­
tained only the M1 polymorph, the addition of UOW did not influence
the alite polymorphism; however, it did influence its quantity. Increases
of 6.44% and 2.39% in the alite content by adding 1.29% and 2.58% of
UOW (0.5% and 1.0% of TiO2), respectively, were observed. The addi­
tion of 5.16% of UOW (2.0% of TiO2) resulted in a reduction of 2.17% in
the alite content. Thus, the incorporation content of 1.29% of UOW was
presented as an optimum content for the formation of alite, the main
mineralogical phase of the clinker, and the primary factor for the me­
chanical strength of the cement in the early ages.
This occurs because the addition of moderate amounts of titanium
(up to 1.0%) in the raw meal reduces the formation temperature and
viscosity of the liquid phase [13,51,52], thus increasing the diffusion of
calcium ions [22]. With this, an increase in the content of alite can be
observed, a mineral formed from the diffusion of calcium ions towards
the crystals of belite. However, at levels greater than 1.0%, there was a
deleterious effect on the formation of alite, as observed by several au­
thors [19,53,54].
6
J.S. Andrade Neto et al.
Fig. 5. Microstructure of clinkers obtained by reflected light optical microscopy. (A) Reference, (B) 1.29% UOW, (C) 2.58% UOW, and (D) 5.16% UOW.
The reason for that is not understood up to date. According to Li et al.
[54], the reduction in alite content is due to perovskite formation
(CaTiO3). This would decrease the calcium content in the silicate min­
eral, thereby increasing the content of C2S and lowering the content of
C3S. However, no perovskite XRD peaks were observed in the studied
clinkers, which agrees with the observations of Ma et al. [25] and Katyal
et al. [53], who observed the formation of CaTiO3 only for TiO2 content
higher than 3% and 4.5% (respectively) in the raw meal. Therefore,
further studies regarding the role of TiO2 on clinker formation are
necessary to understand the reason for the decrease in C3S content when
adding more than 1.0% of TiO2.
As indicated in Table 4, the reference cement already has 0.31 wt.%
of TiO2, as the clay used for the clinker production had TiO2 in its
composition. Therefore, the addition of 1.29% and 2.58% of UOW (0.5%
TiO2 and 1.0% TiO2) resulted in raw meals with 0.81 and 1.32 wt.% of
TiO2, respectively. This explains the higher alite content in the 1.29%
UOW clinker.
As expected, changes in the content of belite demonstrated the
opposite behavior to that of alite, with a reduction of 3.49% for the raw
meals with 1.29% of UOW and increases of 0.23% and 2.22% for the raw
meals with 2.58% and 5.16% of UOW, as these phases are concurrent.
Regarding C3A, it can be observed that the incorporation of UOW
favored the formation of the orthorhombic polymorph over the cubic
polymorph. This behavior could result from the presence of K2O and
Na2O in the composition of the UOW (see Table 2), which are recognized
for stabilizing orthorhombic C3A [13,55,56]. However, the low levels of
K2O (0.40%) and Na2O (2.79%) present in the residue, in line with the
low levels of incorporation of the waste into the raw meal (up to 5.12%),
resulted in low levels of K2O and Na2O in the raw meal. For the raw
meals with 1.29%, 2.58%, and 5.16% UOW, based on the XRF of the raw
materials (see Table 2), Na2O contents equal to 0.04%, 0.07%, and
0.14%, respectively, could be expected. Based on Taylor [13], ortho­
rhombic C3A is found, along with cubic, when the Na2O content in the
raw meal is greater than 1.0%. Regarding K2O, the addition of UOW
marginally reduced the expected content in the raw meal, from 0.74% in
the reference raw meal to 0.72% in the raw meal with 5.16% of UOW.
Thus, the presence of K2O and Na2O in the UOW is not likely responsible
for stabilizing the orthorhombic C3A.
7
Cement 9 (2022) 100036
This behavior is likely related to the increase in titanium content
with the incorporation of UOW. According to Shang et al. [24], incor­
porating TiO2 into the raw meal favors the formation of orthorhombic
C3A to the detriment of cubic C3A. The mechanism by which TiO2 is
incorporated into the C3A structure, changing its polymorphism, has not
been studied in detail to date and requires further investigation. The
change in the C3A polymorphism with the incorporation of UOW could
reduce the workability of the cementitious matrices. Orthorhombic C3A
is more reactive than cubic C3A in the presence of gypsum [56–58] and,
owing to the greater formation of ettringite in the first hours, could
result in increases in viscosity [58,59].
An increase in the C4AF content was expected with the incorporation
of the UOW (see Bogue calculations – Table S1) because, as indicated in
Table 4, the incorporation of the residue reduces the AM. According to
Winter [60], the lower the MA, the higher the C4AF content formed in
relation to the C3A content. However, as indicated in Table 6, the
incorporation of UOW did not significantly change the C4AF content.
This could result from a reduction in the crystallinity of C4AF with the
incorporation of titanium into the raw meal, as noted by Marinho and
Glasser [61] and Shang et al. [24], who added pure TiO2 to Portland
clinker raw meal. Thus, although raw meals with UOW are likely to
result in higher levels of C4AF because of the reduction in MA, the
reduction in crystallinity reduces the content determined by XRD.
Finally, the presence of UOW does not appear to significantly influ­
ence the levels of periclase and free lime, which remained below the
normative limits [62], equal to 6.5% and 2.0%, respectively, in all
clinkers. Thus, expansion problems due to MgO or free lime are not
expected in the studied formulations.
3.2. Microstructural analysis
Fig. 5 displays the microstructures of the reference clinker (0%) and
those containing 1.29%, 2.58%, and 5.16% UOW, obtained by reflected
light OM. Table 7 presents the aspects, sizes, and distribution of the
crystals of alite, belite, periclase, and free lime, as well as the aspect of
the interstitial phase (C3A + C4AF).
All clinkers presented well-formed, equidimensional alite crystals
with sub-rectilinear edges, with a sign of corrosion indicating sudden
J.S. Andrade Neto et al. Cement 9 (2022) 100036

Table 7 changes in viscosity and yield stress in the liquid phase with the incor­
Evaluation of phases identified by optical microscopy. poration of TiO2, which facilitates the crystallization and growth of alite
Clinker Phase Shape and distribution crystals [13,51]. Similar behavior was observed by Katyal et al. [53] by
incorporating TiO2 in clinker raw meal.
Reference Alite Hexagonal crystals, subdimorphic to
(0% (C3S) xenomorphic. Relative to belite, it is possible to observe rounded crystals in regular
UOW) They occur in regular areas. areas in all the clinkers. The interstitial phase, which fills the gaps be­
Inclusions of belite and secondarily of tween silicates, when crystallized, is present in all the clinkers in the
interstitial phase. form of a predominantly clear C3A and C4AF matrix. This phase is
Average size: 30 μm
Belite Rounded crystals.
observed in a crystallized form, indicating a sudden or normal cooling
(C2S) They occur grouped in regular zones. [13]. For free lime, rounded crystals were verified in regular zones and
Interstitial Crystallized dispersed among the other crystals.
phase
Periclase Not observed
3.3. Physical characterization of cements
Free lime Small regular areas and rare scattered crystals
1.29% UOW Alite Hexagonal crystals, subdimorphic to
(C3S) xenomorphic. Table 8 presents the results of the physical characterization of the
They occur in regular areas. cements and the loss on ignition (at 1000◦ C). There is an increase in the
Inclusions of belite and secondarily of density of cements that have UOW in their composition, likely associ­
interstitial phase.
Average size: 35 μm
ated with the presence of elements such as titanium and iron in the
Belite Rounded crystals. composition of the waste, which have a high density. Regarding the loss
(C2S) They occur grouped in regular zones. on ignition, all cements presented values less than the limit established
Interstitial Crystallized by NBR 16697 [62], 4.5%. All cements exhibited similar particle di­
phase
ameters and Blaine surface area.
Periclase Scattered crystals
Free lime Regular zones and scattered crystals.
2.58% UOW Alite Xenomorphic crystals. 3.4. Analysis of hydration process
(C3S) They occur in regular areas.
Inclusions of belite and secondarily of
Fig.s 6A and 6B display the curves of the heat flow and cumulative
interstitial phase.
Average size: 40 μm
heat curves during the first hours of hydration of the cement pastes.
Belite Rounded crystals. Although all cements had the same amount of gypsum (5%), the
(C2S) They occur grouped in regular zones. depletion point varied significantly with the incorporation of UOW into
Interstitial Crystallized the raw meal, as indicated in Fig. 6A. The greater the content of TiO2/
phase
UOW incorporated, the later the depletion of the sulfates and conse­
Periclase Not observed
Free lime Regular zones and scattered crystals. quent resumption of the reactions of the aluminates. Thus, whereas the
5.16% UOW Alite Xenomorphic crystals. reference cement was demonstrated to be undersulfated (sulfate deple­
(C3S) They occur in regular areas. tion occurs before or immediately after the main peak of the hydration of
Inclusions of belite and secondarily of the alite), cements with UOW appear to be properly sulfated. These
interstitial phase.
Average size: 40 μm
differences are likely due to the changes in SO3 present in the clinker
Belite Rounded crystals were beginning to [63]. Based on the XRF analysis of the raw materials (see Table 2), the
(C2S) decompose. reference raw meal and raw meals with 1.29%, 2.58%, and 5.16% of
They occur grouped in regular zones. UOW were expected to have 0.45%, 0.57%, 0.68%, and 0.91% of SO3,
Interstitial Crystallized
respectively. Higher levels of SO3 in the raw meal naturally result in
phase
Periclase Not observed clinkers with higher SO3 levels. Thus, UOW cements require less calcium
Free lime Regular zones and scattered crystals. sulfate in their production.
In addition, there is a decrease in the total heat released in the first 80
hours of hydration with the increase in the content of TiO2/UOW in the
Table 8 raw meal (Fig. 6B). The total heat released after the first 80 hours of
Density, average particle diameter, Blaine surface area and loss on ignition (at hydration for the cements 1.29%, 2,58%, and 5.16% UOW is 10.4%,
1000◦ C) of the cements. 19.6%, and 26.8% lower than the REF cement.
Cement Density Average particle Blaine surface Loss on
This behavior is possibly associated with the increase in the size of
(g/cm3) diameter Dm area (cm2/g) ignition (%) the alite crystals with the increase in the UOW content incorporated into
(µm) the raw meal, as observed in the OM analysis (Table 7), as the smaller
REF 3.10 ± 13.56 3849 ± 124 3.40 ± 0.10 the surface area of the alite, the lower the hydration rate [64].
0.01 The reduction in the total heat released could also be related to the
1.29% 3.20 ± 13.56 4049 ± 154 1.80 ± 0.17 presence of titanium, which, according to Katyal et al. [65] and Shang
UOW 0.01
et al. [24], reacts with calcium ions in the first hours of cement hydra­
2.58% 3.19 ± 11.94 4056 ± 56 2.10 ± 0.17
UOW 0.01
tion, forming CaO.TiO2 on the surface of the alite. These authors stated
5.16% 3.22 ± 10.51 3972 ±38 2.13 ± 0.15 that the CaO.TiO2 acts as a barrier, slowing the hydration process.
UOW 0.01 However, the impermeability of this layer has not been proven and this
seems very unlikely to be the main reason for the delay/reduction in the
total heat released.
cooling [13]. In addition, it was found that the crystals of alite present
Another possibility is the consumption of calcium ions for the for­
shapes and dimensions commonly observed in industrial clinkers,
mation of CaO.TiO2, which would delay the calcium ion saturation,
ranging from hexagonal to xenomorphic, with 30 to 40 μm, presenting
contributing to the retard on the hydration observed. With the results
regular inclusion, consisting of belite and, secondarily, an interstitial
obtained here, it is not possible to conclude the exact reason for this
phase.
significant reduction in the heat released in the first hours.
As indicated in Table 7, there was an increase in the average size of
Further studies on this topic are necessary to verify if an increase of
the alite crystals with the incorporation of UOW. This is likely due to
10 μm on the average size of alite crystals would be responsible for

8
J.S. Andrade Neto et al.
Fig. 6. (A) Heat flow curves and (B) cumulative heat curves during the first hours of cement paste hydration. SD represents the sulfate depletion point.
reducing almost 30% of the total heat released in the first hours of hy­
dration or if the titanium ions have some role on delaying the cement
hydration due to the formation of a barrier as proposed by Katyal et al.
[65] and Shang et al. [24], or by consuming calcium ions.
The DTG curves of the cements pastes at 63 days are displayed in Fig.
s 7(A-D). In all DTG curves the presence of peaks corresponding to free
water (up to 80 ºC) and C-S-H (50–300 ºC), ettringite (approximately
95◦ C), monosulfate (approximately 150◦ C), and portlandite
(450–550◦ C) [45] can be observed.
With the increase in the content of UOW/TiO2 in the raw meal, an
increase in the peak composition of ettringite (approximately 95◦ C) and
a reduction in the decomposition peak of the monosulfate (approxi­
mately 150◦ C) were observed. This occurs because the UOW has SO3 in
its composition (see Table 2), increasing the SO3 content of the raw meal
and, consequently, of the clinker. In the present work, the amount of
added calcium sulfate was fixed at 5%; thus, the higher the UOW content
in the raw meal, the higher the SO3 content of the cements. As noted by
Kirchheim et al. [57], by increasing the SO3/C3A ratio, the ettringite
content was increased and the monosulfate content was reduced.
Table 9 shows the chemically bound water (BW) and portlandite
content (determined by TGA) of the pastes at 63 days. The BW value is
an indication of the amount of hydrated phases formed and the degree of
hydration of the pastes. One can note that all cements with UOW
9
Cement 9 (2022) 100036
presented similar or higher BW contents than the REF cement. This
result indicates that despite the UOW-containing cements presenting
slower hydration in the first days (as observed by calorimetry), this did
not have a negative effect on late ages, which is in accordance with the
results found by Katyal et al. [65] and Shang et al. [24]. Regarding the
portlandite content, the 1.29% UOW cement demonstrated the highest
content, followed by the 2.58% UOW cement, the reference cement, and
the 5.16% UOW cement, which is in accordance with the alite content of
these cements (see Table 6). This was expected because the hydration of
the alite results in a greater amount of portlandite/g at complete hy­
dration compared to the hydration of the belite, as can be observed in
Eqs. 6 and 7 [66]. Thus, cements with higher levels of alite have a higher
content of portlandite at advanced ages.
2C3 S + 6H→C3 S2 H3 + 3CH (6)
2C2 S + 4H→C3 S2 H3 + CH (7)
Fig. S1 shows the X-ray patterns of the pastes of the different cements
studied at 3, 28 and 63 days. In all pastes, diffractometric peaks corre­
sponding to the anhydrous phases (alite and belite) were identified,
indicating that, as expected, up to 63 days, none of the cements was fully
hydrated. In addition, for all evaluated pastes, the diffractometric peaks
related to crystalline hydration products (portlandite, ettringite, and
J.S. Andrade Neto et al. Cement 9 (2022) 100036

Fig. 7. DTG curves of cement pastes with 63 days.

ettringite peak intensity and the lower the AFm peak intensity. The
Table 9
reference cement demonstrated the lowest ettringite peak intensity but
Chemically bound water and portlandite contents of the different cement pastes
the highest AFm peak intensity. This result agrees with the DTG results
with 63 days, determined by TGA.
and is a consequence of the higher SO3 of the cements with UOW, as
Cement used Chemically bound water content (%) Portlandite content (%)
previously discussed.
105 - 550 C
◦
450 – 550◦ C

REF 11.30 10.13

1.29% UOW 12.61 11.28 3.5. Compressive strength
2.58% UOW 13.01 10.24
5.16% UOW 11.74 7.05 Fig. 9 displays the compressive strength over time of pastes produced
with the studied cements. Table S2 (in the Supplementary Materials)
presents the results of the one-way ANOVA of the compressive strength.
monosulfate) can be observed.
According to the ANOVA results, there are significant differences be­
As expected, there was a reduction in the intensity of the diffracto­
tween the cements at 1, 3, and 7 days. At late ages (28 and 63 days) there
metric peaks for the anhydrous phases and an increase in the peaks of
is no significant difference between the compressive strength of the
the hydrated phases from 3 to 63 days, which is due to the dissolution of
cements.
the anhydrous phases and formation of hydrated compounds.
For up to 7 days, the 1.29% UOW cement had the greatest strengths:
Comparing the different evaluated cements, the addition of UOW to the
36%, 37%, and 21% greater than the reference cement at 1, 3, and 7
raw meal did not result in new phases during the hydration of the ce­
days, respectively. The 5.16% UOW cement had the lowest strengths:
ments. This was expected as the incorporation of the waste did not result
32%, 29%, and 38% less than the reference cement at 1, 3, and 7 days,
in different phases in the clinker either (see Fig. 4).
respectively. Finally, the 2.58% UOW cement presented 12% less
Fig. 8 presents the XRD patterns at 8-13 2θ and 19.5-21 2θ, showing
compressive strength at 1 day than the reference cement, with similar
the main XRD peaks of Ettringite (E) and monosulfate (AFm). One can
strength at 3 and 7 days (difference less than 5%).
note that both the ettringite and monosulfate peaks’ intensity varied
These results are in accordance with the content of alite in the clinker
with the UOW content: the higher the UOW content used, the higher the
(see Table 6), which was expected because alite is mainly responsible for

10
J.S. Andrade Neto et al. Cement 9 (2022) 100036

Fig. 9. Compressive strength of pastes of the different cements at 1, 3, 7, 28,

and 63 days.

with lower alite content (with 5.18% of UOW) had higher belite content,
which despite presenting a slower hydration rate, is the main factor
responsible for the strength at late ages [13].
The addition of 1.29% UOW to the raw meal was extremely benefi­
cial for the mechanical performance of the cements in the early ages and
did not influence the late ages. Conversely, the addition of 5.16% of
UOW significantly reduced the compressive strength of the cement in
the first days of hydration.

4. Conclusions

This study evaluated the technical feasibility of incorporating UOW

into raw Portland clinker meals. In addition to the mineralogical char­
acterization of the clinker, the hydration process of the cements pro­
duced with UOW, and their mechanical performance were evaluated.
Based on the results obtained in the present study, it can be concluded
that:

Fig. 8. XRD patterns (8-13 2θ and 19.5-21 2θ) of pastes at (A) 3 days, (B) 28
days, and (C) 63 days. E – Ettringite, AFm – monosulfate, G – Gypsum.
the mechanical strength in the initial ages [13]. The greater strength of
the reference cement compared to the 1.0% TiO2 cement, even with a
similar alite content (see Table 6), is a consequence of the delay in the
hydration process with the incorporation of UOW into the raw meal, as
discussed in Section 3.4.
However, as discussed in Section 3.4, the reference cement was
undersulfated, which probably negatively affected its compressive
strength, especially in the first days. Future studies of sulfate optimi­
zation on UOW-containing cements and their mechanical performance
compared to proper sulfated reference cement are necessary to confirm
the behavior observed here -the increase in the compressive strength on
the first 7 days by adding 1.29% of UOW in the clinker raw meal.
At 28 and 63 days, all cements presented similar compressive
strength (differences less than 10%, not significative according to the
ANOVA analysis – see Table S2). This result was expected as the cement
• All the main phases (C3S, C2S, C3A, and C4AF) were formed in the
clinker using UOW to partially replace limestone at a temperature
significantly less than that used industrially (1340◦ C).
• UOW acts as a mineralizer, accelerating reactions during clinker
production and increasing the percentage of alite present in the
clinker. The optimal formulation in relation to the alite content was a
raw meal with 1.29% of UOW.
• The incorporation of UOW into the raw meal favored the formation
of orthorhombic C3A, compared to cubic C3A, owing to the increase
in the titanium content in the raw meal.
• The incorporation of UOW increased the size of the alite crystals,
likely due to a reduction in the viscosity of the liquid phase during
clinker production.
• Cements produced with UOW demonstrated a lower heat release in
the first hours, indicating a lower hydration rate. This probably
occurred because of the increase in the size of the alite crystals with
the incorporation of UOW. In addition, this result could be associated
with the consumption of calcium ions for the formation of CaO.TiO2,
delaying hydration. This conclusion requires further investigation.
• The time for sulfate depletion increases with the incorporation of
UOW into the raw meal owing to the increase in the SO3 content.
Thus, the incorporation of UOW reduces the demand for sulfates in
the cement.
• Cements with 1.29% and 2.58% of UOW demonstrated the highest
levels of BW at 63 days of hydration, indicating that the delay in
hydration due to the incorporation of UOW into the raw meal
occurred only in the first days.
• At 7, 28 and 63 days, the content of ettringite increased, while the
monosulfate content decreased, with the increase of UOW content

11
J.S. Andrade Neto et al.
incorporated into the raw meals owing to the increase in SO3 with
the incorporation of the residue.
• The portlandite content at 63 days was consistent with the levels of
alite in the clinkers. Cement with 1.29% UOW presented the highest
values; cement with 5.16% UOW presented the lowest.
• Based on the mineralogical characterization of the pastes after 3, 28
and 63 days of curing, the incorporation of UOW into the raw meal
did not result in any different crystalline phases.
• Owing to the higher alite content, cements with 0.5% TiO2 (1.29%
UOW) demonstrated the greatest compressive strength in the first
days. However, after 28 days, all evaluated cements demonstrated
similar mechanical performance.
The use of UOW as a raw material in the production of Portland
clinker is extremely promising. In addition to reusing a residue, up to an
optimal content (1.29%), its addition favors the reactivity of the raw
meal, resulting in increases in the levels of alite and, consequently,
greater mechanical strength of the cements in the early ages. It should be
noted that the optimum level of UOW likely varies from raw meal to raw
meal, mainly depending on the TiO2 content of the other raw materials
used (especially in the clay).
To confirm that the use of waste in the cement industry is feasible,
studies on an industrial scale and studies that evaluate the rheology and
durability of these cements are necessary. Furthermore, future studies
on the sulfate optimization of UOW-containing cements and their me­
chanical performance compared to optimized sulfated reference ce­
ments are required. Finally, it is important to assess the environmental
impact of using UOW by the cement industry.
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.
Acknowledgements
The authors would like to thank FAPESB - Research Support Foun­
dation of the State of Bahia, CNPq - National Council for Scientific and
Technological Development (Brazil) and CAPES - Coordination for the
Improvement of Higher Education Personnel. To the quality control
laboratory of the cement company Mizu Cimentos Especiais, for the
optical microscopy tests. To the Materials Characterization Laboratory
of the Federal Institute of Bahia (IFBA), for scanning electron micro­
scopy and thermogravimetry tests. To the Laboratory of Innovation in
Eco-Efficient Cements (LINCE) at UFRGS, for isothermal calorimetry
tests.
Supplementary materials
Supplementary material associated with this article can be found, in
the online version, at doi:10.1016/j.cement.2022.100036.
References
[1] I.A. Chen, M.C.G. Juenger, Cement & Concrete Composites Incorporation of coal
combustion residuals into calcium sulfoaluminate-belite cement clinkers, Cem.
Concr. Compos. 34 (2012) 893–902, https://doi.org/10.1016/j.
cemconcomp.2012.04.006.
[2] F. Puertas, I. García-Díaz, A. Barba, M.F. Gazulla, M. Palacios, M.P. Gómez,
S. Martínez-Ramírez, Ceramic wastes as alternative raw materials for Portland
cement clinker production, Cem. Concr. Compos. 30 (2008) 798–805, https://doi.
org/10.1016/j.cemconcomp.2008.06.003.
[3] F. Puertas, I. García-Díaz, M. Palacios, M.F. Gazulla, M.P. Gómez, M. Orduña,
Clinkers and cements obtained from raw mix containing ceramic waste as a raw
material. Characterization, hydration and leaching studies, Cem. Concr. Compos.
32 (2010) 175–186, https://doi.org/10.1016/j.cemconcomp.2009.11.011.
[4] F.N. Costa, D. v Ribeiro, Reduction in CO2 emissions during production of cement,
with partial replacement of traditional raw materials by civil construction waste
12
Cement 9 (2022) 100036
(CCW), J. Cleaner Prod. 276 (2020), 123302, https://doi.org/10.1016/j.
jclepro.2020.123302.
[5] E.B. da Costa, T.R.S. Nobre, A.Q. Guerreiro, M. Mancio, A.P. Kirchheim, Clínquer
Portland com reduzido impacto ambiental, Ambiente Construído 13 (2013) 75–86,
https://doi.org/10.1590/S1678-86212013000200007.
[6] A. Sáez-De-Guinoa Vilaplana, V.J. Ferreira, A.M. López-Sabirón, A. Aranda-Usón,
C. Lausín-González, C. Berganza-Conde, G. Ferreira, Utilization of Ladle Furnace
slag from a steelwork for laboratory scale production of Portland cement, Constr.
Build. Mater. 94 (2015) 837–843, https://doi.org/10.1016/j.
conbuildmat.2015.07.075.
[7] M. Yamashita, H. Tanaka, E. Sakai, K. Tsuchiya, Mineralogical study of high SO3
clinker produced using waste gypsum board in a cement kiln, Constr. Build. Mater.
217 (2019) 507–517, https://doi.org/10.1016/j.conbuildmat.2019.05.098.
[8] J. Schoon, L. van der Heyden, P. Eloy, E.M. Gaigneux, K. de Buysser, I. van
Driessche, N. de Belie, Waste fibrecement: An interesting alternative raw material
for a sustainable Portland clinker production, Constr. Build. Mater. 36 (2012)
391–403, https://doi.org/10.1016/j.conbuildmat.2012.04.095.
[9] A.G. Gomes, T.A. Santos, J.D.S.A. Neto, D.V. Ribeiro, Mineralogical analysis of
Portland clinker produced from the incorporation of granitic rock fines (GRF). Key
Engineering Materials, Trans Tech Publications Ltd, 2019, pp. 309–313, https://
doi.org/10.4028/www.scientific.net/KEM.803.309.
[10] T.A. Santos, J.S. Andrade Neto, M.S. Cilla, D. v. Ribeiro, Influence of the Content of
Alkalis (Na2O and K2O), MgO, and SO3 Present in the Granite Rock Fine in the
Production of Portland Clinker, J. Mater. Civ. Eng. 34 (2022) 1–12, https://doi.
org/10.1061/(asce)mt.1943-5533.0004201.
[11] Y. Da, T. He, C. Shi, M. Wang, Y. Feng, Potential of preparing cement clinker by
adding the fluorine-containing sludge into raw meal, J. Hazard. Mater. 403 (2021),
123692, https://doi.org/10.1016/j.jhazmat.2020.123692.
[12] Y. Da, T. He, C. Shi, Y. Lin, Utilizing titanium-containing pickling sludge to prepare
raw meal for clinker production, Constr. Build. Mater. 268 (2021), 121216,
https://doi.org/10.1016/j.conbuildmat.2020.121216.
[13] H.F.W. Taylor, Cement chemistry, 2nd ed., Thomas Telford, 1997 https://doi.org/
10.1680/cc.25929.
[14] J.I. Bhatty, J. Gajda, Use of alternative materials in cement manufacturing, J.I.
Bhatty, F.M. Miller, S.H. Kosmatka. Innovations in Portland Cement
Manufacturing, 2nd ed., Portland Cement Association, Skokie, Illinois, 2011,
pp. 137–166.
[15] L. Simão, J. Jiusti, N.J. Lóh, D. Hotza, F. Raupp-Pereira, J.A. Labrincha, O.R.
K. Montedo, Waste-containing clinkers: Valorization of alternative mineral sources
from pulp and paper mills, Process Saf. Environ. Prot. 109 (2017) 106–116,
https://doi.org/10.1016/j.psep.2017.03.038.
[16] K. Raina, L.K. Janakiraman, Use of Mineralizer in Black Meal Process for Improved,
Cem. Concr. Res. 28 (1998) 1093–1099.
[17] M. Yamashita, H. Tanaka, Low-temperature burnt Portland cement clinker using
mineralizer, Cement Sci. Concrete Technol. 65 (2011) 82–87.
[18] K. Kolovos, P. Loutsi, S. Tsivilis, G. Kakali, The effect of foreign ions on the
reactivity of the CaO-SiO2-Al2O3-Fe2O3 system: Part I. Anions, Cem. Concr. Res.
31 (2001) 425–429, https://doi.org/10.1016/S0008-8846(00)00461-0.
[19] B.B. Mariani, J. da S Andrade Neto, N.S. de Amorim Júnior, D.V. Ribeiro, Efeito da
incorporação de resíduo de TiO2 (MNR) na formação das fases mineralógicas de
clínquer Portland, Ambiente Construído 19 (2019) 57–71, https://doi.org/
10.1590/s1678-86212019000100293.
[20] D.D.M. Albuquerque, J.S. Andrade Neto, N.S. Amorim Júnior, D. v. Ribeiro,
Properties of coating mortars with waste from TiO2 production - UOW, Ceramica
65 (2019) 340–350, https://doi.org/10.1590/0366-69132019653752562.
[21] D.v. Ribeiro, N.S. Amorim Júnior, J.S. Andrade Neto, D.D.M. Albuquerque, B.
P. Mazzilli, Performance and radiological implications of using residue from TiO2
production as a component of coating mortars, Constr. Build. Mater. 306 (2021),
https://doi.org/10.1016/j.conbuildmat.2021.124885.
[22] J.I. BHATTY, Minor Elements in Cement.pdf, J.I. Bhatty, F.M. Miller, S.H.
Kosmatka. Innovations in Portland Cement Manufacturing, 2nd ed., Portland
Cement Association, Skokie, Illinois, 2011, pp. 403–452.
[23] K. Kolovos, S. Tsivilis, G. Kakali, The effect of foreign ions on the reactivity of the
CaO-SiO2-Al2O3-Fe2O3 system: Part II: Cations, Cem. Concr. Res. 32 (2002)
463–469, https://doi.org/10.1016/S0008-8846(01)00705-0.
[24] D. Shang, M. Wang, Z. Xia, S. Hu, F. Wang, Incorporation mechanism of titanium in
Portland cement clinker and its effects on hydration properties, Constr. Build.
Mater. 146 (2017) 344–349, https://doi.org/10.1016/j.conbuildmat.2017.03.129.
[25] X. Ma, H. Chen, P. Wang, Effect of TiO2 on the formation of clinker with high C3S,
J. Wuhan Univ. Technol. 24 (2009) 830–833, https://doi.org/10.1007/s11595-
009-5830-x. Materials Science Edition.
[26] Associação Brasileira de Normas Técnicas, NBR 10007: Sampling of solid waste (in
portuguese), (2004) 25. http://wp.ufpel.edu.br/residuos/files/2014/04/nbr-
10007-amostragem-de-resc3adduos-sc3b3lidos.pdf.
[27] Associação Brasileira de Normas Técnicas, NBR 16372: Portland cement and other
powdered materials - Determination of fineness by the air permeability method
(Blaine method) (in Portuguese), (2015) 11.
[28] American Society for Testing and Materials., ASTM D4892: Standard Test Method
for Density of Solid Pitch (Pycnometer Method), (2019).
[29] Associação Brasileira de Normas Técnicas, NBR NM 18: Portland cement –
Chemical analysis – Determination of loss on ignition (in portuguese), (2012).
[30] J.H. Potgieter, K.A. Horne, S.S. Potgieter, W. Wirth, An evaluation of the
incorporation of a titanium dioxide producer’s waste material in Portland cement
clinker, Mater. Lett. 57 (2002) 157–163, https://doi.org/10.1016/S0167-577X(02)
00723-1.
J.S. Andrade Neto et al.
[31] H.M. Ludwig, W. Zhang, Research review of cement clinker chemistry, Cem. Concr.
Res. 78 (2015) 24–37, https://doi.org/10.1016/j.cemconres.2015.05.018.
[32] N. Husillos Rodríguez, S. Martínez-Ramírez, M.T. Blanco-Varela, S. Donatello,
M. Guillem, J. Puig, C. Fos, E. Larrotcha, J. Flores, The effect of using thermally
dried sewage sludge as an alternative fuel on Portland cement clinker production,
J. Cleaner Prod. 52 (2013) 94–102, https://doi.org/10.1016/j.
jclepro.2013.02.026.
[33] F. Riello, Quantitative Analysis of Amorphous Fraction in the Study of the
Microstructure of Semi-crystalline Materials, in: E.J. Mittemeijer, P. Scardi (Eds.),
Diffraction Analysis of the Microstructure of Materials, Springer, 2004,
pp. 167–184, https://doi.org/10.1007/978-3-642-56680-6.
[34] G.A. Calligaris, T.L.T. da Silva, A.P.B. Ribeiro, A.O. dos Santos, L.P. Cardoso, On
the quantitative phase analysis and amorphous content of triacylglycerols
materials by X-ray Rietveld method, Chem. Phys. Lipids 212 (2018) 51–60, https://
doi.org/10.1016/j.chemphyslip.2018.01.003.
[35] J. da S Andrade Neto, M.J.S. de França, N.S. de Amorim Júnior, D.V. Ribeiro,
Effects of adding sugarcane bagasse ash on the properties and durability of
concrete, Constr. Build. Mater. 266 (2021), https://doi.org/10.1016/j.
conbuildmat.2020.120959.
[36] A.R.D. Costa, S.R.C. Matos, G. Camarini, J.P. Gonçalves, Hydration of sustainable
ternary cements containing phosphogypsum, Sustain. Mater. Technol. 28 (2021),
https://doi.org/10.1016/j.susmat.2021.e00280.
[37] M.N. de Noirfontaine, M. Courtial, F. Dunstetter, G. Gasecki, M. Signes-Frehel,
Tricalcium silicate Ca3SiO5 superstructure analysis: A route towards the structure
of the M1 polymorph, Zeitschrift Fur Kristallographie 227 (2012) 102–112,
https://doi.org/10.1524/zkri.2012.1425.
[38] W.G. Mumme, R.J. Hill, G.W. Bushnell, E.R. Segnite, Rietveld Crystal Structure
Refinements, Crystal Chemistry and Calculated Powder Diffraction Data for the
Polymorphs of Dicalcium Silicate and Related Phases, Neue Jahrbuch Fuer
Mineralogie – Abhandlungen 169 (1995) 35–68.
[39] P. Mondal, J.W. Jeffery, The Crystal Structure of Triealeium Aluminate, Ca3Al2O6,
Acta Crystallogr. (1975) 689.
[40] F. Nishi, Y. Takeuchi, The A16018 Rings of Tetrahedra in the Structure of Cas.
sNaA16O18, Acta Crystallographica Section B Struct. Crystallogr. Crystal Chem. 31
(1975) 1169–1173.
[41] A.A. Colville, S. Geller, Crystal structures of Ca2Fe1.43Al0.57O5 and
Ca2Fe1.28Al0.72O5, Acta Crystallogr. B28 (1972) 3196–3200, https://doi.org/
10.1107/S0567740872007733.
[42] Q. Huang, J.J. Capponi, C. Chaillout, M. Marezio, J.L. Tholence, A. Santoro,
Neutron powder diffraction study of the crystal structure of HgBa2Ca4Cu5O12+
d at room temperature and at 10 K, Physica C 227 (1994) 1–9, https://doi.org/
10.1016/0921-4534(94)90349-2.
[43] S. Sasaki, K. Fujino, Y. Takéuchi, X-Ray Determination of Electron-Density
Distributions in Oxides, MgO, MnO, CoO, and NiO, and Atomic Scattering Factors o
f their Constituent Atoms, Proc. Jpn. Acad. 55 (1979) 43–48, https://doi.org/
10.2183/pjab.55.43.
[44] M. Palacios, H. Kazemi-Kamyab, S. Mantellato, P. Bowen, Laser diffraction and gas
adsorption techniques, K. Scrivener, R. Snellings, B. Lothenbach. A Practical Guide
to Microstructural Analysis of Cementitious Materials, 1st ed., CRC Press, 2016,
pp. 445–480.
[45] B. Lothenbach, P.T. Durdziński, K. de Weerdt, Thermogravimetric analysis, K.
Scrivener, R. Snellings, B. Lothenbach. A Practical Guide to Microstructural
Analysis of Cementitious Materials, 1st ed., CRC Press, 2016, pp. 177–212.
[46] E. Bastos, E.D. Rodríguez, S.A. Bernal, J.L. Provis, L.A. Gobbo, A. Paula, Production
and hydration of calcium sulfoaluminate-belite cements derived from aluminium
anodising sludge, 122 (2016) 373–383. 10.1016/j.conbuildmat.2016.06.022.
[47] H. Zhou, X. Gu, J. Sun, Z. Yu, H. Huang, Q. Wang, X. Shen, Research on the
formation of M1-type alite doped with MgO and SO3—A route to improve the
quality of cement clinker with a high content of MgO, Constr. Build. Mater. 182
(2018) 156–166, https://doi.org/10.1016/j.conbuildmat.2018.06.078.
13
View publication stats
Cement 9 (2022) 100036
[48] L. León-Reina, A.G. de La Torre, J.M. Porras-Vázquez, M. Cruz, L.M. Ordonez,
X. Alcobé, F. Gispert-Guirado, A. Larrãaga-Varga, M. Paul, T. Fuellmann,
R. Schmidt, M.A.G. Aranda, Round robin on Rietveld quantitative phase analysis of
Portland cements, J. Appl. Crystallogr. 42 (2009) 906–916, https://doi.org/
10.1107/S0021889809028374.
[49] P. Stutzman, Quantitative X-ray powder diffraction analysis of portland cements:
proficiency testing for laboratory assessment, Adv. Civil Eng. Mater. 3 (2014),
20130093, https://doi.org/10.1520/acem20130093.
[50] P.M. Suherman, A. van Riessen, B. O’Connor, D. Li, D. Bolton, H. Fairhurst,
Determination of amorphous phase levels in Portland cement clinker, Powder Diffr.
17 (2002) 178–185, https://doi.org/10.1154/1.1471518.
[51] I. Sohn, W. Wang, H. Matsuura, F. Tsukihashi, D.J. Min, Influence of TiO2 on the
Viscous Behavior of Calcium Silicate Melts Containing 17 mass% Al2O3 and 10
mass% MgO, ISIJ Int. 52 (2012) 158–160.
[52] Y. Da, T. He, C. Shi, M. Wang, Y. Feng, Studies on the formation and hydration of
tricalcium silicate doped with CaF2 and TiO2, Constr. Build. Mater. 266 (2021),
https://doi.org/10.1016/j.conbuildmat.2020.121128.
[53] N.K. Katyal, S.C. Ahluwalia, R. Parkash, Influence of titania on the formation of
tricalcium silicate, Cem. Concr. Res. 29 (1999) 355–359, https://doi.org/10.1016/
S0008-8846(99)00172-6.
[54] J. Li, G. Cheng, S. Huang, L. Huang, Effect of Ti on crystal transition and solid
solution characteristics of white Portland cement clinker, Adv. Cement Res. 33
(2021) 304–310, https://doi.org/10.1680/jadcr.19.00163.
[55] L. Gobbo, L. Sant’Agostino, L. Garcez, C3A polymorphs related to industrial clinker
alkalies content, Cem. Concr. Res. 34 (2004) 657–664, https://doi.org/10.1016/j.
cemconres.2003.10.020.
[56] R.J. Myers, G. Geng, E.D. Rodriguez, P. da Rosa, A.P. Kirchheim, P.J.M. Monteiro,
Solution chemistry of cubic and orthorhombic tricalcium aluminate hydration,
Cem. Concr. Res. 100 (2017) 176–185, https://doi.org/10.1016/j.
cemconres.2017.06.008.
[57] A.P. Kirchheim, E.D. Rodríguez, R.J. Myers, L.A. Gobbo, P.J.M. Monteiro, D.C.
C. Dal Molin, R.B. de Souza, M.A. Cincotto, Effect of gypsum on the early hydration
of cubic and Na-doped orthorhombic tricalcium aluminate, Materials 11 (2018)
1–16, https://doi.org/10.3390/ma11040568.
[58] J.S. Andrade Neto, P.R. Matos, A.G. de la Torre, C.E.M. Campos, P.J.P. Gleize, P.J.
M. Monteiro, A.P. Kirchheim, The role of sodium and sulfate sources on the
rheology and hydration of C3A polymorphs, Cem. Concr. Res. 151 (2022), 106639,
https://doi.org/10.1016/j.cemconres.2021.106639.
[59] A.P. Kirchheim, V. Fernàndez-Altable, P.J.M. Monteiro, D.C.C. Dal Molin,
I. Casanova, Analysis of cubic and orthorhombic C3A hydration in presence of
gypsum and lime, J. Mater. Sci. 44 (2009) 2038–2045, https://doi.org/10.1007/
s10853-009-3292-3.
[60] N.B. Winter, Understanding Cement, 1st ed., WHD Microanalysis Consultants Ltd.,
Rendlesham, Woodbridge, 2012.
[61] M.B. Marinho, F.P. Glasser, Polymorphism and phase changes in the ferrite phase
of cements induced by titanium substitution, Cem. Concr. Res. 14 (1984) 360–368,
https://doi.org/10.1016/0008-8846(84)90054-1.
[62] Associação Brasileira de Normas Técnicas, NBR 16697: Portland cement -
Requirements (in portuguese), (2018).
[63] J. da S Andrade Neto, A.G. de la Torre, A.P. Kirchheim, Effects of sulfates on the
hydration of Portland cement – A review, Constr. Build. Mater. 279 (2021),
https://doi.org/10.1016/j.conbuildmat.2021.122428.
[64] F. Zunino, K. Scrivener, Factors influencing the sulfate balance in pure phase C3S/
C3A systems, Cem. Concr. Res. 133 (2020), 106085, https://doi.org/10.1016/j.
cemconres.2020.106085.
[65] N.K. Katyal, S.C. Ahluwalia, R. Parkash, Effect of TiO2 on the hydration of
tricalcium silicate, Cem. Concr. Res. 29 (1999) 1851–1855.
[66] P.K. Mehta, P.J.M. Monteiro, Concrete: Microstructure, Properties, and Materials,
4th ed., McGraw-Hill Professional Publishing, 2014.