Construction and Building Materials 229 (2019) 116860

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Construction and Building Materials

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Environmentally clean construction materials from hazardous bauxite

waste red mud and spent foundry sand
Kirill Alekseev a, Vsevolod Mymrin a,⇑, Monica A. Avanci a, Walderson Klitzke b, Washington L.E. Magalhães c,
Patrícia R. Silva c, Rodrigo E. Catai a, Dimas A. Silva b, Fernando A. Ferraz b
a
Federal Technological University of Paraná, (UTFPR), Brazil
b
Federal University of Paraná (UFPR), Curitiba, Paraná, Brazil
c
Brazilian Agricultural Research Corporation (EMBRAPA), Curitiba, Paraná, Brazil

h i g h l i g h t s

Were developed ceramics from industrial wastes.

Flexural strength of ceramics was till 10.54 MPa.

Values of water absorption coefficient was 2.77 and 14.41%.

New ceramics have mainly glassy structures with some crystal inclusions.

Utilization of industrial wastes will have high environment impact.

a r t i c l e i n f o a b s t r a c t

Article history: This paper demonstrates the possibility of producing new red ceramics composites from red mud of
Received 13 May 2019 hazardous bauxite waste (50–100 wt%), and foundry sand (10–50%) replacing the traditional clay-sand
Received in revised form 5 August 2019 mix and preventing the environment pollution by such industrial wastes. The newly developed
Accepted 1 September 2019
environment-friendly ceramics exhibit high physical properties (flexural strength, linear shrinkage, water
absorption, and density). The ceramics’ analysis by X-rays fluorescence, X-rays diffractometry, atom
absorption spectroscopy, scanning electron microscopy, energy-dispersion spectroscopy, and laser
Keywords:
micro-mass analysis revealed the synthesis of mainly glass-like structures with a small inclusion of
Bayer process’s red mud utilization
Spent foundry sand
crystalline structures. The values of flexural strength reached 10.54 MPa; after sintering at 1150 °C, linear
Sintering till 1150 °C shrinkage varied between 6.62 and 7.92%, water absorption – 2.77 and 14.41% and bulk density – 1.65
Mainly vitreous structure formation and 2.07 g/cm3. The most valuable property of the developed materials is the ecological purity due to
Environmentally clean construction the heavy metal’s complete neutralization from both industrial wastes.
materials Ó 2019 Elsevier Ltd. All rights reserved.

1. Introduction natural materials. World Aluminum’s database [2] made public

According to the calculations of the cosmologist Hawking [1],
the pollution of the atmosphere takes such a dimension that it
already jeopardizes the possibility of humankind’s survival in the
next 300 years. The main polluters of all five of our planet’s envi-
ronment spheres are the industrial and household wastes. Two
hazardous industrial wastes - red mud of bauxite enrichment by
Bayer process before aluminum smelting and spent foundry sand
from machine construction – were used in this research to produce
environment-friendly ceramics without the use of any traditional
⇑ Corresponding author at: 4900, Deputado Heitor de Alencar Furtado Str.,
Curitiba CEP: 81280-340, Brazil.
E-mail address: seva6219@gmail.com (V. Mymrin).
that, in April 2016, 9.2 million tons of alumina and 15–20 million
tons of red mud was produced. Both of these hazardous wastes
were disposed of into the factory’s industrial dumps. One of these
dumps brought about the ecological catastrophe in Hungary [3] in
October 2010. A wave of red mud with pH = 13 and high content of
heavy metals flooded the nearest city, caused the deaths of nine
people, polluted 40 km2 of land and poured into the Danube.
The worldwide technical literature contains information on the
composition and properties, as well as methods of these wastes’
disposal, but for their industrial use, it is necessary to develop
new economically and environmentally more efficient and techno-
logically simpler methods. One of the most difficult problems
regarding waste utilization, especially hazardous waste, is the
consumers’ unwillingness to buy goods from hazardous wastes [4].

https://doi.org/10.1016/j.conbuildmat.2019.116860
0950-0618/Ó 2019 Elsevier Ltd. All rights reserved.
2 K. Alekseev et al. / Construction and Building Materials 229 (2019) 116860

To stimulate the red mud’s recycling, Liu et al. [5] suggested clas-
sifying it as a general industrial waste rather than hazardous
waste. Deelwal et al. [6] showed the diversity of chemical compo-
sitions of the red mud [7] also discovered a significant difference in
red mud composition from different regions of China. Some Wes-
tern Australia red muds showed high levels of radioactivity [8].
Methods of magnetic separation of iron from red mud were devel-
oped by Samouhos et al. [9]. Smiciklas et al. [10] proposed a
method for nickel removal from solutions; Collins et al. [11] used
red mud to withdraw manganese, chromium, cobalt, nickel, cop-
per, and zinc.
Kumar et al. [12] conceived the preparation of cement-free pav-
ing blocks with a flexural strength of 3.2–4.5 MPa and water
absorption of 6–7% from 10 to 20% of red mud and 80–90% of fly
ash. Red mud was used by Tsakiridis et al. [13] for the production
of Portland cement clinker without negatively affecting the cement
quality. [14] Nithya et al. replaced 20% ordinary Portland cement
by calcined red mud and hydrated lime without any loss of poz-
zolanic activity.
The best red mud and clay ratios were determined by Dodoo-
Arhin et al. [15] to attain ceramics sintering temperature of 900–
950 °C with uniaxial compression strength values of 52 MPa. Hua
et al. [16] studied the role of Fe species in geopolymer synthesized
from Bayer red mud, Badanoiu et al. [17] treated red mud and cul-
let soda-glass at 600–800 °C in order to synthesized foamed
geopolymer with a compressive strength of 2.1–8.6 MPa. Singh
et al [18] studied the influence of mechanical activation of red
mud and curing methods on the strength of red mud - fly ash
geopolymer paste.
Spent foundry sand (FS) is the liquid metal casting and molding
residue. As a result of thermal shocks, the sand modifies its granu-
lometric composition and, therefore, is discarded as industrial
waste with a high content of heavy metals. Coppio et al. [19] and
Bhardwaj and Kumar [20] replaced fine natural sand by spent FS
as an aggregate material in concrete production.
Test results of Gurumoorthy and Arunachalam [21] indicated
better performance of concrete with FS than control specimen
and established that concrete with 30% FS is more impermeable
than control concrete. Dyer et al. [22] applied FS for hot asphalt
production. Mymrin et al. [23] suggested foundry sand along with
the addition of other industrial wastes for the sintering of
environmentally-safe ceramics at 950–1050 °C with samples’ flex-
ural strength values of up to 14 MPa.
The main objectives of the research were: (1) to develop new
environment-friendly ceramic composites from hazardous red
mud of bauxite processing and spent foundry sand without tradi-
tional natural material with mechanical properties corresponding
to Brazilian standards; (2) to study the physicochemical processes
of the developed materials structure formation.
2. Methods and raw materials characterization
2.1. Methods
(LAMMA), using a LAMMA-1000, model X-ACT. Lixiviation and sol-
ubility of metals from liquid acid solutions were studied by atomic
absorption in a FAAS or ICP-OES spectrometer; granulometric com-
position - by a laser micro-mass analyzer, model LA-950 – HORIBA;
flexural strength - by EMIC DL-10. Characteristics such as water
absorption as a result of an increase in the weight of the samples
after 24 h of their total immersion in water, linear shrinkage, and
density of the ceramics of the samples after sintering at all temper-
atures were also studied.
The test samples (TS) of the ceramic were prepared by homog-
enization of two industrial wastes used here as raw materials in
different percentages. The TSs were mixed with water content
12–14%, compacted at 5 MPa in a rectangular mold of
60  20  10 mm in size, dried at 100 °C, and burned for three
hours at temperatures of 800°, 900°, 1000°, 1050°, 1100°, 1150°,
1200° and 1225 °C with spontaneous furnace cooling. All physical
properties were replicated ten times. Therefore, the total amount
of the test samples was about 600 pieces.
2.2. Calculations
Water absorption coefficient (CWA) tests were performed after
ceramics’ sintering at all temperatures by the following equation:
CWA ¼ ½ðMSAT  MD Þ=MD   100 ð1Þ
where MSAT - the mass of the test specimen saturated after total
immersion in water for 24 h
MD - the mass of the dry test specimen
The values of linear shrinkage LS (%) were performed according
to the equation:
LS ¼ Li ¼ ½ðLi  LsÞ=Li  100 ð2Þ
where Li - initial length of specimen (mm);
Ls - length of the specimen after the sintering (mm)
The following equation was used to calculate the values of den-
sity D (g/cm3):
D ¼ Md=ðMs  MiÞ ð3Þ
2.3. Raw materials description
2.3.1. Particles size distribution
The particles of both wastes used were tiny (Table 1) due to
their generation processes. The small-grained size’s complex com-
position of red mud was also described by Liu et al. [24]. This com-
position was a favorable factor for the formation of structures and
mechanical properties of the developed materials. RM was the
coarsest material, containing the most massive particles (0.60–
1.19 mm) in the amount of 39.33 wt%. FS exhibited a more uniform

Table 1
The raw materials (red mud and spent foundry sand) and the
Particle size distribution (wt%), bulk density (g/cm3) and humidity (wt%) of the raw
newly developed ceramics were characterized by the following materials.
methods: the particle size distribution was determined by the
Size (mm) Red mud Foundry sand
sieve method; the chemical composition – by XRF, using a Phi-
lips/Panalytical, model PW 2400; the mineralogical composition Grain size distribution 0–0.074 0.32 0.08
– by XRD with a Philips, model PW 1830 with the radiation kCu- 0.075–0.149 1.08 0.62
0.15–0.29 13.14 13.86
Ka; the obtained diffractogram patterns were interpreted using 0.3–0.59 46.13 85.17
the High Score program with the PDF-2 database. The morpholog- 0.6–1.19 39.33 0.26
ical structure was analyzed by SEM, using a Jeol JSM-6360 LV; the 1.2 0.00 0.00
micro-chemical composition – by EDS with a Jeol JSM-5410 LV; Bulk density (g/cm3) 0.86 1.59
Humidity (wt%) 32.2 1.30
and the isotopic composition – by Laser micro-mass analyses
 K. Alekseev et al. / Construction and Building Materials 229 (2019) 116860
size composition, with an 85.17% particle content ranging from 0.3
to 0.59 mm.
The bulk density of foundry sand (1.59 g/cm3) was almost twice
higher than of the red mud (0.86 g/cm3) because of the mainly
siliceous composition.
The foundry sand presented a minimum humidity level (1.30%)
(Table 1) because it is a waste from high-temperature processes,
unlike red mud, which had high (32.2%) humidity due to chemical
reaction with NaOH solution. Yalcin et al. [25] determined the
moisture content of the red mud between 40 and 50%.
2.3.2. Chemical composition of the raw materials
Both raw materials in the study were obtained from local plants
in Brazil. The representative sample of red mud (RM) was received
from an aluminum factory in Sao Paulo; the foundry sand (FS) was
collected in a machine-building plant in the city of Curitiba, Brazil.
The main components of the bauxite red mud were Fe2O3 – 29.9%
(thus this waste had a dark red color from which the material was
named after), Al2O3 – 21.2%, SiO2 – 15.5%, and Na2O – 10.3%. The
high (14.4%) loss on ignition (L.O.I.) value might be explained by
the content of water, and hydroxide OH-group due to the Bayer
thermochemical decomposition of bauxite particles in NaOH solu-
tion with pH = 13.5.
High Na2O content (10.3%) was very beneficial for reducing the
melting point of the ceramics’ composites. Foundry sand consisted
mainly of SiO2 (91.2%). The presence of 3.7% I.L. was most likely the
result of clogging with organic materials when preparing the mold-
ing form and when stored in industrial dumps.
The study of leaching and solubility of metals from red mud by
AAS method showed (Table 3) a high content of all metals, includ-
ing heavy metals, far exceeding Brazilian standards [26].
This fact, together with the high alkalinity of the red mud
(pH = 13.5), required classifying it as a hazardous material. Cur-
rently, the only form of storage of the material used in this study
is open-cast industrial dumps, which inevitably causes extreme
and dangerous pollution of the atmosphere, soils, and surface
and ground waters. A possible path to avoid such pollution is their
complete use at the industrial level as raw materials, using envi-
ronmentally friendly and scientifically based methods.
2.3.3. Mineral composition of the raw materials
The red mud used here presented a typical mineral composition
(Fig. 1-A) for bauxite ore – namely, unbroken of Bayer process rem-
nants of bauxite (Al2O3nH2O), hematite (Fe2O3), magnetite
(Fe3O4), and quartz (SiO2). The low intensity of the X-rays peaks
of the crystalline lattice with almost equal height to the back-
ground evidenced the predominance of the amorphous phase in
the test samples.
Fig. 1. Diffractogram pattern of the red mud and foundry sand by XRD method.
3
Foundry sand was depicted (Fig. 1-B) only by crystalline quartz,
which accorded with the 91.2% SiO2 content detected in the chem-
ical analysis by the XRF method (Table 2). Natural sand particles
were not entirely destroyed by the thermal shocks of the casting
process. Nevertheless, a significant X-ray background acknowl-
edged a high content of amorphous material — a product of the
quartz crystal structure destruction both during the long geological
history of these particles and the casting’s thermal shocks, during
the foundry mold shaping (Fig. 2 – B and C).
2.3.4. Micromorphology of the raw materials (by SEM method)
The raw materials examination by the SEM method (Fig. 2)
revealed particle sizes and surfaces somewhat different between
them. The sizes of the different configurations of the red mud var-
ied from nanoparticles to 0.2 mm, and the foundry sand ranged
between 0.5 and 0.6 mm, confirming the results of the particle size
analysis (Table 1).
2.3.5. Thermochemical characteristics of the raw materials
The principal red mud components were (Table 2) the hydrates
of Fe2O3 (29.9%) and Al2O3 (21.2%) mainly in amorphous and par-
tially crystalline forms (Fig. 1-A).
Therefore, the thermal transformations of these hydroxides,
during red mud’s heating in DTA and TGA analyses (Fig. 2-A), co-
occurred.
The first endothermic effect during the red mud’s firing process
(Fig. 3-A) indicated the loss of free and weakly bound water of the
pores between 28 and 202 °C, with a total material’s weight loss of
3.53%. The second endothermic effect, between 202 °C and 296 °C,
corresponded to the loss of water from the crystalline structure of
gibbsite Al(OH)3 and its transformation in boehmite ɣ-AlO(OH)4,
with a weight loss of 5.25%. The transformation of the amorphous
gel to a, b, ɣ, and d-forms of FeOOH occurred concomitantly [27].
The third endo-effect, at 296–575 °C, coincided with the boeh-
mite ɣ-AlO(OH)4 transition to anhydrous c-Al2O3, with a weight
loss of 4.11%. At the same temperatures, the transformations
FeOOH ? ɣ-Fe2O3 ? Fe3O4 began, with a total weight loss of
4.11%. A strong exothermic effect, between 575 and 1226 °C, was
consistent with the chemical transformations of c-Al2O3 ?
a-Al2O3 (at 850 °C) and Fe3O4 ? Fe (at 700–750 °C), with a total
weight loss of 6.08% [27].
Foundry sand presented more straightforward chemical (SiO2
91.2%, Table 2) and mineralogical (quartz SiO2, Fig. 3-B) composi-
tions. The first endo-effect, at 26–511 °C with a total weight loss
of 2.43%, reflected the evaporation of all types of water with differ-
ent bonding energy to the solid particles of the test samples. The
combination of two small endo-effects between 511° and 595 °C
might be related to two types of transformation of the sol-gel silica
4 K. Alekseev et al. / Construction and Building Materials 229 (2019) 116860

Table 2 mud environment; quartz grains begin to soften already at

The main chemical components of the raw materials. 800 °C (compared ceramics 1 with ceramics 2–6) and interact with
Oxides RM Foundry sand red mud. This interaction explains the significant increase in the
Fe2O3 29.9 1.2 strength of ceramics 2–6 as compared to ceramics 1 at all temper-
SiO2 15.5 91.2 atures, except 1200° and 1225 °C, due to excessive melting of
SO3 0.6 0.7 quartz. The rapid decrease in the strength’s growth of ceramics 1
Al2O3 21.2 2.3 between 1200 and 1225 °C indicates a similar excessive melting
CaO 4.2 0.1
Na2O 10.3 0.3
of RM right after 1225 °C. An increase in FS content to 20% (ceram-
K2O 0.4 0.1 ics 3) reduces the excessive melting up to 1200 °C. The following
MnO 0.2 0.0 increases in FS content to 30, 40, and 50% (ceramics 4, 5, and 6)
TiO2 2.4 0.1 lead to a downtrend in samples strength at almost all
P2O5 0.6 0.0
temperatures.
I.L. 14.4 3.7
Total 99.7 99.7 Nevertheless, these strength values made it possible to manu-
facture bricks of class A and B already after firing at 900 °C and
L.O.I. – Loss on Ignition.
Class C after firing at 1100 °C of all ceramics.

from the destructed surface part of the quartz grains (Fig. 2-B and
C). A strong exothermic peak between 595° and 1226 °C with 0.09%
weight loss might be the result of organic additives firing which
are usually used as binders and plasticizers additives during foun-
dry mold shaping. These additives are employed in casting facto-
ries before the foundry sand is stored as a residue [28,29].
The comparison of the DTA and TGA curves (Fig. 3-A and B), by
the number of thermal effects, the weight loss in each of the effects
and the total weight loss (18.92 versus 2.97%), inferred that the
thermochemical activity of the red mud is much more significant.
This fact is predetermined by the incomparably more complex
chemical and mineral compositions (Fig. 1 and Table 2) of the
red mud. Therefore, in the mixtures of ceramic composites, the
red mud’s chemical influence should be more meaningful than
the sand’s, which more thermochemical passive is. Table 3
3. Results and discussion
3.1. Physical properties of the developed composites
Regarding physical properties, flexural strength (Table 4), linear
shrinkage (Table 5), water absorption (Table 6) and bulk density
(Table 7) of the developed ceramic, sintered at different tempera-
tures, were studied.
3.1.1. Flexural strength of the developed ceramics
According to the Brazilian standard [30], the flexural strength of
solid bricks has the following classification: Class A < 2.5 MPa;
Class B 2.5–4.0 MPa; and Class C > 4.0 MPa. Attempts to use RM
as the only raw material for the production of ceramics (Table 4,
comp. 1) showed that it meets the requirements of this standard
only after firing at a temperature equal or superior to 1100 °C.
Analysis of the results in Table 4 indicates that the maximum
melting point (1050 °C) of quartz sand in a chemically neutral
environment may reduce its stability in strongly alkaline red
3.1.2. Linear shrinkage of the developed ceramics
The shrinkage coefficient values for the materials after firing
until 1225 °C augmented from 1.71 to 12.45% (Table 5). The high-
est shrinkage values were observed in the ceramics of composition
1 with 100% red mud content. The inclusion of 10 to 50% of foundry
sand invariably reduced the sample’s shrinkage values, which
soared with the intensification of the firing temperature. The
ceramics of compositions 2 to 4 at 1225 °C and compositions 5
and 6 at 1200 °C pointed to a reduction in shrinkage, apparently
due to the samples melting onset. There was a decrease in the
strength of the samples (Table 4) at the same temperatures.
The values of standard deviation of the shrinkage coefficient of
all ceramics did not surpass 1.3%.
3.1.3. Water absorption of the developed ceramics
The water absorption values (Table 6) presented a single gen-
eral trend - reduction with increasing firing temperature and flex-
ural strength. They were not associated with the linear shrinkage
(Table 5) of the samples at high temperatures caused by the begin-
ning of the samples melting and the reductions in strength
(Table 4). Monteiro et al. [31] observed a similar ratio of the prop-
erty’s changes. They used blast furnace sludge with 25% amount of
coke for ceramics production. Herek et al. [32], differently, evalu-
ated the growth of the ceramics strength in increasing of water
absorption by the waste catalyst and foamed glass material. The
authors consider that the relationship of these properties depends
on the efficiency of pore formation in the compared materials.
In this study, the firing of the red mud – foundry sand compos-
ites reduced their porosity and water absorption (Table 6) and
increased the shrinkage values (Table 5) and strength.
In accordance with national norms [28], the tolerance limit for
WA in bricks is 20%. The WA values for most compositions varied
from 6 to 10%, thus meeting national standards (Fig. 6). The stan-
dard deviation values of the developed ceramics’ water absorption
coefficient were not superior to 1.37%.

Fig. 2. SEM micro images of red mud (A) and foundry sand (B and C).
 K. Alekseev et al. / Construction and Building Materials 229 (2019) 116860 5

Fig. 3. DTA and TGA curves of the: A - red mud and B – foundry sand.

Table 3
Leaching and solubility of metals from red mud and composition 6 after sintering at 1150 °C.

Elements Leaching, mg/L Solubility, mg/L

Red mud Comp. 6 [26] Red mud Comp. 6 [26]
As 7.63 0.32 1.0 9.56 <0.001 0.01
Ba 94.28 1.58 70.0 95.47 0.032 0.7
Cd 7.34 0.04 0.5 15.41 0 0.005
Pb 4.43 0.22 1.0 7.66 <0.01 0.01
Cr total 18.46 1.49 5.0 22.67 0.02 0.05
Hg 1.47 0.29 0.1 3.81 <0.001 0.001
Se 2.75 0.17 1.0 3.35 <0.001 0.01
Al 28.76 0.14 * 36.44 0.05 0.2
Cu 16.29 0.08 * 30.08 0.87 2.0
Fe 98.31 1.07 * 108.75 0.06 0.3
Mn 55.11 0.41 * 69.43 0.05 0.1
Zn 68.48 0.01 * 84.13 0.69 5.0

Table 4
Flexural strength (MPa) of ceramics after sintering at different temperatures (°C).

N° Compositions, wt% Flexural strength (MPa) of ceramics after sintering at T °C

RM FS 800 900 1000 1050 1100 1150 1200 1225
1 100 0 0.00 0.00 0.45 0.93 4.34 6.06 12.17 12.32
2 90 10 1.83 2.17 3.03 4.37 5.27 8.43 10.54 9.07
3 80 20 1.48 1.79 2.12 4.61 6.33 8.26 7.51 6.91
4 70 30 1.80 2.53 3.05 3.67 5.76 8.02 7.90 6.64
5 60 40 1.25 1.83 2.48 3.47 4.24 7.93 7.70 6.28
6 50 50 1.03 1.55 2.13 2.79 4.10 6.85 6.13 5.69

The standard deviation values of the flexural strength of all ceramics tended to increase with the sintering temperature rise but did not outpace 0.74 MPa.

Table 5
Linear shrinkage (%) of ceramics after sintering at different temperatures (°C).

№ Compos., wt% Linear shrinkage (%) of ceramics sintered at T °C

RM FS 800 900 1000 1050 1100 1150 1200 1225
1 100 0 1.89 2.27 3.42 4.33 5.29 7.24 11.67 12.45
2 90 10 1.84 2.23 3.24 4.14 5.15 7.19 11.45 11.23
3 80 20 1.83 2.17 3.12 4.09 5.02 7.11 11.27 11.04
4 70 30 1.81 2.09 3.03 4.84 4.93 6.97 11.05 10.89
5 60 40 1.74 2.03 2.99 4.80 4.90 6.75 6.62 6.02
6 50 50 1.71 2.00 2.89 4.65 4.70 6.62 6.43 6.26

This decline means that the sand might not only stabilize the red mud samples sizes but also act as a flux due to a large number of heavy metals (Table 3) in highly alkaline
medium.

3.1.4. Bulk density of the developed ceramics 30% of FS demonstrated the beginning of excessive melting of the
The bulk density values (Table 7) of ceramics 1, with 100% of test samples at 1225 °C; increasing FS content up to 40 and 50%
RM, stepped up slowly until 1225 °C. The add-on of 10, 20 and diminished the melting point to 1200 °C. All these changes are in
6 K. Alekseev et al. / Construction and Building Materials 229 (2019) 116860

Table 6
Water absorption of ceramics after sintering at different temperatures (°C).

№ Compositions, wt% Water absorption (%) of ceramics at temperatures (°C)

RM FS 800 900 1000 1050 1100 1150 1200 1225
1 100 0 33.78 31.36 28.68 25.79 24.62 19.98 11.79 9.31
2 90 10 28.37 25.17 23.45 19.67 16.54 14.41 9.45 6.48
3 80 20 25.87 22.19 19.60 16.19 12.01 10.99 8.89 7.20
4 70 30 23.79 20.11 16.23 12.39 9.22 8.93 6.70 4.47
5 60 40 22.39 16.94 13.80 11.40 6.32 5.96 4.60 2.42
6 50 50 18.12 14.75 11.24 8.60 5.54 2.77 2.69 2.35

Table 7
Bulk density of ceramic compositions at different firing temperatures.

№ Composites, wt% Density (g/cm3) of ceramics sintered at T °C

RM FS 800 900 1000 1050 1100 1150 1200 1225
1 100 0 1.28 1.31 1.35 1.42 1.44 1.55 1.89 1.96
2 90 10 1.40 1.43 1.47 1.50 1.55 1.65 1.81 1.75
3 80 20 1.42 1.48 1.52 1.57 1.65 1.78 2.11 2.09
4 70 30 1.52 1.57 1.64 1.68 1.74 1.95 2.09 2.04
5 60 40 1.60 1.64 1.68 1.74 1.87 2.09 1.97 1.95
6 50 50 1.71 1.74 1.80 1.86 1.97 2.07 1.92 1.81

effective agreement with the previously described changes of flex-
ural resistance, water absorption, linear shrinkage, and flexural
resistance strength.
The obtained bulk density values are in reasonable conformity
with the results of Antonovič et al. [33]. The standard deviation
values of the bulk density of the ceramics did not exceed 0.12%.
3.2. Physical-chemical processes of the ceramics 6’s structure
formation
Composite 6 was selected to look into the physicochemical pro-
cesses of the ceramics structure formation due to the higher foun-
dry sand (50%) and red mud (50%) contents as well as the excellent
physical properties, which went beyond the requirements of
national standards. The ceramics sintered at 1000° and 1150 °C
were compared by complementary methods.
3.2.1. Mineral transformation during ceramics 6’s structure formation
The comparison of the ceramics 6’s diffractogram patterns, after
firing at 1000° and 1150 °C, showed (Fig. 4) the presence of the sin-
gle mineral of the foundry sand (quartz SiO2) at the angle
2H = 26.6° (Fig. 1-B), as well as low intensities peaks of quartz at
2H° = 45.8°, 50.1°, and 54.9° with high-temperature modification
of quartz - SiO2. Hematite Fe2O3 peaks barely visible also appeared
in ceramic 6, besides a minimal quantity of two newly synthesized
minerals fayalite Fe2SiO4 and albite NaAlSi3O8 (Fig. 4-A).
However, after sintering at 1150 °C (Fig. 4-B), fayalite minerals
peaks disappeared along with a substantial intensification of the x-
Rays background, evidenced by a drop in the total intensity scale
from 4000 to 3000 counts per second with a decrease of quartz
SiO2 peak at the angle 2H = 26.6°.
It is reasonably possible that the decrease in the intensity of the
quartz peaks and the destruction of the crystalline structures of
fayalite have contributed to such a substantial growth of the amor-
phous phase of ceramics 6 at 1150 °C. The lowering in the flexural
strength of ceramics 6’s samples (Table 4) endorsed the motive for
the increase in the crystal peaks intensity drop and the samples’
amorphous phase growth.
3.2.2. Thermochemical transformation of composite 6 during sintering
The first endothermic effect of composition 6’s thermochemical
analyses (Fig. 5) by DTA and DTG methods was feeble and revealed
the loss of free water present in the pores until 105 °C with a
weight loss of 2.33%. The second endo-effect in the range of
105°–291 °C with a weight loss of 6.33% indicated the removal of
the water. The third endo-effect, between 291 and 574 °C,
corresponded to the transition of boehmite ɣ-AlO(OH)4 to anhy-

Fig. 4. Diffractogram pattern of the composition 6 after firing at: A – 1000° and B –
1150 °C. Fig. 5. Thermochemical reactions of the composition 6 during sintering.
 K. Alekseev et al. / Construction and Building Materials 229 (2019) 116860 7

drous c-Al2O3 and FeOOH ? ɣ-Fe2O3 ? Fe3O4 with a total weight

loss of 5.36%. The strong exothermic effect between 574 and
1226 °C reflected the transformation, at 850 °C, of c-Al2O3 ? a-
Al2O3 and Fe3O4 ? Fe (700–750 °C) [27], with a total weight loss
of 2.38%.
Composition 6 contained two raw materials of ceramics in the
same weight ratio (50: 50%). Nevertheless, as mentioned earlier
in Section 2.2.5, red mud is much more thermochemical active
and therefore it is more influential than the foundry sand, which
is chemically more passive.
As a result of the thermochemical reactions, composition 6
developed the highest flexural strength (6.85 MPa) after firing at
A keV B keV C keV
1150 °C, reducing the strength to 5.69 MPa at 1225 °C. The linear
shrinkage at 1150 °C reached 6.62%, density – 2.07 g/cm3 at Fig. 7. Isotopes composition of the ceramic 6 after sintering at 1150 °C by laser
1150 °C, and the water absorption was 2.77%. micro-mass analysis.

3.2.3. Morphological structure development of composition 6

SEM photomicrograph (Fig. 6-A) of ceramics 6 after firing at
1000C showed a large number of particles of different configura-
tions and sizes within 2–100 mm. Some of them were joined by
molten material, but a much more considerable amount was unre-
lated. There were vast quantities of well visible pores between
these particles also of various sizes and configuration. That was
the main reason for the very low flexural strength values
(2.13 MPa) and the rather high-water absorption value (16.23%)
of ceramics 6 after sintering at 1000 °C. An increase in the firing
temperature to 1150 °C (Fig. 6-B) led to the appearance of exten-
sive fields of almost entirely molten material, pores were very rare,
and the material was almost entirely monolithic. In many spots,
the molten film seemed to be very thin, but still, it might serve
as a thin film of adhesive material. Therefore, the flexural strength
value increased almost thrice (up to 6.12 MPa) and of water
absorption decreased almost twice (8.93%).
3.2.4. Micro-chemical analysis of the ceramic 6 by EDS and LAMMA
analyses
The micro chemical composition of the ceramic 6 provided
information, by EDS method (Fig. 6-B), about the processes occur-
ring in the temperature of 1150 °C. Points 1 and 2 (Table A1) of the
big particle with very similar (81.37 and 82.65%) Si content is the
grain of quartz of foundry sand. The content of each element varied
significantly; for example, Al varied between 1.32 and 19.42%, Si
between 17.60 and 82.65%, and the Fe content was also not uni-
form (between 8.41 and 62.49%). All of this confirmed the high
level of chemical heterogeneity of the ceramic 6, which is typical
for amorphous materials.
The results of laser micro-mass analyses (LAMMA) of isotopes
composition ratified the conclusion on the results of XRD, DTA,
TGA, SEM and EDS methods on the heterogeneity of the compos-
ited 6 after sintering at 1150 °C. All three points of LAMMA demon-
strated (Fig. 7) a very different set of isotopes with very different
values of their intensities (peak height).
3.3. Environmental properties of the developed ceramics
The high leaching and solubility values of heavy metals from
red mud (Table 3) obliged to control these values in the developed
ceramics. The leaching assay was performed according to the pro-
cedure of NBR 10,005 [34]. The samples were dried and milled in
order to obtain particles smaller than or equal to 9.5 mm. A pre-
test was performed using 5 g of the sample, which was transferred
into a beaker where 96.5 mL of deionized water was added. The
mix was vigorously stirred for 5 min. Then the pH was measured.
Since the pH was inferior to 5, the extraction solution was prepared
with 5.7 mL of glacial acetic acid and 64.3 mL of NaOH 1.0 mol L1,
to which distilled, deionized, organic-free water was added until
1 L volume.
The 100% solids residue leaching procedure was followed. For
this purpose, 2 g of the sample was transferred into leaching flasks
to which 40 mL of the extraction solution previously described was
added, so that the solution quantity was 20 times the used mass.
The flask was closed and kept under stirring for 20 h to complete
(18 ± 2) h, at 20 °C of temperature with a rotation of (30 ± 2) rpm
on the rotatory stirrer.

Fig. 6. Morphological structure of the composition 6 after sintering at: A – 1000 °C and B – 1150 °C.
8 K. Alekseev et al. / Construction and Building Materials 229 (2019) 116860

Table 8
Leaching and solubility of composition 6 after sintering at 1100 °C.

Elements Leaching, mg/L Solubility, mg/L

Red mud Comp. 6 [26] Red mud Comp. 6 [26]
As 7.63 0.32 1.0 9.56 <0.001 0.01
Ba 94.28 1.58 70.0 95.47 0.032 0.7
Cd 7.34 0.04 0.5 15.41 0 0.005
Pb 4.43 0.22 1.0 7.66 <0.01 0.01
Cr total 18.46 1.49 5.0 22.67 0.02 0.05
Hg 1.47 0.29 0.1 3.81 <0.001 0.001
Se 2.75 0.17 1.0 3.35 <0.001 0.01
Al 28.76 0.14 * 36.44 0.05 0.2
Cu 16.29 0.08 * 30.08 0.87 2.0
Fe 98.31 1.07 * 108.75 0.06 0.3
Mn 55.11 0.41 * 69.43 0.05 0.1
Zn 68.48 0.01 * 84.13 0.69 5.0

Solubilization assay was performed according to the procedure

of NBR 10,006 [35]. In order to obtain the solubilized extract, the
samples were dried at a temperature of 40 °C. A dried sample of
250 g was placed in a 1500 mL flask, and 1000 mL of distilled
and deionized water was added. The mixture was stirred at low
speed for 5 min and then left resting for 7 days at a temperature
of up to 25 °C, protected by a plastic film (PVC). The suspension
was filtered, obtaining the solubilized extract.
The contents of the elements present in the leaching and solu-
bilization extracts were determined by atomic absorption (FAAS or
ICP-OES).
Analyses of the filtrate showed (Table 8) a reduction of tens and
hundreds of times in the metal content compared with the initial
red mud.
These results suggested the complete sustainability of the
developed ceramics both for the construction materials for various
purposes and their rubble at the end of the materials service.
4. Conclusions
1. The current study has shown the real possibility of using two
hazardous industrial wastes as valuable raw materials for the
production of environmentally friendly ceramic materials. The
widespread reuse of industrial wastes at the industrial level will
make it possible to stop and prevent, in the future, the extre-
mely dangerous pollution of the environment and the death
of the Earth’s population, scientifically calculated and proven
by S.W. Hawking [1]. In the developed materials there are no
traditional natural components such as clay and sand, which
enables to halt the destruction by the quarries of unrecoverable
natural bonds;
2. The physical properties of the developed ceramics far exceeded
the demands of Brazilian technical norms. The values of flexural
strength reached 10.54 MPa, after sintering at 1150 °C, linear
shrinkage varied between 6.62 and 7.92%, water absorption
between 2.77 and 14.41%, and bulk density between 1.65 and
2.07 g/cm3;
3. The study of physical-chemical processes of the structure for-
mation showed the synthesis of mainly amorphous materials,
closure of pores and bonding particles of the original compo-
nents. Thus, high mechanical properties of ceramics and chem-
ical bonding or strong encapsulation in the vitrified mass of
metals, including hazardous heavy metals, are achieved.
4. The calculation of the economic efficiency of the developed
ceramics production on an industrial scale was out of the authors’
scope. However, from a common point of view, free raw materials
(or even surcharges for the use of wastes from their producers)
should be very profitable compared to expensive natural raw
materials, whose price is continuously growing.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.conbuildmat.2019.116860.
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