Ceramics International xxx (xxxx) xxx–xxx

Contents lists available at ScienceDirect

Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Investigation of use of coal fly ash in eco-friendly construction materials:

fired clay bricks and silica-calcareous non fired bricks
⁎
D. Eliche-Quesadaa, , J.A. Sandalio-Péreza, S. Martínez-Martíneza, L. Pérez-Villarejob,
P.J. Sánchez-Sotoc
a
Department of Chemical, Environmental, and Materials Engineering. Higher Polytechnic School of Jaén. University of Jaen, Campus Las Lagunillas s/n, 23071 Jaén,
Spain
b
Department of Chemical, Environmental, and Materials Engineering. Higher Polytechnic School of Linares.University of Jaen, Campus Científico-Tecnológico Cinturón Sur
s/n, 23700 Linares (Jaén), Spain
c
Materials Science Institute of Sevilla (ICMS), Joint Center Spanish National Research Council (CSIC)-University of Sevilla, c/Américo Vespucio, 49, 41092 Sevilla, Spain

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

Keywords: The use of coal fly ash (CFA) as raw material for the manufacture of two construction materials, fired clay bricks
Coal fly ash and silica-calcareous non-fired bricks, was investigated. Fired clay bricks were manufactured using a commercial
Fired clay bricks clay and different waste ratios (0–50 wt%), moulded at 10 MPa and fired at 1000 ºC (4 h). Silica-calcareous non-
Silica-calcareous non-fired bricks fired bricks were prepared using two wastes as raw material: CFA and “geosilex”(G), a hidrated lime residue
Geosilex
which comes entirely from acetylene industry waste. Different proportions CFA (80–30 wt%) – G (20–70 wt%)
Physical and mechanical properties
Leaching
were investigated. Raw materials were moulded at 10 MPa and cured in water at room temperature during 28
days. The results indicated that the incorporation of up to 20 wt% of CFA produced fired clay bricks with
physical and mechanical properties similar to control bricks without waste. However, additions of a higher
amount (30–50 wt%) of residue resulted in a more pronounced decrease in mechanical properties (between
25–50%) due to an increase in open porosity. The technological characterization of the silica-calcareous non-
fired bricks showed a reduction in the values of bulk density and water absorption when the coal fly ash content
decreases. Silica-calcareous non-fired bricks containing between 40 and 60 wt% of CFA had the highest values of
compressive strength in the range 46–43 MPa. These silica-calcareous non-fired bricks, 60CFA-40 G, 50CFA-50 G
and 40CFA-60 G, presented the optimum amount of pozzolanic materials (SiO2 and Al2O3) in the coal fly ash and
calcium hydroxide in the geosilex to give rise to the formation of calcium silicate hydrates and calcium alu-
minate hydrates, the phases responsible for the mechanical resistance increase of the construction materials.
Therefore, CFA-clay fired bricks and silica-calcareous CFA-Geosilex non-fired bricks presented optimal techno-
logical properties that attain the quality standards.

1. Introduction cycle plants, showed the highest production, with generated 55,546
GWh, 37,038 GWh and 29,787 GWh, respectively, in 2016 [1]. There
Electricity can be generated through renewable energy sources are another sources that generate more production, although the dis-
(hydropower, wind, solar photovoltaic, solar thermal, etc.) as well as tance with the renewable sources is gradually reduced.
non-renewable energy sources (nuclear, coal, fuel/gas, combined cycle, On the other hand, of the main challenges today is the management
cogeneration and waste). In Spain, according to the 2016 Advanced of the large amount of wastes and greenhouse gas emissions generated
Report of the Spanish Electricity System, authored by the business by energy generation, industrial production and consumption models.
group "Red Eléctrica de España", electricity was generated in 2016 by Green technologies or eco-friendly production models should be the
renewable sources amounting 41.1%, while by non-renewable sources basic pillars to develop a circular economy. All efforts should focus on
was 58.9%. There is a decrease compared to the year 2015, in which the development of ecological technologies that reduce environmental
63.1% of electricity was generated through non-renewable sources. adverse effects and improve the development of our society. Thanks to
Within the non-renewable energy sources to generate electricity the technological development, human life has improved, however, a large
nuclear power, the thermoelectric power plants of coal and combined amount of by-products and waste are generated. They are not only

⁎
Corresponding author.
E-mail address: [email protected] (D. Eliche-Quesada).

https://doi.org/10.1016/j.ceramint.2017.12.039
Received 9 November 2017; Received in revised form 4 December 2017; Accepted 5 December 2017
0272-8842/ © 2017 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Please cite this article as: Eliche Quesada, D., Ceramics International (2017), https://doi.org/10.1016/j.ceramint.2017.12.039
D. Eliche-Quesada et al. Ceramics International xxx (xxxx) xxx–xxx

Fig. 1. Flowchart of producing C-CFA clay fired

Clay + Coal fly ash Geosilex + Coal fly ash bricks and silica-calcareous non-fired bricks.
(CFA) (CFA)

8-10 wt. % 9-12.5 wt. %

water Solid state mixing water

Compression 10 MPa

Drying 110 ºC Air drying 24 h

Cured in water at 20 ° C 28 days

Firing at 1000ºC
Drying 110 ºC (24 h)

C-x CFA fired bricks xCFA-yG silico-calcareous non-fired

bricks

Table 1 more than 9.5 million tonnes of wastes per year with only 20% of them
Chemical composition of clay, coal fly ash (CFA) and geosilex. are used for different applications [3]. In addition, coal-fired power
plants produced approximately 33 million tonnes of CO2 in 2016, sig-
Oxide content (wt%) Clay CFA Geosilex
nificantly lower than 48 million tonnes of CO2 produced in 2015 [1].
SiO2 54.43 53.34 1.93 Coal fly ash mixed with heavy metals and toxins are currently stored in
Al2O3 12.36 21.02 1.13 landfills and ash lagoons [4]. Thus, it can result a risk to the sur-
Fe2O3 4.58 7.20 0.12 rounding environment causing significant environmental impacts.
CaO 8.76 3.77 67.16
MgO 2.46 1.57 0.09
A considerable effort is being made worldwide on research con-
MnO 0.03 0.05 – cerning the reuse of coal combustion fly ashes as a source of alternative
K2O 3.37 1.87 – raw materials to produce new materials, such as cement, concrete
TiO2 0.60 0,90 0.04 [5–9], zeolites [10,11], glass-ceramics [12–15], adsorbents for cleaning
P2O5 0.11 0.40 0.01
of flue gas, lightweight aggregate, road subbase [16] and clay bricks
SO3 0.68 0.82 1.62
ZnO 0.026 – – [17–20]. The substitution of coal by biomass as fuel causes the gen-
SrO 0.027 – – eration of other biomass ash whose use has also been studied in the
ZrO2 0.033 – – manufacture of ceramic clay bricks as rice husk ash [21–23], sugarcane
Cl – – 0.03 bagasse ash [22,23], fly olive pomace ash [24,25] and fly pine-olive
Cu – 0.01 –
pruning ash [26].
Cr – 0.0–2 –
Ni – 0.02 – On the other hand, fly ash has pozzolanic activity. Thus, its vitreous
Rb – 0.01 – phase can react with lime to form hydration products that contribute to
Zn – 0.02 – the development of the mechanical strength in cementitious systems.
Sr – 0.14 –
The lime manufacturing process produces large CO2 emissions due to its
Ba – 0.23 –
Pb – 0.01 – chemical transformation and the amount of energy required for in-
LOIa 12.51 4.74 27.76 cineration at high temperatures.
Another residue is hidrated lime [Ca(OH)2]. It is generated by
a
LOI: ”Los on ignition”, weigth loss after firing at 1000 ºC. acetylene industry and it has very interesting characteristics for its
reuse. Concerning the applications of this residue are their use as raw
harm people, but also the environment [2]. material in the construction sector and, more specifically, in the
Coal is the most complex and most abundant fossil fuel in the world. ceramic industry. This is because this industry is able to use different
Generally, the calorific value of a fuel is directly related to their content processing materials practically without implementing changes in the
of carbon and hydrogen. The other components contribute to reduce production process [27–32]. The objective of this work is to investigate
heat output and generate by-products whose environmental influence is the use of coal fly ash (CFA) as raw material for the manufacture of two
often negative. By observing coal as a fuel, two fractions can be dis- construction materials: fired clay bricks and silico-calcareous non-fired
tinguished: a) the carbonaceous matter, which contributes the energy bricks. Fired clay bricks were manufactured using clays from the Bailén
content, and b) the sterile fraction, which is constituted by water and (Jaén, Spain) area and considerable amounts of CFA waste ratios
mineral material which is normally released as ash. A thermal power (10–50 wt%). Silico-calcareous non-fired bricks were prepared using
plant with a capacity of about 1000 MW, with an operation of 6600 two wastes as raw material: coal fly ash (CFA) and “geosilex” (G), a
equivalent hours per year, generates some 69,000 tons of slag and hidrated lime residue which comes entirely from acetylene industry.
383,000 tons of fly ash. The amount of 377,000 tons of fly ash particles Different proportions coal fly ash (80–20 wt%) – geosilex (20–80 wt%)
are captured by filters, usually by electrostatic precipitators; which were investigated. It is a novelty applying a calcium-rich waste to get
means a solid waste generation of, approximately, half a million tons coal fly ash-geosilex unfired bricks.
per year per plant [3]. The thermoelectric plants in Spain, generate

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CFA as a source of silica, and geosilex (G) as a source of lime for silica-
calcareous bricks.
The clay was supplied by the company Arcillas Bailén S.L., (Bailén,
Jaén, Spain). For this work, three different types of clays were mixed in
different percentages to achieve the mixture most used in the local
cluster industry of ceramic brick construction: 30 wt% red, 30 wt%
yellow and 40 wt% black clay. As received from the quarry, it was first
dried at 100 º C for 24 h to remove moisture and subsequently crushed
and ground to obtain particle sizes below 500 µm.
The coal fly ash (CFA) comes from a conventional thermal power
plant located in Carboneras, Almería (Spain). The ashes were received
with a very homogeneous particle size, so they were used without
subjecting them to any treatment.
Geosilex (G) is a waste from the acetylene industry and it has been
used as a source of calcium hydroxide (portlandite). The waste has been
supplied by the company Geosilex Trenza Metal S.L. The geosilex waste
was supplied in paste and subjected to a drying process at 80 °C using
an oven to remove moisture. After drying, this residue was ground by
ball milling to obtain a very fine white powder.

2.2. Characterization of raw materials

The pH of the samples was determined using a pH-meter PCE-

PH20S of PCE instruments. The organic matter content was determined
following ASTM D-2974 [33]. Carbonate content (expressed as calcium
carbonate) was determined by calcimetry in a Bernard calcimeter. For
bulk density a volumetric flask (Le Chatelier) was used. The Specific
Surface Area was measured by the Blaine Air-Permeability Method
[34].
A laser diffractometer Malvern Mastersizer 2000 was used to mea-
sure the particle size distribution of raw materials.
Raw materials were evaluated by X-ray diffraction to know their
crystalline components, using an X′Pert Pro MPD automated dif-
fractometer (PANalytical), equipped with Ge (111) primary mono-
chromator using CuKα radiation (λ = 1.5406 Å) coupled with an
X′Celerator detector. The chemical analysis of the raw materials was
carried out using X-Ray Fluorescence (XRF) (Philips Magix Pro equip-
ment, PW-2440 model). Finally, a CHNS-O analyzer from Thermo
Finnigan (Analyzer Flash model EA 1112) was used to evaluate the
content of carbon, hydrogen, nitrogen and sulphur of raw materials.

2.3. Preparation of clay-coal fly ash fired bricks and coal fly ash-geosilex

calcium silicate non-fired bricks

The ceramic fired bricks were prepared by mixing different per-

centages of the coal fly ash (0–50 wt%) and clays. For each of these
percentages (0%, 10%, 20%, 30%, 40% and 50%) ten pieces of each
series were prepared, in order to perform a statistical calculation.
Another series of pure clay was used as reference control bricks. The
amounts of CFA and clay were dry mixed and later water (8–10 wt%)
was added until achieving a good homogenization and adequate plas-
Fig. 2. XRD patterns of raw materials (a) raw clay; (b) coal fly ash and (c) geosilex.
ticity. Once the kneading process was carried out, the specimens were
moulded at 10 MPa using a laboratory press Morh & Federhaff Ac
Table 2 Mannhem. Specimens with 30×10 mm cross sections and length of
pH values, surface area (Blaine) and relative density of raw materials.
60 mm were obtained. Green samples were fired in a laboratory furnace
Raw materials pH Surface area (cm2/g) Relative density (kg/m3)
at a rate of 3 ºC/min up to 1000 ºC for 4 h. Samples were then cooled to
room temperature. The fired specimens were designated as C-xCFA
CFA 9.3 4273 2480 where x it is the coal fly ash content (in wt%).
Geosilex 12.5 6224 2378 On the other hand, silica- calcareous bricks were made mixing CFA
and geosilex (G) as cementing agent. The CFA was dry mixed with G in
different weight ratios (80-30 CFA wt%). To obtain the silica-calcareous
2. Materials and methods
specimens, CFA and G were dry mixed and water (9–12.5 wt%) was
added to give enough plasticity for the compression molding stage at
2.1. Raw materials
10 MPa. Subsequently the green pieces were dried to remove humidity
for 24 h at 105 °C and then subjected to a curing step by immersing the
The materials used were clay, coal fly ash (CFA) for clay bricks and
pieces in water at room temperature (20 °C) for 28 days, in accordance

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Table 3
Organic matters content, carbonate content and CNHS analysis of raw materials.

Raw material Organic matter (%)a Carbonate content (%) %C %H %N %S

Clay 2.29 ± 0.09 7.36 ± 0,33 2.25 ± 0.01 0.34 ± 0.004 0.05 ± 0.002 0.032 ± 0.008
CFA 2.25 ± 0.07 11.98 ± 0,58 4.01 ± 0.15 0.037 ± 0.000 0.05 ± 0.001 0.121 ± 0.008
Geosilex 3.12 ± 0.12 16.6 ± 0,55 1.01 ± 0.02 2.71 ± 0.01 0.09 ± 0.007 0.025 ± 0.009

a
Determined in accordance with ASTM D-2974.

Clay (a)

1
2

20 µm

Spectrum 1 Spectrum 2

Fig. 3. SEM-EDS of (a) raw clay; (b) coal fly ash and (c) geosilex.

with UNE-EN 12390-2 standard [35]. The final stage of these silica- by capillarity was determined according to UNE-EN 772-11 standard
calcareous bricks was a drying in oven at 105 °C until constant [38]. Bulk density was determined by the Archimedes method. The
weighing. The samples were designated as xCFA-yG where x denoted water absorption values were determined according to UNE-EN 772-21
the CFA wt% content and the G content (wt%). standard [39]. Tests on compressive strength were performed according
Fig. 1 shows the flowchart of preparing clay fired bricks and silica- to standard UNE-EN 772-1 [40] using a laboratory press (MTS 810
calcareous non-fired bricks. Material Testing Systems).
In order to know the characteristic absorption bands of the silica-
calcareous bricks and to know their characteristic chemical groups,
2.4. Characterization of fired clay bricks and calcium silicate non-fired measurements of FTIR were made in an equipment (FTIR Bruker Tensor
bricks 27). The samples were analyzed with the method of attenuated total
reflection (ATR) to avoid spectrum saturation. All the spectra were
The dimensions of the shaped specimens were measured according obtained in absorbance mode, in the range 4000–400 cm−1 and with a
to the standard UNE-EN 772-16 [36]. Linear shrinkage of fired clay resolution of 4 cm−1.
bricks was obtained according to ASTM C326 standard [37]. Weight The development of porosity and microstructures in the raw mate-
loss of fired clay bricks was obtained by difference between the weight rials and specimens were evaluated using Scanning Electron
after drying at 110 ºC and after firing at 1000 ºC. The water absorption

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CFA (b)

50 µm

20 µm 20 µm

Spectrum 1 Spectrum 2

Geosilex (c)

30 µm

Fig. 3. (continued)

Microscopy and Energy Dispersive X-ray Spectroscopy (SEM/EDS) 3. Results and discussion
using a high-resolution transmission electron microscope JEOL ( model
SM 840) combined with EDS chemical analysis (20 kV). Samples were 3.1. Characterization of raw materials
placed on an aluminum grate and coated with carbon using an ion
sputtering device JEOL (model JFC 1100). The clay presents a chemical composition similar to that of clays
The environmental viability of fired and non-fired bricks was stu- used in the manufacture of industrial bricks. The chemical analysis by
died by leaching of heavy metals using the toxicity characteristic XRF indicates that silica (54.4 wt%), aluminum oxide (12.4 wt%) and
leaching procedure (TCLP) according to EPA method 1311 [41]. The calcium oxide (8.8 wt%) are the main constituents of the clay, pre-
concentrations in the filtrate were measured with an Inductively Cou- senting a lower amount of iron oxides (4.6 wt%), oxides of potassium
pled Plasma-Atomic Emission Spectrometer (ICP-AES Agilent 7500). (3.4 wt%) and magnesium oxides (2.5 wt%) (Table 1).
Coal fly ashes are mainly composed (> 70 wt%) of: SiO2 (53.3 wt%)
and Al2O3 (21.0 wt%). The oxides Fe2O3, CaO, K2O and MgO, in de-
creasing order of abundance, are present in percentages of 1–8 wt%,
while the sulfate content is low, 0.8 wt%. The CFA composition is

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4 carbon content of geosilex (1.01 wt%) comes from the decomposition of

CFA calcite, and contains a small amount of sulphur.
Geosilex SEM micrograph of clay (Fig. 3a) indicates that this raw material is
3 composed of particles of different angular sizes and, to a lesser extent,
Clay
spherical sizes. The EDS analysis indicates some areas rich in silica and
others rich in aluminosilicates.
Volume (%)

The CFA presents a powdered appearance, with brown coloration,

2 due to its iron content. The SEM micrograph allows observe numerous
irregular glassy particles and hollow compact spherical particles, called
cenospheres, of various sizes, being composed mainly of silica and
1 alumina (Fig. 3b). In the micrograph it can see a type of geometry
characteristic of the CFA, called pleurospheres or cenospheres with
other smaller spheres inside. Its chemical composition is rich in Si, Al
and Fe. The particles with a high content of calcium are spherical and
0
0.01 0.1 1 10 100 1000 10000 smooth as granules, while those with higher iron content are more
vitreous spheres with a rough surface.
Particle size (μm)
SEM micrograph of geosilex waste (Fig. 3c) shows irregular and
Fig. 4. Particle size distribution of raw materials: raw clay, coal fly ash (CFA) and geo- spherical particles with a great variety of sizes. The EDS analysis shows
silex. that all particles are composed mainly of calcium with traces of Si, Al,
and S.
Table 4 The particle size distribution of the raw materials is presented in
Particle size distribution of raw materials: clay, coal fly ash and geosilex. Fig. 4. The particle sizes of the CFA are finer than those of the clay and
the geosilex as shown by the mean particle size, D50, ranging from
Particle size distribution (mm) Clay (wt% CFA (wt%) Geosilex (wt%)
19.61 µm for CFC being 21.84 µm for geosilex and 24.37 µm for the
Clay content < 0.002 7.10 9.56 4.35 clay. The percentage of fine particles (< 2 µm) varies from 4.35% by
Silt content (0.002–0.063) 69.22 69.62 74.68 volume for geosilex to 9.56% by volume for CFA (Table 4). All the raw
Sand content (0.063 −2) 23.67 20.82 20.97 materials are made up mainly of particles of the size of silt and the sand.
The pozzolanic activity increases as the specific surface of the particles
increases, as well as the rate of the hydraulic reaction [42].
similar to the clay used as raw material, so its use can reduce the
consumption of raw materials in the manufacture of ceramic bricks. The
3.2. Characterization of C-CFA fired bricks and CFA-G non-fired bricks
CFA according to their composition can be classified as class F ashes,
silico-alumina of pozzolanic character. The loss of ignition of 4.7 wt%
After the firing process the bricks change in color, mass and di-
indicated a low content of unburnt elements.
mensions. The color of the bricks before the firing process was greyish
The geosilex is composed mainly of CaO (67.2 wt%), presenting a
brown and gray as the content in CFA increases. After the firing process,
high loss ignition (27.7 wt%) due to the easy carbonation of the residue.
due to the content of iron oxides, the bricks presented a red-orange
Fig. 2a shows the X-ray diffractogram of the raw clay. The pre-
color, independent of the amount of incorporated residue. Defects, such
dominant phases correspond to quartz, calcite and dolomite. In addi-
as bloating and fissures, or the defect known as black core (due to the
tion, small diffraction peaks assigned to feldspar and a small amount of
incomplete combustion of the organic matter) were not observed
phyllosilicates and gypsum are observed. The CFA is constituted by
(Fig. 5a). Samples with compositions 80–30 wt% CFA (20–70 wt%
partially vitreous mineral particles due to the high temperature of the
Geosilex) have been prepared for the silica-calcareous non-fired bricks
combustion process and to the fast cooling with a smaller proportion of
(Fig. 5b). Samples with compositions outside this range underwent
crystalline phases, as indicated by the pattern of XRD (Fig. 2b). The
cracking in the water-curing process for 28 days (Fig. 5c). This could be
crystalline components present in coal fly ash are mullite
due to the alkali-carbonate expansion reactions when water absorption
(3Al2O3·2SiO2), quartz and hematite, being observed a relative lower
occurs due to an increase in volume, causing the material to rupture
proportion of gypsum, calcite and calcium oxide.
[43].
The XRD data of the geosilex residue (Fig. 2c) indicate that this is
mainly composed of portlandite [Ca(OH)2], with identification of dif-
3.2.1. Linear shrinkage and loss on ignition of C-CFA fired bricks
fraction peaks of calcite (CaCO3), indicating the carbonation of the
It should be noted that linear shrinkage reflects the expansion /
residue.
contraction behaviour during the firing treatment. It depends on the
Considering the pH, both the CFA and the geosilex wastes have an
fluxing agents, or the amount of liquid phase formed during the firing
alkaline pH (Table 2). The bicarbonates, carbonates, oxides and hy-
process, which reduces the space between particles, and the gaseous
droxides present in the raw materials are responsible for the alkalinity.
components decomposition, which expand the pores. The linear
High pH values are required for the pozzolanic reaction between the
shrinkage of the clay was −0.24% showing an expansion behaviour.
silica and the alumina of the CFA, and the lime of the geosilex to take
Addition of CFA decreased linear shrinkage as increasing amounts of
place. Cementitious materials are formed of a similar nature to those
waste (Table 5). With the addition of 20 wt% CFA a slight expansion
obtained by the hydration of the cement.
occurs. However, with the addition of higher amounts of waste
The specific surface values of the residues obtained by the Blaine
(30–50 wt%) a contraction occurred. This could be due to the lower loss
method [34] are higher for geosilex than for coal fly ash, both of which
on ignition (LOI) of CFA waste (4.7%) compared to the LOI of the clay
have similar relative density.
(12.5%) (Table 3), indicating a higher release of gases in the clay.
The CHNS analyses of clay, CFA and geosilex wastes are shown in
The weight loss on ignition of the clay at 1000 °C was 10.85%. The
Table 3. The C content of the CFA is low (4.0 wt%), which indicates an
addition of higher percentages of the CFA waste decreased the loss of
efficient combustion of the thermal power plant. The carbon content in
ignition, due to the lower LOI of the CFA (Table 5). The weight loss
the clay and the CFA is equivalent to the organic carbon present in the
could be assigned to the dehydroxylation reactions of the silicates, the
raw materials and to that coming from the decomposition of the car-
combustion of the organic matter and the decomposition of the car-
bonates. The nitrogen content is very low and contains sulphur. The
bonates.

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Fig. 5. (a) C-CFA fired bricks and (b) CFAx-Gy non-fired bricks

C-10CFA
C-10CFA (a) (x:80–30 wt% and y 20–70 wt%) and (c) 20CFA-80 G and 10CFA-90 G
non-fired bricks.

C-20CFA C-20CFA

C-30CFA C-30CFA

C-40CFA C-40CFA

C-50CFA C-50CFA

80CFA-20G
(b)

70CFA-30G
20CFA-80G 10CFA-90G
(c)

60CFA-40G

50CFA-50G

40CFA-60G

30CFA-70G

3.2.2. Bulk density, apparent porosity and water absorption of C-CFA fired fired bricks, being slightly reduced with additions of more than 30 wt%
bricks and CFA-G non-fired bricks of waste. The fired clay bricks presented the highest degree of densi-
The addition of CFA waste hardly changed the bulk density of the fication having a bulk density of 1881 kg/m3. The bulk density is

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Table 5 3.5

Water absorption by capillarity

Linear shrinkage and loss on ignition of C-xCFA fired bricks.
(a)
Fired bricks Linear shrinkage (%) Loss on ignition (%)
3

C −0.239 ± 0.053 10.85 ± 0.09 2.5

C−10CFA −0.056 ± 0.022 10.20 ± 0.05

(kg/m2min)
C−20CFA −0.036 ± 0.020 9.56 ± 0.04
C−30CFA 0.008 ± 0.041 9.17 ± 0.06 2
C−40CFA 0.148 ± 0.045 8.60 ± 0.10
C−50CFA 0.034 ± 0.066 7.90 ± 0.12
1.5

2000 35 1
(a)

Apparent porosity /Water

30
1800 0.5

absorption (%)
Bulk density (kg/m3)

25
0
1600 20 0 10 20 30 40 50

15 Coal fly ash content (wt %)

1400
Bulk density
10 3
1200 Apparent porosity
5
(b)

Water absorption by capillarity

Water absorption
2.5
1000 0
0 10 20 30 40 50
2
Coal fly ash content (wt %) (kg/m2min)
45 1.5
(b)
Apparent porosity /Water

40
1400 35 1
absorption (%)
Bulk density (kg/m3)

30
25
0.5

20
1200 0
15 80 70 60 50 40 30
Bulk density
10
Apparent porosity Coal fly ash content (wt %)
Water absorption 5
Fig. 7. Water absorption by capillarity as a function of coal fly ash (wt%) for (a) C-CFA
1000 0 fired clay bricks and (b) silica-calcareous CFA-G non-fired bricks.
80 70 60 50 40 30
Coal fly ash content (wt %) produced by heating increase the ceramic matrix volume during the
firing process. The organic matter content was 2.29% and 2.25% and
the carbonates content was 7.36% and 11.98% for clay and CFA waste,
Figure 6 respectively. When the temperature increased from room temperature
Fig. 6. Bulk density, apparent porosity and water absorption as function of coal fly ash to 1000 °C, both the organic matter combustion, at approximately
(wt%) for (a) C-CFA fired clay bricks and (b) silica-calcareous CFA-G non-fired bricks. 550 °C, and the carbonate decomposition starting at approximately
800 °C, generate CO2. Samples with higher clay content contained a
higher content of fluxing agents. This fact increases the amount of li-
reduced to 1732 kg/m3 for the sample with the highest amount of CFA
quid phase and its formation at a lower temperature that during the
waste, 50 wt%, a reduction of 7.9%. The apparent porosity increased
fired process, producing molten material that compresses the interstices
from 28.3% for control bricks to 32.6% for C-50 CFA bricks. The open
[44,45]. This process generates a higher density and a lower porosity in
porosity was evaluated by the water absorption data, being a key factor
the bricks containing only clay, prevailing the fluxing effect on the pore
for the bricks durability. Water absorption followed the same tendency
formed due to the gas decomposition. As the CFA content increases, the
as the apparent porosity with the addition of CFA regarding to the re-
content of the fluxes is reduced, resulting a slight lower densification
ference bricks. The water absorption of the brick without waste was
and a greater apparent porosity in the samples containing the CFA
15.7%, reaching the maximum value of 18.8%, with the incorporation
waste.
of 50 wt% of CFA (Fig. 6a). This behaviour could be due to the chemical
For the non-fired bricks obtained by the cementation method, after
composition of the clay and the CFA waste. Si and Al as SiO2 and Al2O3,
curing in water for 28 days at room temperature (Fig. 6b), the bulk
and the weight percentages of the clay and the CFA was 66.8% and
density is lower, decreasing by increasing the geosilex content. Thus the
74.4%, respectively. These elements are forming the skeleton of
80CFA-20 G non-fired bricks has a bulk density of 1481 kg/m3 de-
ceramic materials. In addition, the raw materials are composed of
creasing to 1341 kg/cm3 for 30CFA-70 G specimens, resulting a re-
fluxes, alkaline and alkaline earth oxides that lower the formation
duction of 9.5% with the incorporation of 70 wt% geosilex. This result
temperature of the liquid phase (K2O, MgO and CaO) in proportions of
can be associated to the lower relative density of the geosilex waste
14.6% and 7.2% for clay and CFA, respectively. Gas components

8
D. Eliche-Quesada et al. Ceramics International xxx (xxxx) xxx–xxx

70 (2378 kg/m3) with respect to CVC waste (2480 kg/m3). The apparent
(a) porosity of the silica-calcareous non-fired bricks ranges from 37.2% for
Compressive stength (MPa)

60 70CFA-30 G non-fired bricks up to 34.68% for 40CFA-60 G specimens.

It is followed not any trend. The water absorption slightly increased
with the amount of geosilex, varying this property from 24.42% for
50
80CFA-20 G to 26.64% for 30CFA-70 G non-fired bricks.
The ASTMC67-07a standard [46] establishes the maximum value of
40 water absorption depending on the main purpose of the bricks and the
environment to which they are exposed. For bricks exposed to severe
30 weather conditions, the water absorption has to be less than 17%. For
bricks exposed to moderate weather conditions, water absorption may
20 not exceed 22%, and no limit is set for bricks not exposed to the
weather. The present results indicated that fired clay bricks containing
up to 30 wt% CFA met the standards for use in severe weather condi-
10
tions, while fired clay bricks with higher contents in CFA (40 and 50 wt
%) can be used for moderate meteorological conditions. However, si-
0 lica-calcareous non-fired bricks only could be used when they are not
0 10 20 30 40 50 exposed to the outdoor. High water absorption values could lead to the
Coal fly ash content (wt %) solubilization of soluble sulphates, resulting in efflorescence when they
were used under very humid conditions.

60
3.2.3. Water absorption by capillarity of C-CFA fired bricks and CFA-G
(b) non- fired bricks
Compressive strength (MPa)

50 The water absorption by capillarity of the bricks and the water

power retention of the mortar determine the union of the bricks and the
mortar. As can be seen in Fig. 7a, for C-CFA fired bricks, the addition of
40 carbon fly ash increased the water absorption by capillarity from
2.81 kg/m2 min in the control samples, with 100% of clay, to 3.26 kg/
m2 min for C-50CFA fired bricks.
30
In Fig. 7b, it can be observed that the water absorption by capillarity
for the specimens obtained by the CFA-G cementing method did not
20 follow a trend. Water absorption by capillarity was maximum, 2.64 kg/
m2min, for the 80CFA-20 G non- fired bricks, obtaining values between
1.00 kg/m2 min and 1.65 kg/m2 min for the rest of compositions.
10 According to regulation RL-88 [47], water absorption by capillarity
values higher than 4.5 kg/m2 min should be avoided to ensure adequate
curing of the mortar, since a brick with high water suction values could
0
dehydrate the mortar. For this reason, it is recommended to wet the
80 70 60 50 40 30
bricks prior to placement when the water absorption by capillarity
Coal fly ash content (wt %) values are greater than 1.5 kg/m2 min. As can be seen, all the bricks
agree with the regulations although they should be moistened before
Fig. 8. Compressive strength as a function of coal fly ash (wt%) for (a) C-CFA fired clay they are placed.
bricks and (b) silica-calcareous CFA-G non-fired bricks.

3.2.4. Compressive strength of C-CFA fired bricks and CFA-G non- fired
Table 6 bricks
USEPA TCLP test results (ppm) of fired clay bricks and silica-calcareous non- fired bricks Fig. 8 shows the results of the compression tests performed on both,
and the maximum concentration of contaminants for toxicity characteristics.
the C-CFA fired bricks (Fig. 8a) and the silica-calcareous CFA-G non-
Component Fired clay bricks Silica-calcareous non- Limits US- fired bricks obtained by the cementation method (Fig. 8b).
(ppm) fired bricks EPA (ppm) In the case of fired clay bricks, the value of the compressive strength
decreased with increasing content of coal fly ash waste. It is noteworthy
C C-50CFA 80CFA- 30CFA-
that the addition of 10–20 wt% of CFA to clay composition did not
20 G 70 G
produce a significant decrease in the compressive strength with respect
As 0.025 0.549 0.00081 0.00114 5 to control bricks. However, the incorporation of higher amounts of CFA
Ba 0.096 0.171 1.449 2.762 100 residue (50 wt%) produced a decrease in compressive strength up to
Cd 0.0002 0.00004 0.00004 0.00003 1
26.25 MPa, which represents approximately a 56% decrease in this
Co 0.001 0.00631 0.00043 0.00145 –
Cr 0.115 0.0174 0.00462 0.00007 5 properties with respect to control bricks (59.34 MPa). These data are in
Cu 0.277 0.116 0.143 0.135 5 agreement with the obtained values of bulk density, apparent porosity
Ni 0.010 0.008 0.002 0.008 – and water absorption. The specimens with lower bulk density, higher
Pb 0.0001 0.0002 0.0001 0.0025 5 apparent porosity and higher open porosity had lower values of this
Sb 0.0010 0.0022 0.0019 0.00006 –
mechanical property. It is explained considering that irregular elon-
Se 0.005 0.0221 0.0506 0.0086 1
V 0.138 0.2660 0.0047 0.0003 – gated pores can act as stress concentrators that decrease the compres-
Zn 0.004 0.0028 0.0007 0.0032 300 sive strength.
Mechanical strength results in the silica-calcareous CFA-G non-fired
bricks obtained by the cementation method are not only attributed to
densification, as in the case of fired bricks, but also to the cementitious
products formed in the pozzolanic reaction.

9
D. Eliche-Quesada et al. Ceramics International xxx (xxxx) xxx–xxx

Fig. 9. SEM micrographs of C, C-20CFA and C-

50CFA fired bricks.
C

10 µm

C-20CFA C-50CFA

20 µm
90 µm

Fig. 10. SEM micrographs of 80CFA-20 G; 50CFA-

80CFA-20G 50CFA-50G 50 G and 30CFA-70 G non-fired bricks.

10µm
80µm

30CFA-70G

20µm

The results of the compressive strength test showed that 60CFA- compositions, compressive strength values of about 45 MPa are ob-
40 G, 50CFA-50 G and 40CFA-60 G non-fired bricks presented the op- tained, being reduced to about 26–32 MPa for compositions in-
timum amount of materials (SiO2 and Al2O3) present in the CFA and corporating a higher amount of coal fly ash waste (80–70 wt%) and a
calcium hydroxide (present in the geosilex) to give rise to a higher lower amount of coal fly ash waste (30 wt%). In the former, this loss of
fraction of calcium silicate hydrates (CSH) and calcium aluminate hy- mechanical properties may be due to a Ca(OH)2 deficiency due to an
drates (CASH). Both phases are responsible for the increase in the va- insufficient amount of geosilex, while in the latter it may be due to a
lues of mechanical strength of the silica-calcareous bricks. For these deficiency of SiO2 and Al2O3 due to a small amount of CFA waste.

10
D. Eliche-Quesada et al. Ceramics International xxx (xxxx) xxx–xxx

*
* calcareous non-fired bricks, leaching tests have been carried out using
300CFA-70G ●
(b) the 1311 method established by the United States Environmental
*
□ + ●
+
□
* * Protection Agency (USEPA). Samples of control fired clay bricks and
● + ● + *
● with the highest carbon fly ash content (C-50CFA), silica-calcareous
500CFA-50G non-fired bricks, with the extreme compositions in both residues CFA,
and Geosilex (80CFA-20 G and 30CFA-70 G), were subjected to the test.
As can be seen in Table 6, heavy metals concentrations in all cases were
700CFA-30G
below the limits established by the USEPA. So, it can be concluded that
CFA were suitable raw materials for the manufacture of both clay fired
bricks and silica-calcareous non-fired bricks and its use will not produce
environmental problems associated with heavy metals.
800CFA-20G
3.2.6. Microstructural study (SEM) of C-CFA fired bricks and CFA-G non-
fired bricks
The textural evolution and porosity of C-CFA fired bricks and silica-
10 20 300 2θ (º) 40 550 60
calcareous CFA-G non-fired bricks were analyzed by SEM. In Fig. 9 it
22θ (degreess) can be seen that the porosity of the fired clay barely changes with the
addition of low amounts of CFA, 20 wt%, being this change more
substantial when 50 wt% of CFA waste was added. The porosity of the
samples was mainly open porosity, and small closed pores could be
observed. The amount of liquid phase and its viscosity was not suffi-
cient to efficiently close the open porosity, observing an incomplete
glass phase. The low melting capacity of the CFA waste caused high
incorporations of residue to produce a smaller amount of glassy phase.
Therefore, the pores were not filled, connected, giving rise to a greater
open porosity according to the water absorption data. There was a
predominance of the pore formation effect due to the low amount of
flux materials present in the CFA waste. In addition, in the samples
containing CFA cenospheres present in the residue could be observed.
In the SEM micrographs (Fig. 10) of the silica-calcareous non-fired
bricks the hydrated calcium silicate gel was observed, with little crys-
tallinity and amorphous appearance, mainly in samples with a mean
CFA content (50 wt%). In the sample with the highest ash content
(50CFA-50 G), a large number of unreacted cenospheres were observed.
Fig. 11. XRD patterns of (a) fired clay bricks. + quartz; □ augite; • gehlenite and (b)
As geosilex was added to the CFA, an increase of the gel phase was
silica-calcareous non-fired bricks.+ quartz; □ mullite;*portlandite; • calcite;■CHS. observed, mainly in the sample 50CFA-50 G. New additions of geosilex
produce a reduction of the hydrated calcium silicate phase, observing
the portlandite phase [Ca(OH)2], unreacted, that crystallizes in hex-
agonal sheets.

3.2.7. Mineralogical study (XRD) of C-CFA fired bricks and CFA-G non-
fired bricks
The mineralogical composition of C-CFA fired bricks was de-
termined by XRD (Fig. 11a). The incorporation of CFA did not produce
a significant variation in the crystalline mineralogical phases with re-
spect to the control bricks containing only clay. The crystallinity of the
samples increased with the CFA waste content. Quartz is the pre-
dominant phase, although diffraction peaks could also be observed due
to the presence of aluminosilicates, mainly akermanite, tetragonal
gehlenite Al1Ca2Mg0,5O7Si1,5, or tetragonal gehlenite Al1,25Ca1,96 Fe0,12
Mg0,24Na0057Si1,39. The presence of monoclinic augite
Al1388Ca0742Fe0162Mg0016O6Si is also observed.
Fig. 11b shows the diffraction peaks present in the raw materials
with identification of quartz and mullite present in the coal fly ash
waste, as well as calcium hydroxide and calcite of the unreacted geo-
Fig. 12. FTIR spectra of silica-calcareous non-fired bricks. silex. As expected, the samples with higher CFA content presented
higher amounts of quartz and mullite, whereas in the samples with
Compressive strength values of 10 MPa or 20 MPa establishes the higher content of geosilex, a higher intensity of the peaks corresponding
standards EN- 772-1 [40] and ASTM C62-10 [48] for bricks used in to calcite and portlandite were observed. The presence of small dif-
normal and severe weathering, respectively. All fired bricks and silica- fraction peaks were observed in all diffractograms due to their amor-
calcareous non´-fired bricks met the standards. phous character, corresponding to hydrated calcium silicates formed by
the pozzolanic reaction between the silica present in the CFA and the
lime present in the geosilex.
3.2.5. Leaching test of C-CFA fired bricks and CFA-G non- fired bricks
Due to the large amount of pollutants in coal fly ash and to assess 3.2.8. Infrared Spectroscopy (FTIR) of CFA-G non-fired bricks
the degree of immobilization in both clay fired brick and silica- In the Fourier Transform Infrared Spectrometry (FTIR) spectra,

11
D. Eliche-Quesada et al. Ceramics International xxx (xxxx) xxx–xxx

three regions have been of interest (Fig. 12). In the region of mechanical strength of the silica-calcareous non-fired bricks.
3800–3000 cm−1 were observed a band centered at approximately 6. The use of coal fly ash for the manufacture of fired clay bricks and
3645 cm−1 and a very wide band centered at approximately 3410 cm silica-calcareous non-fired bricks did not suppose an environmental
−1
, related to the modes of OH elongation vibration. The first band risk due to leaching of heavy metals.
could be assigned to the free OH present in the portlandite, which in-
creased as the geosilex content increases, while the broad band could be Acknowledgments
assigned to the elongation vibration of the water molecules present in
the CSH gel formed during hydration of raw materials. This work has been funded by the Project “Valuation of various
The second region, between 1800 and 1200 cm−1, showed the types of ash for the obtaining of new sustainable ceramic materials”
presence of a small band centered at 1645 cm −1 and an intense band (UJA2014/06/13), Own Plan University of Jaen, sponsored by Caja
centered at 1420 cm−1. The first one was assigned to the flexion modes Rural of Jaen. The authors thank the companies “Thermal Power Plant
of the water molecules, and the most intense band was attributed to the Litoral SS” and “Geosilex Trenza Metal S.L.” for supplying the ashes and
symmetrical and asymmetric modes of vibration of the (CO3)2-, which geosilex, respectively. Technical and human support provided by CICT
confirmed the presence of carbonates, being more intense as the of Universidad de Jaén (UJA, MINECO, Junta de Andalucía, FEDER) is
amount of geosilex increased, due to the carbonation of this residue. gratefully acknowledged.
The third region, between 1200 and 850 cm−1, showed a wide band
centered at 985 cm −1 characteristic of the SiO2 stretching modes that References
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