Construction and Building Materials 304 (2021) 124506

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Construction and Building Materials

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Application of hard coal combustion residuals in the production of ceramic

building materials
R. Kusiorowski *, A. Gerle , K. Dudek , K. Związek
Łukasiewicz Research Network – Institute of Ceramics and Building Materials, Refractory Materials Division, ul. Toszecka 99, 44-100 Gliwice, Poland

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

Keywords: The combustion of solid fuels results in solid by-products, i.e. slags and ashes. This waste is a potential source of
Coal combustion residuals (combustion waste) many valuable mineral materials that should be used to the maximum extent. The amount of solid waste
Recycling generated in combustion processes depends on the quality of coal and its natural ash content. In addition, the
Clinker ceramics
amount of waste is increased by a portion of unburnt coal depending on the furnace efficiency. The paper
presents the results of research on the application of combustion waste as an additive to the ceramic mass used in
the production of ceramic clinker products. Two furnace slags differing in origin were used in the investigations.
Their physicochemical characteristics and the effect of this waste on the properties of clinker ceramics were
determined. The required test specimens were formed from plastic ceramic masses containing wt. 30% of the
waste. After firing at temperatures ranging from 1100 to 1200 ◦ C, the linear shrinkage, water absorption, open
porosity, apparent density and compressive strength of the obtained materials were determined. The results of
the conducted research indicate that combustion waste can be considered as a valuable secondary raw material
for the production of ceramic clinker products, because it intensifies the sintering process of clinker ceramics.

1. Introduction
The heating period is a time of increased production of waste (ashes
and slags) in the process of power generation for commercial and do­
mestic purposes, i.e. from places fired with coal raw materials. Generally
speaking, this waste is a solid residual after the combustion process. The
main source of such waste is commercial power industry, which gen­
erates significant amounts of combustion by-products every year.
Currently, 80% of domestic power engineering is based on coal. For
example, in the Turów Power Plant, where eight brown coal-fired power
units are in operation, the average annual amount of waste reaches
approximately 2 million tons [1]. At the same time, there are approxi­
mately 3.5 million coal-fired households in Poland. The sector of small
consumers is the second important recipient of power coal, consuming
approx. 20% of coal in the country, which gives approx. 10–14 million
tons of coal annually [2].
Of course, the quantity and quality of the generated waste depends
on the type of coal burned (hard or brown coal) and its individual
properties. Apart from the commercial power industry, which is
responsible for generating the largest amounts of combustion waste, the
second, no less important source of the above-mentioned categories of
waste are coal furnaces from households, local housing communities,
etc. The amount of solid waste generated in small consumers’ furnaces
fired with hard coal depends on the quality of coal and its ash content. In
addition, the amount of waste is increased by the proportion of un­
burned coal, which depends on the efficiency of the furnace.
Waste generated in the coal combustion process is a potential source
of many valuable minerals, which should be used to the maximum
extent. Such materials usually consist – in terms of oxides – of various
amounts of silicon, aluminium, iron, calcium, magnesium, sodium, po­
tassium, titanium or manganese compounds. They are often accompa­
nied by trace amounts of heavy metals [3]. Combustion waste, due to its
chemical composition and properties, does not necessarily have to be
stored, especially that according to the waste management hierarchy,
pursuant to the Act on Waste [4,5], landfilling should be the final so­
lution, and if appropriate possibilities arise, other, less environmentally
harmful methods of waste management should be applied (Fig. 1). The
application of different types of ashes from the commercial power in­
dustry is successfully used in the inorganic binders industry [6]. In
practice there is substantial use of ashes from coal fired power plants in
clinker production of the cement industry [7]. The utilization of fluid­
ized bed combustion fly ashes may be performed in the direction of

* Corresponding author.
E-mail addresses: r.kusiorowski@icimb.pl, robert.kusiorowski@icimb.lukasiewicz.gov.pl (R. Kusiorowski).

https://doi.org/10.1016/j.conbuildmat.2021.124506
Received 2 April 2021; Received in revised form 28 July 2021; Accepted 7 August 2021
Available online 3 September 2021
0950-0618/© 2021 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
R. Kusiorowski et al. Construction and Building Materials 304 (2021) 124506

2. Experimental part

2.1. Raw materials

Two kinds of combustion waste (marked as B and S) from local,

Fig. 1. Hierarchy of waste management.
adapted from [4,5]
fertilizer and soil amendment as well as cement replacement, as light­
weight aggregates and mine backfilling material [8]. One of such
possible directions may be also the use of waste in the production of
building ceramics [9–15]. In particular, the fired clay ceramics are
materials that can tolerate some compositional fluctuations of re-used
materials [16]. Studies on the use of coal combustion residues in fired
clay ceramics have been also presented [17–21], but they concern
mainly on fly ashes from industrial coal power plants. It was shown that
bottom ash from thermoelectric power plant reduces the melting point
of the liquid phase and shows particular features like fluxing agent [16].
As a result the obtained ceramic samples shows decreased water ab­
sorption and open porosity with the increasing amount of introduced
coal combustion by-products.
The aim of the study was to determine the possibility of using
combustion waste from the process of power generating combustion of
hard coal by small consumers as a potential secondary raw material for
the production of building ceramic products with a sintered body.
household boiler houses fired with hard coal were used in the in­
vestigations. The characteristics of the fossil fuel and furnaces from
which the waste was collected for testing have been given in Table 1.
Due to the presence of larger, sintered fragments in the materials, each
of the materials was ground to grain size below 1 mm and homogenized.
The chemical composition of the wastes was determined using XRF
while phase composition by means XRD and the behaviour of the raw
materials during heating were determined using thermal analysis
methods (DTA-TG-DTG). Due to the considerable loss of ignition
(~10%) of the combustion residuals, resulting from the presence of
incompletely burned coal, they were added to the ceramic masses after
additional heat treatment (1200 ◦ C/ 6 h, which was aimed at burning
the residual carbon; marked as BW and SW, respectively).
The illite-kaolinite, lime-free red triassic clay from the “Patoka” de­
posit was used as a plastic material for ceramic building products with a
sintered body (clinker products) [22,23]. The reference mass was based
on a commercial clinker mass used by Patoka Industries Ltd. Sp. z o.o.,
which consists of the above-mentioned clay and the so-called slimming
material in the form of quartz sand and brick flour made from scrap of
clinker products.
2.2. Process of obtaining ceramic materials
Five test masses were prepared from the raw materials – a reference
mass and masses with a 30% content of combustion waste, both raw and
previously burnt (Table 2). For so composed ceramic masses, linear
changes in the material occurring in the process of their firing were
determined by the dilatometric method, and the characteristic temper­
atures were determined using high-temperature microscopy.
After weighing and thoroughly mixing the ingredients in a dried
state, the raw material mixtures were gradually mixed with water until
they were plastic. Before starting the moulding, the masses were
conditioned for 24 h in a tightly closed foil bag in order to homogenize

Table 1
Characteristics of combustion ashes used in the research.
Symbol of waste S B

Origin of waste
Type of fuel
Coal calorific value
Content of ash in coal
Content of sulphur
Description of heating
boiler
local boiler room of the school building in Mikołów, local boiler house of a housing community in Mikołów, Poland, which consists of three
Poland apartment blocks
Pea type hard coal Pea type hard coal
5–25 mm 5–25 mm
KWK Chwałowice (Chwałowice Coal Mine) KWK Wesoła (Wesoła Coal Mine)
minimum 27 MJ/kg minimum 28 MJ/kg
5.5 % 5.0 %
0.66 % 0.60 %
Steel water boiler type Beta 75 Stelmark boiler with a piston feeder
Power: 75 kW Power: 120 kW
Heating area: 7.5 m2 Heating area: 11 m2
Max working pressure: 0.2 MPa Max working pressure: 0.15 MPa

Table 2
Composition of ceramic masses and their basic properties.
Symbol of Ingredient content; wt. % Mixing water; Linear drying shrinkage;
mass % %
Commercial clinker mass based on „Patoka” “Patoka” Waste B Waste S Waste Waste
clay clay BW SW

0 100 14.3 ± 0.1 4.9 ± 0.4

B 70 30 11.2 ± 1.7 1.6 ± 0.2
S 70 30 12.5 ± 1.5 1.9 ± 0.3
BW 70 30 14.3 ± 0.2 4.3 ± 0.4
SW 70 30 14.3 ± 0.1 4.1 ± 0.9

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R. Kusiorowski et al. Construction and Building Materials 304 (2021) 124506

Table 3 the humidity. Next, using a laboratory screw press, a band of ceramic
Chemical composition of combustion residuals. mass with a round cross-section (diameter approx. 30 mm) was
Component/ Content; wt.% extruded, from which smaller fragments were cut to form cylindrical test
waste samples, having a height of approx. 30 mm. After forming, the samples
B S BW SW
were dried – first freely at ambient temperature, and, then, in a labo­
L.O.I. at 1025 ◦ C 12.42 ± 7.55 ± 0.76 0.15 ± 0.02 0.22 ± 0.02 ratory drier with a slow temperature increase to 110 ◦ C. The dried
1.24
SiO2 37.29 ± 35.55 ± 42.67 ± 37.87 ±
samples were next fired in an electric silite furnace at three pre-set
0.93 0.89 1.07 0.95 temperatures (1100, 1150 and 1200 ◦ C) with a holding time of one hour.
Al2O3 23.16 ± 26.70 ± 26.39 ± 28.81 ±
0.58 0.67 0.66 0.72
Fe2O3 10.38 ± 11.30 ± 11.35 ± 12.30 ± 2.3. Research methodology
0.52 0.57 0.57 0.62
TiO2 1.00 ± 0.10 1.09 ± 0.11 1.11 ± 0.11 1.17 ± 0.12
CaO 7.09 ± 0.35 8.54 ± 0.43 7.99 ± 0.40 9.47 ± 0.47 The chemical composition was determined by the X-ray fluorescence
MgO 4.02 ± 0.20 4.67 ± 0.23 5.21 ± 0.26 5.29 ± 0.26 method (XRF) in accordance with PN-EN ISO 12677: 2011 entitled:
K2O 0.64 ± 0.32 0.87 ± 0.44 0.78 ± 0.39 0.92 ± 0.46 “Chemical analysis of refractory products by X-ray fluorescence (XRF) –
Na2O 2.33 ± 0.23 1.91 ± 0.19 2.72 ± 0.27 2.03 ± 0.20
Fused cast-bed method”. The tests were performed on an XRF PAN­
P2O5 0.19 ± 0.10 0.51 ± 0.26 0.22 ± 0.11 0.55 ± 0.28
MnO 0.19 ± 0.10 0.22 ± 0.11 0.22 ± 0.11 0.25 ± 0.13 alitical Magix PW-2424 spectrometer.
Cr2O3 0.03 ± 0.02 0.03 ± 0.02 0.01 ± 0.01 0.07 ± 0.04 The phase composition of the raw materials used in the research and
ZrO2 0.03 ± 0.02 0.10 ± 0.05 0.01 ± 0.01 0.01 ± 0.04 of the obtained ceramics was determined by the X-ray diffraction
method (XRD) in accordance with the relevant parts of the PN-EN 13925
standard. The tests were carried out using an X’Pert PRO diffractometer

Fig. 2. Results of thermal analysis of raw combustion waste: waste B (a); waste S (b).

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R. Kusiorowski et al. Construction and Building Materials 304 (2021) 124506

Fig. 3. X-ray diffraction patterns of raw and burned combustion waste.

by PANalytical (CuKα radiation, Ni filter, 40 kV, 30 mA).
The process of thermal decomposition of the combustion waste was
tracked by heating the test sample to the pre-set temperature, recording
changes in temperature and mass, and analysing the gases released by
the tested material on a Netzsch STA 409PC thermoanalyzer equipped
with a QMS 403C Aëolos quadrupole mass spectrometer. The tests were
carried out on samples weighing ca 50 mg, in alumina crucibles, in an air
atmosphere, at a heating rate of 5 K/min.
Changes in linear dimensions of the ceramic mass samples were
determined by the dilatometric method in an air atmosphere up to
1200 ◦ C, using a Setaram TMA92 dilatometer, at a heating rate of 7.5 K/
min. The tests were carried out with a 2-minute hold at the maximum
temperature.
Characteristic temperatures of phenomena occurring in the material
during its heating (sintering, softening and melting temperature) were
determined by high-temperature microscopy using a Leitz high-
temperature microscope. The test was carried out in an air atmosphere
at a heating rate of 5 K/min; test specimens were formed without
additives.
The basic technological properties of the obtained ceramic masses
and fired clinker materials were determined in accordance with gener­
ally accepted laboratory practice and methods used [24]. After drying
the ceramic masses, the amount of mixing water (Wz) and drying
shrinkage (Ss) were determined. For fired plastics, total linear shrinkage
(Sc) as well as water absorption by the soaking (NM) and boiling (NG)
method were determined. The open porosity (PO) and apparent density
(dp) were also determined by the hydrostatic weighing method. The
obtained ceramics’ compressive strength (RC) was also measured. Based
on the determined water absorption values, the frost resistance coeffi­
cient (K) was calculated. Each above parameter of the material was
determined on at least three samples; the final result was based on the
mean value of measurement.
In order to clarify the possible mechanism of the ash influence on the
production of building ceramics, the FactSage 6.4 software was used in
this study. The used module was “Equilib” with the databases “FactPS”
and “FToxid”. Based on chemical composition of prepared ceramic
masses (0, SW and BW, respectively in accordance with Table 2 and
Table 3) the calculations were made to determine the amount of the
liquid phase (slag) that appears in the considered systems, depending on
the temperature. The simulation was based on determining the amount
of liquid phase produced per 100 g of ceramic mass versus temperature.

Table 4
3. Discussion of results
Quantitative phase composition of the combustion waste.
Phase component/raw raw ash burnt ash raw ash burnt ash 3.1. Raw materials
material B BW S SW

Quantitative share, [%] Two kinds of combustion residuals (a mixture of slag and ash) from
amorphous phase 66.6 ± 36.8 ± 0.7 64.3 ± 42.3 ± 0.7 two local coal-fired boiler houses were used as the material for
1.0 1.0 neutralization and recycling. The boilers were fired with pea coal from
Mullite 9.3 ± 0.2 7.2 ± 0.3 10.6 ± 11.5 ± 0.3 two different mines, although the fuel materials used had similar char­
0.2
Quartz 3.0 ± 0.1 3.1 ± 0.1 1.0 ± 0.1 –
acteristics, i.e. the calorific value of coal was approx. 27–28 MJ per ki­
Anorthite 11.4 ± 36.5 ± 0.3 12.0 ± 27.4 ± 0.3 logram of fuel, ash content – approx. 5% and sulphur content – approx.
0.2 0.2 0.6% (Table 1).
Hematite 0.9 ± 0.1 3.9 ± 0.1 1.0 ± 0.1 3.8 ± 0.1 In terms of chemical composition, raw combustion residuals are
Diopside 3.8 ± 0.1 6.3 0.2 3.8 ± 0.1 7.1 ± 0.3
±
similar – their chemical composition is dominated by: silica (approx.
Spinel 2.3 ± 0.1 2.7 ± 0.1 4.1 ± 0.1 3.4 ± 0.1
Periclase 0.7 ± 0.1 1.3 ± 0.2 0.7 ± 0.1 – 36–37%), aluminium oxide (23–27%), iron compounds (as iron trioxide
Magnesioferrite 1.4 ± 0.1 1.6 ± 0.1 1.5 ± 0.1 1.4 ± 0.1 approx. 11%), calcium oxide (7–8%) or magnesium oxide (approx.
Gehlenite 0.5 ± 0.1 0.2 ± 0.1 1.0 ± 0.1 0.5 ± 0.1 4–5%). The only significant difference in the chemical composition is
Olivine – 0.5 ± 0.2 – 0.9 ± 0.1 that resulting from the loss on ignition. In the case of waste B, the loss of
Akermanite – – – 1.0 ± 0.1

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R. Kusiorowski et al. Construction and Building Materials 304 (2021) 124506

Table 5 mass was almost twice bigger after firing the material at 1025 ◦ C in
Characteristic temperatures of phenomena occurring in ceramic masses during comparison to waste S. The ignition loss itself is mainly related to the
their heating in a high-temperature microscope. more complete combustion of unburnt coal in the boiler – hence the
Ceramic mass Sintering point; Softening point; Melting point; presence of the so-called residual carbon. Its presence was confirmed by
symbol [◦ C] [◦ C] [◦ C] thermal analysis tests (Fig. 2), where at temperatures ranging from 400
0 975 1410 1460 to 900 ◦ C, a strong exothermic effect was recorded, combined with a
B 975 1250 1375 significant loss of mass (approx. 14% for B and approx. 8% for S), related
S 945 1250 1380 to the release of carbon dioxide as a gaseous product of thermal
BW 990 1280 1370
decomposition. At the temperature of 1200–1400 ◦ C, a slight loss of
SW 945 1250 1380
weight was recorded on the TG curves of both types of waste, which may
be related to the thermal decomposition of sulphate compounds. Due to
a quite significant loss on ignition resulting from the presence of
incompletely burned carbon, the above-mentioned waste used for tests

Fig. 4. Characteristic temperatures recorded in a high-temperature microscope.

Fig. 5. Sample chart showing a change in the cross-sectional area of the sample and its appearance as a function of temperature, recorded in a high-temperature
microscope for ceramic mass B.

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R. Kusiorowski et al.
Fig. 6. Dilatometric curves of the ceramic masses.
related to the addition of waste into the ceramic masses was also sub­
jected to prior heat treatment (BW and SW) in order to burn the residual
carbon.
Due to the nature of the incomplete hard coal combustion process
and the relatively short time in the furnace, the phase composition of the
raw bottom ash is quantitatively dominated by the amorphous phase
(>60%), with a small content of mullite and anorthite (approx. 10%
each) and a number of other compounds containing Fe, Al, Mg, Si, Ca
(Fig. 3). Pre-firing of the waste before adding it into the ceramic masses
resulted in partial crystallization – a decrease in the content of the
amorphous phase was observed with a simultaneous clear increase in
the content of the remaining crystalline phases (Table 4).
3.2. Ceramic masses
The addition of raw combustion waste reduces the masses’ sensi­
tivity to drying. As shown in Table 2, in the case of ceramic masses
prepared with waste B and S, a slightly smaller amount of mixing water
was needed to obtain the plastic state, allowing for the formation of
samples. The determined amount of mixing water in the case of adding
the pre-fired waste is similar to that of the reference mass. The amount of
mixing water used translates directly into the value of linear drying
shrinkage – in the case of the masses based on B and S waste, the
determined value of drying shrinkage is approximately 2.5 times lower
than of other prepared masses. The de-sensitizing effect of the ceramic
mass can be correlated with the presence of residual carbon in the
Fig. 7. Appearance of the shapes after firing the mass with an addition of combustion waste B: general view and fracture.
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Construction and Building Materials 304 (2021) 124506
discussed waste, which has hydrophobic properties and is difficult to
wet with water [25].
Tests carried out in a high-temperature microscope revealed a wide
temperature interval of the process of ceramic mass sintering. The ma­
terial began to sinter at a temperature of approx. 1000 ◦ C (Table 5,
Fig. 4) and only after exceeding the temperature of 1400 ◦ C, charac­
teristic phenomena related to the dominance of the liquid phase in the
system were observed. On the other hand, the addition of combustion
waste as a slimming material clearly influenced the recorded charac­
teristic temperatures. For each of the waste used – both raw and previ­
ously fired – a similar sintering temperature was observed, with a
simultaneous significant decrease of the softening point (by ca 150 ◦ C)
and melting point (by ca 70 ◦ C). Although the softening point consid­
erably drops, the existing difference between the softening and sintering
points, the so-called sintering interval, still ensures safe firing without
deformation. It should be expected that the addition of waste will
intensify the sintering process, and in the case of ceramic masses without
the addition of waste, the same effect will be obtained at a lower tem­
perature, which may bring economic benefits due to a lower energy
consumption of the firing process.
In the case of the masses in which raw combustion waste (masses B
and S) was used, in the initial measurement period, up to the tempera­
ture of approx. 900 ◦ C, a slight increase in the cross-sectional area of the
sample was observed (most visible in the case of mass B, Fig. 5), which
might be due to a release of gaseous carbon dioxide from the combustion
of residual carbon contained in this waste, and, in consequence, a slight
R. Kusiorowski et al. Construction and Building Materials 304 (2021) 124506

Table 6
Properties of the obtained ceramic materials.
Mass Firing Total Soaking Boiling Frost resistance Apparent density; Open Compressive
temperature; ◦ C shrinkage; % absorbability; % absorbability; % coefficient g/cm3 porosity; % strength; MPa

0 1100 7.4 ± 0.3 5.6 ± 0.4 7.4 ± 0.4 0.77 2.24 ± 0.01 12.6 ± 0.9 37 ± 3
1150 8.6 ± 0.4 3.1 ± 0.2 5.0 ± 0.3 0.62 2.31 ± 0.03 7.2 ± 0.5 41 ± 3
1200 8.9 ± 0.4 2.3 ± 0.1 4.3 ± 0.1 0.54 2.35 ± 0.01 5.4 ± 0.3 42 ± 4
BW 1100 7.8 ± 0.4 4.1 ± 0.5 6.8 ± 0.5 0.59 2.27 ± 0.02 9.2 ± 1.0 41 ± 4
1150 8.3 ± 0.3 2.4 ± 0.1 5.2 ± 0.1 0.46 2.31 ± 0.01 5.6 ± 0.3 48 ± 3
1200 8.4 ± 0.4 2.2 ± 0.1 4.8 ± 0.2 0.45 2.31 ± 0.01 5.0 ± 0.2 49 ± 4
SW 1100 7.5 ± 0.6 4.1 ± 0.6 6.4 ± 0.6 0.63 2.28 ± 0.03 9.2 ± 0.7 39 ± 3
1150 8.4 ± 0.5 2.1 ± 0.2 4.1 ± 0.3 0.52 2.36 ± 0.01 5.1 ± 0.4 43 ± 4
1200 8.8 ± 0.7 1.8 ± 0.2 3.7 ± 0.4 0.48 2.37 ± 0.02 4.2 ± 0.5 55 ± 3

Fig. 8. Dependence of linear changes and water absorbability of clinker ma­

terials with the addition of combustion waste in relation to the firing
temperature.
swelling of the material.
Similar conclusions could be drawn when following the course of
dilatometric curves (Fig. 6). The greatest linear changes – reaching over
10% – were found in ceramic masses containing raw combustion waste,
while in the case of combustion waste S, the maximum value was
approx. 14%. The investigations also confirmed that the slimming ma­
terial used in the commercial ceramic mass was quartz sand, as at a
temperature of approx. 600 ◦ C the researchers observed an effect
evidently related to the change of sample height, for which the poly­
morphic transformation of quartz is responsible. The thermal charac­
teristics of the masses with previously fired waste (mass BW and SW) are
closer to those of the commercial mass. The linear dimensional changes
reach ca 4–6%, and there is no characteristic effect of silica.
3.3. Ceramic materials
In the case of firing ceramic masses that contain raw combustion
waste, all the materials obtained were considerably deformed, which
was most probably caused by a release of volatile products of decom­
position of residual carbon contained in the waste. In addition, the
samples were found to contain so-called “black cores”, formed as a result
Fig. 9. Dependence between the open porosity and compressive strength of
clinker materials with the addition of combustion waste in relation to the firing
temperature.
of the reduction of highly ferrous clay raw material with carbon com­
pounds and firing in a furnace without circulation and gas atmosphere
exchange (Fig. 7).
A black core is formed during the firing process if reducing condi­
tions exist inside the fired shape. The most common reasons for their
formation include [26–29]: incomplete combustion of the organic sub­
stance contained in the ceramic mass and reduction of iron oxides;
therefore, the main phase components causing the dark colour of the
inside are carbon and lower iron oxides (FeO and Fe3O4). Both unfav­
ourable factors coincided in the analysed case, contributing to the for­
mation of black cores. In addition, the fired samples were swollen, which
is an evidently negative phenomenon observed when the oxidation of
organic matter and sulphur compounds occur above the temperature of
ceramic body vitrification and the degree of sintering of the product’s
surface layer prevents the gaseous phase produced in the product core
from diffusing through the surface. For the above reasons, the materials
based on ceramic masses, i.e. B and S, were rejected from the further part
of the study and their basic physical properties were not determined.
The results of all the determined ceramic parameters are summarized
in Table 6, and some of them are additionally presented in a graphical

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R. Kusiorowski et al. Construction and Building Materials 304 (2021) 124506

Fig. 10. FactSage modelling results on the slag–liquid formation in a considered ceramic masses sintering process.

form in Figs. 8 and 9. For all the materials, an increase in total shrinkage
and apparent density was observed as the firing temperature increased
from 1100 to 1200 ◦ C. In the case of the reference material (mass 0), the
material shrinkage after firing increased from 7.4 to 8.9%, which
resulted in the increased apparent density of the clinker material by
approx. 0.1 g/cm3 (from 2.24 to 2.35 g/cm3). Similar changes in prop­
erties were noted in the case of materials produced with an addition of
combustion waste, for which the total shrinkage increased by approx.
8% (for mass BW) or by 17% (for mass SW) in relation to the lowest
firing temperature. The sintering process intensification at 1200 ◦ C
contributed to a significant decrease in the water absorbability and open
porosity of all the materials – in the case of using the soaking method to
determine water absorption, it was almost twice lower for all the ce­
ramics, e.g. for material SW this value dropped from 4.1 to 1.8%. On the
other hand, a comparison of the results for different firing temperatures
revealed a favourable increase in the compressive strength of individual
materials, for example, for the reference mass, the CCS value increased
from 37 to 42 MPa (i.e. by approx. 15%). A similar increase was noted
for mass BW (from 41 to 49 MPa). The greatest increase in strength was
observed in the case of mass SW – the value of this parameter increased

Fig. 11. Comparison of frost resistance coefficients of the obtained clinker materials.

8
R. Kusiorowski et al.
by approx. 40% (from 39 to 55 MPa). A comparison of different types of
waste seems to indicate that waste SM has a more favourable influence,
because in this case a slightly larger percentage change in particular
parameters was observed. Compared to material BW, material SW was
characterised by a greater total shrinkage, apparent density and
compressive strength at 1200 ◦ C, with a lower water absorbability
(determined both by the soaking and boiling methods) and open
porosity (Figs. 8 and 9). This is indicated by the previously determined
lower sintering temperature of mass SW (Table 5). The reasons for this
should be sought in a slightly different chemical composition of waste
SW, in the case of which the total content of oxides responsible for the
formation of eutectic solutions with the lowest temperature, i.e. N2O,
K2O, Fe2O3, CaO, MgO in the multicomponent aluminosilicate system is
slightly higher than for material BW (Table 3). This sum reaches 28% for
waste BW and 30% for waste SW, respectively.
The analysis of the obtained results also demonstrates the beneficial
effect of both bottom ashes on the properties of ceramic materials,
because in the case of a lower firing temperature, clinker materials with
better parameters were obtained compared to the reference materials.
At a lower firing temperature, the water absorbability was lower by
approximately 1–1.5%, and for materials fired at 1200 ◦ C, the me­
chanical strength increased by ca 20% compared to ceramics without
the addition of combustion waste.
This statement was supported by the results of thermodynamic cal­
culations using FactSage software. The results obtained with the
FactSage determines specific temperature range where slag–liquid for­
mation is taking place in considered systems. From Fig. 10, it is impor­
tant that the slag–liquid formation occurs at around 925 ◦ C, but in much
larger quantities for ceramic masses with the addition of ash. The
highest values of slag amount was calculated for material SW.
This chemical modification resulting from coal combustion residuals
addition could have impacts in the thermodynamic processes during the
firing as well as in the ceramic properties. Iron as well as other elements
like sodium, pottasium, calcium in proper amounts, are considered as a
fluxing agent that reduces the melting point of the liquid phase, having
potential to act as a glassy phase former during the sintering process.
This promotes cohesion of the ceramic matrix [30]. In fact, it has been
reported that wastes with a significant amount of these components can
be used as a good flux agent in ceramic manufacturing [31].
The obtained materials should be expected to display full frost
resistance, as the values of coefficient k are clearly lower than 0.85. This
method of determining the frost resistance of a ceramic material should
only be used as an indication. The determined coefficient k points to the
presence of additional pores in the material, i.e. the narrowest capil­
laries, which are not filled with cold water (soaking absorbability), but
only with boiling water (boiling water absorption). These additional
capillary pores create additional space for the expanding freezing water.
Owing to that, the forming ice first fills this free space without damaging
the product. The higher the content of such additional pores in the
product (i.e. the lower the soaking-to-boiling ratio), the greater the ex­
pected frost resistance of the product. The value of coefficient k for all
the considered clinker materials is clearly lower than 0.85; it addition­
ally decreases as the firing temperature increases (Fig. 11). In all the
cases, the obtained clinker materials with the addition of combustion
waste were characterized by a lower coefficient k compared to the
reference materials (series 0) without it. Moreover, none of the materials
contained soluble salts or grains of the so-called harmful marlstone, as
the conducted tests gave a negative result (absence).
4. Conclusions
The conducted research and the obtained results allow concluding as
follows: (1) bottom ash can be used to obtain clinker ceramic materials,
but it is preferable to have a material without residual carbon or with its
limited content; (2) the addition of ashes containing incompletely
burned carbon to ceramic masses causes the formation of swollen,
9
Construction and Building Materials 304 (2021) 124506
deformed materials characterized by the presence of black cores, which
disqualifies such products from commercial use; (3) the addition of
combustion waste from the process of hard coal combustion allows
obtaining clinker materials with lower water absorbability and higher
mechanical strength compared to the reference material, especially at a
higher firing temperature; (4) the addition of combustion waste in­
tensifies the sintering process – the same effect can be obtained when the
waste-containing material is fired at a lower temperature than that in
the case of ceramic masses without combustion waste; (5), there were no
significant differences in the impact of the previously fired waste on the
final properties of clinker ceramics.
CRediT authorship contribution statement
R. Kusiorowski: Conceptualization, Methodology, Investigation,
Formal analysis, Resources, Writing - original draft, Writing - review &
editing, Visualization. A. Gerle: Investigation, Writing - review & edit­
ing. K. Dudek: Investigation, Writing - review & editing. K. Związek:
Investigation.
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 article was financed from the funds for statutory activities of the
Refractory Materials Division of the Łukasiewicz – Institute of Ceramics
and Building Materials.
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