Firing Process

Related terms:

Energy Engineering, Amplifier, Resistors, Oscillators, Transistors, Transducers-

, Thermocouples, Transformers, Clay Brick

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Types of waste, properties and durabil-

ity of toxic waste-based fired masonry
bricks
M. Coronado, ... A. Andrés, in Eco-Efficient Masonry Bricks and Blocks, 2015

7.4 Firing conditions used in the manufacture of waste-based

fired bricks
The firing process is the key step in the manufacturing of ceramic products because
it controls their properties. The materials experience irreversible structural changes
reaching the proper ceramic structure that is responsible for the final properties
of the product. Depending on the initial materials and the desired product, the
firing conditions, firing temperature, firing rate and soaking time in the kiln are
different. The temperature at which the liquid phase is created varies according
to the composition and mineralogy of the clay. The Reference Document on Best
Available Techniques in the ceramic manufacturing industry (EU, 2007) establishes
that vitrification usually starts at about 900 °C and is completed at about 1050 °C.
However, fluxing agents such as iron oxides, lime and alkalis lead to lower initial
melting temperatures, promoting the amount of liquid phase formed at any given
temperature contributing to a lower consumption of energy. This is particularly true
when the clays are calcareous in nature.

Tables 7.2–7.4 show the firing conditions used in the studied works incorporating
waste from the EWC codes 01, 10 and 19. Most of these works have studied
the behavior of mixtures containing different amounts of clay and waste using
constant heating rates in electric laboratory kilns up to temperatures between 800
and 1200 °C. In some of these publications, the authors select the amount of waste
to be introduced in the process and study the effect of the firing conditions on the
properties of the products. Some works assess the effect of the amount of waste
added at a fixed temperature, while others vary not only the temperature and/or the
firing conditions but also the proportion of waste in the mixtures. There are works
that simulate the industrial firing cycle on a laboratory scale, while others are carried
out on a pilot or even at an industrial scale.

Table 7.2. Firing conditions used during firing products containing wastes from
exploration, mining, quarrying, physical and chemical treatment of minerals (EWC
01)

Source Waste % Waste Furnace Firing Firing rate Soak time Reference
tempera-
ture
Ornamen- Granite ≤30% Laborato- 920 °C 1 °C/h n/a Duc-
tal stone waste ry kiln
industry man,
Kopar,
and
Sanchez
(2005)
20–60% Laboratory 800–1200 °C 9 °C/min 2 h Menezes,
kiln
Ferreira,
Neves, and
Ferreira
(2002)
Pilot kiln 1150–1200 °C 30 min
20–60% Laboratory 1150–1200 °C 9 °C/min 30 min Menezes,
and industrial
kiln Ferreira,
Neves, Lira,
and Ferreira
(2005)
≤40% Laboratory 850–1100 °C 4 °C/min 3 h Monteiro,
kiln
Peçanha,
and Vieira
(2004)
≤40% Hoffman ind. 970 °C n/a 6 h Vieira and
Kiln
Monteiro
(2004)

1.Granite 1.≤ 50%- Laboratory 1000–1150  36–39 °- 5 min

kiln °C C/min
waste2.- 2.≤ 50%
Kaolin Campos
waste et al.
(2007)

1.≤100%2.- Laboratory 1000–1150 °C 36 °C/min 5 min Menezes

kiln
≤100% et al. (2008)

1.25–35%2.- Laboratory 1000–1150 °C 36 °C/min 5 min Menezes

kiln
10–38% et al. (2009)
1180–1240 °C 38 °C/min
1.Kaolin 1.50%2.- Laboratory 1100–1175 5 °C/min 4 h El-Mahllawy (2008)
kiln °C
waste2.- 10–40%3.-
Granite 10–40%
waste3.-
Blast
furnace
slag (EWC
10)
Granite 30% Laborato- 950–1100  5 °C/min 2 h Acchar,
and ry kiln °C
marble Vieira,
rejects
and
Hotza
(2006)
≤50% Laborato- 500–900  10 °C/min 2 h Dhana-
ry kiln °C
pandian
and
Shanthi
(2009)
≤30% Laborato- 1100–1150 °C
8 °C/min 2 h Segadaes et al. (2005)
ry kiln
1.Gran- 1.- Laborato- 1100–1200 °C
n/a 1 h Torres
ry kiln
ite 35–70%- et al.
sludge2.- 2.- (2007)
Quartzite sludge
35–70%
Marble ≤20% Laborato- 750–950  5 °C/min n/a Saboya,
waste ry kiln °C
Xavier,
and
Alexan-
dre
(2007)
15–35% Laborato- 975–1050  n/a n/a
ry kiln °C
 Mon-
tero,
Jordán,
Hernán-
dez-Cre-
spo, and
Sanfeliu
(2009)
Powder ≤20% Laborato- 850–1150  n/a 2 h Moreira,
rock ry kiln °C
Man-
hães,
and
Holanda
(2008)
Quarrying Coal-min- 20–50% Laborato- 950 °C n/a 2 h Leme-
and ing waste ry kiln
mining shev,
Gubin,
Savelev,
Tu-
manov,
and
Leme-
shev
(2004)
Clay waste 5–20% Laborato- 1140–1200 °C
n/a n/a Özkan,
ry kiln
Çolak,
and
Oyman
(2010)
Iron ore 30–50% Laborato- 1060–1200 °C
10 °C/min n/a Das,
tailing ry kiln
waste Kumar,
and
Ra-
machan-
drarao
(2000)
Residual 40–80% Laborato- 950 °C n/a 4 h Ra-
clay ry kiln
madan,
Saleh,
Taha,
 and
Mo-
haram
(2001)
1.Miner- 1.- Laborato- 1100–1150 °C
5 °C/min 40 min Junkes,
ry kiln
al 5–65%- Carval-
wastes2.- 2.- ho,
Sewage 10–65% Segadães, and Hotza (2011)
sludge
(EWC
19)
Aluminum Red mud 10–80% High 1000–1100 °C
2.5 °- 2 h He et al.
industry tempera- C/min
ture box (2012)
resistance
furnace
1.Red 1.- n/a 1150–1200 °C
n/a n/a Svider-
mud2.- 38–75%- skii,
Mining 2.- Strash-
waste 15–38% nenko,
and
Chernyak (2007)

Table 7.3. Firing conditions used during firing products containing wastes from
thermal processes: power stations and other combustion plants, iron and steel
industry and aluminum, lead and zinc thermal metallurgy (EWC 10)

Source Waste % Waste Furnace Firing Firing rate Soak time Reference
tempera-
ture
Biomass Fly ash ≤50% Laborato- 950 °C 10 °C/min n/a Pérez-Vil-
thermal ry kiln
power larejo
plant
et al.
(2012)
Gasification 15–20% Pilot-scale 1000–1075  1–3 °C/min 4 h Fernán-
ashes kiln (electric) °C
dez-Pereira et al. (2011)
3–4 °C/min
Coal power Fly ash 85–90% Laborato- 800–1000  3 °C/min 1 h Baspinar, Kahraman, et al. (2010)
plant ry kiln °C
≤15% Laboratory 800–1000 °C n/a n/a Cultrone
kiln
and
Sebastián
(2009)
1.5–6% Laboratory 750–890 °C n/a 3–5 h Dondi et al.
kiln
(2002a)

Dondi et al. (2002b)

≤20% Pilot-scale kiln 1050 °C 4.5 °C/min 15 min Koukouzas
et al. (2011)
≤60% Laboratory 850–1000 °C n/a n/a Kute and
kiln
Deodhar
(2002)
≤80% Laboratory 1000 °C 0.8–1.6 °C/h 8 h Lingling,
kiln
Wei, Tao,
and Nanru
(2005)
10–50% Laborato- 850–1150  5 °C/min 2 h Mon-
ry kiln °C
teiro,
Lima,
et al.
(2008)
25–40% Industrial kiln 950–1050 °C n/a n/a Rego, 2009
20–80% Laboratory 1125–1200 °C 150 °C/h 6 min Zimmer
kiln
and
Bergmann
(2007)

1.Fly 1.≤10%2.- Refractory 1020 °C n/a 34 min Olgun,

roller
ash2.Tin- ≤10% furnace Erdogan,
cal ore Ayhan,
waste and
Zeybek
(2005)

1.Fly 1.≥90%2.- Laboratory 1000–1250  20 °C/min 1 h Little,

kiln °C
ash2.Met- ≤10% Adell,
al Boccacci-
finishing ni, and
waste Cheese-
(EWC 11) man
(2008)
Metallurgi- Foundry Green or Industrial 1020–1030 °C
1.4 °- 3.5 h Alon-
cal and sand core sand kiln C/min
steel ≤50% so-San-
industry
turde,
 Coz,
Quijor-
na,
Viguri,
and
Andrés
(2010)
≤50% Laboratory 800–900 °C 1.6 °C/min 4 h Alonso-San-
kiln
turde et al.
(2011)
Industrial kiln 850 °C n/a n/a
10–50% Laboratory n/a n/a n/a Quaranta,
kiln
Lalla,
Caligaris,
Boccaccini,
and Vieira
(2010)
Waste 20–100% Laborato- 1100–1350 °C
10 °C/min 1 h Furlani,
olivine ry kiln
powders Aneggi,
(foundry
industry) and
Maschio
(2013)
Blast furnace 30–70% Laboratory 1200–1220  10 °C/min 30 min Karamano-
slag kiln °C
va,
Avdeev,
and
Kara-
manov
(2011)
≤100% Laboratory 1150–1200  n/a 1 h Ozdemir
kiln °C
and
Yilmaz
(2007)
Steel slag ≤20% Box kiln 800–1000 °- n/a 4 h Bantsis,
C
Sikalidis,
Betsiou,
Yioultsis,
and
 Bourliva
(2011)
5–10% Laboratory 1100 °C 2–4 °C n/a Faria et al.
kiln
(2012)
5–30% Laboratory 800–1100 °- 2–3 °C/min 6 h Shih, Wu,
kiln C
and Chi-
ang (2004)
20–30% Industrial 850–930 °C Ind. Process 3.5 h Quijorna,
kiln
Miguel,
and
Andrés
(2011)
20–40% Industrial 850 °C 0.85 °C/min n/a Quijorna,
kiln
Coz, and
Andrés
(2012)
Siderurgical ≤3% Industrial 950 °C 0.85 °C/min n/a Oliveira
waste kiln
and
Holanda
(2004)
Ceramic 1.Sani- 1.50%2.- Laborato- 1100–1300 °C
5 °C/min 5 h Martelon, Jarrige, Ribeiro, Ferreira,
manufac- ry kiln
turing tary 25%3.-
ware 25%
sludge2.-
Anodiz-
ing
sludge
(EWC
11)3.-
Glass
waste
(EWC
19)

1.Sanitary 1.30%2.- Laboratory 1100 °C 2–4 °C/min n/a Faria

kiln
ware 5–20% (2011)
waste2.-
Steel slag
Table 7.4. Firing conditions used during firing masonry bricks containing wastes
from waste management facilities, off-site waste water treatment plants and the
preparation of water intended for human consumption and water for industrial use
(EWC 19)

Source Waste % Waste Furnace Firing Firing rate Soak time Reference
tempera-
ture
Waste- Sewage ≤15% Propane 1000 °C 2.6 °C/h 3 h Cusidó,
water sludge kiln
treatment Cre-
plant
mades,
and
González (2003)
15% Propane lab. 1050 °C Standard 1 h Cusidó and
kiln heating cycle
Soriano
(2011)
≤24% Propane kiln 980 °C 2.6 °C/min 3 h Devant,
Cusidó, and
Soriano
(2011)
≤10% Laboratory kiln Standards cycle for Jordán,
porous materials
Almendro-Candel,
Romero and Rincón
(2005)
5–40% Laboratory 1000–1050 °C n/a 4 h Kizinievic,
kiln
Žu-
rauskiene,
Kizinievic,
and
Žurauskas
(2013)
1–15% Laboratory 950 °C 10 °C/min n/a Martínez-García, Eliche-Quesada, Pér
kiln
≤10% Laborato- 700–1100°C3°C/min 1 h Mon-
ry kiln
teiro,
Alexan-
dre,
et al.
(2008)
≤100% Special tubu- 150–1100 °C 2–4 °C/min 20 min Souza, Tole-
lar oven for
gas detection do, Holan-
 da, Vargas,
and Faria
(2008)
≤10% Laboratory 900–1000 °C n/a 2 h Szoke and
kiln
Muntean
(2009)
≤30% Laboratory 850–1200 °C n/a n/a Teixeira
kiln
et al. (2011)
≤40% Combustion 880–1000 °C n/a 6 h Weng, Lin,
chamber
and Chiang
(2003)
Municipal Munici- 15–30% n/a 950 °C n/a n/a Haiying,
solid waste pal
incinera- sewage Youcai,
tion plant sludge
ash and
Jingyu
(2011)
≤50% Laboratory 950–1050 °C n/a n/a Lin and
kiln
Weng (2001)
13–100% Laboratory 900–1200 °C 2 °C/min 1 h Merino,
kiln
Arévalo, and
Romero
(2007)

1.- 1.- Industrial 980 °C, n/a n/a Ander-

kiln 72 h
Sewage 5–10%- son,
sludge 2.4–6%- Elliott,
ash2.- 3.≤5% and
Sewage Hickson
sludge3.- (2002)
Carpet
yarn
(EWC
04)
Municipalsol- ≤40% Laboratory 800–1000 °- 10 °C/min 6 h Lin (2006)
id waste kiln C
incinerator
fly ash slag
≤50% Laboratory 800–1050 °C n/a 2 h Shin and
kiln
Kim (2009)
Fly ash ≤40% Laboratory 1100 °C n/a n/a Gar-
kiln
cia-Ubaque, Giraldo, and Moreno-
7.4.1 Gaseous emissions during the firing process
The firing process inevitably leads to the release of gaseous compounds, mainly
derived from the raw materials due to the decomposition of minerals present
in these materials, but fuels, if used, also contribute to gaseous pollutants. The
chemical and mineralogical composition, as well as the specific firing conditions,
firing temperature, time and rate, during the ceramic process play important roles
in the emission of atmospheric pollutants. In general, increasing the temperature
promotes an increase in the release of contaminants to the atmosphere, while faster
firing cycles generally result in reduced emissions.

The Integrated Pollution Prevention and Control Directive (IPPC) (IPPC, 2007) and
the reference document on best available techniques in the ceramic manufacturing
industry (EU, 2007) establish the pollutants to be assessed in ceramic processes:
fluorine, chlorine, sulfur and nitrogen oxides, carbon monoxide and dioxide, volatile
organic compounds (VOC), metals and particulate matter. In addition, the document
on best available techniques in the ceramic manufacturing industry also determines
the range of temperature over which emissions of pollutants are released during
firing (Figure 7.4).

Figure 7.4. Temperature ranges for the release of pollutants during the firing of
bricks (BREF, 2007).

The temperature at which these emissions occur depends on the mineral phases
containing the pollutant and other phases that contain compounds that may affect
emissions. Fluorine emissions generally depend primarily on the firing temperature
and, to a lesser extent, on its content in the raw material, which at the same time is
a function of mineralogy (González, Galán, & Miras, 2006). In the ceramic industry,
the emissions of fluorine are observed at two main intervals of temperature, the
first one at about 600 °C due to the clay mineral de-hydroxylation and the second
one at higher temperatures (>900 °C) from the decomposition of fluorite (CaF2)
formed by the chemical reaction of the fluorine released during the clay mineral
de-hydroxylation with the CaO liberated from the decomposition of carbonates
(Eqns (7.1) and (7.2)).

(7.1)

(7.2)

Sulfur emissions are conditioned by the mineralogy and the possible reactions
that take place during firing that form stable compounds, avoiding the emissions up
to certain temperatures. When mixtures contain high amounts of calcite and sulfur,
anhydrite and/or efflorescence in the fired product can be formed during firing, and
there will be no emissions, at least none of those that depend on the raw materials.
The emission of sulfur is derived from the decomposition of pyrite and organic
matter at low temperatures ( 400–550 °C) and gypsum and anhydrite at higher
temperature ( 1200 °C). Anhydrite (CaSO4) is formed, as shown in Eqn (7.3), under
oxidizing conditions by reaction of CaO evolved from the dissociation of CaCO3
(Eqn (7.1)) and the SO2 produced from the decomposition of sulfur containing
compounds.

(7.3)

The emission of chlorine at low temperature is caused by the decomposition of

micas, halite and organic matter, while at temperatures above 850 °C, the decompo-
sition of chlorine-containing mineral salts is responsible for the second emission of
chlorine. Due to the high temperatures used in ceramic processes (normally above
850 °C), all the chlorine is emitted, and thus, emission mainly depends on the initial
content in the raw material.

The emissions of CO2 from the clays are observed in two main temperature ranges.
The first emission peak occurs at temperatures between 350 and 500 °C, due to
the combustion of the organic matter. The second emission peak at temperatures
above 800 °C is attributed to the decomposition of carbonates. Due to the high
temperatures used in ceramic processes, the all-carbon content in the materials
is emitted, and thus, emission mainly depends on the initial content in the raw
material.

Most of the publications are focussed on the assessment of the technical and
environmental performance of the new ceramic products. It is important to stress
that less than 10% of the total number of reviewed publications have studied the
emissions during the firing process. Table 7.5 shows the emissions during the firing
of alternative ceramic containing waste from the EWC codes 01, 10 and 19 and
summarizes the information about the method of assessment, the studied pollu-
tants and the regulatory emission threshold limits used to evaluate the potential
environmental impact during firing waste-based products. Some of these works
have been carried out on an industrial or semi-industrial scale, but most of them
have been simulated at laboratory scale. The most studied compounds are fluorine
(HF), chlorine (HCl), sulfur (SO2) and carbon (CO2) dioxides.

Table 7.5. Gaseous emissions during firing waste-based fired masonry bricks (meth-
ods and the regulatory emission threshold limits)

EWC Source Waste Method Studied Regula- Reference

compounds tions
threshold
limits
Coal power Fly ash Mass SOX and V n/a Dondi
plant balance:
chemical et al.
analysis
before/after (2002b)
firing by
ICP/OES/MS ISE (Electron selective)
10 Metallurgi- Foundry Mass CO2, NOX- n/a Quijorna
cal and steel sand and balance: , SO2, HF,
industry Waelz slag chemical HCl et al.
analysis
before/after (2012)
firing by
ICP/OES/MS ISE (Electron selective)
Steel slag (Waelz Mass balance: CO2, NOX, SO2- n/a Quijorna et al.
slag) chemical analysis , HF, HCl
before/after firing (2011)
by ICP/OES/MS
ISE (Electron se-
lective)
Siderurgical solid Thermal analy- CO2, H2O n/a Oliveira and
waste sis and
mass spectrome- Holanda (2004)
ter (DTG-MS)
Gas capturing by simu- SO2, CO, NO2, HCl, Argentinian emissions Quaranta et al.
lating a stack sampling PM10 regulations
(2010a)
19 Wastewater Sewage Gas sam- VOCs, SO2- Royal Cusido
treatment sludge pling and , CO, NOX, Decree
plant analysis (US HCl, HF and 833/1975 et al.
EP, 1994) metals and Decree
323/1994 (2003)
Generalitat
de
Catalunya
(DOGC,
1994)
European Space Agency: WLM, VCM CO, TOC European Space Cusidó and Soriano
ESA PSS-01-729 - ESA Agency
PSS-01-702 (2011)
European Space Agency: CO, TOC, VCM, TLM European Space Devant et al. (2011)
ESA PSS-01-729 - ESA Agency
PSS-01-702
Infrared gas analyzer CO, CO2, CH4 n/a Souza et al. (2008)
system URAS 14
Municipal sol- Sewage Ion selective HF, SO2, HCl, Environmen-
id waste incin- sludge ash electrode, NOX, VOC, tal Protection
eration plant optical Act EPA 1190
 emission PM10 and Anderson
spectrometry, metals
NLP et al. (2002)
standards,
non-disper-
sive infrared
analyzer,
hydrocarbon
analyzer

The emissions from the firing process can be assessed by different techniques, as
shown in Table 7.5. The main methods are analyzing off-gases, using evolved gas
analysis (EGA) and using a mass balance approach. Analysis of the off-gas emissions
of HF, HCl, SO2 and CO2, is frequently used at industrial scale. Evolved gas analysis
involves the combination of different thermal techniques which usually are: ther-
mo-gravimetry (TGA), quadrupole mass spectrometer (QMS) and Fourier transform
infrared spectrometer (FTIR). On the other hand, the mass balance approach can be
used to estimate the emission values ( ), taking into account the concentration of
the element in the materials before and after the firing process, using the following
equation:

(7.4)

where i = polluting compounds; j = constituting elements of the polluting com-

pounds; i = emission (in mg of compound i per kg of ceramic produced); LOI = loss
on ignition (%); Mwi = molecular weight of the polluting compounds; Amj = atomic
mass of the element;  = concentration of element (j) in the raw material, and
 = concentration of element (j) in fired product.

> Read full chapter

The design and mechanical perfor-

mance of high-performance perforated
fired masonry bricks
P.B. Lourenço, G. Vasconcelos, in Eco-Efficient Masonry Bricks and Blocks, 2015

2.3.2 Use of by-products and other additives in the production

of fired bricks
As the production technology based on the firing process contains high embodied
energy, due to the need of reducing the natural source material and aiming at
obtaining more efficient solutions in the thermal point of view, several research
studies have been studying the possibility of adding distinct by-products as a substi-
tution of part of the raw clay material. In fact, the conventional bricks are produced
from clay with high temperature kiln firing, leading to high energy consumption and
release of greenhouse gases. The clay bricks have an embodied energy of 2.0 kWh
and release an average 0.41 kg of carbon dioxide (CO2) per brick (Venkatarama Reddy
& Jagadish, 2003). On the other hand, the quarrying operations for obtaining clay
are energy consuming and generate high levels of wastes. Therefore, the idea is
often to obtain modified clay brick blends with waste and by-products and use the
traditional technology for the production of hollow bricks. It is also expected that
no remarkable differences on the general properties of hollow clay bricks, such as
compressive strength and water absorption, are obtained.

With this respect, very different by-products have been used to replace the clay with
reasonable results in terms of physical and mechanical properties, mainly as related
to compressive strength of the fired material. A general overview of the different
residues that have been used in the past can be found in Raut, Ralegaonkar, and
Mandavgane (2011) and in Zhang (2013). It should be stressed that fly ash (particu-
larly class F) has been largely used by different authors (Demir, Baspinar, & Orhan,
2005; Gorhan & Simsek, 2013; Sutcu & Akkurt, 2009). All the authors found that the
fly ash can replace clay at high volume ratios. In general, the compressive strength of
modified clay bricks is higher than in standard clay bricks and the water absorption
presents lower values. Additionally, it was observed that the bond strength and dura-
bility (resistance to freeze-thawing cycles) is also better than in standard clay bricks.
The use of stone residues such as granite-sawing wastes (Menezes, Ferreira, Neves,
Lira, & Ferreira, 2005), granite-basalt fine quarry residues (Sutcu & Akkurt, 2009), and
waste-marble powder (Bilgin et al., 2012) revealed also to be adequate for replacing
conventional clay raw material. The granite sawing wastes have similar physical and
mineralogical characteristics to conventional clay raw materials and demonstrated
to lead to final products with characteristics fitting the requirements of Brazilian
standardization. In general, the use of these residues revealed to be adequate, taking
into consideration the needed physical and mechanical requirements.

The thermal conductivity of a hollow brick is related to the geometry of the hollow
cells, and can be optimized according to different geometries of the hollow cells,
as discussed in Section 2.2. Additionally, the thermal performance of hollow clay
bricks is also dependent on the thermal conductivity of the bulk of the material that
constitutes the brick. In this way, the thermal performance of the hollow clay bricks
can also be improved by acting on the thermal conductivity of the solid part. The
enhancement (reduction) of the thermal conductivity of the material can be obtained
by the addition of pore-forming agents to the brick material before firing, like wood
sawdust, polymers, leather residues, paper-making sludge, powered limestone, and
polystyrene (Zhang, 2013). Lourenço et al. (2010) refers to the use of organic wastes
from the wood and paper industry, namely sawdust from wood (SD), cork dust (CD)
and paper mill sludge (PM). In this work, distinct percentages of the organic wastes
were added to the paste in order to decide for an optimum composition. From
Figure 2.4 it is observed that an increase on the percentage of organic waste leads
to a reduction of the specific mass and of the thermal conductivity. The introduction
of industrial paper residues was also investigated by other authors (Raut et al., 2011;
Sutcu et al., 2014). The raw materials blends containing up to 30 wt% of wastes
experienced a reduction of the thermal conductivity of approximately 50% without
decreasing the compressive strength below the recommended values. Of course, a
balance between mechanical performance and thermal insulation of the brick has
to be found as, in general, the addition of wastes results in the decrease of the
compressive strength. In the work carried out by Demir et al. (2005), it was confirmed
that the addition of kraft pulp residues in clay brick production can be effectively used
as an organic pore forming in clay body without any detrimental effect on the other
brick manufacturing properties. Both density and compressive strength reduce but
these are still higher than the ones required by codes. After the work carried out by
Gorhan and Simsek (2013), it was observed that the thermal conductivity can also be
improved by adding rice husk, which is effective as a preforming agent in the clay
body, in a proportion between 2.5% and 5% to the clay.
Figure 2.4. Evaluation of different additives on the physical and mechanical behavior
of the clay material: (a) conductivity; (b) mass. Here, the reference solution is a clay
paste without any additives.

> Read full chapter

Sintering
José S. Moya, ... Pilar Miranzo, in Encyclopedia of Physical Science and Technology
(Third Edition), 2003

V.A Rate Controlled Sintering

The traditional view of industrial sintering thinks of optimization of the firing
process in terms of “time-at-temperature” (i.e., the duration of isothermal treat-
ments), temperature being the independent variable. The heating rates employed
in reaching the soak temperature are generally considered to have only secondary
importance.

However, the effects of the nonisothermal portion of the heat treatment could
determine the properties of the final product. In fact, densification proceeds rapidly
through the initial and intermediate stages, before the soak temperature is reached,
and slows appreciably once the density of the compact is about 90% of theoretical.
This kind of firing path facilitates entrapment of occluded gases, formation of
intragranular porosity, and exaggerated grain growth. It has been demonstrated that
for each stage of densification, there is a critical densification rate that cannot be
exceeded without jeopardizing some subsequent stage.

An alternative firing process to avoid the above undesirable effects is “rate controlled
sintering.” Even though the theoretical basis for this method was established in 1965,
it is only now that considerable experimental work is being carried out.

For rate-controlled sintering, the independent variable is considered the densif-

ication rate. Rate-controlled sintering experiments set up a density–time profile
adequate to the studied compact in order to get a fully dense fine-grained material.
In general, rate-controlled sintering firing profiles traverse slowly the permeable
intermediate stages of densification (density between 75 and 90% of theoretical),
leading to an elevated outgassing of the compact. Besides, temperatures are kept as
low as possible, thus minimizing transport processes, such as pore coarsening and
grain growth, which do not necessarily aid densification.

At the present stage of development, optimization of the density–time profile for a

given material is usually accomplished empirically in an iterative fashion relating
experimental results with basic knowledge of the sintering process. In general,
the programming criterion can be summarized as “avoiding excessive densification
rates.”

Rate controlled sintering alters the resultant microstructures significantly in com-

parison to those achieved by conventional sintering. In general, finer and more
uniform microstructures as well as low porosity materials are obtained. In addition,
the possibility of a direct scaling-up from laboratory results is claimed by rate
controlled sintering researchers.

> Read full chapter

Figures
S.P. Deolalkar, in Designing Green Cement Plants, 2016

Chapter No. Fig. No. Title Source

Section 3
1 3.1.1 Flow chart for oxyfuel Carbon Capture Tech-
firing process nologies

3.1.2 Flow chart for amine PCA R&D Serial 3022

scrubbing process
3.1.3 Flow chart for carbona- Greenhouse Gases Sci-
tion calcination loop ence & Technology
Section 4
5 4.5.1 Flow chart for accep- CII—Case study Manual
tance and rejection of for AF&R
wastes proposed for
use
4.5.2 Steps to prepare wastes GEPIL—Waste prepara-
for use as AF by ISP tion facility
4.5.3 Steps to prepare AF As above
from wastes in greater
detail
6 4.6.4 Flow chart for prepar- ANZBP Hobart Road
ing waste sludge for Show 2011
use as AF
8 4.8.1 Savings in GHG emis- AF in cement manuf.,
sions Technical & Environ-
mental Review a Cem-
bureau Presentation
Section 5
6 5.6.11 Flow chart for WHR NCCBM Presentation
system showing two see References Section 5
turbines on same shaft
5.6.12 Flow chart for com- Kawasaki Plant Systems
mon turbine and sep- See references in Sec-
arate WHRBs for Pre- tion 5
heater & Cooler
 Section 6
7 6.7.1 Relation between wind Brochure of Suzlon En-
speed and power gen- ergy Ltd
erated
6.7.2 Simple scheme of Wind generation appli-
grid-connected wind cation for Cement In-
power plant for a ce- dustry
ment plant
8 6.8.1 Circuit diagram for a Report IISC-DCCC 11
PV solar power plant RE 1
6.8.2 Common types of solar Science & Technology of
power systems Photovoltaics by P. Ja-
yarama Reddy
Section 7
7 7.7.2 Control of NOx by mul- VDZ Activity Report
tiple feeds and injec- 2003-2005
tions of ammonia

> Read full chapter

Unfired clay materials and construction

John M. Kinuthia, in Nonconventional and Vernacular Construction Materials (Sec-
ond Edition), 2020

13.7.1 Formation
Unfired clay systems may be formulated in the same manner as fired systems, the
only difference being the firing process. Heath et al. (2009), for example, undertook
research work on unfired clay systems by starting with wet extruded bricks that
were originally meant for firing. An alternative process to extrusion is the use of
purpose-made molds. For fired bricks, the extruded or wet moulded material is
allowed to condition to reduce the excess moisture prior to firing. The moisture
conditioning has been observed to minimize volume changes upon firing so as to
maintain shape, volume and dimensional stability. After this conditioning, systems
meant to be used in unfired applications may be allowed to dry further (Heath
et al., 2009). This approach is sometimes unsuitable for unfired systems due to the
excessive water content used, and most unfired systems are designed to contain
less water from the start, by compacting in a semidry state. This results in denser
and stronger material. In the absence of additives such as stabilizers (lime, Portland
cement or any other emergent stabilizers), the control of moisture is less restrictive.
However, with hydraulic stabilizers, especially Portland cement, careful control of
the amount of water used is essential.
Ability to handle the freshly made unfired clay materials is critical, for both manual
and automated production (see Fig. 13.8(a)). The automated handling is the more
critical one, as massive losses can be incurred if larger production batches are
damaged during early movement. In order to minimize breakage, most unfired
clay-based materials have rounded or chamfered edges, unlike their fired or ce-
ment-based counterparts (see Fig. 13.8(b)).

Fig. 13.8. (a) Unfired bricks illustrating possibility of automated production, and

ability to withstand edge breakage in the manufacturing process (bricks produced by
author during trials at P D Edenhall concrete brick plant at Bridgend, South Wales,
UK) and (b) Unfired clay bricks with rounded or chamfered edges to minimise edge
wear in clay-based construction.

> Read full chapter

Sulfoaluminate cement-based concrete

Kedsarin Pimraksa, Prinya Chindaprasirt, in Eco-Efficient Repair and Rehabilitation
of Concrete Infrastructures, 2018

14.3.2 Production of calcium sulfoaluminate cement using hy-

drothermal–calcination process
The hydrothermal–calcination process was developed several years ago by Jiang
and Roy (1992). It has several advantages over the clinkerization or firing process.
The obtained products have finer particle sizes, greater surface area and a more
homogenous morphology. In addition, the energy required for processing is much
lower. However, its drawback is the requirement of a two-step process that can
obstruct its final use. Hydrothermal synthesis consists of two reaction steps under
high pressure (>1 atmospheric pressure) and temperature; dissolution, and precip-
itation. The precipitates are commonly in the form of hydrated phases so called
“intermediate phases” which would be transformed to the final cement product
after heat treatment or calcination. The hydrothermal process was used to synthesize
highly reactive belite (C2S) cement in the first era by Ishida et al. (1992) and Garbev
et al. (2014). Ishida et al. (1992, 1993) and Sasaki et al. (1993) showed that the in-
termediate phases after the hydrothermal process are crucial to obtain various types
and characteristics of products after calcinations. From these previous works, the
-dicalcium silicate hydrate (Ca2(HSiO4)(OH)), hillebrandite (Ca2(SiO3)(OH)2), and
dellaite (Ca6(SiO4)(Si2O7)(SiO4)(OH)2) phases were obtained as intermediate phas-
es by hydrothermal treatment at temperatures between 100–250ºC. Hillebrandite
phase is recommended to produce more reactive C2S than -dicalcium silicate
hydrate and dellaite phases.

Only a few works used the hydrothermal–calcination process to synthesize ye’elimite

(C4A3Ŝ). This is possibly due to the difficulty in processing that requires two main
working steps. Rungchet et al. (2016) synthesized calcium sulfoaluminate-belite
cement (CSAB) from industrial waste materials such fly ash (FA), aluminum-rich
sludge, and FGD–gypsum. Commercial grade hydrated lime (Ca(OH)2) was also used
to correct the stoichiometry of the mix. The mix proportion was stoichiometrically
weighed by combining the raw materials at 45:20:25:10 of Ca(OH)2:FA:aluminum
sludge:FGD–gypsum to obtain a raw mix with 4:3:1 for CaO:Al2O3:SO3 and 2:1 for
CaO:SiO2 in combination. The hydrothermal treatment was carried out using an
autoclave at 130°C. The studied factor was the reaction time under hydrothermal
treatment at 1, 3, 6, and 9 hour. The second stage of the synthesis was calcination of
the hydrothermal products in an electric furnace at various temperatures between
750°C and 1150°C, with a heating rate of 5°C/min and remaining at the maximum
temperature for 1 hour. At 6 hour of hydrothermal treatment, nonalkaline activation
hydrothermal treatment (H2O) led to a complete dissolution of anhydrite containing
FA and a precipitation of AFt from the reaction between the dissolved anhydrite
and aluminum species present in aluminum sludge (AS) and FA. The formation of
cebolite, a calcium aluminum silicate hydroxide (Ca5Al2Si3O12(OH)4 C5AS3H2) could
also be observed. The presence of C–S–H (Ca1.5SiO3.5.xH2O; C1.5SHx) was confirmed
by differential scanning calorimetry (DSC) with an endothermic peak at 160–180°C.
The sources of silicon and aluminum for both cebolite and C–S–H formations came
from the dissolution of amorphous phases of FA and AS. The alkaline-activated
hydrothermal treatment (1 M NaOH) resulted in the formation of new hydration
phases called katoite (Ca3Al2SiO4(OH)8; C3ASH4). The reflection of portlandite indi-
cated that the pozzolanic reaction of FA under steam pressure and alkaline activation
were limited. Whereas the reaction without alkali under the same hydrothermal
temperature showed no portlandite leftover. In the alkaline activated system, sulfate
available from the dissolution of anhydrite was found as thenardite (Na2SO4; NŜ),
according to the following reaction: CaSO4+NaOH Ca(OH)2+Na2SO4 (Kacimi et al.,
2010). However, no trace of either AFt or monosulfoaluminate (AFm) was found,
even though sulfates were available in the system. This was probably due to the
formation of calcium aluminum silicate sulfate gel, as confirmed by the presence
of a broad hump around the 10–30 degrees (2 ) region using XRD. Moreover, with
the use of water without hydrothermal treatment, phase development was similar
to those with hydrothermal treatment, showing the presence of AFt and AFm. The
only difference was the higher content of AFt and AFm phases with the hydrothermal
treatment. Hydrothermal treatment assisted more rapid precipitation and growth of
the products.

After calcination (1050°C), ye’elimite (C4A3Ŝ) and -C2S phases were obtained in
all conditions, but the intensities or quantities of phases differed depending on
the treatment used. Fig. 14.2 shows the formation of ye’elimite and belite phases
using different conditions of synthesis. Mixtures with non-alkaline activation under
hydrothermal treatment gave the highest content of C4A3Ŝ, but only a small amount
of -C2S. In addition, the calcination products contained anhydrite indicating an
incomplete combination of calcium, aluminum and sulfate to form the C4A3Ŝ phase.
However, C12A7—an intermediate phase formed during calcination—reacted further
with anhydrite and formed C4A3Ŝ, one of the hydraulic phases as shown in Eq.
(14.11). Here, an intermediate phase such an AFt played an important role in the
conversion reaction to form C4A3Ŝ as shown in Eq. (14.12). It is worth noting that
without alkaline treatment, cement mix preferred the formation of C4A3Ŝ instead of
C2S. Alkaline activation with 1 M NaOH conditions led to the complete formation
of both C4A3Ŝ and -C2S phases. Although no AFt phase was developed under
hydrothermal treatment, C4A3Ŝ could be formed via the reaction between katoite,
gibbsite, portlandite, and thenardite. In addition, katoite also played an important
role in the formation of -C2S, as shown in Eq. (14.13), where N=Na2O. The alkaline
activation also enhanced the formation of C12A7 instead of C4A3Ŝ after calcinations.

Figure 14.2. XRD pattern of calcinations products after calcining at 1050°C obtained
from hydrothermal products (A) under water and hydrothermal treatment, (B) under
1 M NaOH and hydrothermal treatment, and (C) under water with no hydrothermal
treatment. Y, Ye’elimite; L, Belite; A, Anhydrite; M, Mayenite; Th, Thernardite; F,
Brownmillerite; C, Lime (Rungchet et al., 2016).

(14.11)

(14.12)

(14.13)

After calcinations at 1150°C, C12A7 lost its stability and converted to tricalcium
aluminate (C3A), a new-formed product. At this temperature, the partial melting
of aluminate and silicate phases led to the decomposition of C4A3Ŝ and -C2S.
With this method of synthesis, C3A which is normally formed about 1,300ºC using
the clinkerization, could be obtained at only 1150°C. To summarize, CSAB cement
could be synthesized at temperatures between 950°C and 1050°C, which is about
200–300°C lower than the temperature used in the traditional CSAB production.
Additional 20 wt% of FGD–gypsum (CaSO4·2H2O) was added to observe hydration
of the synthesized CSAB cement. The resulting cement set very quickly, with ac-
ceptable compressive strengths of 30.0 MPa and 23.0 MPa at 28 days of curing for
nonalkaline-activated cement and alkaline activated cement, respectively. The initial
setting times of nonalkaline-activated cement and alkaline-activated cement were 15
and 7 minutes, respectively. The faster setting time of nonalkaline-activated cement
(lower C4A3Ŝ than alkaline-activated cement) was due to the presence of C12A7 which
was more reactive than C4A3Ŝ. It is notable that the water to cement ratio used
in this research was 0.8 which was more than the one used in previous research
works. This was due to the larger surface area of CSAB cement obtained from
the hydrothermal–calcination method. In practice, water reducing agent should be
added to keep its flow ability as well as higher strength.

> Read full chapter

Clay bricks
Francisco M. Fernandes, in Long-term Performance and Durability of Masonry
Structures, 2019

1.3.1 Production/manufacture
A first source of problems comes from the presence of coarse materials in the clay
mixture, namely calcium oxide particles or lime (CaO). During the firing process, the
calcium oxide is changed into calcium carbonate and, when in contact with water,
crystallizes into hydroxide of calcium, Ca(OH)2, leading to an increase of volume of
the brick. This causes an accumulation of stresses, cracking, and, finally, partial or
total disintegration of the brick. Another aspect is the addition of sand to raw clay to
lowering its plasticity. When sand content is insufficient, the produced bricks tend
to exhibit large shrinkage and irregular shape. On the other hand, if the sand content
is too high, clay bricks will be too fragile. Moreover, clay mixtures that contain sand
grains of large size might lead to localized cracking around such grains.

The use of defective molds, or an inadequate molding process, can provoke warping,
nonparallel opposed faces, rough faces, etc. The use of a wire of rope to remove the
excess of clay from the mold is responsible for the presence of small holes in the
bedding faces of the bricks, especially if very plastic clay was used. Generally, the use
of hands or a wire will produce a more deformed surface than a wood ruler. The use
of bottomless molds makes one of the faces of the bricks with very coarse aspect,
or with glued sand grains, due to the use of fine sand to prevent the adhesion of
the brick to the support. It is also possible that contamination with organic matter
occurs if the bottom surface is soil.

During the drying phase, shrinkage affects the strength and shape of clay bricks.
Fissures can be observed when a too fast drying was allowed, originating high
stresses inside the brick that can produce cracking or local rupture. According to
Binda and Baronio (1984), clay bricks that show local vitrification are due to high
firing temperature or excessive firing time. The existence of zones of distinct color
within the same brick indicated a heterogeneous firing process that resulted in zones
with distinct firing levels.

> Read full chapter

Proton conductors for solid oxide fuel

cells (SOFCs)
E. Traversa, E. Fabbri, in Functional Materials for Sustainable Energy Applications,
2012

16.5.2 Protonic SOFC based on barium zirconate electrolytes

Scarce SOFCs based on BZY materials have been fabricated so far, due to the low
BZY sinterability, which makes the fabrication of dense thin BZY layers after a
co-firing process at around 1400°C impossible. Larger anode/electrolyte co-firing
temperatures cannot be used because they will cause anode coarsening, and thus
anode porosity reduction, and also because they might favour chemical reactions at
the interface. Recently, a novel ionic diffusion strategy was developed to fabricate
anode-supported BZY-based SOFCs (Bi et al., 2010). Starting from a thin layer of
In-doped barium zirconate co-pressed on a NiO-BZY anode, In evaporation and Y
migration from the anode to the electrolyte during the co-firing process allowed
the formation of a dense BZY membrane. Using a composite cathode, this protonic
SOFC showed a peak power output density of 169 mWcm−2 at 600°C.

Remarkable results in developing BZY-based cells were obtained using pulsed laser
deposition (PLD), which enabled fully dense BZY membranes of about 4 |m in
thickness to be obtained on top of a porous anode substrate made by Ni and BZY
(Pergolesi et al., 2010b). Table 16.2 summarizes the main results reported in the
literature about SOFCs based on BZY electrolytes or other chemically stable HTPC
electrolytes.

Table 16.2. Comparison of the fuel cell performance reported in the literature for
SOFCs based on chemically stable HTPC electrolytes

Anode/electrolyte/cathode Peak power density output Reference

Ni–BZY/BZY/PBCO–BZPY 169 mWcm−2 at 600°C (Bi et al., 2011)
BZY–NiO/BZY/BSCF 23 mWcm−2 at 600°C (Guo et al., 2009)
Ni–BCZY/BZY/SSC–SDC 70 mWcm−2 at 600°C (Sun et al., 2010)
Ni–BZY/BZY/LSCF–BCYb 110 mWcm−2 at 600°C (Pergolesi et al., 2010b)
Ni–BZPY/BZPY/LSCF–BZPY 108 mWcm−2 at 650°C (Fabbri et al., 2011)
Ni–BZY/Li–BZY/LSCF–BZY 26 mWcm−2 at 700°C (Sun et al., 2011)

BZY: BaZr0.8Y0.2O3– BZPY: BaZr0.7Pr0.1O3– PBCO: PrBaCo2O5+ BSCF: Ba0.6Sr0.4-

Co0.2Fe0.8O3- BCZY: BaZr0.1Ce0.7Y0.2O3- SSC: Sm0.5Sr0.5CoO3- SDC: Ce0.8Sm0.2O3--
LSCF: La0.6Sr0.4Co0.2Fe0.8O3- BCYb: BaCe0.9Yb0.1O3-

> Read full chapter

Calculation of physical and chemical ex-

ergy
undefined Sala Lizarraga, Ana Picallo-Perez, in Exergy Analysis and Thermoeconom-
ics of Buildings, 2020

3.6.1 Exergy of construction materials

In the construction of a building various types of materials are used. Among stone
materials, the most used are limestone, marble, granite and aggregates. There are
also ceramic materials from clays that are subjected to firing processes in ovens at
elevated temperatures, such as flooring tiles, glazed tiles, refractory bricks, etc. Glass
is a mixture of sand with potash or soda, with the addition of other bases, and can
be given different colors by the addition of metal oxides.

Binding materials are also used in buildings to join together other materials, such as
plaster and cement. Another type is compounds, which are formed of mixtures of
different materials with different properties: this is the case of mortars, which are a
mixture of sand, cement and water or concrete which are mixtures of cement, aggre-
gates and water. There are also metals, the most commonly used being ferrous and
forged steel, and among non-ferrous metals, copper and aluminum. Additionally,
there are plastic materials, which are organic materials made from polymers, among
which we find PVC, polystyrene, polyurethane, etc. see Fig. 3.7.

Figure 3.7. Various construction materials.

For the calculation of the physical exergy of building materials, we apply Eq. (3.43),
for which we need to know the specific heat of the material and the temperature
at which we find it. As the temperature of these materials is usually the ambient
temperature, their physical exergy is zero. For the calculation of chemical exergy we
need to know the composition of the material and use Eq. (3.96), or the alternative
method applying Eq. (3.105).

> Read full chapter

Environmental performance and ener-

gy assessment of fired-clay brick ma-
sonry
D. Hotza, B.G.O. Maia, in Eco-Efficient Masonry Bricks and Blocks, 2015
 Abstract
This chapter deals with the assessment of environmental and energy aspects applied
to the fabrication of ceramic bricks, blocks, and roof tiles. Ceramic masonry units
are usually made from one or more clays, which are subjected to milling/mixing,
forming and firing processes. When a life cycle assessment (LCA) is carried out on the
production and use of ceramics, normally the highest impact associated from both
the environmental and energy perspective is the firing step. This process requires
a high amount of heat that is generally gained from the combustion of fossil or
biomass fuels. The intent of this chapter is to analyze conventional and alternative
fuels used to produce ceramic masonry units, in particular bricks, considering the
manufacturing plant as a system boundary. Process efficiency and environmental
impacts are assessed and compared.

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