978 1 53618 730 4a

ADVANCES IN MATERIALS SCIENCE RESEARCH
ADVANCES IN MATERIALS
SCIENCE RESEARCH
VOLUME 43
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ADVANCES IN MATERIALS SCIENCE RESEARCH
SCIENCE RESEARCH
VOLUME 43
MARYANN C. WYTHERS
EDITOR
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CONTENTS
Preface vii
Chapter 1 Reviewing the Role of Coal Bottom Ash as an
Alternative of Cement 1
Navdeep Singh
Chapter 2 Chemical Aspects of Interaction of Portland
Cement with Alkali-free Set Accelerators 55
Alexey Brykov
Chapter 3 Indian Cement Industry: A Perspective 93
Mainak Ghosal
Chapter 4 Single Crystal and Multi-Layer Composite
Heavy-Oxide Scintillators for Efficient
Fast Neutron Detection 103
Sergei V. Naydenov, Vladimir D. Ryzhikov
and Craig F. Smith
vi Contents
Chapter 5 Scintillation Crystals of Thallium and Cerium

Doped Potassium Dihydrogen Phosphate (KDP:
Tl and KDP: Ce) for Selective Detection of
Fast Neutrons 143
Sergei V. Naydenov, Alexei P. Voronov,
Igor M. Pritula and Craig F. Smith
Chapter 6 Thermodynamic Evaluation and Process
Simulation of the Production of Hydrogen-Syngas
Using Mixed Iron-Based Oxides with Methane 175
V. Collins-Martinez, J. F. Cazares-Marroquin,
J. M. Salinas-Gutierrez, M. J. Melendez-Zaragoza
and A. Lopez-Ortiz
Chapter 7 Development of Rotational Device in Magnetron
Sputtering System for Civil Construction and
Electric Power Distribution Sectors Application 201
Maurício Marlon Mazur, Sidnei Antonio Pianaro,
Kleber Franke Portella,
Mariana d´Orey Gaivão Portella Bragança,
Emerson Luís Alberti and
Viviane Teleginski Mazur
Contents of Earlier Volumes 225
Index 231
PREFACE
Advances in Materials Science Research. Volume 43 begins with a

review of the mechanical and durability properties and microstructural
characteristics of concrete made with partial incorporation of coal bottom
ash.
Following this, the chemical aspects of interactions of aluminum-
containing accelerators in Portland cement-based materials are described,
explaining their effect on the kinetics of Portland cement hydration and the
stability of Portland cement materials when exposed to various corrosive
factors.
A review of India’s cement industry is provided, particularly focusing
on water positive manufacturing, consuming wastes like fly ash and slag,
reducing CO2 emissions, and taxes.
Several different types of single crystal and multilayer composite
heavy-oxide scintillation materials are discussed, having been developed
and characterized for fast neutron detection for homeland security and
nuclear safeguards applications.
A new class of inorganic hydrogen-containing scintillators based on
potassium dihydrogen phosphate and related compounds activated by ions
of thallium or cerium is also investigated.
viii Maryann C. Wythers
The use of mixed metal oxides as oxygen carriers under the chemical
looping reaction scheme is proposed to overcome the current
disadvantages of the partial oxidation of methane processes.
In the concluding study, titanium, aluminum nitride and hafnium oxide
thin films are applied to ceramic electrical insulators to promote surface
self-cleaning properties to minimize the effects of leakage current.
Chapter 1 - Coal bottom ash (CBA) is a by-product of the coal industry
and is produced to a large extent from coal-fired thermal power plants. The
utilization of CBA in the manufacturing of concrete proposes an economic
and ecological way of its disposal. Simultaneously, its usage conserves
natural resources and promotes sustainability. This review article focuses
on the utilization of CBA incorporated in place of Portland Cement (PC)
used in the manufacturing of concrete. The reduction in particle size of
CBA leads to an increase in the surface area while its incorporation as
partial replacement of PC feedbacks in improved strength, durability and
microstructural features of concrete. The studies related to the use of CBA
are scarce in quantum to date in which various properties of concrete have
been investigated. Since the current area needs more attention as most of
the investigations have favored in use of CBA as partial replacement of PC
whereas few of them have reported against its use. The current
investigation reviews fresh, mechanical, durability properties and
microstructural characteristics of concrete made with partial incorporation
of CBA. The literature demonstrates that CBA has significant potential to
be used as a replacement of PC for structural grade concrete.
Chapter 2 - Aluminum-bearing compounds - amorphous aluminum
hydroxides, aqueous solutions of aluminum sulfate and hydroxysulfates -
find application in composition of alkali-free accelerators of setting and
hardening of Portland cement (PC) concrete in modern machine-concreting
technologies, like shotcreting and 3D printing. Compared with alkaline-
containing, alkali-free accelerators are safer to use, they do not participate
in alkali-silica reactions and do not promote salt efflorescence. A high
reactivity of these admixtures in PC pastes and mortars is due to an
intensive formation of calcium trisulfoaluminate hydrate (AFt phase) when
reacted with components of the paste. Although notable practical
Preface ix
experience has already been gained in the use of alkali-free accelerators,

some features of their interaction with cement components, including those
aspects of this interaction that may later affect durability of cement
concretes and mortars, remain unclear. This chapter describes chemical
aspects of interactions of aluminum-containing accelerators in PC-based
materials, explaining their effect on kinetics of PC hydration and stability
of Portland cement materials when exposed to various corrosive factors. In
writing this chapter, the author relied, among other things, on results of his
own studies on the hydration of PC with the mentioned admixtures using
27
Al- and 29Si-MAS NMR spectroscopy - a method that provides unique
information in this regard.
Chapter 3 - Despite India’s GDP hovering to a new low rate of growth
at around 5% or more, its cement sector is booming and poised to achieve
new heights in water positive manufacturing, consuming wastes like fly
ash and slag, cutting on energy and enjoying cost benefits, lowering the
carbon footprint by reducing CO2 emissions, in paying taxes. Most Indian
cement plants conform to the ISO 9001:2008 Quality Management
Certification, ISO 14001:2004 Environment Management Certifications
and the OHSAS 18001 Occupational Health and Safety Standard
Certification. 50 percent of Indian Cement Industry’s capacity today is less
than ten years old and is part of the construction sector that is the second
largest in employment generation, with 20,000 downstream jobs being
created for every one million tonnes of cement produced and consumed.
According to a study by IIM Bangalore, cement companies in India are
spending more than the mandated 2% on CSR while their peers spend a
mere 0.3-1.5%. It is said that the cost of cement in India is less than half of
common salt costing around INR 20/Kg, which is more than that of cement
costing around INR 7/Kg - an unchallenged economy.
Chapter 4 - Several different types of single crystal and multilayer
composite heavy-oxide scintillation materials have been developed and
characterized for fast neutron detection for homeland security and nuclear
safeguards applications. In particular, for the detection of fast neutrons,
large-sized (diameter 40-50 mm, length 80-100 mm) scintillation blocks
based on the heavy-oxide single crystals of CdWO4 (CWO), ZnWO4
x Maryann C. Wythers
(ZWO), PbWO4 (PWO), Bi4Ge3O12 (BGO), Gd2SiO5(Ce) (GSO(Ce)) have

been conceived, fabricated and tested. These crystals demonstrate fast
neutron detection efficiencies of not less than 50% without using an
external plastic moderator. Based on these detectors, an experimental
prototype of a portal monitor to detect mixed neutron/gamma radiation has
also been created. Additionally, a new heterogenous detection structure,
referred to as “ZEBRA”, has been developed. The ZEBRA detectors
consist of layers of a composite material comprised of microgranules of the
same heavy-oxide scintillators dispersed in transparent plastic, alternated
with layers of clear plastic that serve as scintillation light guides and as a
neutron moderator material. The detection efficiency and sensitivity of
ZEBRA detectors compare favorably with those of detectors based on
large-size single crystals, but the composite structures are much less
expensive and can be manufactured in much larger dimensions. These
composite detectors represent a significant advancement from earlier
single-crystal detector types and are the result of recent efforts to explore
alternatives and improvements to conventional 3He counters. The high
detection efficiency of ZEBRA scintillators is due to not only to the
contribution from inelastic scattering of fast neutrons by heavy constituent
nuclei, but also from internal energy reduction (i.e., moderation) from
processes such as elastic scattering (and proton recoil), and the subsequent
resonant absorption of moderated fast neutrons.
Chapter 5 - A new class of inorganic hydrogen-containing scintillators
based on potassium dihydrogen phosphate (KDP) and related compounds
(i.e., KH2PO4, KD2PO4, NH4H2PO4, etc.) activated by ions of thallium
(Tl+) or cerium (Ce3+) (KDP:Tl and KDP:Ce) has been investigated and has
been found to provide high internal selectivity for the detection of fast
neutrons against the background of gamma radiation. These scintillation
crystals occupy an intermediate position between organic and inorganic
scintillators, and their fairly high concentration of hydrogen nuclei enables
the detection of fast neutrons based on proton recoil reactions. At the same
time, the entire crystalline matrix of the KDP crystal is not overly sensitive
to gamma radiation, since this crystalline material has a low effective
atomic number and density. Additionally, the specific mechanism of
Preface xi
luminescence by excitation of the internal hydrogen sub-lattice occurs

predominantly by heavy particles (i.e., neutron, protons, alpha-particles,
etc.), and less so by gamma rays or electrons. Theoretical calculations and
experiments show that the efficiency of fast neutron detection by small
(e.g., 10×10×10 mm3) KDP scintillator crystals can reach 12% for KDP:Tl
and 16% for KDP:Ce, levels that are as good or better than for organic
scintillators. However, the internal separation of neutron/gamma signals
(i.e., the ratio of detection efficiencies for separate registration of fast
neutrons versus gamma rays) for activated KDP crystals is 70-80 times
higher than for traditional plastic scintillators.
Chapter 6 - Syngas production through partial oxidation of
hydrocarbons is one of the actual challenges in the petrochemical and
petroleum refining industry, where a process that exhibits an optimal
industrial efficiency and usage is needed. In this context, partial oxidation
through a chemical looping (CL) can be an option to face these challenges.
In the present research, the use of mixed metal oxides (FeMoO4, Fe2ZnO4,
Fe2MnO4) as oxygen carriers under the CL reaction scheme is proposed to
overcome the current disadvantages of the partial oxidation of methane
process. The objective of the present work is to identify potential metal
oxides that are aimed for the production of syngas and able to regenerate
within favorable conditions. This was accomplished by a thermodynamic
simulation of an arrangement of two reactors using the Aspen-Plus©
process simulator. Metal oxide reduction was carried out in the first
reactor: CH4 + Fe2MO4 = H2 + CO + Fe + M, while in the second reactor
the oxidation of the reduced metals was achieved: Fe + M + H2O =
Fe2MO4 + H2, where M = Mo, Zn or Mn. Results indicate that FeMoO4,
Fe2ZnO4 and Fe2MnO4 produced syngas gas at 750°C, 730°C and 600°C,
respectively. However, FeMoO4 was not fully regenerated at favorable
conditions. Otherwise, Fe2ZnO4 and Fe2MnO4 were completely regenerated
at 440°C and 640°C. Finally, Fe2MnO4 shown the more favorable
operating conditions among the studied oxygen carriers.
Chapter 7 - Contaminants from harmful gases and natural agents are
the main source of chloride ions and sulfates, which promote deleterious
chemical reactions to civil and energy sector structures. In the civil sector,
xii Maryann C. Wythers
the main agent of degradation is the alkali-aggregate reaction (AAR),

which propagates micro cracks and reduces the lifetime of Portland cement
structures. Some papers present alternatives to reduce AAR deleterious
effects with additions of pozzolanic materials, nano-Fe3O4 and nano-TiO2.
In the electricity sector, the contaminants are responsible for increasing the
so-called surface leakage currents on the electrical insulator, whose
intensity may cause the device to fail in service. To minimize the effects of
leakage current, titanium, aluminum nitride and hafnium oxide thin films
were applied to ceramic electrical insulators to promote surface self-
cleaning properties. In this sense, a multifunction rotational system was
developed for deposition of titanium thin films. The results obtained from
the deposition process of nanostructured titanium or thin films by the
technique of magnetron sputtering plasma proved to be favorable for both
applications, namely, the reduction of the AAR in concrete structures and
reduction of the leakage current and formation of hydrophobic films with
self-cleaning characteristics in porcelain electrical insulators.
In: Advances in Materials Science Research. ISBN: 978-1-53618-716-8
Editor: Maryann C. Wythers © 2020 Nova Science Publishers, Inc.
Chapter 1
REVIEWING THE ROLE OF COAL BOTTOM

ASH AS AN ALTERNATIVE OF CEMENT
Navdeep Singh*
Civil Engineering Department, Dr. B. R. Ambedkar National Institute
of Technology, Jalandhar, Punjab, India
ABSTRACT
Coal bottom ash (CBA) is a by-product of the coal industry and is

produced to a large extent from coal-fired thermal power plants. The
utilization of CBA in the manufacturing of concrete proposes an
economic and ecological way of its disposal. Simultaneously, its usage
conserves natural resources and promotes sustainability. This review
article focuses on the utilization of CBA incorporated in place of Portland
Cement (PC) used in the manufacturing of concrete. The reduction in
particle size of CBA leads to an increase in the surface area while its
incorporation as partial replacement of PC feedbacks in improved
strength, durability and microstructural features of concrete. The studies
related to the use of CBA are scarce in quantum to date in which various
properties of concrete have been investigated. Since the current area
needs more attention as most of the investigations have favored in use of
* Corresponding Author’s E-mail: navdeeps@nitj.ac.in.

2 Navdeep Singh
CBA as partial replacement of PC whereas few of them have reported

against its use. The current investigation reviews fresh, mechanical,
durability properties and microstructural characteristics of concrete made
with partial incorporation of CBA. The literature demonstrates that CBA
has significant potential to be used as a replacement of PC for structural
grade concrete.
Keywords: concrete, coal bottom ash, microstructure, mechanical and

durability properties
1. INTRODUCTION
Flexibility, robustness, sustainability, and inexpensiveness are some of

the advantages which have made concrete one of the most usable material
on the globe. It has been expected by the designers that the designed
concrete mixes will last long for at least their expected service life (Hooton
and Bickley 2014). Such expectations lead to the formation of the concrete
which resists most of the deterioration practices to which it may be
subjected during its service life. Concretes which survive against natural as
well manmade deterioration processes are classified as durable concretes.
Generally, the exposed concrete deteriorates through internal and external
factors which are mostly in physical, chemical and mechanical form. After
achieving the mechanical criterion, improving the durability aspect is the
key factor for enhancing the overall performance of concrete. Considering
the durability aspect, permeability and pore structure are the most prudent
aspects of any type of concrete (Hooton and Bickley 2014; N. Singh,
Mithulraj, and Arya 2018; Mehta and Burrows 2001). The researchers and
technocrats are focusing on various by-product either mineral or artificial
to resolve the concern of continuing exhaustion of natural resources.
It is well known that the cement industries are creating much more
times of carbon dioxide than other industries. According to estimation in
the previous studies, 50% of the world’s carbon dioxide (CO2) emissions
come from the cement manufacturing sector (Mehta and Burrows 2001).
The production of one ton of PC generates around 0.55 tons of CO2 and
Reviewing the Role of Coal Bottom Ash … 3
requires an additional 0.39 tons of CO2 in fuel emissions for baking and
grinding, accounting for approximate one ton of CO2 (N. Singh, Mithulraj,
and Arya 2018; Mehta and Burrows 2001; CEA New Delhi 2018;
Heidrich, Feuerborn, and Weir 2013). On an average, for every one-ton
production of PC roughly generates one ton of CO2 (Mehta and Burrows
2001; CEA New Delhi 2018; Heidrich, Feuerborn, and Weir 2013; M.
Singh and Siddique 2015a). To reduce the constant depletion of natural
resources and cutting the carbon footprints, the use of mineral admixtures
has become an essential requirement of the current time. Currently,
common mineral admixtures like Fly ash (FA) (Wang and Park 2015;
Balakrishnan and Awal 2014; Huang et al. 2013; N. Singh, M, and Arya
2019), coal bottom ash (CBA) (Jaturapitakkul and Cheerarot 2003;
Kurama and Kaya 2008), silica fume (SF), metakaolin (MK), ground
granulated blast slag (GGBS), limestone powder (LP), rice husk-bark ash
(RHA), bagasse ash (BA) (Mangi et al. 2017; Bahurudeen et al. 2016),
copper slag (CS) etch., (Awal and Shehu 2013; Abdul Awal and Warid
Hussin 2011; Safiuddin, Salam, and Jumaat 2012) are adopted as partial
replacement of ordinary Portland cement (PC) to improve the properties of
concrete.
Coal bottom ash is one of the biggest sources of industrial wastes that
have been produced from coal-based thermal power plants (Nikbin et al.
2016; Baite et al. 2016; H. K. Kim and Lee 2015). In an estimate, India is
generating around 105 million metric tonnes (Mt) of coal ash comprising
fly ash (FA) and CBA ranging from 70-80% and 10-20% respectively. Out
of the total generation, around 60% - 65% of coal ash has been reused out
of which a marginal utilization of CBA has been carried out only in the
construction sector (CEA New Delhi 2018). According to the study of
World of Coal Ash (WOCA) the estimated generation of CBA from coal
thermal power plants has been moved to an approximate amount of 730
Mt. Out of which Asian countries are having share more than 66% out of
total generation followed by European/American countries (Heidrich,
Feuerborn, and Weir 2013).
Table 1.1 presents coal combustion products (CCPs) worldwide. Coal
bottom ash is generally reclaimed in ash ponds or is disposed of in landfills
4 Navdeep Singh
and adjoining areas thereby posing risk to human health and environment
(M. Singh and Siddique 2015a; Hyeong Ki Kim 2015). The hazardous
components present in CBA tend to dissociate and contaminate the
groundwater/surface water as well the surrounding air thereby affecting the
ecosystem. It has been expected that the significant and productive use of
CBA can potentially ease the burden on natural resources as well as in
balancing the ecosystem. The incorporation of CBA in structural grade
concretes in form of either mineral admixture or place of fine aggregates is
a novel move in the concrete manufacturing sector and would probably
revolutionize the current and future construction industry (Bahurudeen et
al. 2016; Awal and Shehu 2013)]. Further, its usage would probably
sustain the economy in the cement industry to some extent and offers a
probable reduction in the carbon footprints.
Table 1.1. Coal combustion products (CCPs) worldwide

(CEA New Delhi 2018)
Countries CCP’s production )Mt( CCP’s Utilisation )Mt(

Canada 6.8 2.3
Japan 11.1 10.7
Australia 13.1 6
Russia 26.6 5
China 395 265
U.S.A 118 49.7
Europe 52.6 47.8
The Middle East and Africa 32.2 3.4
India 105 14.5
The current chapter reviews some of the important investigations

which emphasize fresh, mechanical, durability properties and
microstructural characteristics of the concrete made with Natural
Aggregates (NA) with the incorporation of Grinded CBA at alternate
replacement levels of PC. Also, based on the literature it has been observed
that the behavior of CBA has not been widely explored with various types
of aggregates, though its considerable potential to use as a substitute
material in the concrete industry successfully.
2. COAL BOTTOM ASH
Across the globe, coal is one of the most recommendable natural

resources that has been used for in form of fuel for energy and steam
production for around more than one and half past century. The coal
demand in energy generation has significantly grown within the
developing and developed countries (M. Singh and Siddique 2015a). Coal
is generally black and it comprises mainly carbon as its prime compound.
According to Pei 2015, coal is classified as an organic sedimentary rock.
On the burning of coal in coal-fired boilers, it leaves behind the various
types of ashes like fly ash, coal bottom ash, boiler slag, flue gas
desulfurization materials, other types of fluidized bed combustion ash,
chemosphere’s and scrubber residues etch. are obtained (Gorme et al.
2010).
Fly ash is also known as pulverized fuel ash which is emitted from the
furnace of the coal thermal power plants. It is collected through
electrostatic precipitators that are installed to lower air pollution (Kochert
et al. 2009; Bhatt et al. 2019; Stoch 2015). Silica, alumina and ferric
oxides, MgO, SO₃, and Na₂O are its chief constituents. Also, FA is
considered as an artificial pozzolan, which is normally used with PC as
addition/partial replacement (Kochert et al. 2009; Bhatt et al. 2019; Stoch
2015; N. Singh, Kumar, and Goyal 2019).
Boiler slag is one of the other residues which has been generated in
thermal power plants. It is generally present in two types of wet-bottom
boilers (slag-tap boiler and cyclone boiler). Slag is collected from the top
of molten iron and at the bottom of the furnace. Likewise, FA, SiO₂ (27-
42%), Al₂O₃ (5-33%), MgO (0-21%) and CaO (30-50%) are its chief
constituents (Stoch 2015; Ramme and Tharaniyil 2013; Ramzi Hannan et
al. 2017).
Further, Flue gas desulfurization materials (FGD) are solids particles
generated in coal-fired power plants. These particles are formed when the
sulfur dioxide (SO₂) gas is removed before releasing the generated exhaust
gases to the atmosphere (Ramme and Tharaniyil 2013; Ramzi Hannan et
al. 2017). Furthermore, FGD is responsible for producing scrubber sludge
6 Navdeep Singh
or scrubber ash. The obtained discharge from the scrubber is in form of

off-white color slurry with the percentage of solids content ranges from 5-
10% (Ramme and Tharaniyil 2013; Butalia, Wolfe, and Amaya 2017).
Fluidized bed combustion ash (FBD) has a dark gray or black
appearance which indicates high carbon content compared to the amount
present in that of FA. Fluidized bed combustion ash contains large amounts
of calcium-based minerals along with calcium sulfates which are produced
during the capture of SO₂ (Butalia, Wolfe, and Amaya 2017).
Cenospheres are inert, hollow, lightweight spherical shaped particles
mainly comprising silica and alumina. Cenospheres are normally filled
with air or gases and are residues of the coal thermal power plants. The
different types of coal having varying mineral content influences the
formation of cenospheres. Cenospheres generally have characters like high
strength, improved workability, high thermal resistance and low bulk
density (Kolay and Singh 2001; Ranjbar and Kuenzel 2017; Kuenzel and
Ranjbar 2019).
Out of the mentioned residues, the heavier and coarser particles that
are collected from the bottom of the boiler furnace are generally termed as
CBA (M. Singh 2018). The chief residues have been collected in the form
of FA and CBA (CEA New Delhi 2018; H. K. Kim and Lee 2015).
Physically, CBA is generally coarser in size, porous, light and glassy with
granular in shape and is having similar color to that of PC (Silva and Da
Boit 2011).
2.1. Chemical Composition of Coal Bottom Ash
Depending on the type of coal burnt and the furnace conditions, the
chemical composition of CBA may vary and it further influences its
overall performance. In general, CBA obtained from lignite comprises
calcium and other alkaline elements while CBA attained from anthracite is
lower in calcium and higher in iron content (Muhardi et al. 2010; Namkane
et al. 2016). The results of the experimental investigation carried out by
(Muhardi et al. 2010) indicate that mullite (Al₆Si₂O₁₃), SiO₂, and silicon
phosphate (SiPO4) are the predominant crystalline forms which are present
in CBA. Further, silica (SiO₂) was also found to be present partly in the
crystalline forms of quartz (SiO₂) and partly in combination with alumina
as Al₆Si₂O₁₃. Also, the presence of iron (Fe) was identified partly as the
oxide magnetite (Fe₃O₄) and hematite (Fe₂O₃). Coal bottom ash also
comprises heavy metals such as Ni, Cu, Zn, Pb, Ba, and Cd which are
generally considered as hazardous materials under various environmental
protection sources (Hashemi et al. 2019; Silva and Da Boit 2011; Cenni et
al. 2001).
Table 2.1 is based on the observations sourced from the most of the
existing literature (Jaturapitakkul and Cheerarot 2003; Kurama and Kaya
2008; Hyeong Ki Kim 2015; Mangi et al. 2018; Targan et al. 2002; 2003;
Arenas et al. 2013; Aydin 2016; Abdulmatin, Tangchirapat, and
Jaturapitakkul 2018; Canpolat et al. 2004; Wongkeo and Chaipanich 2010;
Menéndez et al. 2014; Brás and Faustino 2016; Kula et al. 2001; Martins
and Gonçalves 2010; Oruji et al. 2017; Argiz, Sanjuán, and Menéndez
2017; Kizgut, Cuhadaroglu, and Samanli 2010; Khongpermgoson et al.
2019; Rathnayake et al. 2018( demonstrates the chemical composition of
CBA. In general, CBA has a higher percentage of silica (50.8±9.26),
alumina (21.7±4.26) and iron (8.4±2.75) with a lesser amount of calcium
(8.0±6.11), magnesium (2.1±1.33) and sulfate (0.8±0.85). According to
ASTM C618 (ASTM C618 2019),. the pozzolanic materials are classified
as Class-F if the summation of SiO₂, Al₂O₃, Fe₂O₃ is more than 70%. The
desired pozzolanic activity can be obtained after grinding the CBA
particles until 70% - 80% by weight is passed through a 45-µm sieve
(Martins and Gonçalves 2010). The presence of higher silica content
makes CBA hydrophilic which eventually attracts water to its surface (M.
Singh and Siddique 2015a). Correspondingly, because of the chemical
aspect, the presence of silicon dioxide (SiO₂) and aluminum oxide (Al₂O₃)
in CBA are the prime compounds that attribute to its additional pozzolanic
nature similar that in FA (Filipponi et al. 2003). These compounds react
with calcium hydroxide (Ca(OH)₂) during the hydration process of cement,
to form additional calcium silicates hydrates (C-S-H) and Calcium
aluminate hydrates (C-A-H) (M. Singh 2018).
Table 2.1. Chemical composition of CBA
Author )s( SiO₂ Al₂O₃ Fe₂O₃ CaO Na₂O LOI MgO SO₃ K₂O Mn₂O₃ TiO₂ P₂O₅ Others
Hopkins et al. 79.8 11 4.6 2.5 0.34 0.3 0.8 0.05 0.67 0.08 - - -
Kula et al. 50.98 14.96 9.63 2.63 0.47 15.7 4.01 0.16 1.3 - - - -
Targan et al. 42.39 21.35 6.41 17.57 - 10.17 1.52 2.34 1.11 - - - -
Canpolat ]47] 44.26 21.48 6.4 17.57 0.29 - 1.29 2.17 0.77 - - - -
Jaturapitakkul and 48.12 23.47 10.55 11.65 0.07 4.02 3.45 1.76 3.45 0.07 - - -
Cheerarot
Targan et al. 42.39 21.35 6.41 17.57 - 10.17 1.52 2.34 1.11 - - - -
Kurama and Kaya 55.95 16.65 9.69 4.39 0.084 4.65 5.14 0.7 1.44 - - - -
Martins 52.02 23.23 9.11 6 0.49 2.94 2.17 0.65 1.14 1.23 0.71 -
Kizgut et al. 61.36 21.86 6.78 2.55 0.44 1.75 2.1 trace 3.5 - 1.03 - 0.38
Wongkeo et al. 42.51 23.52 10.2 12.55 2.2 3.82 2.45 - 2.12 0.05 0.41 0.17 -
Wongkeo et al. 44.56 22.48 14.93 10.54 0.77 1 2.54 0.65 1.76 0.12 0.46 0.19 -
Arenas 52.32 25.14 9.23 2.37 0.66 1.07 1.84 0.03 3.72 0.07 1.45 0.25 -
Menendez et al. 49.97 26.95 8.34 8.28 0.14 1.85 1.12 0.11 0.78 0.05 2.25 0.95 0.07
Kim 45.37 25.12 5.81 0.99 0.64 13.1 1.16 - 3.87 0.06 2.84 0.18 -
Aydin 55.1 28.1 8.3 1.1 - 3.9 0.3 0.3 1.5 - - - -
Bras and Faustino 49.7 22.6 6.7 6.9 - 5.1 4.9 0.3 - - - - -
Oruji 58.7 20.1 6.2 9.5 0.1 0.8 1.6 0.4 1 - - - -
Argiz 52.4 27.5 6.6 2.4 0.36 3.8 1.83 0 3.48 0 0.97 0.12 0.006
Abdulmatin et al. 35.6 19.6 14.9 18.7 1.2 3.6 2.4 1.7 2.3 - - - -
Mangi et al. 52.5 17.65 8.3 4.72 - 4.01 0.58 0.84 - - 2.17 -
Rathnayake et al. 34.49 17.74 14.24 21.97 - - 1.90 1.71 1.42
Khongpermgoson et al. 35.6 19.6 14.9 18.7 - 3.6 2.4 1.7 2.3 - - - 0.01
Table 2.1 depicts the higher loss on ignition (LOI) values for CBA
which indicates the presence of unburnt carbon. Increased figures of LOI
also confirm the porous nature of CBA particles which subsequently
captivates more water. The exceptional LOI values of CBA considerably
affect the several characteristics of concretes/mortars which are made with
CBA as an alternate ingredient over conventional ones. The inclusion of
CBA with higher LOI leads to discoloration, weak air entrainment,
segregation and low compressive strength (M. Singh and Siddique 2014a;
Chusilp, Jaturapitakkul, and Kiattikomol 2009).
According to ASTM C618 (ASTM C618 2019), CBA with LOI less
than 7% can be inculcated in cement mortar and concretes. Also, as per
recommendations, the content of silicon trioxide (SO₃) must not exceed 5%
out of total composition to avoid loss in strength and bulging phenomenon.
Moreover, over the amount of SO₃ (≥3%) increases the probability of
drying shrinkage (ASTM C618 2019). Coal bottom ash also bears some
percentage of heavy metals like Cu, Cd, Ni, and Pb, etc. The probability of
leaching of theses metals is less when CBA has been used as a
cementitious material. The tendency of trapping of these heavy metals is
better for the mixes containing CBA as partial replacement of PC
(Hashemi et al. 2019). Coal bottom ash is generally attained from different
processing stages which finally exhibit, unlike physical and chemical
properties.
2.2. Microstructure of Coal Bottom Ash
2.2.1. Mineralogical Characteristics

The combustion temperature and cooling rate are vital parameters in
the incineration process which considerably influence the microstructure of
CBA. Figure 1 presents the SEM images acquired at a magnification of
range varying from 10-20 μm. Asokbunyarat et al. (Asokbunyarat et al.
2015) demonstrated that at the magnification of 20μm the spherical
geometries with irregular texture were spotted in CBA. Further, at a
magnification of 10μm, the agglomerated and unevenly amorphous
10 Navdeep Singh
particles were observed in CBA which were mainly in the form of

polycrystalline, amorphous and glassy. Figure 1 presents some of the prime
features of CBA particles.
Figure 1. Morphology images of coal bottom ash by SEM at 20 μm magnification (a)

and 10 μm magnification (Asokbunyarat et al. 2015).
The observations from Asokbunyarat et al. (Asokbunyarat et al. 2015)

investigation verified that the major elements in CBA were silicon (Si), Al,
iron (Fe) and calcium (Ca) as oxides. Also, on the other hand, principal
elements in all the mentioned points of Figure 1 on the surface of CBA are
shown in Table 2.2. Further, the diffractogram in as mentioned in Figure 2
shows the X-ray diffraction (XRD) analysis of the CBA samples. The
results indicated that CBA was highly amorphous besides the presence of
crystalline phases like mullite, feldspar, magnetite, and quartz
(Asokbunyarat et al. 2015).
Furthermore, another experimental investigation supported Muhardi et
al. (Muhardi et al. 2010) the microstructural analysis of CBA. The findings
illustrated the presence of mullite, silicon oxide and silicon phosphates are
vital crystalline forms that are present in CBA. It has also been confirmed
from the aforesaid investigation that silica was present partially in the
crystalline shapes of quartz and blend of Al as mullite. Also, the presence
of iron was detected partly in the form of oxide magnetite and hematite.
Similar findings have been experienced by Gorme et al. (Gorme et al.
2010).
Figure 2. X-ray Diffraction pattern of coal bottom ash (Asokbunyarat et al. 2015).
Table 2.2. Elements in CBA from SEM-EDS analysis

(Asokbunyarat et al. 2015)
Point Surface Morphology Element

1, 2, 3, 8, 9 Smooth surface texture Silicon )Si(, Aluminum )Al(, Iron )Fe(, Calcium
)Ca( as oxides
4 White sphere surface texture Iron )Fe( as oxides
5, 7 White and black irregular Silicon )Si(, Calcium )Ca( as oxides
surface texture
6, 10 White bar surface texture Aluminum )Al(, Silicon )Si(, Calcium )Ca( as
oxides
2.3. Pozzolanic Activity and Reactivity of Coal Bottom Ash
In general, the pozzolanic response of the material is the capacity to

react with Ca(OH)2 (Thomas 2013). According to Massazza (Massazza
2003) the entire quantum of calcium hydroxide with which pozzolanic
12 Navdeep Singh
materials can associate governs on various aspects like, duration of curing,

silica content of reactive phases, the ratio of Ca(OH)2 to pozzolan, and
content of reactive phase in the pozzolan. Also in addition to preceding
factors, the frequency of reaction of pozzolanic materials with Ca(OH)2 is
strongly dependent on the surface area of the pozzolan, alkaline content in
PC, temperature, and water/solid ratio. The pozzolanic action of material is
generally estimated by chemical, physical and mechanical methods. In the
chemical method, the drop of calcium ions is evaluated generally when the
pozzolanic material is dissolved in a saturated lime solution. The procedure
which is adopted for this measurement is under the International
Organization of Standards (ISO) recommendations R863-1968. The
strength activity index offers the idea of mechanical pozzolanic activity.
As per European standard EN-450, the strength activity index is defined as
‘the ratio of compressive strength of mortar bar prepared with 75% PC and
25% ash or pozzolanic material by mass and that of mortar bar prepared
with cement alone’.
According to European standard EN-450, the coal ash is only
permissible to be used as a pozzolan in concrete if the strength activity
index is greater than 0.75 after 28 days and 0.85 after 90 days of curing.
Cheriaf et al. (Cheriaf, Rochaa, and Pérab 1999) conducted an
experimental investigation in which the influence of CBA and calcium
hydroxide was studied in concrete. The findings proved that at a curing
period of 7-90 days, the compressive strength of CBA based concrete
mixes (50% CBA + 50% Ca(OH)2 with water/solid ratio=0.42) was 1.8-
17.3 MPa respectively. Likewise, for the same curing ages, the
consumption of Ca(OH)2 for the aforesaid mixes was reported to be 5%,
15%, 37%, and 60% of total amount respectively. Besides, the strength
activity index of these concrete mixes was noted as 0.72, 0.764, 0.88, and
0.97, respectively. The investigation revealed that the advantageous
pozzolanic action of CBA initiates after crossing 14 days of curing while
the utilization of Ca(OH)2 comes in to play after crossing 90 days of
curing. Figure 3 demonstrates the corresponding effect of CBA and
Ca(OH)2.
It has already been mentioned that CBA has a strong reactive fraction
along with additional pozzolanic characteristics. In addition to that, CBA
holds vitreous fractions in the form of mullite. Hashemi et al. (Hashemi et
al. 2018) discussed the microstructural characterization of CBA based
mortars. The microstructural analysis was conducted using SEM and XRD
analysis on various combinations of mortars containing CBA as a
replacement (0% to 100% with a regular increment of 20%) of fine
aggregates.
Figure 3. Coal bottom ash particle starting to react with Ca(OH)₂ (Cheriaf, Rochaa, and
Pérab 1999).
The SEM and XRD results of different combinations indicate the

presence of higher reactive silica in CBA which consequently results in the
formation of more amount of C-S-H gel. The investigation also reported
that the quantification of reactive silica obtained through XRD analysis
specifies the better dissolvability of CBA which subsequently proved to be
beneficial for PC based composites. An identical validation has been
previously conducted for the dissolution process adopted for FA where it is
subjected to alkali activation in the process of geopolymerization. Herein,
it is worthwhile to mention that the ratio of Si/Al (aluminosilicate
precursors) share equivalent importance as that of the quantum of other
reactive materials (Kuenzel and Ranjbar 2019).
14 Navdeep Singh
2.4. Physical Properties of Coal Bottom Ash
The physical properties of CBA depend on the variability of parent

rock fragments collected from different sources. The degree of
pulverization and firing temperature are additional factors that affect the
physical properties of CBA. In general, the particles of CBA are much
coarser than the particles of FA. For, CBA the unit weight/density ranges
from 1200-1620 kg/m³ while the density of FA ranges from 1900-2800
kg/m³ (Wordpress Ash Coal English n.d.; Federal Highway Administration
2016). As mentioned above, the particles of CBA are coarser in size but are
not heavy than that of FA particles.
Also, the particles of CBA are mostly angular and irregular in shape
with visible apertures and have rough/gritty texture along with interlocking
features (M. Singh 2018; M. Singh and Siddique 2014b; Pant et al. 2019).
Mangi et al. (Mangi, Wan Ibrahim, et al. 2019) indicate in his experimental
program that pulverization or grinding of CBA significantly affects its
physical behavior. The grinding periods proportionally vary the specific
gravity of CBA as it increases with an increase in time. Similarly, a
continuous variation has been noticed for values of the specific surface
with increment in time of grinding. A range of 2.36-3.10 of specific gravity
and 2347.73-4870.81 cm²/g has been reported after a grinding period of 2
hours to 40 hours (Mangi, Wan Ibrahim, et al. 2019).
In a similar investigation conducted by Bajare et al. (Bajare, Bumanis,
and Upeniece 2013), a range of 1164-9849 m²/g of the specific surface has
been noticed after grinding period ranging from 4-45 minutes. Further,
Hannan et al. quoted that a good correlation exists between sizes of CBA
particles with that of compressive strength (Ramzi Hannan et al. 2017).
According to M. Singh, the firing temperature affects chemical properties
more compared to that of physical variation (M. Singh 2018).
The physical examination shows that the particle size of CBA is
comparable to that of the fine aggregates and it is lighter, weaker and more
brittle material in its comparison. Jaturapitakkul and Cheerarot, Singh and
Siddique indicated that gradation of CBA resembles that of natural fine
aggregates (NFA) (Jaturapitakkul and Cheerarot 2003; M. Singh and
Siddique 2014a; 2014b). The gradation also depicts that 80%-90%

particles of CBA pass through 4.75 mm sieve, 10%-60% particles pass
from the 600-μm sieve and 0%-15% particles pass through a 75-μm sieve
(M. Singh 2018).
Table 2.3. Physical properties of CBA (%) reported by various authors
Author(s) Physical Properties

Specific gravity Water absorption (%) Fineness modulus
Naik et al. (Naik et al. 2007) 2.09 13.6 -
Andrade et al. (Andrade, Rocha, 1.67 - 1.55
and Cheriaf 2007)
Yuksel and Genc 1.39 6.1 -
Kou and Poon 2.19 28.9 1.83
(Kou and Poon 2009)
Ghafoori and Bucholc 2.33 7.0 2.8
Kim and Lee 1.87 5.4 2.36
(H. K. Kim and Lee 2011)
Singh and Siddique 1.5 30.4 -
Malkit and Rafat 1.39 31.5 1.37
The specific gravity (SG) and fineness modulus (FM) of CBA varies
from 1.20-2.47 and 1.39-2.88 (Table 2.3) depending on the quality and
source of coal respectively. The CBA bearing low SG has a porous texture
comprising micro and macropores. Rashidi and Yusup (Rashidi and Yusup
2016)reported the observed BET surface area for raw sub-bituminous as
7.62 m²/g while Hussain et al. (Hussain et al. 2019) has mentioned BET
surface area value of CBA as 17.64 m²/g. Further, CBA obtained from
low-rank coals and having high sulfur is dense and less porous (Ghafoori
and Bucholc 1996). Besides, the dry unit weight generally varies from
7.07-15.72 kN/m³, the water absorption of CBA lies between 5%-32%,
respectively. Table 2.3 presents the wide variation in the physical
properties of CBA as reported in some of the earlier investigations. Coal
for thermal power stations is generally obtained from the sedimentary
rocks, the nature of these rocks varies from source to source with the effect
of their age as well as the depth of occurrence. Hence, the parameters like
water absorption, density and specific gravity show wide variation
16 Navdeep Singh
following their parental source (Butalia, Wolfe, and Amaya 2017; M.

Singh 2018; Pant et al. 2019; “Coal | National Geographic Society” n.d.).
3. GENERAL ENVIRONMENTAL CONSIDERATIONS
The transportation of raw coal and the availability of cooling water

normally favors the proposed sites for the construction of coal-based
thermal power plants. The coal ashes (FA, CBA, slag and other products)
obtained as residue are generally dumped nearby the coal power plants.
These ashes are usually discarded from the bottom of boilers with the
application of pressurized water (Cheriaf, Rochaa, and Pérab 1999; Bajare,
Bumanis, and Upeniece 2013). The toxic trace elements like cadmium,
chromium, lead, etc., of coal ashes, dissolve and percolate in the form of
leachate which subsequently contaminates the groundwater. The use of
CBA as alternate material can minimize the quantity of harmful leachate.
Further, the concentration of trace elements like Cadmium, Chromium,
lead, etc., makes CBA less toxic than FA as in the latter the same are found
in higher levels (Goodarzi and Huggins, 2001). The presence of acidic
conditions in the surroundings of the CBA dumps enhances the leachability
of Chromium and Nickel compared to that of FA (Goodarzi and Huggins
2001).
Furthermore, Eshel et al. (Eshel et al., 2001) investigated the radiological
safety characteristics of concrete with CBA. In terms of radioactive
exposure, the use of CBA in the concrete industry reduces the damage to
the environment to some more extent rather than its application in piles and
ponds. From Table 2.1 it has been noticed that the content of TiO₂, Mn₂O₃,
K₂O, P₂O₅, etc holds approximately 3% of the total chemical composition.
Though these chemical compositions of heavy compounds are sufficient to
cause significant loss of living beings in the form of various life-
threatening diseases. The presence of CBA in open spaces enhances the
probability of inhalation of heavy metals containing mercury, cadmium,
chromium arsenic, lead and aluminum, antimony, barium, cobalt,
manganese, nickel, and zinc, etc. The intake of these metals consequently
leads to the risk of permanent damage of lungs, respiratory systems,

kidneys, reproductive systems, gastrointestinal, birth defects and weaker
bone intensity in children.
In the case of landfills, solidification and stabilization techniques are
preferred as of the most practical methods for pre-treatment of hazardous
or toxic materials like CBA. Coal bottom is considered hazardous material
due to the contamination of heavy metals such as Ni, Cu, Zn, Pb, Ba, and
Cd. Hashemi et al. (Hashemi et al. 2019) conducted an experimental
investigation in which the possibility of heavy metals leaching of Cu, Cd,
Ni, and Pb has been evaluated by solidification and stabilization
techniques. The experimental investigation infers the probability of
leaching of heavy metals in the environment is more for higher contents of
CBA. Further, the rate of controlling leaching is not similar for various
types of leachates like deionized water, acetic acid, and nitric acid
leachates. Herein, it is worthy to mention that the leaching is generally
dependant on the type of sample since CBA particles bear higher surface
areas thereby elevates the probability of more leaching towards the ground
surface (Hashemi et al. 2019).
4. PROPERTIES OF CONCRETE MADE WITH CBA AS

REPLACEMENT OF PC
The following paragraphs summarize the influence of CBA used as

partial replacement of PC on fresh, mechanical, durability properties and
microstructural characteristics of concrete. The discussion in the following
sections includes nearly most of the investigations (to date) in which fresh,
mechanical and durable behavior/performance has been examined whereas
few of the important investigations related to microstructure analysis have
been presented in brief. Herein it is worthwhile to mention that the current
review focuses only on the utilization of CBA as partial replacement of
PC, irrespective of the variation of aggregates (coarse and fine) with
alternate materials. In brief, the current review investigation also
18 Navdeep Singh
summarizes the mechanical behavior of CBA based mortars in which

Grinded CBA has been replaced with PC.
4.1. Fresh Properties of Coal Bottom Ash Based Concrete
The behavior of freshly made concrete is of vital importance as it

permits in understanding the overall performance of concrete. In general,
the workability of freshly made concrete is primarily influenced by surface
area, shape, water content and texture of the added materials (M. Singh
2018). The presence of CBA as an alternate material for PC affects the
fresh properties of concrete. The linking feature of CBA particles enhances
the inter-particle friction thereby hampering the free flow of fresh concrete
(Cadersa and Auckburally 2013). The influence of CBA as a replacement
for PC has been discussed scarcely as a couple of investigations are
available in the literature.
It has been reported that the workability of concrete/mortar containing
Grinded CBA as alteration of PC depends on various factors like grinding
period, fineness modulus/gradation, source of collection, etc. Out of the
aforesaid, the effect of the grinding period has been discussed by Mangi et
al. (Mangi et al. 2019). The findings confirmed that concrete containing
10% of Grinded CBA results in lower values of slump flows in contrast to
flow spread of control concrete.
Mangi et al. (Mangi et al. 2019) prepared the concrete mixes (M1 and
M2) with 0% and 10% replacement of PC with ground CBA. The results
indicate that a reduction of around 10% has been noticed in slump values
due to the incorporation of ground CBA (Figure 4) in comparison to that of
control concrete. The loss in the workability was mainly due to the
presence of Grinded CBA in concretes which captivate additional water
during the time of mixing. The uneven surface texture of CBA particles
also accounts for lower slump values (Mangi et al. 2019). On the contrary,
conflicting observations for different combinations of mortars were
observed in which the slump values are enhanced (Jaturapitakkul and
Cheerarot 2003). Three control mortar mixes (CC25, CC35, CC45) were
prepared correspondingly with three combinations of ground CBA

(GBC25, GBC35, GBC45). The investigation revealed that with an
increase in the content of ground CBA the slump values of ground CBA
based mortars were found to be increased, however, the anticipated
clarification has not been discussed by the authors (Figure 4).
Figure 4. Slump flow values of Grinded CBA based concrete mixes.
4.2. Compressive Strength of Coal Bottom Ash Based Concrete

and Mortar
The most reliable and hand to hand tests performed on concrete to

evaluate its performance is the compressive strength test. A compressive
strength test generally gives an idea about several characteristics of
concrete (Bhardwaj and Kumar 2017). Several mechanical and durability
properties of concrete are directly or indirectly correlated to its
compressive strength. The overall quality of concrete can be easily judged
by knowing the compressive strength. Abdulmatin et al. (Abdulmatin,
Tangchirapat, and Jaturapitakkul 2018) investigated the influence of partial
replacement of PC in concrete with Grinded CBA. The effect of grinding
has been discussed under the percentage by-weight of CBA retained
specifically on 45 µm sieve. Five different levels (3.7, 14.5, 24, 35.3, and
20 Navdeep Singh
43.7) of percentage by-weight were adopted for studying the effect of

Grinding of CBA. The results revealed that the compressive strength
values corresponding to 3.7% by weight with a median particle size of 4.3-
µm showed an increase at all curing ages. An increase to an extent of 6%,
has been noted for this percentage level while for the remaining levels (as
mentioned above) the compressive strength values have been dropped from
8%-30% after 28-90 days of curing compared to that of control concrete.
However, the observed gap in compressive strength tends to drop when
the curing age is extended to 90 days. Cheriaf et al. (Cheriaf, Rochaa, and
Pérab 1999) have mentioned the probable reason for improvements in
compressive strength of concrete after 90 days of curing containing
Grinded CBA as a PC replacement. Since the pozzolanic activity of CBA
initiated after 28 days of curing, hence due to higher formation of
hydration products at later ages consequently increased the compressive
strength. Further, the incorporation of finer CBA i.e., 4.3-µm depicted an
improvement in compressive strength due to inherent pore refinement
action as finer particles filled the pores in the paste thus increasing the
hydration products formed during pozzolanic reactions (Abdulmatin,
Tangchirapat, and Jaturapitakkul 2018).
Brás and Faustino (Brás and Faustino 2016) evaluated the performance
of Grinded CBA as partial substitution of PC with contents of 10%, 15%
and 20% by weight. The equivalent compressive strength was obtained
with the incorporation of 15% and 20% replacement level of Grinded CBA
at 28 days of curing age. A considerable increase of about 15%-20% was
noticed at 60 days of curing for the aforesaid levels of Grinded CBA. Brás
and Faustino (Brás and Faustino 2016) also confirmed in his findings that
repair mortars up to 20% substitution levels of Grinded CBA in place of
PC results in satisfactory performance as decrement in the porosity levels
has been noticed compared to that of control mix.
Further, Jaturapitakkul and Cheerarot (Jaturapitakkul and Cheerarot
2003) used two different approaches to evaluate the behavior of Grinded
CBA in mortar and concrete. In the mortar mixes Ground CBA was used at
the rate of 10%, 20% and 30% by weight of cementitious material. It was
noticed that the compressive strength was increased by 8-12% at a curing
period of 90 days compared to that of control mortar. Likewise, in the

second approach, the cement content was varied from 260-440 kg/m³ while
maintaining a constant w/c ratio. The replacement level of Grinded CBA as
an alteration of PC in concrete mixes was limited to 20%. The rate of
development of compressive strength was found to be much quicker with
an increase in cement content due to the pozzolanic reaction between
Ca(OH)2 and Ground CBA.
Many previous studies considered the variation of Grinded CBA at
9%, 23%, 33% and 41% by percentage weight of binder with constant w/c
ratio of 0.55 in the degree of fineness by grinding for periods of ½ hour
and 3 hours (Jaturapitakkul and Cheerarot 2003; Abdulmatin,
Tangchirapat, and Jaturapitakkul 2018; Oruji et al. 2017). An enhancement
in compressive strength up to 10% after 28 days of curing for 3 hours of
the grinding period was reported for all replacement levels of Grinded
CBA.
It has also been reported that for percentage weight of binder beyond
33%, the compressive strength was not improved significantly for ½ hour
of grinding period after 90 days of curing. However, the overall trend of
low compressive strength is similar for the higher replacement levels
where the grinding period is constricted to ½ hour. The alike investigation
was conducted by Khan and Ganesh (Khan and Ganesh 2016) in which
equivalent results were reported up to 20% variation of Grinded CBA for
½ hour grinding at 28 days of curing in terms of compressive strength in
comparison to control concrete. Similarly, in another investigation, the
effect of Grinded CBA up to 20% have shown a maximum drop of around
15% in compressive strength for same age of curing compared to control
concrete (Kurama and Kaya 2008; Hyeong Ki Kim 2015; Menéndez et al.
2014; Hopkins et al. 1998). The presence of cement additions affects the
compressive strength of Grinded CBA based concretes significantly.
Hopkins et al. (Hopkins et al. 1998) used 4% of Silica fume with a
replacement level of 20% with Grinded CBA. The enhancement in
compressive strength to an extent of 22% was reported at 28 days in
comparison to control concrete. Likewise, Targan et al. (Targan et al.
2003) observed the enhancement in compressive strength of concrete with
22 Navdeep Singh
an increase in the content of Grinded CBA (with a fineness of 25 by

percentage mass on 40 µm sieve). Five different levels (5%, 10%, 15%,
20% and 25% by mass) of replacement of PC were used for investigating
the mechanical properties of CBA based concrete. The compressive
strength at 28 days of curing was found to be increased by 5-16% in
contrast to that of control concrete mix. As quoted above the compressive
strength was increased considerably for low replacement levels of Grinded
CBA while the same was not true for replacement level ≥20%. The
observed decrement in compressive strength was attributed to relatively
low reactivity of Grinded CBA at early ages in relation to higher
increments at 90 days of curing. Similar to the investigation conducted by
Wongkeo and Chaipanich (Wongkeo and Chaipanich 2010), Hopkins et al.
(Hopkins et al. 1998) reported the consistent increment in compressive
strength of CBA based concrete with fusion of SF (5% by weight) up to
30% replacement level of Grinded CBA with PC.
Table 4.1. Compressive strength of concrete at 28 days of

curing at different contents of Grinded CBA
Author)s( Ground Coal Bottom Ash )%(

0% 5% 10% 15% 20% 25% 30% 35% 40%
Khan and Ganesh 28 - 35 - 35 - 32 - -
Bras and Faustino 65 - 58 55 50 - - - -
Kim 80 - - 72 - - - - -
Menendez et al. 52.5 - 55 - - 42.5 - 35 -
Bajare et al. 47 - - - 45 - - - 27
Kizgut et al. 46 44 42 41 40 38 - - -
Kurama and Kaya 40.9 40.4 40.3 33.6 - 29.1 - - -
Jaturapitakkul and 40.8 - 40.5 - 39.7 - 38.3 - -
Cheerarot
Kula et al. (Kula et al. 2002) have conducted his investigation in

making different concrete combinations by using tincal ore waste with
Grinded CBA in varying proportions. The tincal ore is also known as borax
and is a natural as well as a by-product of the tin mining industry. Kula et
al. (Kula et al. 2002) found that the addition of tincal ore waste up to 5%
by weight with Grinded CBA at 10% replacement of PC results
incomparable values of compressive strength to that of control concrete

combination at 90 days of curing. However, the compressive strength has
been dropped with tincal core waste for a higher proportion of Grinded
CBA (≥10%) as a replacement of PC.
Further, in a similar investigation conducted on mortar specimens, the
change in compressive strength results of mortar mixes made with a fusion
of colemanite waste along with Grinded CBA as replacement of PC. It has
been found that the use of colemanite ore waste (at 4% by weight) in
combination with Grinded CBA (at 10% by weight) enhanced the
compressive strength of PC based mortar for a curing period of 90 days
(Wongkeo and Chaipanich 2010). Apart from the abovementioned Targan
et al. (Targan et al. 2003) studied the influence of natural pozzolan at
varying proportions (10%, 15%, 20%, 25%, and 30%) with a fixed amount
of Grinded CBA (10% by weight). The investigation confirmed the
substantial enhancement in compressive strength at all curing ages. The
possible reason for this improvement attributes to the bridging between the
pastes of PC, Ground CBA, and natural pozzolan. Though higher
replacements (>15%) with natural pozzolan along with Grinded CBA
causes a significant drop in compressive strength of concrete. The
observed reduction was possibly due to excess of small-sized particles of
pozzolan and Ground CBA which further tend to dissociate PC particles,
thereby causing a reduction in compressive strength. Targan et al. (Targan
et al. 2002) also studied the effect of Grinded CBA (with a varying
fineness) along with the addition of bentonite. The addition of bentonite
dropped the compressive strength at all percentages (5-20%) irrespective
of varying dosage levels along with a constant proportion of Grinded CBA
(at 10% with PC) for all curing regimes. As described in the investigation
the increased in level of porosity due to the presence of bentonite ascribes
a negative influence on the mechanical performance of the mortar (Targan
et al. 2003). Ground Coal bottom ash has been used further in ternary
blended concrete mixes. The studies on ternary blends with zeolite and
Ground CBA (5% by weight) in place of PC (in fixed proportion)
increased in the compressive strength of concretes. As it has been noticed
24 Navdeep Singh
that comparable mechanical properties (compressive strength) with greater

resistance to aggressive agents have been noted (Canpolat et al. 2004).
Ground Coal bottom ash has also been used in high proportions as a
replacement for PC. For example, Aydin (Aydin 2016) studied the
feasibility of developing concretes with 70% and 80% replacement levels
of PC with Grinded CBA. However, the compressive strength was dropped
considerably compared to the control concrete. Further, the compressive
strength tests were performed with the incorporation of lime (5% by
weight) with Grinded CBA (70% by weight) in place of PC. The
investigation concludes that a significant increase (around 20%) in
compressive strength was noticed in comparison to the control concrete
combination. The addition of lime with a high volume of Grinded CBA
enhanced the hydration process and lead to a reduction in the voids which
are present in the paste of concretes.
A mixed behavior in compressive strength test results has been noticed
in the preceding paragraphs comprising most of the available studies in
which Grinded CBA has been used in place of PC. The general trend of the
compressive strength based on the literature at 28 days of curing has been
summarized in Table 4.1.
4.2.1. Microstructural Analysis of Concrete with Incorporation of

Coal Bottom Ash
The arrangement comprising C-S-H gel, Ca(OH)2, ettringite, calcium
hydrates (CH), aggregates and interfacial transition zone (ITZ) among
aggregates (coarse/fine) and other cement hydration products constructs
the microstructure of concrete (M. Singh 2018). Commonly, the
microstructure considerably impacts on the mechanical properties of
concretes. Besides, the microstructure is affected primarily by numerous
parameters like water-cement (w/c) ratio hydration period, type of cement
and mineral/cement additions used in concrete, etc. The microstructure of
CBA based concretes made with replacement of FNA has been explored
widely compared to the concretes containing Grinded CBA as replacement
of PC.
According to previous studies (M. Singh and Siddique 2014b; 2015b),

during the maturation of concrete, the elite and elite converts into C-S-H
and Ca(OH)2. The presence of C-S-H can be identified from the geometry
of the fibrous structure along with sometimes reticular networks at the
initial stage of hydration. With further progress in the hydration process,
the C-S-H phase can be envisaged in the form of equant grains. The
concrete containing CBA also projects the presence of Ca(OH)2 which can
be seen in various geometries/shapes like giant platy form, large-thin
elongated and blocky masses to finely dispersed crystals. Calcium
sulfoaluminate hydrates (C-A-H) also appear as in the form of ettringites
and monosulfates. Ettringite generally appears as needle-like Ettringites
generally appear as needle-like crystals while the monosulfates appear as a
hexagonal form of crystals. Figure 5 highlights some of the aforesaid
geometries in concrete specimens containing 75% CBA by weight of PC at
28 days of curing. Correspondingly, Figure 5 also presents the EDS
spectrum of C-S-H gel for the same concrete specimen. Likewise, the
microstructural investigation has been conducted by Yuksel et al. (Yüksel,
Bilir, and Özkan 2007) on concrete specimens containing CBA and FA
(10% by weight) as alteration of FNA and PC respectively. On the use of
CBA as an alternate of FNA (10%,20%,30%,40%, and 50%), the granular
phase of hydration products reformed into circular geometry with an
appropriate reduction in pores compared to concrete made with natural
river sand. The investigation also revealed that the observed improvement
in the overall microstructural network attributes to the regular increments
in the content of CBA in concrete mixes. A series of investigations have
been conducted by Heidrich et al. (Heidrich, Feuerborn, and Weir 2013),
Singh and Siddique (M. Singh and Siddique 2014b; 2015b) where the
microstructure of CBA based concreters have been studied. The beneficial
pozzolanic activity of CBA has been re-validated in these investigations.
Figure 3 shows the ongoing reaction phase of CBA with the portlandite.
26 Navdeep Singh
Figure 5. SEM and EDS spectrum of concrete containing 75% CBA at 28 days
showing ettringite (needle-shaped) in the concrete matrix (M. Singh and Siddique
2015a).
A duality in the pozzolanic activity of CBA in concrete has been

noticed as for low replacements, the pozzolanic action improved the
overall microstructure whereas it deteriorates for higher contents at 28
days. For example, at 50% content of CBA, delay the microstructural
improvements in the form of lower production of C-S-H gel has been
experienced. The preceding statement can be validated from the observed
Scanning electron microscopy (SEM) image which presents, needle-shaped
ettringite adjacent to the round-shaped particles of CBA with part of
Ca(OH)2 crystals near the cracks. Figure 6 presents the SEM image of the
concrete specimen made with 50% of CBA as FNA. Significant
improvements have been noticed at 90 days of curing in the microstructure
of CBA based concretes. Similarly, the SEM investigations of CBA based
concrete made as replacement of FNA has been conducted by Yuksel and
Genc, Bilir (Yüksel, Bilir, and Özkan 2007; Yüksel and Genç 2007). The
SEM images indicate the establishment of discrete grains and porous areas
adjacent to the aggregate surfaces. The addition of CBA disturbs the
microstructure of concrete and results in the formation of pores. Likewise,
as reported by Rafieizonooz et al. (Rafieizonooz et al. 2016) the inclusion
of CBA enhances the quantum and size of voids along with less formation
of C-S-H gel i.e., non- monolithic and less compacted in nature compared
to control concrete.
Mangi et al. (Mangi et al. 2019) investigated the effect of Grinded
CBA with an alteration of PC with 10% by weight. The SEM tests were
conducted on the specimens that were immersed in (i) water (ii) 5% of
sodium sulfate (Na2SO4) and (iii) 5% sodium chloride (NaCl) for 56 days.
For water cured specimens, well-defined/monolithic shapes of C-S-H
crystals have been noticed. Likewise, the development of ettringite for 5%
of Na2SO4 solution partially clogged the voids, thereby enhancing the
strength development of concrete mix (Mangi et al. 2019; Ming, Deng, and
Li 2016). The negative effect of 5% of NaCl in concrete mixes can easily
be judged from the SEM image which depicts the weak formation of C-S-
H gel. The ingression of 5% of NaCl results in the initiation of cracks
thereby lead to a reduction in the strength properties of concrete. The SEM
images for the abovementioned solutions are shown as Figure 7 (a-c).
Figure 6. SEM image of concrete containing 50% CBA at 28 days (M. Singh and
Siddique 2015b).
28 Navdeep Singh
Figure 7. SEM micrograph of a) with water solution b) with 5% Na2SO4 solution c)

with 5% NaCl solution (Mangi et al. 2019).
4.3. Flexure Strength of Coal Bottom Ash Based Concrete

and Mortar
In general, the flexural strength represents the maximum stress and the
force experienced within the unreinforced concrete specimens to withstand
any bending failures. Kurama and Kaya (Kurama and Kaya 2008) used
pretreated CBA which was subjected to wet screening for removal of
floated particles, primarily the carbon particles. After pretreatment, the
CBA was ground in a ball mill to achieve the fineness of 25% by mass
retained on 38µm sieve. The results after achieving the desired level of
fineness confirmed the increment in compressive strength up to 15%
substitution level whereas the decrement in the same was reported beyond
15% replacement of Grinded CBA with PC. The rate of gain in
compressive strength increases with the addition of Grinded CBA as an
alteration of PC at the curing of 28 and 56 days compared to the base
concrete. The probable cause for the observed drop in the compressive
strength (28 days and 56 days) beyond the 15% level of Grinded CBA was
due to lower binder content.
Table 4.2. Flexural strength of concrete mixes at different curing ages
Aydin 0% CBA 70% CBA 100% The flexural strength tends to decrease with
Curing period CBA an increase in partial/full replacement of CBA
7 days 1.68 1.25 0.25 with PC at 7 and 28 days of curing age
28 days 2.28 1.65 0.39
Targan et al. Reference 5% B+ 10%B+ 15%B+10 20%B+ Similar trend has
Curing period Mix 10% 10% % CBA 10% CBA been followed for
CBA CBA curing age of up to
7 days 5.4 4.2 4.1 3.2 3.9 90 days of curing
28 days 7.6 7.2 6.2 4 5.6 age
56 days 7.8 7.8 7.2 6.7 6.1
90 days 7.9 8 7.8 7.2 6.8
Kurama et al. Reference 5% CBA 10% CBA 15% CBA 25% CBA At later ages )28
Curing period Mix and 56 days of
7 days 6.08 6.27 6.07 5.77 4.72 curing age(, the
28 days 6.6 6.75 6.62 6.57 6.22 flexural strength
56 days 6.86 7.35 7.6 7.2 6.69 increases for
different
replacement levels
of CBA
Wongkeo et Reference 0% CBA 10% CBA 20% CBA 30%CBA Higher
al. Mix replacement of
Curing period CBA in concrete
28 days 4 2.6 2.7 2.7 3.2 mixes tends to
have lower flexural
strength compared
to the reference
mix
Targan et al. Reference 5% 10% NP+ 15% NP+ 20% NP+ 25% NP 30% NP
Curing period Mix NP+10% 10%CBA 10% 10% CBA + 10% +10%
CBA CBA CBA CBA
7 days 5.5 5.9 5.2 5.1 4.8 4.3 3.5
28 days 7.5 7.2 6.4 6.2 5.8 5.2 4.8
56 days 7.8 7.8 7.2 6.9 6.5 5.8 5.4
90 days 7.9 8 7.4 7.2 6.6 6 5.6
30 Navdeep Singh
Further, Wongkeo et al. (Wongkeo et al. 2012) revealed the outcomes

of concrete mixes made up to 30% replacement levels of Grinded CBA
which was grounded for 6 hours in a ball mill with 0.2% by weight of
Aluminum (Al) powder. The flexural strength has been increased around
23% with 30% content of Grinded CBA as a replacement of PC concerning
control concrete. However, for the concrete mix made without Al powder,
the flexural strength tests results containing 30% of Grinded CBA as
replacement of PC was comparable to the control concrete mix.
Furthermore, Targan et al. (Targan et al. 2002) investigated the effect
of Grinded CBA with a fusion of bentonite on the flexural strength of
concrete. The results for the flexural strength tests pursued similar trends as
that of the compressive strength tests for 10% replacements level of
Grinded CBA with PC. Likewise, identical figures in flexural strength were
observed with the incorporation of natural pozzolan as cement replacement
along with Grinded CBA. Aydin, Targan et al. (Aydin 2016; Targan et al.
2003) reported the decrement in flexural strength in concrete mixes with
the presence of Grinded CBA as high volume substitution of PC (70% by
weight). The concrete mixes made with lime (5% by weight) as substitution
of PC along with Grinded CBA (70% by weight) results in higher flexural
strength at all curing ages. In a concrete mix containing 100% of Grinded
CBA as alteration of PC results in a sheer drop in compressive and flexural
strength in comparison to control concrete at lower and higher curing
periods (Aydin 2016). The aforementioned discussion on flexural strength
test results offered by various authors is shown in brief in Table 4.2. Table
4.2 also presents the effect of different levels of replacement of Grinded
CBA and curing age. Herein, it is worthwhile to mention that limited
investigations are available on the behavior of flexural strength of concrete
having Grinded CBA as replacement to PC. However, the noticed results
of flexural strength tests have been found in good correlation with
compressive strength tests results.
4.4. Capillary Water Absorption and Carbonation of Coal

Bottom Ash Based Concrete
Capillary suction is the degree of the medium to absorb liquid by the

action of capillarity. In this particular test, the increment in the mass of the
concrete specimens is recorded with time. It has been noticed from the
available sources that the performance of concretes made with Grinded
CBA in terms of capillary water absorption is quite insufficient. Most
probably, Martins and Goncalves (Martins and Gonçalves 2010) performed
an investigation on the capillary absorption of concrete mixes containing
Grinded CBA at two different replacement levels (25% and 33% by
weight) for different curing periods. The CBA based concrete mixes were
compared to concretes made with a similar amount of FA (25% and 33%
by weight) along with the same binder (300, 350, 400 kg/m3) and curing
ages.
The observations confirmed that the capillary absorption values of
concrete specimens were decreased with increasing binder content for both
types of concretes. Specifically, the concrete mixes in which PC was
replaced by Grinded CBA resulted in a marginal drop in terms of capillary
absorption coefficients as compared to concrete mixes made with FA. The
expected drop in capillary absorption coefficients was noticed due to a
reduction in overall porosity levels. Figure 8 presents the Capillary
absorption test results of concretes with varying binder contents at 28 days.
Martins and Goncalves (Martins and Gonçalves 2010) also evaluated the
effect of Grinded CBA and FA in concrete in terms of carbonation
resistance. The probability of concrete corrosion can be estimated through
accelerated carbonation test. Accelerated carbonation tests were conducted
for 65 days of exposure at 65 days of curing. The carbonation resistance
has been evaluated for concrete specimens made with two different
replacement levels of each, Grinded CBA (25% and 33%) and FA (25%
and 33%). The investigation disclosed that the carbonation resistance of
concrete mixes made with Grinded CBA in place of PC depicts equivalent
values of carbonation depth as that of the concrete mix made with FA at 65
days curing periods (Martins and Gonçalves 2010). Figure 9 presents the
32 Navdeep Singh
observed variation of carbonation resistance for concrete mixes made with

Grinded CBA and FA (Martins and Gonçalves 2010).
Figure 8. Capillary absorption tests result in concretes with varying binder contents at
28 days of curing (Martins and Gonçalves 2010).
Figure 9. Carbonation resistance with varying binder contents (Martins and Gonçalves
2010).
4.5. Chloride Permeability of Coal Bottom Ash Based Concrete
From a general perspective, for any concrete structure, it is essential to

have satisfactory performance while maintaining the required strength and
serviceability characteristics. The test of chloride permeability is an
indication of the durable performance of concrete under severe exposure.
Usually, concrete durability is negatively influenced by the penetration of
chloride ions. In general, the addition of Grinded CBA in concrete leads to
lower migration and diffusion coefficients than the concrete made without
Grinded CBA. Argiz et al. (Argiz, Moragues, and Menéndez 2018) found
the effect of Grinded CBA and FA (10% and 25% by weight of PC) on the
vibrated concrete. The chloride diffusion coefficients were evaluated at
lower and at higher curing periods (28 and 132 days). The results for
different concrete mixes made with Grinded CBA present the lower
chloride migration coefficients compared to concretes containing FA. The
possible cause for the noticed variation was due to the increase in fineness
of concrete mixes due to the fusion of Grinded CBA thereby making the
concrete dense and make impermeable. On comparison of coal ashes (CBA
and FA), it has been revealed that the chloride migration
values/coefficients of concretes with made with Grinded CBA (on
replacement of 10% by weight) was around 1.7 times lower compared to
that of the concretes made with the same amount of FA (on replacement of
10% by weight).
Likewise, the chloride diffusion coefficient of concrete mixes having
25% Ground CBA was around 3.8 times slower than the concrete mixes
made with 25% FA. In the case of the control concrete, the chloride
penetration depth was significantly high with a value of nearly 76 mm.
Further, at the replacement level of FA by 10% in concrete, the chloride
ingression was noted near to 37 mm. However, the improvement in
chloride ingression was noticed with the use of Grinded CBA as the depth
has been restricted to about 27 mm. On increasing the amount of FA in
concrete mixes (from 10% to 25%), the penetration depth was found nearly
to be 22 mm. The observed value was further reduced to 17 mm on
increasing the content of Grinded CBA (Argiz, Moragues, and Menéndez
34 Navdeep Singh
2018). The noticed improvement in chloride resistance was due to similar

reasons as discussed in the previous section. Figure 10 and Figure 11
present the depth of chloride penetration and the migration coefficient with
varying content of FA and Ground CBA respectively.
Figure 10. Depth of chloride penetration of concrete mix at different replacement

levels (%) (Argiz, Moragues, and Menéndez 2018).
4.6. Acid and Sulphate Resistance of Coal Bottom Ash

Based Concrete
Acid and sulfate resistance are the two another important parameter,
which relates to the long term/durable performance of concrete. Khan and
Ganesh (Khan and Ganesh 2016) studied the resistance against acid in
concrete mixes made with different replacement levels of PC by Grinded
CBA (10%, 20%, and 30%) at several curing ages presented in Figure 12. In
this test, the loss in mass due to deterioration of the concrete specimens
was estimated before and after the immersion period of 28-90 days of
curing. It was noticed that concrete mixes having the highest percentage of
Grinded CBA (at 30% by weight) offer the highest resistance against
weight loss. Simultaneously, the concrete mixes containing the lowest
percentage of Grinded CBA (10% by weight of PC) results in less

resistance against weight loss at all curing periods. The observed pattern
for variation in resistance to acid attack was seemed to be alike to that of
the compressive strength tests.
Figure 11. Migration coefficient of concrete mixes at different replacement levels (%)
(Argiz, Moragues, and Menéndez 2018).
The resistance against sulfate attack of concrete mixes made with

replacement of PC with Grinded CBA by 10% was measured at different
curing periods (28-90 days). The findings were compared with the values
of control concrete mix made without Grinded CBA. The variations in the
weight of control concrete and concrete containing 10% of Grinded CBA
at the curing of 28-90 days were evaluated. The results confirmed that
concrete containing Grinded CBA shows the marginal gain in weight in
comparison to the percentage weight gain in the control concrete mix. The
reduction in the penetrability of migrated salts could be the most probable
reason for the noticed improvement due to the presence of Grinded CBA
(Mangi et al. 2019).
36 Navdeep Singh
Figure 12. Percentage loss in weight of concrete mixes at different curing ages (Khan
and Ganesh 2016).
4.7. Drying Shrinkage of Coal Bottom Ash Based Concrete
The removal of water from concrete stored in unsaturated air generally

causes drying shrinkage. Kim (Hyeong Ki Kim 2015) studied the effect of
drying shrinkage on concrete made with Grinded CBA (30% by weight of
PC) and FA (30% by weight of PC). The concrete specimens individually
were compared with the control concrete mix at different curing periods (6
and 32 days). The investigation demonstrated that up to 6 days of curing,
the shrinkage of the concrete mix made with Grinded CBA was dropped by
approximately 30% in comparison to shrinkage of control concrete mix.
The observation proved to be vital with the durability of concrete
structures. At an early age when the concrete has not gained the desired
strength the probability of the crack nucleation is more due to shrinkage.
On the other hand, while increasing the curing period (up to 32 days) the
shrinkage of the control concrete mix was still found to be in the range of
15%–30% than concretes made with partial replacements of Grinded CBA
and FA (Hyeong Ki Kim 2015).
4.8. Sound Absorption of Coal Bottom Ash Based Concrete
The impact of Grinded CBA has been analyzed on concrete concerning

effective sound absorption. Generally, the acoustic absorption of any
material is dependent on the thickness of the samples. It has been
experienced from the impedance tube method that with the increase in the
thickness of the sample/specimen the maximum absorption coefficients
expatriated towards low frequencies. Arenas et al. (Arenas et al. 2013)
studied the effect of Grinded CBA mixed with PC in the use of highway
noise barriers. For this study, the sound absorption values of a porous
material were related to the loss in energy by friction in walls. The best
sound absorption coefficients have been estimated in the mortar specimens
made from the bigger particle size of CBA, with higher porosity. As a
result, the mortar made with Grinded CBA bearing higher void ratios
resulted in improved sound absorption coefficients for every series of
frequencies.
4.9. Thermal Conductivity of Coal Bottom Ash Based Concrete
The property of thermal conductivity is mainly dependent on the pore

structure of the aggregates (light/heavy; natural/recycled etc.), the density
of concrete and cement matrix (Topçu and Uygunoǧlu 2007). Wongkeo et
al. (Wongkeo et al. 2012) revealed the performance of concrete in terms of
thermal conductivity in an experimental investigation. The thermal
conductivity of autoclave aerated concrete made with partial substitution of
PC with Grinded CBA at 10%, 20% and 30% by weight of PC was
estimated. Apart from the aforementioned substitutions, the Al powder
(0.2% by weight of PC) was incorporated to generate the aerated concrete
which further reacts with Ca(OH)2 to form hydrogen (H2) gas. The results
revealed that the addition of Al as cement addition considerably affects the
thermal conductivity of the concrete mixes. A drop was noticed from 0.88
to 0.57 W/mK on a comparison of Grinded CBA and Al-based concrete
mixes with control concrete. Further, it has been observed that the thermal
38 Navdeep Singh
conductivity was increased with increment in Grinded CBA replacement of

PC as its addition enhances the overall unit weight of concrete specimens
(Wongkeo et al. 2012). The noticed variation of thermal conductivity in
different concrete mixes at different Grinded CBA replacement levels is
presented in Figure 13.
5. CRITICAL COMMENTS
It is worthwhile to mention that different authors have tested a wide

range of parameters in their investigations. Further, the authors of this
investigation have selected some previous studies and the considered
parameters such as w/b, w/c ratio, curing period, percentage replacement of
CBA and compressive strength are listed in Table 5.1. However, the
authors believe that in such varying situations, it is rather difficult to arrive
at a meaningful comparison.
Figure 13. Thermal conductivity of concrete mixes at different CBA replacement level
(%) (Wongkeo et al. 2012).
Furthermore, to the best of the authors following inferences have been

made based on the earlier findings:
Table 5.1. Comparison of some of the previous studies

with various parameters
Author )s( Curing % CBA W/C W/B Compressive

period )Cementitious strength
)days( material( range
)N/mm²(
Hopkins et al. 28 20 0.56 0.45 50.50
Jaturapitakkul 28 10 - 0.72 28.40
and Cheerarot 20 0.80 20.10
30 0.90 13.60
10 )Grinded( 0.69 40.50
20 )Grinded( 0.69 39.70
30 )Grinded( 0.68 38.3
Kurama and 28 5 0.52 0.50 40.38
Kaya 10 0.55 40.28
15 0.58 33.57
25 0.66 29.13
Kizgut et al. 28 5 )Grinded( 0.52 0.50 44.00
10 )Grinded( 0.55 42.00
15 )Grinded( 0.58 41.00
20 )Grinded( 0.62 40.00
25 )Grinded( 0.66 38.00
Menendez et al. 28 10 )Grinded( 0.50 - 55.00
25 )Grinded( 42.50
35 )Grinded( 35.00
Aydin 28 70 )Grinded( - 0.45 12.34
100 3.12
5% Lime + 70% 14.73
GCBA
5% Lime + 80% 11.15
GCBA
5% Lime + 85% 10.71
GCBA
Mangi et al. 28 10 )Grinded( 0.55 0.50 43.5
40 Navdeep Singh
i. With the incorporation of Grinded CBA as the addition of PC, the

mechanical properties of concrete have not been affected
significantly on instances where compressive strength is the
governing factor. The fineness is an important aspect of CBA
when used as supplementary cementitious materials (in place of
PC). The grinding of CBA for a specified time and up to specific
size/fineness has made it possible to achieve the equivalent
compressive strength and other mechanical properties to that of the
respective reference/control concretes.
ii. Based on the earlier findings, the Grinded CBA is presented as
another durable supplementary cementitious material that has
considerable potential to be used as an alternate ingredient in
concrete/mortars due to similar chemical composition with coal
FA and good performance in durability.
iii. The microstructural studies confirm the variation in the behavior
of concretes/mortars on the inclusion of CBA as cement
addition/supplementary cementitious material. Concretes made
with Grinded CBA are denser and compact with an improved
microstructure which is mainly dependent on the fineness of CBA.
iv. The appropriate recommendations of probable usage of Grinded
CBA in the civil engineering industry and other engineering
construction applications will probably prevent the unviable use of
natural resources to some extent. The utilization of Grinded CBA
in the cement/concrete industry assuredly contributes to resolving
energy, resources and conservation concerns.
v. The inclusion of Grinded CBA can only be proposed in concrete
before the well thorough knowledge of the source of disposal
(dry/wet) and mode of collection. The quality of parental coal
(sub-bituminous/lignite/anthracite/bituminous) has a direct
influence on the amount of cementitious/pozzolanic compounds
with varying contents of silica, calcium, iron, alumina, etc. which
are responsible for imparting better performance. Considering, the
benefits and significant preservation of existing resources, it is
advisable to utilize Grinded CBA in the concrete industry for

various applications.
CONCLUSION
The current review investigation highlights mainly the chemical,

microstructure, physical, fresh, mechanical, durability properties of
concretes made with Grinded CBA. In addition to this, the chapter covers
the environmental considerations of Grinded CBA in brief. The available
literature has been summarised and subsequently, the conclusions are
drawn based on the aforementioned properties:
i. Chemically, CBA resembles class FA as a percentage of silica,

alumina and iron oxide are generally greater than 70% out total
composition. Coal bottom ash particles are generally coarser in
size compared to FA particles and there is a wide variation in the
physical properties. The specific gravity, fineness modulus and dry
unit weight generally depend on the quality of coal. In general, the
structural grade concretes made with Grinded CBA fulfills the
workability requirements.
ii. The microstructure analysis of concrete containing Ground CBA
clarifies the possible reasons for the observed variations in
mechanical and durability performance. The observed SEM
images concluded that reformation and the change in geometry of
various hydration products come into being in concrete due to the
increased fineness of CBA.
iii. Grinded CBA resembles FA both physically and chemically.
Based on almost all investigations it was observed that the addition
of Grinded CBA reduces the compressive strength at early ages but
for longer curing periods (≥28 days) the same is more concerning
their respective control concretes. The fusion of cement addition
(s) has been proved to be favorable for refining the compressive
42 Navdeep Singh
strength. Likewise, the flexural strength has been improved only

for low alteration levels of Grinded CBA.
iv. In context to the durability aspect of concretes, replacing PC up to
a certain level with Grinded CBA helps in increasing the resistance
towards chloride penetration, acid attack, and sulfate attack.
Amongst of aforementioned, the maximum beneficial effect of
Grinded CBA has been noticed against chloride penetration.
Moreover, concrete containing Grinded CBA offers in delivering
acceptable strength performance under acid and sulfate attack. The
capillary water absorption has been dropped with an increase in the
content of Grinded CBA. The capillary water absorption
coefficients have been reduced more effectively in CBA based
concretes compared to FA based concretes.
v. The resistance against carbonation has been enhanced on the
addition of Grinded CBA along with an increase in binder content.
The sound absorption coefficients of concrete have been reduced
with the inclusion of coarser CBA in contrast to medium and fine
CBA. Likewise, the thermal conductivity is considerably affected
by the porous nature of CBA. Ground CBA up to 30% in concrete
mixes helps in lowering the drying shrinkage values for low and
higher curing ages compared to the shrinkage values of the control
concrete.
vi. The utilization of Grinded CBA as a pozzolanic material probably
presents a viable solution for solving the concerns like scarcity of
dumping sites, environmental impacts, and reduction in the overall
production cost of concrete.
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Chapter 2
CHEMICAL ASPECTS OF INTERACTION

OF PORTLAND CEMENT WITH ALKALI-FREE
SET ACCELERATORS
Alexey Brykov, DSc

Department of Chemical Technology of Silicate Materials,
Saint Petersburg State Institute of Technology, Saint Petersburg, Russia
ABSTRACT
Aluminum-bearing compounds - amorphous aluminum hydroxides,

aqueous solutions of aluminum sulfate and hydroxysulfates - find
application in composition of alkali-free accelerators of setting and
hardening of Portland cement (PC) concrete in modern machine-
concreting technologies, like shotcreting and 3D printing. Compared with
alkaline-containing, alkali-free accelerators are safer to use, they do not
participate in alkali-silica reactions and do not promote salt efflorescence.
A high reactivity of these admixtures in PC pastes and mortars is due to
an intensive formation of calcium trisulfoaluminate hydrate (AFt phase)
when reacted with components of the paste.

Corresponding Author’s E-mail: brykov@yahoo.com.
56 Alexey Brykov
Although notable practical experience has already been gained in the

use of alkali-free accelerators, some features of their interaction with
cement components, including those aspects of this interaction that may
later affect durability of cement concretes and mortars, remain unclear.
This chapter describes chemical aspects of interactions of aluminum-
containing accelerators in PC-based materials, explaining their effect on
kinetics of PC hydration and stability of Portland cement materials when
exposed to various corrosive factors. In writing this chapter, the author
relied, among other things, on results of his own studies on the hydration
of PC with the mentioned admixtures using 27Al- and 29Si-MAS NMR
spectroscopy - a method that provides unique information in this regard.
Keywords: Portland cement, hydration, alkali-free set accelerators,

aluminum hydroxide, aluminum sulfate, aluminum hydroxysulfate
INTRODUCTION
Improvements in concreting technologies, introduction and

development of new fast and flexible construction methods, as well as
tightening of safety requirements for use of construction materials have
significantly increased the importance of aluminum compounds in the
construction industry in the last 2 decades. First of all, there should be
noted an active transition to alkali-free accelerators in shotcreting (Rixom
and Mailvaganam 1999, Myrdal 2007, Aïtcin 2016, Lundgren at al. 2018)
and intensive development of 3D printing concrete techniques (Ma and
Wang 2018).
Shotcreting (concrete spraying) is a high-tech concreting method in
which a concrete mixture is sprayed under pressure by a special shotcrete
machine on the surface to be treated, and self-compacts upon an impact
(Hofer et al. 2011). Shotcrete layers, in some cases more than 30 cm in
thickness, must quickly and firmly fix on uneven vertical surfaces and
frameworks, on crowns of tunnels and shafts, on hard-to-reach areas.
Accelerating admixtures applied in spraying operations control rapid
set of the concrete (within up to 3-10 minutes) and intensive development
Chemical Aspects of Interaction of Portland Cement … 57
of very early strength (4-7 MPa) just hours later (Prudencio 1998, Rixom
and Mailvaganam 1999, Hofer at al. 2011, Lundgren et al. 2018).
Shotcreting is widely used when tunneling, in mining industry and
hydrotechnical construction, for excavation support, slope stabilization,
shaft lining, concrete repair, and in many other applications.
The shotcreting may be carried out in a “dry” or “wet” manner. In
“dry” shotcreting, a dry concrete mixture is supplied to the nozzle of the
shotcrete machine by compressed air, where it is mixed with water and
then shot to the surface to be treated. The accelerator may be supplied in
liquid form directly to the nozzle or may be pre-mixed as a powder in the
dry concrete mixture itself. In case of “wet” shotcreting, ready-mix
concrete is supplied into nozzle of shotcrete machine by compressed air,
and liquid accelerator is also supplied to the point of ejection. Due to its
advantages, the wet method of shotcreting has become the most common
by now, especially in large-capacity works.
Currently, instead of previously used alkaline accelerators (sodium
silicates and aluminates), accelerating admixtures containing no alkali
metal compounds are getting adopted increasingly: firstly, they are safer to
use; secondly, they have a much less negative effect on the strength of
mature concrete; finally, in contrast to alkaline substances, they are unable
to activate destructive alkali-silica interactions involving aggregates in
concrete (Lundgren at al. 2018). Main constituents of modern alkali-free
accelerators are highly dispersed amorphous aluminum hydroxides,
aluminum sulfate and hydroxysulfates. A dosage of aluminum-containing
accelerators in shotcrete is 3-10% of cement weight (Prudencio 1998,
Myrdal 2007).
Aluminum-containing alkali-free accelerators have proved to be in
demand in a relatively new and promising construction technique which is
a 3D printing (Marchon at al. 2018, Ma and Wang 2018). The extrusion
method of 3D printing has become the most common to date, it involves
layer-by-layer placing of material extruded from a nozzle
of printing device.
The printing material used for 3D printing is to have rheological
characteristics ensuring its supply to the printer and subsequent extrusion;
58 Alexey Brykov
after placing, it must solidify within a relatively short time and obtain
sufficient strength to hold up overlying layers of material without
deforming. Talking about cement-based materials, these and many other
characteristics are provided by a balanced combination of functional
additions, including accelerators.
By now, thanks to their practical advantages, alkali-free accelerators
have taken a market quite quickly and firmly, so that the rate of their
adoption for industrial applications, at least in some aspects, is faster than
the rate of accumulation of scientific data on the nature of their properties,
that is: the number of patents in this field significantly exceeds the number
of scientific articles. In contrast to accelerators of previous generation,
modern alkali-free accelerators have a complex multicomponent
composition, though developed predominantly by semi-empirical means;
certainly, the manufacturers do not disclose formulations of commercially
available accelerators in detail. For these reasons, some insights into
effects of such accelerators on Portland cement hydration and durability of
Portland cement concrete are still debatable or even contradictory.
SETTING OF PORTLAND CEMENT AND ACTION

PRINCIPLE OF CHEMICAL ACCELERATORS
As far as is known, in the absence of admixtures affecting hydration

kinetics, the period of time between mixing cement with water and the
initial set of cement paste (known as an “induction period”) is
usually ~1.5-2 hours (Taylor 1997, Hewlett 2003, Gartner at al. 2008). The
duration of the induction period is determined by the time when a liquid
phase achieves a point of significant supersaturation with Ca2+-ions in
respect of Ca(OH)2 and C-S-H, and the formation of nucleation centers
capable of further growth becomes possible. When the C-S-H gel is formed
in an amount sufficient to form contacts between cement grains, the setting
is pronounced. The final set and formation of early strength occur during
an acceleration period of hydration (up to about 10 hours from the moment
of cement paste preparation), during which the space between particles,

originally occupied by water, is filled with hydrated phases. Throughout
this period, a hydration activity of aluminate phase (C3A) is controlled by a
setting regulator (typically a gypsum) introduced into the cement at the
stage of clinker grinding. The aluminate phase reacts with gypsum with the
participation of water to form ettringite, or calcium trisulfoaluminate
hydrate (an AFt phase):
C3A + 3 C S H2 + 26H → C6 AS3H32 (C3A·3CaSO4∙32H2O) (1)
As a rule, a gypsum amount of up to 5% by weight of the clinker is

sufficient to ensure a normal setting time of the Portland cement. However,
not all gypsum is involved in the formation of ettringite; a large portion of
it, up to 70-80%, is trapped mechanically in the main hydration product – a
C-S-H gel (Hewlett 2003, Bensted 2008).
Depending on the conditions of the grinding of clinker with gypsum,
which is typically carried out in ball mills, the gypsum is dehydrated to
some extent, turning partially or completely into a semi-hydrate form
(CaSO4∙0.5H2O) or soluble anhydrite (CaSO4). These modifications have
different solubility and dissolution rates in water, and therefore the state of
gypsum in Portland cement largely determines its effect on setting times.
The content of gypsum in ordinary Portland cement is typically about
20% of the amount required to completely convert С3А phase into
ettringite. The full depletion of gypsum occurs about 1-2 days after the
beginning of hydration, but as already noted, partly owing to its
mechanical inclusion in hydration products of Portland cement; at this
moment the content of ettringite in the hardening paste reaches its peak
value. Further transformations then occur involving ettringite and the
remaining С3А phase into reactions to produce calcium
monosulfoaluminate hydrate (the AFm phase):
2C3A + C6AS3H32 + 4H → 3 C4 AS H12 (C3A·CaSO4·12H2O) (2)

60 Alexey Brykov
In this conversion stage, ettringite is in deficiency, so products

containing no sulfate anions (calcium aluminate hydrates) are formed
along with calcium monosulfoaluminate hydrate.
In some cases, there may occur a “flash setting” of Portland cement
when it is mixed with water. In ordinary practice, this process is referred to
as undesirable. Typically, the problem of flash setting arises if the amount
of gypsum introduced at the stage of clinker grinding is insufficient, which
allows for a hydration of calcium aluminate phase to proceed at a moderate
rate. Rapid setting can also occur if low-soluble components, for example
anhydrite, dominate in the composition of set regulator. In these cases, the
calcium aluminate phase actively reacts with water to form AFm phases
with plate morphology – calcium aluminate hydrates and (with the
participation of sulfate ions) calcium monosulfoaluminate hydrate.
In practice, for the purpose of controlled acceleration of setting and
very early strength gain of Portland cement mortars and concretes, special
accelerating admixtures are used, which can be characterized as substances
that gets involved in: 1) rapid formation of C-S-H gel and/or stimulating
hydration of silicate phases of Portland cement; 2) rapid formation of AFm
and AFt phases and/or stimulating hydration of C3A phase.
The rate of setting and hardening of concrete mixes expected in
shotcreting, as a rule, cannot be achieved only by stimulating hydration of
clinker phases. In composition of chemical accelerators for shotcreting,
components capable of taking a direct role in the rapid formation of almost
insoluble hydrated phases (ettringite or C-S-H gel) are hence of a great
importance.
The effect of alkali-free aluminum-containing Portland cement setting
accelerators is to initiate an immediate and extensive crystallization of
ettringite in a cement paste, mortar or concrete (Figure 1) and to
chemically capture and fixate a significant amount of free water in the
mixture. Formation of ettringite causes not only a rapid loss of flowability,
but also provides some early strength in the first 1-2 hours. A heat
evolution accompanying this type of reaction also contributes to this. It
should be emphasized that the processes initiated by the introduction of the
accelerator and resulting in loss of flowability, do not cancel the induction

period, but certainly have an effect on its duration.
Ettringite is essentially insoluble in water (the value of the pKSP is no
less than about 43.9÷45.1 (Chrysochoo and Dermatas 2006)); it crystallizes
from the oversaturated water solutions containing Ca2+, OH-, Al(OH)4-,
SO42- ions:
6Ca2++ 4OH-+ 2Al(OH)4- + 3SO42- + 26H2O → C3A·3CaSO4∙32H2O

(3)
Substances with a sufficiently high solubility (Ca(OH)2, Al2(SO4)3) can

be used as sources of ions required for ettringite formation, so in practice
obtaining an ettringite-oversaturated aqueous solutions is not a hard task.
An essential precondition for the formation and long-term stability of
ettringite is an alkaline environment (pH 11÷12.5). Perhaps for this reason,
ettringite is rare as a mineral in nature. It should be noted that due to its
properties, ettringite is not only of interest in binder technology but is also
considered a promising material in other fields (Chrysochoo and Dermatas
2006, Chen et al. 2019).
Figure 1. SEM image (carried out by the Author) of deposited ettringite crystals on the
fracture surface of PC mortar with an addition of Al2(SO4)3·18H2O (8% of cement
weight); the sample age is of 60 mins.
62 Alexey Brykov
Alkali-free aluminum-containing accelerators are substances that

produce aqueous solutions of aluminum ions of high concentrations upon
dissolution or hydrolysis, or releasing them (as Al(OH)4-) under alkaline
condition of cement paste; as defined, these substances should not contain
alkali, more precisely, their Na2Oe content is limited to 1% (Myrdal 2007).
As mentioned above, amorphous aluminum hydroxides, aluminum sulfate
and hydroxysulfates are of primary practical importance as alkali-free
aluminum-containing accelerators. Calcium aluminates, like vitreous
12CaO·7Al2O3, are of limited use and will not be discussed herein.
In PC-based materials the source of calcium ions for the formation of
ettringite according to reaction (3) are clinker phases and calcium sulfate
from the sulfate component of PC; alkaline condition in liquid phase is
provided as a result of hydrolysis of silicate phases when mixing cement
with water:
С3S (C2S) + H2O → C-S-H + Ca2+ + 2OH- (4)
The source of sulfate ions in the reaction (3) is an accelerating

admixture (e.g., aluminum sulfate), as well as gypsum and other sulfate-
containing phases; in the absence of sulfate ions in the accelerator (e.g.,
Al(OH)3), cement constituents are the only source thereof.
In field conditions and in laboratory the accelerator can be introduced
into cement mixture in different ways, in accordance with existing
techniques of sprayed concreting: 1) the accelerator in the powdered form
of, for example, Al(OH)3 and/or Al2(SO4)3·18H2O can be mixed previously
with other dry components and after that the mixing water is added; 2) the
accelerator may be dissolved or dispersed in water in advance, with
subsequent mixing of this solution/dispersion with cement premix (the
alternates 1 and 2 correspond to “dry” shotcreting); 3) accelerator (in
dissolved or dispersed form) can be introduced into ready-mixed concrete,
this is used in “wet” shotcreting.
In wet shotcreting, the time elapsed from the preparation of concrete
batch to the injection of the accelerator may vary from a few minutes, i.e.,
almost immediately after the mixing, to 1 hour or more; in practice, this
time is required to deliver ready-mixed concrete from a plant to a

construction site. Therefore, plasticizers and retardants are employed
widely. This is also required due to lower w/c (0.42-0.45) values utilized in
sprayed concretes compared with concretes placed in conventional ways.
MAIN COMPONENTS OF ALKALI-FREE ACCELERATORS
Highly water-soluble aluminum sulfate is the basis of almost every

alkali-free accelerator for shotcreting performed by the most common
“wet” method, and as such it has replaced previously used alkaline
accelerators – sodium and potassium aluminates and silicates (Prudencio
1998, Rixom 1999).
In the “wet” shotcreting, the accelerator is used in a form of solution or
a suspension and is mixed with ready-mixed concrete directly at the nozzle
of shotcrete machine. Generally speaking, the higher the concentration of
the accelerating admixture solution or its dosage, the more the
oversaturation of the concrete mixture liquid phase with ettringite and the
stronger the accelerating effect (Angelskar 2012, Salvador et al. 2016a).
According to (Salvador et al. 2016a), the effect reaches a maximum at
accelerator amount of about 0.2 mmol Al3+/g cement; at higher amounts,
the rate of dissolution of the sulfate component becomes a limiting factor
in the ettringite formation reaction. It is possible that certain portion of
aluminum ions from the admixture is trapped into other hydrated phases.
Solubility of aluminum sulfate in water is of 27.5 wt% at 20 °C (8 wt%
in terms of Al2O3). Consequently, in case of a solution with concentration
even close to the saturation, its dosage should be in the order of 14-15%.
However, along with such quantities of accelerating admixture, a large
amount of water is additionally introduced into the concrete or mortar
mixture, which is undesirable. Therefore, the method of increasing the total
concentration of the aluminosulfate solution, means the equivalent
concentration of Al2O3 which determines the activity of the accelerator,
consists in subsequent dissolution of aluminum hydroxide in the solution
of Al2(SO4)3:
64 Alexey Brykov
nAl(OH)3 + Al2(SO4)3 → nAl(OH)3·Al2(SO4)3, or Al n 2 (OH) nSO 4 (5)

3
The structure of the aluminum hydroxysulfates solutions is represented

by aqueous aluminum hydroxide polyoxocations like
7+
[AlO4Al12(OH)24(H2O)12] (Casey 2006). The polymer composition of
these solutions varies with time towards the formation of high-polymeric
forms up to the origination of low-soluble products. An important feature
of these solutions is their tendency to crystallize. Their structure and
stability depend on various factors: рН, Al3+/SO42- ratio, concentration,
temperature and others, typically, these solutions are stable for at least few
days, after which they are subjected to bulk precipitation and gelatination.
In industrial production of accelerators, stabilization of prepared solutions
is achieved by addition of mono- and polyatomic organic and mineral acids
(formic, citric, phosphoric or other) until the pH reaches 2 to 3.
In accordance with literature data, including patent sources (Hofmann
2004, Sommer et al. 2004, Weibel 2009, Angelskar 2012, Kolomiets et al.
2015), an industrial production of liquid accelerators for wet shotcreting
involves preparation of aluminum hydroxysulfates solutions, their
stabilization and modification with organic, inorganic and mineral
additives. The total weight content of solids in modern accelerators (in
dissolved and dispersed state) is up to 40-50%, where Al2O3 content is of
8-15 wt% and Al3+/SO42- molar ratio varies from 0.7 to 2 and more (n in
formula 5 is in range from 0.1 to 4 and above). Thus, compared with
aluminum sulfate, the use of aluminum hydroxysulfates significantly
increases the amount of Al2O3 for the same amount of accelerator.
Amorphous modifications of aluminum hydroxide capable of
producing ettringite on its own upon a reaction with Portland cement
components, have a strong accelerating effect on the setting (Myrdal 2007,
Xu and Stark 2008, Brykov et al. 2012):
2Al(OH)3 + 3Ca(OH)2 + 3(CaSO4·2H2O) +20H2O→

C3A·3CaSO4∙32H2O (6)
These substances, which are almost insoluble in water, in the form of

fine powders are used in “dry” shotcreting and can be introduced into dry
mortar or concrete mix (which may or may not also include a powdered
aluminum sulfate) prior to water addition, or they can be dispersed in
mixing water. In the alkaline medium of Portland cement matrix, they
exhibit high reactivity by releasing aluminate ions into liquid phase.
Amorphous aluminum hydroxides also find use as accelerators in some
formulations of dry building mixes (Ilyasov et al. 2005).
EFFECTS OF ALKALI-FREE ACCELERATORS

ON PORTLAND CEMENT HYDRATION
Deceleration and Acceleration Factors
The most intensive period of ettringite formation in cement matrix

with accelerator lasts for 10-15 min, which in turn affects all hydration
processes where clinker phases and PC sulfate component participate. This
is accompanied by an uprise of factors that stimulate hydration and factors
that have a slowing effect on it.
A deficiency of sulfate and calcium ions in the liquid phase caused by
the rapid crystallization of ettringite stimulates dissolution of gypsum and
clinker phases of cement (Salvador et al. 2016b). The dissolution and
hydration of the clinker phases are also facilitated by a temporary
destabilization of pH value of the system due to acidic nature of the
accelerator introduced, as well as by an exothermic nature of the ettringite
formation reaction (if hydration proceeds under non-isothermal
conditions).
Effects that facilitate dissolution and hydration of cement constituents
mainly play role in a relatively short period that follows the initial rapid
formation of ettringite in which aluminum-containing accelerators
participate. Put together, all these chemical transformations cause rapid
setting and promote fast hardening of early cement stone structure. Beyond
66 Alexey Brykov
that, industrial accelerators may also contain specific components that have
a prolonged stimulating effect on hydration of cement or its individual
phases.
After the initial rapid ettringite formation is complete, factors that
slows hydration processes kick in. A list of these inhibiting factors
includes:
• Depletion of the sulfate component that, consequently, leads to

passivation of dissolution and hydration of Portland cement silicate
phases by a surplus of aluminum ions adsorbing on surface of
particles of these phases (see the next Section);
• Incapsulating of the surface of silicate phases with calcium
sulfoaluminate hydrates and other products;
• Reducing water reserve available for the hydration of clinker
phases due to its quick binding into ettringite and AFm phases;
• Reduction in free space available to accommodate hydration
products of silicate phases due to occupation by ettringite and
AFm phases.
Besides, shotcrete admixtures, mortar or concrete compositions may

contain specific cement retardants on their own.
Determination of cement hydration patterns in the presence of
aluminum-containing accelerators is based primarily on application of
calorimetric methods supplemented by an X-ray diffraction (XRD) and
scanning electron microscopy (SEM) (Maltese et al. 2007, Xu and Stark
2008, Salvador et al. 2016a, Han et al. 2016). The overall trend of heat
release during a hydration of Portland cement with accelerators is alike to
that of pure PC, but accelerator affects duration and characteristics of the
individual stages (Figure 2).
Induction period is an integral stage of Portland cement hydration
whether in the presence of the accelerator or not. If accelerating action
shares the same time window with the beginning of the hydration of
Portland cement (for example, if the accelerator is present in the dry
mixture or is introduced through the mixing water), the induction period
takes place after the initial quick ettringite formation is complete. If the
accelerator is introduced into ready-mix mortar or concrete, it disturbs, at
least for some time, a normal flow of the induction period.
Figure 2. Schematic diagram of the differential heat curve of setting and hardening
Portland cement paste and an effect of aluminum-containing accelerators on it.
Upon completion of the induction period, the hardening and strength

development are controlled by a process of Portland cement silicate phases
hydration, that passes through stages of acceleration, deceleration and slow
reaction (the stages of acceleration and deceleration are predominantly
controlled by hydration of alite; belite contribution becomes significant in
late hydration stages). Duration of induction period, as well as an onset and
duration of subsequent stages of cement hydration are identified by
location and features of a main peak on differential curve of heat release.
Studies indicate that when alkali-free accelerators are introduced, this peak
may drift to the left ((Salvador et al. 2016a, Yang et al. 2020), or to the
right (Han et al. 2016, Maltese et al. 2007) relative to the peak position of
the reference sample (i.e., the hydration rate reaches its maximum earlier
or later compared with the control sample), or be synchronous with it (Xu
and Stark 2008). This depends on which of the factors - stimulating or
inhibiting - have a predominant effect in controlling hydration of the
Complimentary Contributor Copy

68 Alexey Brykov
clinker phases. A result of a competition between accelerating and

decelerating effects at different hydration stages depends on the dosage of
the accelerating admixture and its composition, the composition of the
Portland cement, the method of introducing of the accelerator, and other
reasons.
Effect of C3A/SO3 ratio Upon a Completion of Ettringite

Formation on Hydration of С3А and Silicate Phases
Aluminum ions are known to passivate the dissolution of silicate

phases (Garrault et al. 2011, Matschei and Costoya 2012, Saout et al.
2012); therefore to maintain an ordinary behavior of alite it is important
that the concentration of aluminum ions in the liquid phase during the
induction and post-induction period must be kept at the lowest possible
level. In this regard, it should be emphasized that the role of the sulfate
component of PC is not only to inhibit a hydration of aluminate phase of
clinker immediately after mixing cement with water, but is also to control
the concentration of aluminate ions in the cement matrix pore liquid during
the period of intense alite hydration. A most optimal situation is when the
sulfate component is preserved in the system during the whole acceleration
period, and its depleting takes place approximately at the same time with
transition of C3S from acceleration to deceleration stage of hydration.
Premature consumption of gypsum suppresses hydration of silicate phases
of cement, extends induction period and slows strength gain, as it
contributes to enhancement of hydration activity of C3A, intensive
formation of plate morphology products (AFm phases), increase in
concentration of aluminate ions in pore liquid, their sorption on alite and
belite particles.
The higher the Al3+/SO42- ratio in the admixture and the higher the
dosage, the faster the pace of a sulfate component consumption should be.
Hence, aluminum compounds can obviously be ranked based on their
potency to consume sulfate as following, low to highs: aluminum sulfate,
aluminum hydroxysulfates, amorphous Al(OH)3. This is indeed confirmed

in experimental data from a variety of sources. According to (Xu and Stark

2008), in the cement paste with amorphous Al(OH)3 (1.5 wt%, or 0.8 wt%
in terms of Al2O3) gypsum and anhydrite are almost completely consumed
in 10 to 60 min, respectively, while observed in the reference sample
for ~1 day. According to (Salvador et al. 2016b), after addition of 7 wt%
(0.95% Al2O3) of a commercial liquid accelerator based on aluminum
hydroxysulfate (Al2O3 13.5 wt%, SO42- 21.0 wt%, Al3+/SO42- molar ratio
1.24) to CEM I cement paste, the sulfate component of PC - calcium
sulfate in the form of semi-hydrate and dihydrate - almost completely
reacted in a span of 4 h. According to the results of (Han et al. 2016), in the
presence of aluminum sulfate (6% Al2(SO4)3·18H2O of the cement weight,
or 0.9 wt% in terms of Al2O3) the speed of consumption of anhydrite in
cement paste was the same as in a reference sample. Experiments
performed on a series of liquid accelerators with different values of
Al3+/SO42- ratio also show that the rate of consumption of the sulfate
component increases with an increase in the Al3+/SO42 ratio (Salvador et al.
2016a).
Obviously, the more the content of sulfate component in the Portland
cement, the longer it will reside in the system. However, it should be
considered that the speed of consumption of sulfate component is also
determined by its origin, since gypsum, hemihydrate and anhydrite have
different solubility.
The work (Salvador et al. 2016a) shows that a ratio between C3A phase
and sulfate component (setting regulator) upon completion of the rapid
ettringite formation stage subsequently affects the hydration of silicate
phases of clinker. This ratio is a function of the initial content of C3A and
sulfate component in the cement, a composition of the sulfate component,
a dosage and composition of the accelerator. The optimal range of
C3A/SO3 molar ratio by the end of the rapid ettringite formation stage is of
0.67-0.9. In order to meet this condition, the Al2O3/SO3 molar ratio of the
accelerator should not exceed 0.60, while providing a concentration of
0.12-0.18 mmol Al3+/g cement; simultaneously a sufficient amount of
sulfate component shall be presented - not less than 4% in terms of calcium
sulfate dihydrate. Therefore, one can imagine a situation when an

70 Alexey Brykov
accelerator with a particular Al2O3/SO3 ratio can influence hydration of a

certain cement in a desired manner, but at the same time happens to be less
effective towards a cement of some other composition. Such a situation is
possible, for example, when comparing ordinary and sulfate-resistant
cements (Salvador 2016a).
The C3A/SO3 value is calculated assuming that the accelerator fuels
only the reaction that leads to formation of ettringite, just like the sulfate
component of cement. In fact, however, processes that take place may
present a more complicated picture. In research (Xu and Stark 2008,
Salvador et al. 2016b) it is noted that there is no AFm phase observed in
cement paste with accelerators (aluminum hydroxide and hydroxysulfate)
for quite a long time after depleting of sulfate component - up to 1-2 days.
Meanwhile, as previously stated, under conditions where sulfate
component is consumed quickly enough, hydration of С3А phase is to
proceed at high pace and formation of products of plate morphology
(AFm) shall prevail.
In the same work (Xu and Stark 2008) it was described that depletion
of sulfate component in samples with accelerators do not trigger a boost in
С3А hydration, when compared with reference sample. A prolonged
control over C3A hydration is explained by a gradual release of SO42- ions
that were previously sorbed by C-S-H gel into the liquid phase. Differences
in rate of hydration of С3S in cement pastes with and without amorphous
Al(OH)3, as is disclosed by XRD, are within the measurement accuracy of
the method. It is fair to say that authors have noted a lower compressive
strength of samples with Al(OH)3 in comparison with reference and
explained it with a smaller amount of C-S-H gel formed by that time.
Another subtle aspect is the possibility of AFm phase to exist in an X-ray
amorphous or submicroscopic state (Han et al. 2016) that sometimes does
not allow it to be identified by experimental methods employed
(XRD and SEM).
There is another example that may indicate that, beside C3A/SO3 ratio,
other factors, like overgrowing of the interstitial space with sulfoaluminate
hydration products, creating water deficiency conditions, etc. are also
responsible for suppressing hydration of silicate phases of clinker. As

noted above, aluminum sulfate has no significant effect on the

consumption of sulfate component and therefore should not suppress the
hydration of alite (at least not for this particular reason). However,
according to (Han et al. 2016), an increase in the dosage of aluminum
sulfate in cement paste led to an increase in the amount of ettringite
produced, alongside with an increase in the duration of the induction
period and a decrease in the intensity of the main hydration peak (i.e., a
slowdown in hydration). At higher doses of aluminum sulfate (8%), the
main hydration stage was delayed indefinitely.
Studies with 27Al- and 29Si-MAS NMR Spectroscopy
Effects of ultrafine amorphous Al(OH)3 and aluminum hydroxysulfate

solution (Al3+/SO42- molar ratio 1.64) on hydration of Portland cement
were investigated by the author utilizing 27Al- and 29Si-MAS NMR
spectroscopy (Brykov et al. 2012, Brykov et al. 2013a). These accelerators
were introduced with mixing water in the dosages equivalent to 0.5 and
1.5% Al2O3 of cement weight. Based on obtained data of 29Si-MAS NMR
spectroscopy, one may calculate a degree of Portland cement hydration, an
average length of silicate chains and other parameters of the cement stone.
Table 1 shows a degree of hydration of PC in cement paste samples
with an addition of Al(OH)3 and aluminum hydroxysulfate as well as a
compressive strength of these samples. It follows from Table 1 that both
admixtures at amounts equivalent to about 0.5 wt% Al2O3 accelerate
cement hydration at an early age. Increasing the amount of Al(OH)3 to
about 1.5 wt% by Al2O3 leads to an almost complete suppression of
hydration in the early period and reduces the one-day strength of cement
paste by several times compared with reference sample. A similar increase
in the aluminum hydroxysulfate amount leads to a slowdown in the
hydration of silicate phases, but the one-day strength of the cement paste
with this compound exceeds the strength of reference sample, possibly due
to the influence of ettringite that is involved in the formation of the cement
stone structure along with the C-S-H gel.

72 Alexey Brykov
Table 1. Influence of aluminum compounds on the degree of cement

hydration and strength of cement paste (Brykov et al. 2013a)
Compound Dosage, wt%/ dosage in Cement hydration Compressive strength,

admixed terms of Al2O3, wt% degree, % MPa, age, days
1 day 28 days 1 3 28
Ref. sample - 20.4 41.7 16.0 74.3 90.7
Aluminum 1/ ~0.5 22.3 - 25.6 76.6 95.7
hydroxide 3/ ~1.5 4.4 33.2 3.8 30.0 80.6
Aluminum 3/ ~0.5 26.3 45.2 39.0 66.8 93.3
hydroxysulfate 9 / ~1.5 13.7 36.8 25.0 37.2 70.0
At later age, differences in degree of hydration between the reference

sample and samples with aluminum-containing admixtures are still
noticeable, although are getting less pronounced with time. A slower
hydration rate of samples with high content of the admixtures results in
lower strength than in case of the reference.
The 27Al-MAS NMR spectra characterize distribution of aluminum
ions in different phases of cement paste and allow for observing of phase
transformations with the participation of accelerators at semi-quantitative
level. The application of 27Al-MAS NMR spectroscopy helps to extend the
knowledge obtained by XRD and SEM, because its results, unlike with
other methods, depend less on the degree of ordering of the examined
structures.
Figure 3 shows 27Al-MAS NMR spectra for cement paste with and
without aluminum-contained accelerators at one-day age. There are also
shown fragments of spectra in the area of 30-90 ppm (on an enlarged
scale), that reveal changes in content of 4- and 5-coordinated aluminum
ions.
In the spectra of cement pastes with high content of aluminum
admixtures there is a signal in the area of 60-70 ppm (Figure 3, spectra 2
and 4), which is not found in two other spectra. This signal is likely
relevant to slowdown of the hydration of Portland cement; in view of this it
was suggested that a formation of non-crystalline phase (aluminosilicate
hydrogel) which envelops cement particles takes place (Brykov et al. 2012,
Brykov et al. 2013a).

Figure 3. 27Al-MAS NMR spectra of one-day age cement paste samples:

1 – reference sample, 2 - 3% Al(OH)3; 3, 4 - aluminum hydroxysulfate, 3 and 9%,
respectively, in terms of Al2O3 (Brykov 2013a).
As already mentioned, as a result of the formation of ettringite with the

participation of a highly reactive Al(OH)3, the liquid phase of the cement
paste rapidly becomes deficient in SO42- ions which are originally released
as the sulfate component dissolves. Under these conditions, the formation
of aluminosilicate hydrogel from Al(OH)3, which is in an excess supply
compared with sulfate component, competes with the ettringite formation.
An aluminum hydroxysulfate solution is, obviously, a source not only
of aluminum but also of sulfate ions, which in this case are brought in a
system directly in the dissolved state. The total amount of sulfate ions from
the accelerator and from gypsum is estimated to be sufficient to fixate
aluminum ions from the accelerator in ettringite. In this case a quantitative
formation of ettringite from the aluminum hydroxysulfate solution is
completed within a period not exceeding several tens of minutes, whereas
the formation of the aluminosilicate gel is much slower than
when using Al(OH)3.
The proposedly formed phase of aluminosilicate gel is unstable; its
components gradually transit into sulfoaluminate phases and C-S-H gel. A

74 Alexey Brykov
less intensive formation of the aluminosilicate gel and, consequently, its

faster decay in case of the aluminum hydroxysulfate accelerator result in
less of a delay in cement hydration in presence of this compound than in
the case of Al(OH)3.
ROLE OF OTHER COMPONENTS OF COMMERCIAL

ACCELERATORS AND ASPECTS
OF SHOTCRETE TECHNOLOGY
Role of Other Components
As has been discussed in previous sections, the aluminum compounds

in alkali-free accelerators have some application-specifics features,
namely: 1) they possess unstable properties over time and 2) at increased
dosages they cause a slowdown in the hydration of cement (Han et al.
2016, Brykov et al. 2012, Brykov et al. 2013a). As a consequence,
commercially-available alkali-free accelerators are multicomponent
systems: beside aluminum compounds, they may also include mineral and
organic acids (mono- and polyatomic, as well as hydroxycarboxylic),
polyatomic and amino alcohols, colloidal SiO2, organic polymers, fluorine
compounds (acids, salts) and other constituents (Sommer et al. 2003,
Myrdal 2007, Kolomiets 2015, Yang et al. 2020). It should be noted that
many of the organic compounds used in accelerators formulations show
complexing and chelating properties with regard to calcium, aluminum,
iron ions, and so they may influence a hydration of clinker phases in some
manner. Structure-forming and stabilizing agents may also complement the
composition to give a mortar or concrete desired rheological properties; an
example of such agent is hydrated magnesium silicates (Kolomites et al.
2015).
The role of aluminum compounds is to provide for a quick setting and
very early strength gain of 1-1.5 MPa in first 1-2 hours (Hofer 2011). For
the reasons discussed above, their effect on strength of aged mortar or

concrete may be more on a negative side, especially at high dosages

required to ensure rapid setting. This decrease in strength occurs not only
because of the deceleration of hydration, but partly due to properties of a
rapidly growing structure, such as inhomogeneity, disorder, porosity
(Salvador et al. 2017, Salvador et al. 2020). Hence, the role of some of the
other components in commercial accelerators is to stimulate hydration of
clinker phases - so as to provide strength gain of sprayed concrete in early
age, and to further partially or even completely compensate for the strength
reduction incurred by the aluminum compounds. Quite often, the same
components in the accelerator perform a stabilizing function, to guarantee
time-stable behavior of the admixture.
Some organic acids (formic, acetic and hydroxyacetic, oxalic, lactic
and others) found in commercial accelerators not only play a role of a
stabilizing agent but can also stimulate hardening process (Myrdal 2007).
An actual effect will be determined by the content of acids with regard to
the content of cement in shotcrete formulation, which in turn depends on
the amount of accelerator and the content of corresponding organic acids in
it. It should be noted that accelerating effect of certain acids (e.g., formic,
oxalic, citric) is only exhibited at high dosages, while at low concentrations
the effect is negligible or even retarding. Some others (e.g., hydroxyacetic
and lactic) acids have a positive effect on late strength when introduced in
small amounts. Meanwhile a phosphoric acid, which is also utilized for
stabilization purposes, can result in a slowdown of hydration of silicate
phases due to formation of low-soluble calcium phosphates.
In view of the forgoing, it is interesting to note that an accelerating
effect of formic acid increases with an increase of C3A/SO3 ratio.
Polyatomic amino alcohols - triethanolamine and, especially,
diethanolamine - as constituents of accelerators stimulate hydration of С3А
phase. Diethanolamine is a more common component of accelerators than
other compounds of this type (see, for example, Kolomiets et al. 2015); it
does not reduce the strength of concrete in late age, and even contributes to
its development. Diethanolamine also has a stabilizing function.
Triethanolamine is less preferred because of the complex dependence of

76 Alexey Brykov
the nature of its action (slowing, or vice versa, resulting in instantaneous

setting) on its dosage (Myrdal 2007).
Highly dispersed forms of SiO2, including colloids, serve as nucleation
centers for cement hydration products and are readily involved in
pozzolanic reactions (Kontoleontos et al. 2015); they increase the strength
of concrete and its resistance to chemical corrosion.
Impact of Shotcrete-Specific Techniques
Laboratory samples of concrete prepared by manual operations and

typical laboratory equipment cannot fully reproduce the qualities of
concrete placed by shotcreting. The results of the study (Salvador et al.
2016c) show that shotcreting ensures a more thorough and even
distribution of the accelerating admixture in concrete batch than manual
mixing. On the one hand, this further promotes efficiency of the admixture,
but on the other contributes to build up of sulfate ions deficit. Under these
conditions, a hydration activity of С3А phase is increased, and products of
its reaction (mainly of AFm type) fill the interstitial space, thus limiting the
volume available for deposition of alite hydration products. As a result,
alite hydration may proceed more slowly in sprayed concrete than in a
concrete prepared using conventional laboratory equipment. Generally,
lower w/c ratios are utilized in sprayed concrete, and this also
compromises C3S hydration.
When commercial aluminum sulfate accelerator is introduced into a
pre-mixed Portland cement paste or mortar, its effectiveness depends on
the form in which calcium sulfate (gypsum, hemihydrate or anhydrite) is
present in the cement (Maltese et al. 2007). The rate of dissolution of the
setting regulator determines the morphology of the ettringite nucleation
centers formed when the cement is mixed with water, and that in turn
affects the shape of growing ettringite crystals upon accelerator addition.

The accelerator reacts more readily if slowly dissolvable forms of

calcium sulfate (anhydrite, gypsum) predominate in cement composition,
thus, the shortest setting time relates to anhydrite and the longest - to β-
hemihydrate.
Mixing technique also affects the morphology of ettringite crystals. In
sprayed concrete, ettringite is deposited as short needle crystals well
distributed in the matrix; this may be further influenced by functional
admixtures such as water-soluble organic compounds like plasticizers and
retarders used in ready-mixed mortars or concretes (Chen et al. 2016).
In EU countries, CEM I, including sulfate-resistant CEM I 42.5 N-SR,
and CEM II/A (-L, -LL, -S, -V, etc.), are nowadays the most common
types of cement used in production of sprayed concrete (Lundgren et al.
2018). A preference for CEM I or CEM II/A is due to the fact that mineral
constituents of cement except of clinker itself generally do not contribute
to development of very early strength required in shotcreting. However,
silica fume is often found among the components of shotcrete
compositions, which reduces the rebound of the concrete and further
contributes - more efficiently than any other mineral constituent - to
increase a resistance of concrete to various corrosive factors.
Among CEM II-type cements, Portland-limestone cements (e.g., CEM
II/A-LL 42.5 R) have been studied to the most extent regarding their use in
accelerated shotcretes mainly because they are more commonly used in
practice compared with other cements of this type, provided that the
concrete is exploited under conditions where a risk of thaumasite formation
can be avoided. The presence of limestone in cement increases accelerator
efficiency and has positive effect on hydration of clinker phases (Salvador
et al. 2016a). Calcium carbonate particles can act as seeds for nucleation of
ettringite. By partially binding aluminum ions into calcium
carboaluminates and in some way competing with the sulfate component,
calcium carbonate thereby prevents rapid depletion of the sulfate
component and formation of AFm phases by C3A hydration.

78 Alexey Brykov
INFLUENCE OF ALUMINUM-CONTAINING ACCELERATORS

ON CONCRETE RESISTANCE TO SULFATE ATTACK
The cause for deterioration of concrete when exposed to solution of

sulfates is usually the crystallization of ettringite in micropores of C-S-H
gel, which causes significant internal stresses, bulk deformations,
appearance and opening of cracks, the loss in strength (Bensted et al.
2007).
Crystallization of ettringite in aged concrete becomes possible if the
concentration of sulfate ions capable of reacting with aluminum-containing
phases and Ca(OH)2 increases in the pore liquid for some reason.
Depending on the origin of sulfate ions, the “internal” and “external”
forms of sulfate attack are distinguished. The most common cause of
sulfate corrosion of sprayed concrete is an imbibition of sulfate solutions,
like groundwater, into concrete from the environment (Galan et al. 2019).
Research suggests that aluminum-containing accelerators contribute to
development of these destructive processes and reduce the strength of
mortars and concretes exposed to sodium sulfate solution ((Paglia et al.
2002, Paglia et al. 2003, Brykov et al. 2013b, Brykov et al. 2015, Salvador
et al. 2020). Aluminum compounds influence a phase composition of
cement matrix and distribution of Al3+ and SO42- ions between phases. The
more aluminum ions get introduced with the accelerator into the concrete,
the more destructive is the effect. Figure 4 shows the trend of development
of linear deformations of mortar samples with amorphous Al(OH)3 and
Al2(SO4)3 during storage in sodium sulfate solution. By comparison, the
effect of iron (II, III) sulfates, which are also sometimes found in some
functional additives, is shown. Noticeable, the presence of iron sulfates
does not cause deformations (Brykov et al. 2015).
An introduction of aluminum-containing accelerators (especially if
their Al3+/SO42- ratio is higher than in ettringite) favors formation of low-
sulfate aluminum-containing hydrates (AFm phases) at early stages of
hardening. When sulfate ions are introduced from the environment into

such concrete, the AFm phases get involved in formation of ettringite in

micropores of the cement gel:
C4AS H12 +2Ca2++ 2SO42- +20H2O → C6AS3H32 (7)
Figure 4. Linear elongation of mortar samples with aluminum and iron compounds in
Na2SO4 solution: 1 - reference sample; 2 - Al(OH)3 (0.02), 3 - Al2(SO4)3 (0.02),
4 - Al2(SO4)3/FeSO4 (0.01/0.01), 5 - Fe2(SO4)3 (0.02), 6 - Fe2(SO4)3 (0.01); numbers in
parentheses indicate an amount of Al3+, Fe2+, Fe3+ introduced, mol/100g cement
(Brykov et al. 2015).
Some portion of aluminum ions from the accelerator may be trapped

into the structure of C-S-H either by incorporation of AlO4-tetrahedra into
silicate chains (in this case the notation “C-A-S-H” is more correct) or by
absorption. Later, when “environmental” sulfates come into the cement
stone, the C-A-S-H gel can serve as a source of aluminum ions to produce
“late” ettringite.
Effects of sulfate environment on phase composition of hardened
cement paste with aluminum sulfate additions can be investigated using
capabilities of 27Al-MAS NMR spectroscopy. Figure 5 shows 27Al-MAS
NMR spectra of hardened PC paste samples with aluminum sulfate (1 wt%
in terms of Al2O3), which 7 days after preparation were put into sodium
sulfate solution (50 g/l) or were kept submerged in pure water for 28 days

80 Alexey Brykov
(Brykov et al. 2015). It follows from Figure 5 that when the cement stone
is stored in Na2SO4 solution, a decrease in content of 4-coordinated
aluminum in C-S-H composition is accompanied by an increase in content
of ettringite. The same period of exposure to pure water does not lead to
any further changes in the content of ettringite and aluminum ions in the C-
S-H compared to the composition of cement stone of 7 days age; the
amount of calcium monosulfoaluminate in the water-stored cement stone
increases only as a result of hydration of aluminum-containing clinker
phases.
Sulfate resistance of concrete depends not only on the chemical
composition of cement, but also on physical characteristics of the concrete
article overall: its porosity, strength, permeability etc. These parameters
directly influence the rate of diffusion of sulfate ions from the
environment; their development over time depends on quality and
composition of concrete, namely the water-cement ratio, grain-size
composition of its components, type and amount of mineral constituents in
cement and concrete.
Figure 5. 27Al-MAS NMR spectra of cement paste with Al2(SO4)3: 1 - 7 days (moist
cured for 1 day and water cured for 6 days); 2 and 3 - after the subsequent storage for
28 days in water or in sulfate solution, respectively. Fragments of the spectra in range
of 50 - 90 ppm (an area of 4-coordinated Al) are given on the enlarged scale (Brykov
et al. 2015).

It is important here to note that evidences of negative effects of

aluminum-containing accelerators on sulfate resistance of concrete are
obtained based primarily on results of laboratory studies and tests. There
are objections that put these results in doubt: 1) the industrial-grade
sprayed concrete is generally of a higher quality than hand-prepared
laboratory samples; 2) the conditions recreated in laboratory standardized
methods for determining sulfate resistance are generally more strict and
severe than actual condition of concrete exploitation (Myrdal 2007,
Lundgren et al. 2018). It is also important that resistance of concrete to
sulfate attack is promoted by lower values of w/c applied in sprayed
concretes (≤0.45), in comparison with ordinary concrete. Consequently,
results obtained under laboratory conditions lead to underestimation of
sulfate resistance, and it is hence believed that positive result obtained by
laboratory means should guarantee the untroubled exploitation of concrete
in sulfate environments. Nevertheless, the employment of alkali-free
accelerators does not yet have a long enough history record to confirm this
in practice. Meanwhile, there are known cases of sprayed concrete
deterioration in real objects due to the use of alkaline accelerators (Tritthart
et al. 2011); these can serve as an argument for a more cautious attitude
towards alkali-free accelerators.
Ultrafine mineral materials such as fly ash, silica fume, metakaolin,
increase the resistance of concrete to sulfate attack by binding Ca(OH)2
and reducing porosity (Lundgren at al. 2018). Fly ash is a part of CEM
II/A-V cement, which is also used in sprayed concrete; silica fume is more
often utilized as a constituent of concrete mixtures for sprayed concrete.
The effect of high-calcium materials (high-calcium fly ashes and blast
furnace slags) on concrete sulfate resistance is generally less predictable
and less pronounced. It should be noted that in some European countries,
cement with slag (mainly CEM II/A-S) is employed in the production of
sprayed concrete. In work (Salvador et al. 2020) it was found that the more
the dosage of alkali-free accelerator (aluminum hydroxysulfate solution
with Al2O3/SO3 molar ratio of 0.46) in shotcrete based of blast furnace
cement (CEM II/B-S 42.5 R, w/c 0.5) the lower the sulfate resistance this
concrete had.

82 Alexey Brykov
Summarizing, to this day there aren’t that many research evidences

available, especially those dedicated to actual placing and working
conditions of shotcretes, to make for an unambiguous picture of this
subject, neither it is time to draw definitive conclusions yet. Work in this
field should continue.
ALKALI-FREE ACCELERATORS
AND ALKALI-SILICA REACTION
Destructive processes that take place in PC concretes due to formation

of expansive alkali-silicate hydrogel produced by a reaction between
certain categories of silica-containing aggregates and alkaline medium in
concrete pores are quite widespread in practice (Thomas and Folliard
2007). Alkali-silica reaction (ASR) leads to the development of stress in
structure that leads to cracking of concrete body and often open ways for
other types of corrosion which may eventually present an imminent danger
to safe exploitation of a concrete structure.
Several measures for reducing the risk of alkali-silica reactions are
known: 1) the use of low-alkali cements and alkali-free functional concrete
admixtures; 2) use of aggregates in which the content of reactive materials
is limited; 3) use of low water-cement ratios; 4) use of pozzolanic
materials, fly ashes, blast furnace slags and others.
The utilization of mineral admixtures is an efficient way of preventing
or slowing down the alkali-silica reaction even in unfavorable formulations
and environments (Thomas 2011). In this regard, aluminum-containing
mineral additives show higher inhibiting activity towards ASR than
materials in which aluminum content is low. This is because aluminum
ions inhibit dissolution of silica in an alkaline medium by adsorbing on
reactive aggregate particles and forming hardly soluble aluminosilicates
(Chappex and Scrivener 2012). It is known that pretreatment of reactive
silica species with an aluminum sulfate solution inhibits their dissolution in
NaOH solution (Natesaiyer and Hover 1992).

Figure 6. Linear expansion of mortars with reactive aggregate stored in 1М NaOH

(80°C): 1 - reference sample; 2 - Al(OH)3 (0.02), 3 - Al2(SO4)3 (0.02), 4 -
Al2(SO4)3/FeSO4 (0.01/0.01), 5 - Fe2(SO4)3 (0.02), 6 - Fe2(SO4)3 (0.01); numbers in
parentheses indicate an amount of Al3+, Fe2+, Fe3+ introduced, mol/100g cement
(Brykov et al. 2015).
Aluminum compounds found in alkali-free accelerators are also

capable of effective suppression of ASR (Ishii et al. 2007, Brykov et al.
2014, Brykov et al. 2015). Their positive effect is primarily explained by a
chemical binding of Ca(OH)2, a colmatation of pores in the cement matrix
by ettringite and other insoluble products they form. It is worth noting that
iron (II, III) sulfates possess similar properties. The data presented in
Figure 6 show that these compounds can effectively inhibit deformations
of cement mortars with reactive aggregate under standard conditions
stimulating alkali-silica reaction.
Thus, unlike alkaline accelerators, alkali-free aluminum-containing
accelerators are not only safe in terms of triggering alkali-silica reaction,
but actually they are capable of suppressing its harmful effects.

84 Alexey Brykov
CONCLUSION
Modern shotcrete accelerators must guarantee an almost instantaneous

setting of concrete, its correct placing and rapid development of very early
strength, but they also shall not adversely affect performance and
properties of concrete in mature age, do not compromise its durability, be
safe and come at a moderate cost.
The foundation of modern alkali-free accelerators are several
aluminum compounds (mainly hydroxysulfates) which, when introduced
into concrete mixture, form ettringite and ensure rapid setting. However,
due to a large number of factors, chemical, steric and others, this process
leads to a slowdown of hydration of cement and renders difficulties in
obtaining desired strength of concrete in the subsequent period.
Product engineers, when developing formulations of alkali-free
accelerators based on aluminum compounds, in order to optimize their
properties and effects on concrete, employ a lot of experience gained in
fields of utilizing various chemical and mineral functional additions, but at
the same time rely upon semi-empirical techniques. As a result, aluminum-
containing accelerators in market nowadays may have a complex multi-
component composition that was never disclosed by its manufacturers. In
addition to main constituents, they include components that stimulate
hydration of clinker phases, increase early and maintain late-age strength
(complexing organic compounds, nano-dispersed mineral particles, etc.).
The industrial practice of alkali-free accelerators does not yet have a
long history, so that some features of their interaction with cement
components, including such aspects of this interaction that may affect the
durability of cement concrete and mortar, remain yet unclear. For example,
research suggests that aluminum-containing accelerators may induce
deterioration of concrete under external sulfate attack. Therefore,
investigations should continue to gain a more thorough understanding of
the influence of alkali-free accelerators on durability of sprayed concrete in
actual conditions of its application and exploitation.

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with alkali-free and alkaline admixtures: Laboratory vs. field. Cement
and Concrete Research 32:665-671.
Paglia, C., Wombacher, F., and Bohni, H. (2003). The influence of alkali-
free and alkaline shotcrete accelerators within cement systems.
Influence of the temperature on the sulfate attack mechanisms and
damage. Cement and Concrete Research 33:387-395.
Prudencio, L. R. (1998). Accelerating admixtures for shotcrete. Cement
and Concrete Composite 20:213-219.
Rixom, R., and Mailvaganam, N. (1999). Chemical Admixtures for
Concrete, London: E&FN Spon.
Salvador, R. P., Cavalaro, S. H. P., Cincotto, M. A., and Figueiredo, A. D.
(2016a). Parameters controlling early age hydration of cement pastes
containing accelerators for sprayed concrete. Cement and Concrete
Research 89:230-248.
Salvador, R. P., Cavalaro, S. H. P., Segura, I., Figueiredo, A. D., and Pérez
J. (2016b). Early age hydration of cement pastes with alkaline and
alkali-free accelerators for sprayed concrete. Construction and
building materials 111:386-398.
Salvador, R. P., Cavalaro, S. H. P., Cano, M., and Figueiredo, A. D.
(2016c). Influence of spraying on the early hydration of accelerated
cement pastes. Cement and Concrete Research 88:7-19.
Salvador, R. P., Cavalaro, S. H. P., Monte, R., and Figueiredo, A. D.
(2017). Relation between chemical processes and mechanical
properties of sprayed cementitious matrices containing accelerators.
Cement and Concrete Composites 79:117-132.

Salvador, R., Rambo, D., Bueno, R., Lima, S., and Figueiredo, D. (2020).
Influence of accelerator type and dosage on the durability of wet-
mixed sprayed concrete against external sulfate attack. Construction
and Building Materials 239: Article 117883 https://doi.org/10.1016/
j.conbuildmat.2019.117883.
Saout, G., Lothenbach, B., Hori, A., Higuchi, T., and Winnefeld, F. (2012).
Hydration mechanism of quick hardening cement based on OPC
blended with an amorphous calcium aluminate. Paper presented at 18th
Int. Baustofftagung “Ibausil”, Weimar, September 12-15.
Shi, C., Zhang, G., He, T., and Li, Y. (2016). Effects of superplasticizers
on the stability and morphology of ettringite. Construction and
Building Materials 112:261-266.
Sommer, M., Wombacher, F., and Burge, T. A. (2003). Alkali-free setting
and hardening accelerator. US 6,537,367. Issued Mar. 25, 2003.
Sommer, M., Mader, Urs, Wombacher, F., and Lindlar, B. (2004). Setting
and hardening accelerator for hydraulic binders and process for its
production. EP 1 422 205. Issued May 26, 2004.
Taylor, H. F. W. (1997). Cement Chemistry. 2nd Edition, London: Thomas
Telford.
Thomas, M. D. A., and Folliard, K. J. (2007). “Concrete aggregates and the
durability of concrete.’’ In Durability of Concrete and Cement
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York: CRC Press.
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thaumasite formation in an Austrian tunnel. Paper presented at XIII Int.
Congr. on the Chemistry of Cement, Madrid, July 3-8.
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92.

90 Alexey Brykov
Weibel, M. (2009). Stable shotcrete accelerator dispersion with high

content in active matter. Pat. EP 187 87 13. Issued Apr. 22, 2009.
Yang, R., He, T., Guan, M., Guo, X., Xu, Y., Xu, R., and Da, Y. 2020.
Preparation and acceleration mechanism of aluminum sulfate-based
alkali-free accelerating additive for sprayed concrete. Construction and
Building Materials 234: Article 117334 https://doi.org/10.1016/
j.conbuildmat.2019.117334.
BIOGRAPHICAL SKETCH
Alexey Brykov
Affiliation: Department of Chemical Technology of Silicate Materials,

Saint Petersburg State Institute of Technology, Saint Petersburg
Education: Chemical engineer, DSc.
Research and Professional Experience: expert in the chemistry of

silicate binders, the author of more than 120 scientific publications, 20
monographs and tutorials, 10 patents.
Professional Appointments: Professor
Publications from the Last 3 Years:
1. Voronkov M. E., Brykov A. S., Nekrasova O. K., Pavlov S. S.

Effect of pyrocatechin on the properties of cement-free refractory
concrete mixtures based on silica-containing colloidal binders//
Refractories and Industrial Ceramics. 2019. Vol. 59. No. 5. P.
545-548.

2. Brykov, A., Voronkov, M., Nekrasova, O., Mokeev, M. Miserly

Amounts of Pyrocatechol on Calcium Aluminate Cement
Hydration//Materials Sciences and Applications. 2018. V. 9. P.
455-463.
3. Brykov A., Paritskaya N., Velichko A., Mokeev, M. Influence of
Benzenediols—Pyrocatechol and Resorcinol—On the Resistance
of Portland Cement Mortars with Aluminum Sulfate to Sulfate
Attack//Materials Sciences and Applications. 2018. V. 9. P. 305-
313.

Chapter 3
INDIAN CEMENT INDUSTRY:

A PERSPECTIVE
Mainak Ghosal
Dr. M. N. Dastur School of Material Science & Engineering,
Indian Institute of Engineering Science & Technology (IIEST),
Shibpur, Howrah, West Bengal, India
ABSTRACT
Despite India’s GDP hovering to a new low rate of growth at around

5% or more, its cement sector is booming and poised to achieve new
heights in water positive manufacturing, consuming wastes like fly ash
and slag, cutting on energy and enjoying cost benefits, lowering the
carbon footprint by reducing CO2 emissions, in paying taxes. Most Indian
cement plants conform to the ISO 9001:2008 Quality Management
Certification, ISO 14001:2004 Environment Management Certifications
and the OHSAS 18001 Occupational Health and Safety Standard
Certification. 50 percent of Indian Cement Industry’s capacity today is
less than ten years old and is part of the construction sector that is the
second largest in employment generation, with 20,000 downstream jobs
being created for every one million tonnes of cement produced and

Corresponding Author’s E-mail: mainakghosal2010@gmail.com.

94 Mainak Ghosal
consumed. According to a study by IIM Bangalore, cement companies in

India are spending more than the mandated 2% on CSR while their peers
spend a mere 0.3-1.5%. It is said that the cost of cement in India is less
than half of common salt costing around INR 20/Kg, which is more than
that of cement costing around INR 7/Kg - an unchallenged economy.
Keywords: cost, cement, certification, India
INTRODUCTION
India today with about 540 million tonnes installed cement capacity, is
the 2nd largest producer of cement in the world after China and projected to
grow over 600 Mt per annum by 2025. Due to India’s growth process and
increased urbanization combined with the proposed development of 100
smart city mission and affordable housing projects announced by the
government, the cement industry is poised to overtake China in the near
future. The housing sector accounts for 67% of the total cement
consumption in India while the other consumers of cement include
infrastructure at 13%, commercial construction at 11% and industrial
construction at 9%. Growth expectations have been fueled significantly by
the government’s speedy approval of the proposed investment schemes
announcements in the previous Union Budget by releasing an affordable
housing fund of approximately Rs. 25, 000 crores which is to be utilized
for easing credit to the homebuyers- a move which will certainly boost the
demand of cement from the housing sector [1].
The history of the cement industry in India dates back to 1889 when a
Kolkata-based company started manufacturing cement from Argillaceous
(kankar). But the industry started late, getting the organized shape in the
early 1900s, which was much later than that of other developing countries
like China who started in 1889 or South Africa where the cement industry
got started in 1892 by De Eerste Zement Fabrieken Beperkt when the first
Portland cement manufacturer was created. In 1914, India Cement
Company Ltd was established in Porbandar with a capacity of 10,000 tons.
First World War gave the initial thrust to the cement industry in India and

Indian Cement Industry 95
the industry started growing at a fast rate in terms of production,

manufacturing units, and installed capacity. This stage was referred to as
the nascent stage of Indian cement Company. In 1927, Concrete
Association of India was set up to create public awareness on the utility of
cement as well as to propagate cement consumption. Acquisition &
mergers of cement companies started from 1936 and the cement industry in
India saw the price and distribution control system in the year 1956,
established to ensure fair price model for consumers as well as
manufacturers. Later in 1977, government authorized new manufacturing
units (as well as existing units going for capacity enhancement) to put a
higher price tag for their products and a couple of years later, the
government introduced a three-tier pricing system with different pricing on
cement produced in high, medium and low-cost plants [2]. The Indian
cement industry has finally arrived in its maturity stage as it is beginning to
gather the benefits of its decontrol by the government in 1989-90.
BRIEF DESCRIPTION
The Construction sector of India accounts for almost 8% of the

country’s GDP. As housing and infrastructure development activities
increase, construction will have an ever-increasing significance in the
national economy. As the second largest premium input (after iron and
steel) in construction, cement will play an important role in generating
growth and employment in the years to come. Cement industry is one of
the leading sectors of the building materials industry. Cement is used in the
production of concrete, mortars, and in the petroleum and other industries.
The different types of cement are ordinary Portland cement, white cement,
rapid hardening cement, colored cement, expansive cement, hydrographic
cement, low heat cement, quick setting cement, and others. They are
produced strictly as per the Bureau of Indian Standards (BIS)
specifications and their quality is comparable with the best in the world.
Figure 1 plots the cement production data in M. tons for the current
decade.

96 Mainak Ghosal
Figure 1. Cement production in India in million tonnes.
Significance of Cement for Growth and Employment
India exported about 6.62 million tonnes cement valued at Rs. 2, 276
crores in 2017-18 (4.08 million tonnes of clinker, 2.54 million tonnes of
cement) to Sri Lanka, Nepal, Bhutan, Angola, Yemen, Madagascar,
Maldives and Mozambique. The Government of India has been trying to
place a massive emphasis on infrastructure development, with 100 smart
cities, modernization of 500 other cities, affordable housing for all by
2022, cement concreting of national highways, provision of sanitation
facilities, interlinking of rivers, etc. All of which are in the pipeline over
the course of the next few years. Most of the cement plants in India are
operated by state-of-the-art technology and with advanced production
facilities. The liberalization policies in the cement industry enabled the
achievement of strong growth in the sector.
The working group on cement Industry, constituted by the Planning
Commission for the 12th Five-Year Plan period, had projected a demand
growth @ 10.75% per annum during the plan period. This was calibrated
against a 9% GDP growth rate, which, however, did not materialize. The
working group had expected that the installed capacity requirement would
be 1,045 million tonnes by 2027, which would suggest that the growth
would pick-up further and there will be increased demand for cement. Less
than anticipated GDP growth rates in the last few years have not only
slowed down the growth in capacity, it has also increased the gap between
installed and utilized capacities and with the economic slowdown looming
large, it will be worth noticing how the cement industry manages itself out

of this situation. This has been further aggravated by the unavailability of

coal, which at the moment is the primary source of energy in cement
factories.
The significance of cement in the national economy does not depend
only on its share of GDP or total employment (Tables 1 and 2), but also on
its backward (sectors feed into cement) and forward (sectors fed by
cement) integrations. Backward linkages show each tonne of cement
requires quarrying of 1.65 tonnes of limestone and 0.4 tonnes of clay with
up to 0.25 tonnes of coal as energy. In weight proportions, typically 67%
of limestone, 22% of silica & 11% of metals and other products are used in
cement production though compositions vary according to the specific
product types. On the flip side, 90% cement produced is used in
construction sector and the rest 10% in other products. These
direct/indirect effects along with their total impact on economy are
typically assessed using CGE (Computable General Equilibrium) models
and in practice done by SAM (Social Accounting Matrix). SAM allows us
to study these impacts at a disaggregated level - by sectors and by socio-
economic groups in a country.
The SAM allows us to assess the economy wide impact of growth in a
particular sector (say for here, cement). The ‘turnover multiplier’ is defined
as the amount by which the turnover of the economy increases for a unit
increase in the turnover of that sector.
Table 1. Manufacture of cement, lime and plaster
Year (1) Nos. of Turnover (Rs. Total Average

factories in in lakhs) (3) persons employment/factory
operation (2) engaged (4) (5)
2011-12 1208 9210955 155783 129
2012-13 1124 10231300 155266 138
2013-14 1273 10170967 164740 129
2014-15 1270 11408302 175512 138
2014-16 1263 10987491 180504 143
Source: Annual Survey of Industries, Volume 1, 2011-16.

98 Mainak Ghosal
Table 2. Manufacture of articles of concrete, cement and plaster
Year (1) Nos. of Turnover Total Average

factories in (Rs. lakhs) persons employment/factory
operation (2) (3) engaged (4) (5)
2011-12 2007 1637888 83127 41
2012-13 2244 1985422 82169 37
2013-14 2274 1546580 79461 35
2014-15 2452 2419995 90167 37
2014-16 2312 2217909 81456 35
Source: Annual Survey of Industries, Volume 1, 2011-16.
Table 3. Effect of a rupee in cement turnover
Total effect on output (Rs.) 3.16

Direct effect on output (Rs.) 0.58
Indirect effect on output (Rs.) 2.58
Income effect (Rs.) 1.53
Rural household consumption effect (Rs.) 0.51
Urban household consumption effect (Rs.) 0.52
Employment effect (in persons) 0.14*10-5
Source: Calculations by India Development Foundation (IDF).
Table 3 shows the effects of an increase in cement production value by

one rupee. For better understanding let us combine the data in Table 1 & 3.
From Table 1, the value production of an average cement factory is
approximately Rs. 85 crores (Avg. of col (3)/col (2)) or 11,155,023.87
USD. The increased production of cement will increase the turnover of all
inputs going to cement like limestone, electricity, coal, etc. So the
immediate total turnover growth will be 85 crores cement + an increase of
about 49 crore rupees (0.58 x 85 crores) in inputs going to the cement,
giving us the direct effect. Then follows the indirect effect for as inputs
into cement grow, so does the entire economy thus churning the whole
economy and the resulting improvement of activities increases the total
turnover by an additional 219 crores (2.58 x 85 crores) or 28,741,881.23
USD. Table 3 shows the effects of an increase of cement production value
by one rupee. From Table 1, the value of production of an average factory

is about 85 crore rupees. Thus if a new factory is built, which is similar to

an average cement factory, it will yield a total turnover in the economy. In
short, an additional average turnover cement plant will increase the
economy by 354 crore rupees (85 crores + 3.16 x 85 crores) or
46,459,479.25 USD. GDP will increase by about 130 crore rupees (1.53 x
85 crores) or 17,064,179.43 USD. Last but not the least, it will generate
close to 1200 new jobs throughout the economy. The + ve effects continue
improving the rural household consumption by 43 crore rupees (0.51 x 85
crores) or 5,644,305.5 USD & urban household consumption by a slightly
larger amount of 44 crore rupees (0.52 x 85 crores) or 5,775,568.42 USD
[3].
Cement and the Environment
Cement is one of the major industries that affect climate change and it
is second most consumed product after water. Overall the cement industry
consumes 2% of all energy consumption and 5% of the total industry
consumption and contributing 5% of total CO2 emission per year. Globally,
cement production is under pressure for environmental concerns. There is a
need to reduce CO2 emissions in India and the world are to meet the
climate change goals set out in the Paris agreements. There are 3 critical
pathways - (i) improving energy efficiency throughout the process, (ii)
reducing the clinker component with mineral/material substitutes, (iii)
replacing coal & petcoke through lower carbon alternate fuels.
Indian cement industry is among the world leaders in the first two
aspects. Based on CDP’s (Carbon Disclosure Project) report, the Indian
cement industry is at the forefront in reducing the carbon footprint in
cement production. Indian companies outperform international peers in
having a clinker ratio of 69% v/s 78% which have largely been possible
due to usage of alternative by-product materials like flyash and slag
coming from other carbon intensive sectors like thermal power & steel
plants. Figure 2 shows the reductions in gross CO2 emission from cement
plants across the globe. The efficiency achieved by the Indian cement

100 Mainak Ghosal
plants in the last 25 years by cutting down emission by 27%, is

considerably higher compared to other major cement manufacturers of the
world. During 90s, plants in the EU were less polluting but today Indian
cement plants are more efficient than EU plants. The 3rd mitigation strategy
is an opportunity as well as a challenge for Indian cement plants as Indian
plants are comparatively new and more efficient and better equipped to use
alternative fuels (AFs) in their production w.r. to their European
counterparts that depend on older cement plants. One important source of
AF is refuse derived fuel (or, RDF) which is a fuel produced from various
waste types like municipal solid waste, industrial waste or commercial
waste (Wikipedia). There are many advantages in using RDF like
minimizing CO2 emission and ash residue, producing more homogenous
fuel, having higher calorific value content and lower moisture content. This
and increasing use of RDF in European cement production has encouraged
the Indian government to insist on using RDF in Indian cement plants but
there are inherent issues involved like steady supply of a pre-specified
quality at a stable rate. International Finance Corporation (IFC) in its 2017
report entitled the use of alternative fuels at Cement Plants. One important
source of alternative fuels in cement plants is plastic and other municipal
solid waste (MSW). International best practice lists the various steps that
must be undertaken in the society for municipal solid wastes to be used as
a fuel source in cement plants. Firstly, the municipal bodies must take
responsibility in the collection of waste and its disposal, even if sub-
contracting some these tasks are involved. It must also make available land
for sorting line creation. Secondly, the city supplying MSW must be
having a population of at least 1 million people and must be situated within
100 kilometers of the cement plant. Thirdly; the cement plant itself must
have a kiln capacity of at least 1 million tonnes/year. Last but not the least,
RDF must be so priced that it should be beneficial for the cement plants to
substitute fossil fuels.

Figure 2. Percentage reduction in per tonne emission between 1990-2016 (3).
Thus, to address societies concern, municipalities and cement plants

have to work in tandem to reap the benefits of alternative fuels in the
production of cement, thus making it a viable model in waste disposal &
management as well as help in reducing landfill areas which have a
negative impact on environment and health.
CONCLUSION
The calculations in this Paper are based on very conservative

estimates. The average production in a factory which is made up of some
large plants and a greater number smaller plants is taken into consideration
keeping sustainability parameters in mind. However, if a large plant comes
up, the calculated amounts will be much higher. The assumption behind
these calculations is that this increased production will have little impact
on the end price of a bag of cement.
Indian cement industry has contributed substantially in sustainable
construction in the past. By sustainable development we mean the
definition defined at the 1992 Earth Summit in Rio de Janerio as an
Economic activity that is in harmony with the earth’s ecosystem or that

102 Mainak Ghosal
defined by the World Commission on Environment & Development in 1987

as the development that meets the needs of the present without
compromising the ability of the future generations to meet their own needs.
However, there is a long way to go ‘build more with less.’ The day we
consume our entire industrial by-products like flyash, blast furnace slag,
etc. we can claim that we have contributed effectively to the nation in
particular and to the world at large. It is widely known that the World
Business Council for Sustainable Development (WBCSD) has laid out a
roadmap for low-carbon transition of the Indian Cement Industry with the
involvement of Cement Sustainability Initiative (CSI), which includes
several major Indian cement companies, in 2013, using 2010 as the base or
reference year. This roadmap was reviewed in 2018 and the review
reported that only 5% reduction of CO2 was achieved between 2010 to
2017. With a record comparable % reduction in emission as shown in
Figure 2, India’s next target is set up for the year 2050, to reach a direct
CO2 emission intensity of about 45% lower than that of 2010 levels. Will
Indian cement industry be able to achieve this feat?
REFERENCES
[1] 6th Edition of “Survey of Cement Industry & Directory 2019,”

Labour & Industrial Chronicle, Hyderabad.
[2] https://business.mapsofindia.com/cement/.
[3] Importance of Cement in India, published by Cement Manufacturers
Association (CMA), 2018.
[4] Chatterjee Anjan K., Blended Cements and Sustainability: An Indian
Perspective, Cement, Energy and Environment, Vol. 18, No. 1, Jan-
Jun, Cement Manufacturers Association (CMA), 2019, 16-26.

Chapter 4
SINGLE CRYSTAL AND MULTI-LAYER

COMPOSITE HEAVY-OXIDE SCINTILLATORS
FOR EFFICIENT FAST NEUTRON DETECTION
Sergei V. Naydenov1,*, Vladimir D. Ryzhikov2

and Craig F. Smith3
1
Institute for Single Crystals, Kharkov, Ukraine
2
Institute for Scintillation Materials, Kharkov, Ukraine
3
Naval Postgraduate School, Monterey, CA, US
ABSTRACT
Several different types of single crystal and multilayer composite

heavy-oxide scintillation materials have been developed and
characterized for fast neutron detection for homeland security and nuclear
safeguards applications. In particular, for the detection of fast neutrons,
large-sized (diameter 40-50 mm, length 80-100 mm) scintillation blocks
based on the heavy-oxide single crystals of CdWO4 (CWO), ZnWO4
(ZWO), PbWO4 (PWO), Bi4Ge3O12 (BGO), Gd2SiO5(Ce) (GSO(Ce))
have been conceived, fabricated and tested. These crystals demonstrate
*
Corresponding Author’s E-mail: sergei.naydenov@gmail.com.

104 Sergei V. Naydenov, Vladimir D. Ryzhikov and Craig F. Smith
fast neutron detection efficiencies of not less than 50% without using an
external plastic moderator. Based on these detectors, an experimental
prototype of a portal monitor to detect mixed neutron/gamma radiation
has also been created. Additionally, a new heterogenous detection
structure, referred to as “ZEBRA”, has been developed. The ZEBRA
detectors consist of layers of a composite material comprised of
microgranules of the same heavy-oxide scintillators dispersed in
transparent plastic, alternated with layers of clear plastic that serve as
scintillation light guides and as a neutron moderator material. The
detection efficiency and sensitivity of ZEBRA detectors compare
favorably with those of detectors based on large-size single crystals, but
the composite structures are much less expensive and can be
manufactured in much larger dimensions. These composite detectors
represent a significant advancement from earlier single-crystal detector
types and are the result of recent efforts to explore alternatives and
improvements to conventional 3He counters. The high detection
efficiency of ZEBRA scintillators is due to not only to the contribution
from inelastic scattering of fast neutrons by heavy constituent nuclei, but
also from internal energy reduction (i.e., moderation) from processes such
as elastic scattering (and proton recoil), and the subsequent resonant
absorption of moderated fast neutrons.
Keywords: fast neutrons, radiation detectors, heavy-oxide scintillators,

multi-layer detectors, composite scintillators, 3He alternatives, nuclear
safeguards
INTRODUCTION
Modern fast-neutron detectors play a key role for homeland security

and homeland safeguards applications in addition to applications related to
radiation monitoring in nuclear facilities and nuclear power plants, neutron
radiography in non-destructive testing, nuclear medicine, environmental
pollution control, monitoring of soil moisture capacity, geophysical
research of mineral and hydrocarbon deposits, and other fields.
Of particular importance is the use of portable or stationary fast
neutron detectors to identify and prevent the dissemination of fissile
nuclear materials (i.e., prohibited special nuclear materials such as
enriched uranium or weapons-grade plutonium), or to detect the transport

Single Crystal and Multi-Layer Composite … 105
of other radioactive materials such as those that may be incorporated into

“dirty” bombs. The ultimate detecting capability of these devices can be
characterized by their (internal) fast neutron detection efficiency (i.e.,
cps/nps)1 and neutron flux sensitivity (cps/nv)2. To increase the sensitivity,
it is generally necessary to increase the detector area in the direction of the
incident radiation and thereby increase the scintillator volume and its cost.
One of the main challenges in nuclear security is the creation of
detection systems for fast neutrons and mixed neutron/gamma radiation
that would be highly efficient, compact, inexpensive, robust with respect to
unfavorable conditions, and reliable in operation (see, for example,
(Caruso, 2010) and additional references therein). Reliable recognition of
special nuclear materials (e.g., highly enriched Uranium and weapons
grade Plutonium), and other neutron-emitting radioactive materials
requires the creation of detectors with high detection efficiency for fast
neutrons (intrinsic efficiency not less than 50-60%). At the same time,
practically all of the state-of-the-art detectors proposed for the replacement
of 3He counters due to the shortage of 3He (Kouzes et al., 2015) can
directly detect only slow and/or thermal neutrons, relying on the radiative
capture reactions of light nuclei such as 6Li or 10B with high thermal-
neutron absorption cross-sections, but with relative insensitivity to fast
neutrons. Many types of such neutron detectors have been proposed (see,
for example, (Kojima et al., 2004; Peerani et al., 2012; Lacy et al., 2013;
Alemberti et al., 2014; Cherepy et al., 2015; Marin et al., 2015; Lam et al.,
2018)). The probability of detection of fast neutrons with these detectors
without using external plastic moderators is greater than an order of
magnitude lower than for thermal neutrons, and the intrinsic efficiency of
detection of fast neutrons therefore does not exceed a few percent. Even
with massive moderators to moderate and thermalize the fast neutrons, the
intrinsic efficiency of such systems for fast neutrons is ordinarily not
higher than 10-20%, and for 3He detectors about 10%.
1
cps/nps: counts per second registered in the detector per neutrons per second entering the
detection medium.
2
cps/nv: counts per second registered in the detector per neutron flux. The neutron flux density is
calculated as the neutron density (n) multiplied by neutron velocity (v). Actual units of flux
density are neutrons/(s∙cm2).

Traditionally, organic liquid and solid scintillators, including organic

single crystals (anthracene, stilbene), and plastic scintillators have been
used for detection of fast neutrons. Recently there were proposed
composite capture-gated plastic detectors (see, for example, (Flaska et al.,
2010; Paweczak et al., 2011; Liu et al., 2016; Galunov et al., 2016))
containing heavy nuclei such as 113Cd, 155Gd, 157Gd with very high thermal
neutron radiative capture cross-sections. Unfortunately, all these detectors
have relatively low sensitivity to fast neutrons and intrinsic efficiencies not
greater than 15-20%. Moreover, plastic scintillators have high sensitivity to
gamma radiation, and this interferes with and reduces sensitivity to fast
neutrons.
At the same time, theoretical considerations, actual experiments and
numerical simulation of the interaction processes of fast neutrons passing
through materials with heavy nuclei indicate that, alongside radiative
capture, which is not sufficiently efficient in the fast energy range, another
interaction mechanism can be used for efficient fast neutron detection – the
reaction of inelastic scattering of fast neutrons (Hausser et al., 1983;
Kubota et al., 1989; Anelli et al., 2007; Ryzhikov et al., 2010, 2014a,
2014b; and references therein). It has been found (Ryzhikov et al. 2011,
2014a, 2014b, 2015a, 2015b, 2018, and others) that promising materials
for such detectors are heavy oxide scintillators with relatively large cross-
sections for inelastic scattering of fast neutrons on the heavy nuclei of their
constituent atoms (i.e., 113Cd, 155Gd, 157Gd, 184W, 209Bi, etc.). Such
scintillators – CdWO4 (CWO), ZnWO4 (ZWO), PbWO4 (PWO), Bi4Ge3O12
(BGO), Gd2SiO5(Ce) (GSO(Ce)), etc. have been used to create novel
single-crystal detectors of fast neutrons and mixed gamma-neutron fields
(Grynyov et al., 2011; Ryzhikov et al., 2015a, 2015b, 2018). In these
scintillators the energy of fast neutrons is directly converted into the
energy of gamma-quanta and conversion electrons, without the stage of
preliminary moderation of the neutrons. In this case, the single-crystal
scintillator plays a double role as an efficient converter of neutrons into
secondary gamma-quanta of intermediate energies, and as a scintillator that
detects these internal gamma-quanta. These detectors show high detection
efficiency of fast neutrons (in the range of 50-70%) and high sensitivity

(up to 49 cps/nv) with compact scintillation assemblies using single

crystals of dimensions ø40x80 mm coupled to 2″-photomultipliers. This
allows the use of such neutron detectors in compact stationary systems and
portal monitors for the detection of radioactive and fissionable nuclear
materials (Ryzhikov et al., 2017a, 2017b).
Recent studies (Ryzhikov et al., 2015a, 2015b, 2016, 2017a, 2017b)
have also shown the possibility to create fast neutron detectors of
comparable efficiency on the basis of a novel multi-layer composite
scintillation structure that relies similarly on direct detection of fast
neutrons through their interaction with materials of high effective atomic
number as well as those at intermediate or low energies following various
interactions within the getector itself.
These studies describe an original heterogeneous scintillation structure
(named ZEBRA), which is comprised of a series of alternating plates of
two types – plates consisting of small particles of heavy crystalline
scintillator material (i.e., CWO, ZWO, PWO, BGO, GSO(Ce), etc.)
embedded in an organic matrix (silicon rubber), and plates of a clear
plastic material (PMMA, polystyrene or others), which simultaneously
serve as a moderating material and a light guide for the output of
scintillation photons. In detecting fast neutrons, such a detector medium
utilizes, to the maximum extent, not just one, but several channels of
neutron interactions with heavy nuclei – inelastic scattering of fast
neutrons scattered at different angles into the moderator, as well as
resonance scattering and radiative capture of neutrons moderated inside the
detector by elastic scattering in hydrogen-containing plastic. The detection
of fast neutrons simultaneously over several channels of their interaction
substantially increases the total detection efficiency. It should also be noted
that such an approach, with a transition from homogeneous (single-layer)
to heterogeneous (multi-layer) detectors has been also considered in
several other works (Bowden et al., 2009; Chernukhin et al., 2015;
Mohsen, 2015; Flaska et al., 2010; Paweczak et al., 2011; Liu et al., 2016)
searching for new, more efficient types of composite neutron detectors.

THEORETICAL BACKGROUND FOR FAST NEUTRON

DETECTION BY HEAVY-OXIDES SCINTILLATORS
There are several principal interaction phenomena related to detecting

an incident flux of fast neutrons by materials comprising single crystal or
multi-layer heavy-oxide scintillators described here. In this sub-chapter, we
consider only those possible neutron reactions which are most important
with respect to fast neutron detection by the corresponding detectors. Note
that there are many other neutron reactions (including reactions such as (n,
2n), (n, p) and other non-elastic processes apart from inelastic scattering)
that are not the principal mechanisms for many detection systems. To
provide additional discussion about such reactions would only add
unnecessary detail, and could introduce misunderstanding as to the
processes that are most important.
Several types of reactions of direct importance should be singled out:
(i) inelastic scattering of fast neutrons on heavy nuclei in the heavy-oxide
single crystal scintillator or in the heavy-oxide composite scintillator
layers; (ii) elastic scattering and deceleration (moderation) of neutrons of
intermediate energies in the plastic layers of the multi-layer design
detector; (iii) elastic and (iv) non-elastic resonance interactions, including
resonant capture of neutrons of resonance energies (from several eV to tens
of keV) in the scintillator layers after their moderation in the plastic layers;
and (v) radiative capture of neutrons reaching the range of thermal
energies, which would be especially efficient for scintillators with odd
neutron-capturing nuclei, such as 113Cd, 155Gd, 157Gd, etc.
The neutron inelastic scattering  n, n  reaction
 A, Z   n   A, Z   n   (1)
in the range of energies up to ~50 MeV occurs mainly through the

formation of a compound nucleus  A  1, Z  . At fast neutron energies
about 5-6 MeV and higher, the excitation energy falls into a quasi-
continuous spectrum of the compound nucleus levels, which allows the use

of the statistical model of the nucleus (Akhiezer and Pomeranchuk, 1950;

Blatt and Weisskopf, 1979). Within this model, the excitation energy (i.e.,
the incident neutron energy minus the nucleus recoil energy) is distributed
onto the statistical fraction of the level spectrum, which determines the so-
called nucleus temperature. The nucleus temperature T is evaluated from
the excitation energy E* as T  E * a , where the level density parameter
a  10 (see, e.g., Akhiezer and Pomeranchuk, 1950). The excitation
energy E* is the kinetic energy En brought by the incident neutron to the
nucleus, i.e., for heavy nuclei it is about the energy En of the incident fast
neutron. For a nucleus with mass number A  150 and an excitation energy
of about ~5-6 MeV, the nucleus temperature is T  0.75 MeV . In the
statistical model of nucleus, the average nucleon energy in the nucleus is
 n  2T (see, e.g., Akhiezer and Pomeranchuk, 1950). The average kinetic
energy of a neutron emitted from the compound nucleus is approximately
equal to En   n  2T . The incident neutron energy, in this case, is of the
239
order of the average energy of fast neutrons for a Pu-Be source, i.e.,
En  4.5 MeV . Therefore, in this case, En  1.5 MeV . In the residual
nucleus, the remaining energy is ~3 MeV. This is sufficient for the
excitation of several lower levels of the residual nucleus. This excitation is
removed, as a rule, by emission of accompanying prompt gamma-quanta
from de-excitation of the compound nucleus and delayed (in the 0-30 µs
range) gamma-quanta from the de-excitation of the residual excited
nucleus
 A  1, Z    A, Z   n   prompt ;  A, Z    A, Z    delay
* * *
(2)
and/or conversion electrons in the transfer of the excess excitation of the

residual nucleus  A, Z  to the atomic orbitals of the final nucleus  A, Z  .
*
For heavy nuclei, the energies of secondary gamma-quanta are in the range
from tens of keV to several MeV. The conversion electron energies

correspond to energies of the inner atomic shells, i.e., they are in the range
of soft X-rays, typically tens of keV.
A peculiar feature of fast neutron inelastic scattering on heavy nuclei
for neutrons in the 2-14 MeV energy range is a rather significant (up to
80%) energy loss as a result of this reaction. Thus, the inelastically-
scattered neutron has much lower energy than the incident neutron.
Because of this, fast neutrons of energies up to 10 MeV can be subject to
inelastic scattering only once (or at most a few times), after which their
energy becomes lower than the threshold required for inelastic scattering.
The inelastic scattering channel is therefore closed, and such neutrons are
not registered by a detector based on further inelastic scattering within the
heavy oxide scintillator. Therefore, when the scintillator thickness is
increased, the recorded signal from inelastic scattering becomes saturated
when such neutrons are detected. As a result, the detection efficiency
becomes nearly constant after the thickness reaches 40-60 mm (Ryzhikov
et al., 2015). However, if the energy of these inelastically-scattered
neutrons is lowered even more (to resonance energies of 1-10 keV or to
thermal energies below the cadmium threshold of 0.5 eV), an additional
detection channel of resonance scattering, radiative capture and thermal
capture is opened. Note that certain nuclei have large cross-sections for
such interactions (see Table 1 below). Resonance and thermal captures are
accompanied by the emission of gamma-quanta in a broad energy range,
the recording of which can substantially increase the fast neutron detection
efficiency.
In the heavy-oxide scintillator layers of the composite ZEBRA
structure there is practically no deceleration of fast neutrons from elastic
scattering reactions because energy transfer from neutrons to heavy and
middle mass nuclei (as well as to oxygen nuclei) of the scintillator material
is inversely proportional to atomic number, E  2 EA  A  1  2 E A for
2
A  1 , and on average it does not exceed several percent of the neutron

energy. If the detector includes periodically alternating plastic layers,
which contain large amounts of hydrogen nuclei, the picture is
substantially changed. Theoretical estimates show that 35-40 mm of the

total thickness of the plastic layers is sufficient to moderate the neutron

energy of 1-2 MeV to 1 keV. The multi-layered design detector is better
than a double-layered design (i.e., one layer of scintillator plus one layer of
moderator) or a three-layered design (i.e., a scintillator layer between two
moderator layers), because the thicker scintillation layers record more
completely the total flux of resonance neutrons – coming from deceleration
of both the initial incident neutrons and the intermediary neutrons formed
by inelastic scattering in the outer scintillation layers.
The interaction of neutrons with resonance energies that appear as a
result of deceleration of the initial fast neutrons in the plastic layers of the
multi-layer detector opens new channels for energy transformation in the
composite heavy-oxide scintillators. As a result, in addition to the inelastic
processes (1)-(2), the following products can be generated: prompt gamma-
quanta from resonance non-elastic reactions, including resonant capture:
 A, Z   nres   A  1, Z    res ; (3)
prompt gamma-quanta from radiative capture  n,   in the thermal neutron

range:
 A, Z   nth   A  1, Z    capture ; (4)
electrons from beta-decay of the excited parent compound nucleus into the
ground state or an excited state of the daughter nucleus:
 A, Z   nmoderate   A  1, Z    A  1, Z  1    ;
* *
(5)
as well as delayed (up to 30 µs) gamma-quanta:
 A  1, Z  1   A  1, Z  1   delay
*
(6)

and/or conversion electrons, which can be emitted in de-excitation of the

excited daughter nucleus.
The resonance neutron cross-sections (mostly due to radiative capture)
for many heavy and middle mass nuclei are not generally less than the
characteristic cross-sections for inelastic scattering of neutrons (and
sometimes they are even larger). Comparative values of microscopic
radiative capture cross-sections, based on an IAEA nuclear data base
(JENDL, 2014), are presented in Table 1. Cross-section values are given in
barns (1 barn is equal to 10-24 cm2). They include cross-section data for
radiative capture (in the energy range from 0.0253 eV to 0.5 eV),
resonance scattering with gamma-quanta escape (the resonance integral
covers the energy range from 0.5 eV to 10 MeV), and inelastic scattering
(for a fixed fast neutron energy 14 MeV) on nuclei that enter the
composition of our heavy oxide scintillators comprised of ZWO, CWO,
GSO(Ce), or BGO.
Table 1. Cross-sections of neutron interactions with nuclei (mixtures of

natural isotopes) present in heavy-oxide scintillators
Nuclei Capture Resonant Inelastic

30Zn 1.063 2.539 0.619
32Ge 2.218 5.997 0.566
48Cd 3.294 × 103 6.659 × 101 0.416
64Gd 4.119 × 104 4.011 × 102 0.652
74W 1.819 × 101 3.551 × 102 0.428
82Pb 0.154 0.142 0.324
83Bi 0.342 0.172 0.361
Note that the resonance integral for the resonance interactions (i.e.,
resonant scattering plus capture) of such nuclei as 184W or 157Gd can reach
hundreds of barns. Therefore, for recording of resonance neutrons, a
sufficient thickness of the composite scintillator layer when based on ZWO
or GSO(Ce) does not exceed 1 mm. Thus, with additional registration of
resonance neutrons, the detection efficiency is increased, even though the
total thickness of the active layers of heavy-oxide composite scintillators in

our heterogeneous detectors is much smaller than the thickness of a single

crystal scintillator made of the same material (as used in a conventional
neutron detectors with comparable efficiency).
Analysis of nuclear data (including the data from Table 1) shows that
promising scintillators for the production of heavy-oxide scintillator
detectors for fast neutron detection might be scintillation materials based
on: (i) BGO, due primarily to resonance neutron capture and inelastic
scattering on the stable nuclei 70Ge, 74Ge, 76Ge and the large internal
conversion potential for the excited nuclei 71Ge*, 73Ge* (from inelastic
scattering), and 75Ge*; (ii) ZWO due to resonance capture on all the stable
nuclei 182W, 183W, 184W, 186W and internal conversion on excited 183W*
(from inelastic scattering), 185W*, 187W* and (iii) GSO(Ce) due to the huge
resonance capture and internal conversion electron emission for stable and
excited nuclei 155Gd, 157Gd, respectively.
FAST NEUTRON DETECTION EFFICIENCY

AND SENSITIVITY
The ultimate detecting capability of a scintillator (or more precisely, a

scintillator detector) for fast neutron detection is determined by some
important physical characteristics, and is characterized by the intrinsic
detection efficiency and the detection sensitivity of the detector device.
This intrinsic detection efficiency  is defined as the ratio of the number
of registered neutrons N reg to the total number of neutrons N entering the
detector during a specified time interval
  Nreg N . (7)
In the spectrometric mode, by limiting the working energy range from

the detector’s output spectrum to the energy range most responsive to the
reaction energies of importance to the targeted neutron interaction
processes and summing up the number of recorded pulses, we can

determine the counting rate V (expressed in units [cps], counts per second)
for the pulses of all recorded neutrons, as well as the background counting
rate V0 without the source. The counting rate can also be measured in the
counting mode. After calibration of the detecting system, we obtain the
detection efficiency as:
 V  V0 
  kc  , (8)
 F  F0 
where kc is the calibration coefficient in the case when shielding from

gamma-quanta is present; F and F0 are neutron fluxes (expressed in units
[nps], neutrons per second) from the neutron source and in the absence of a
source (background), respectively, at the point of recording by the detector.
The intrinsic efficiency is normally expressed as a percent.
Ordinarily, studies of intrinsic detection efficiency of different solid
scintillator detectors for fast neutron detection are carried out under
irradiation by 239Pu-Be and/or 252Cf fast neutron sources.
If the shielding substance is introduced in a form that can mainly
scatter neutrons (for example, an ideal sphere of diameter D ), but
practically does not absorb them (e.g., an iron or lead sphere), the number
of neutrons coming out of the shielding will not change along any direction
from the source to detector (for example, due to spherical symmetry), so
the neutron current will be unchanged in any point of the detector. If the
distance between the source and detector is sufficiently large (e.g.,
r 2D ), the isotropic character of the radiation is preserved. If we
neglect also the dependence of the intrinsic detector efficiency upon
neutron energy,   E   const , the counting rate of the detector, if spherical
shielding from gamma-quanta is used, can change only because of possible
absorption of neutrons in the shielding material. In this case the appropriate
correction, which is the same for all measurements, is equal to:
kc  exp  na a D  , (9)

where na is the concentration of heavy nuclei in the shielding material,  a

is the absorption cross-section of fast neutrons in the shielding material, D
is the thickness of the shielding. The concentration of atomic nuclei is
1
na  N A  M , where N A  6.023  10 mol is the Avogadro number, 
23
is the density of shielding material and M is the molar (atomic) mass. For
lead shielding (the molar mass is 208 g/mol; the density is 11.3 g/cm3; the
neutron absorption cross-section averaged over the energy spectrum of
235
U fission is  a  0.0024 barn ) with a spherical layer of 4 cm thickness,
the correction factor is kc  0.97 , i.e., losses of the full neutron beam in the
shielding are about 3%. For other spectra of fast neutron energies, these
losses are typically smaller. For example, in lead the capture cross-section
of 14 MeV neutrons is 0.00011 barn, which gives neutron losses in the
gamma shielding not exceeding 0.14%. The multiple elastic scattering of
neutrons in the shielding substantially distorts the simple expression (9),
since multiple changes in neutron direction would violate the spherical
symmetry of the distribution of scattered beams, and the advantages of the
spherical geometry of irradiation are lost. However, elastic neutron
scattering cross-sections are not large for heavy nuclei such as iron and
lead in contrast to light nuclei (in lead, the mean free path reaches 15 cm at
a neutron energy of 4 MeV). This makes it possible to use spherical
shielding of large thickness, which will be sufficient for full absorption and
discrimination of gamma-quanta emitted by the source up to energies of
several MeV.
The detection sensitivity  is defined as the ratio of the counting rate of
the useful detector signal to the flux density of the incident neutrons, i.e.,
 V  V0 
  kc  , (10)
 I  I0 
where I and I 0 are the neutron flux density (expressed in units

[nv]=[nps/cm2]) of source and background. Within the geometry of “narrow
beams”, the following relationship can be obtained:

   Seff , (11)
where Seff  S  cos  is the effective area of the total sensitive surface of
the detector; S is the apparent area of the detector surface in the direction of
irradiation;  cos  is the average value of the cosine of angle between the
normal surface and the direction of irradiation. For scintillators of rectangular
shape, Seff coincides with the area of their side surface in the direction of
irradiation (normal to the surface) S , i.e., Seff  S . For example, for a

cubic scintillator with cross-sectional area 10×10 mm2, the sensitivity is
   cps/nv.
The generally accepted standard IEC 62244 (IAEA, 2006) for portal
monitors provides that sensitivity to fast neutrons should not be less than 2.5
cps/ng for reliable recording of the 252Cf source at the distance 2 m from the
detector. If we assume that the activity of 1 ng of “fresh” nuclide 252Cf per unit
solid angle is 2.314×103 nps/ng (see, for example, Kouzes et al., 2009), the
flux of fast neutrons at a distance of 2 m passing through a surface of area S ,
expressed in [cm2] units, is equal to 0.058× S nps/ng. Hence, there is a
convenient relationship between absolute detector sensitivity  in units of
cps/nv and the equivalent IAEA-threshold  IAEA of the counting rate from a
252Cf neutron source:
IAEA  0.058 . (12)
From Eq. (12) it follows that detection sensitivity of effective neutron

detection system should be not lower than 43 cps/nv.
Ordinarily, the measurements of detection efficiency and detection
sensitivity are carried out in conditions of broad beam and spherical geometry
accounting for corrections for natural background. In some cases, the
experimental installation may be located in a closed space, and near the
detector and neutron source there may be elements of metal construction,
laboratory furniture, concrete walls etc., so, there could be a high potential for
accumulation of scattered radiation from reactions of fast neutrons  n, n 

(iron) and  n,   (concrete, etc.), as well as from scattered gamma radiation

emitted by the neutron sources and scattered by external metal and concrete
materials. Nonetheless, it is possible to measure the intrinsic detection
efficiency under these conditions by elimination of above-mentioned
scattering radiation factors.
SINGLE CRYSTAL HEAVY-OXIDES SCINTILLATORS

FOR FAST NEUTRON DETECTION
To evaluate the detection of neutron radiation by heavy-oxide single

crystal scintillators, crystals comprised of CWO, ZWO and BGO were
fabricated by the Institute for Scintillation Materials (ISMA), Kharkiv,
Ukraine. These crystals (see Figure 1), with dimensions of up to 40-50 mm
diameter and height up to 80-100 mm, were subsequently cut into cubic
form, integrated into detector housings and tested. Additionally, several
other scintillation crystals were obtained for comparative testing. These
include crystals of GSO(Ce), LSO(Ce), LuAG(Ce), YSO(Ce) and 6LiI(Eu).
For baseline comparisons, a conventional 3He counter was also obtained
and included in the testing.
For neutron sources, a 239Pu-Be source with a neutron emission of
0.95х105 n/s (i.e., a flux at 100 cm from the source of 0.76 n/s cm2) or a
252
Cf source with a neutron emission of 2.35x106 n/s (i.e., a flux at 100 cm
from the source of 1.7 n/s cm2) were used. Each source was placed inside a
lead sphere of 10 cm diameter with a 10 mm opening. The lead shield
ensured elimination of the accompanying gamma-radiation from the
sources. Additionally, to separate the effects of thermal and fast neutrons,
screens of either gadolinium oxide or cadmium foil could be placed
between the source and the detection system to eliminate thermal neutrons.
Table 2 presents, for comparison, the measured intrinsic detection
efficiencies for fast neutrons, neutrons moderated to resonance, and
neutrons of all energies down to and including thermal, in detectors with
the heavy oxide single crystal scintillators ZWO, CWO, BGO, GSO(Ce),

LSO(Ce), LuAG(Ce) and YSO(Ce) in comparison with a 6LiI(Eu) detector

of thermal neutrons and a 3He counter of fast neutrons. All of the single
crystal heavy-oxide scintillators had the same dimensions of 10x10x10
mm3. The neutron flux at the recording point at a distance of 26 cm from
the source 239Pu-Be was 12.8 nps/cm2. As shown in Table 2, the intrinsic
detection efficency in the absence of a moderator is  fast , the detection
efficency with a thin moderator (paraffin) of 1 cm thickness is  fast res and
the detection efficency with a thick moderator (paraffin) of 6 cm thickness
is  fast res  slow .
Figure 1. Scintillator single crystals ZWO (left) and BGO (right) used for fast neutron
detection.
To exclude contributions from slow neutrons (i.e., those with energies

below 0.5 eV) screens made of cadmium with thickness 0.5 mm or
gadolinium oxide Gd2O3 with thickness up to 10 mm were used. The
cadmium nuclei, when absorbing slow neutrons, can emit hard gamma-
quanta with energies up to 7.5 MeV, which do not fall into the working
spectrometric range of the detector (i.e., 20-300 keV), and are thus cut out
of the measurements. The gadolinium nuclei absorbing slow neutrons also
essentially do not emit gamma-quanta in the working energy range. For

deceleration of fast neutrons in our measurements, the detector was

surrounded from the outside by layers of hydrogen-containing moderator
(i.e., paraffin of 1 cm and 6 cm thicknesses, respectively).
Table 2. The detection efficiency of fast neutron scattering

by single crystal scintillators
Scintillator  fast , %  fast res , %  fast res  slow , %

ZWO 54 70 44
CWO 42 46 67
BGO 48 83 34
GSO(Ce) 46 90 65
LSO(Ce) 43 – –
LuAG(Ce) 41 68 –
YSO(Ce) 17 – –
6LiI(Eu)* 25 30 93**
3He counter*** 5-8 – 95
* Size of detector ø12х10 mm.
** Response to the radiative capture reaction 6Li(n,α)3H at En = 0.0253 eV.
** With a massive 1000x200x50 mm plastic moderator of about 10 kg weight.
The results presented in Table 2 show that opening the additional

channels of resonance scattering and capture (  fast res ) in the detection of
fast neutrons always increases the detection efficiency. At the same time, if
the moderator thickness is too great (i.e., above 40 mm), for most single
crystal heavy-oxide scintillators not containing the neutron-capturing
nuclei of cadmium or gadolinium, the detection efficiency is somewhat
decreased (  fast res  slow ). This is caused by the following: after moderation,
the number of fast neutrons in the incident beam is decreased; their energy
becomes lower than the inelastic scattering threshold. This strongly
reduces the contribution of this reaction to the signal recorded by the
detector. Both of these facts suggest physical reasons that make the
alternative multi-layer design (with several alternating moderator layers of
small thickness between layers of heavy oxide scintillator) appear to be a

more efficient approach for detection of fast neutrons. The multilayer

detection system concept will be discussed in a later section.
NEUTRON PORTAL MONITORS BASED

ON SINGLE CRYSTAL HEAVY-OXIDE SCINTILLATORS
Using large-sized ZWO and BGO scintillators, portal monitors for fast
neutron detection were prepared for the first time at ISMA (Ryzhikov et al,
2017b).
The general appearance and schematic design of these “ISMA” portal
monitors are shown in Figure 2. The portal has a weight of 25 kg, a height
of 1.5 m, and a frame diameter of 140 mm. In developing the electronics
and the receiving-detecting circuit, the counting pulse formation time was
experimentally chosen to be from 1 to 30 µs, depending on the decay time
(fast or slow) of the scintillator. Such a choice appears to be optimal for the
detection of the total effect of multiple (about 103-104 events) neutron
interactions with the scintillator, though the characteristic time of
interaction of a single neutron with nucleus normally does not exceed 1 ns.
The expected performance of the “ISMA” portal monitor with such
detectors in comparison with existing analog portal systems of similar
purpose for detection of radioactive substances was evaluated (see Tables
3-4). The results show that such monitors fully conform to IAEA standards
for detection of special nuclear materials, and yet are substantially smaller
is mass and physical dimension than existing or other proposed systems.
The obtained results show that detection ability of the new “ISMA”
portal design is comparable to portals with 3Не-detectors for gamma
sources (such as YANTAR etc.), and is superior for the detection of
nuclear materials; moreover its size and weight are substantially lower.
One should note the high sensitivity of these detectors (and portals
based thereon) to neutrons and gamma-quanta, which can simultaneously
detect with high efficiency both fast neutrons and the accompanying
gamma-radiation from nuclear materials.

Figure 2. Fast neutron portal monitor based on ZWO or BGO scintillators. The portal
frame as a whole (on the left); block-scheme (on the right).
Table 3. Comparative characteristics of “ISMA” neutron portal

monitor and other detection systems
(distance between portal frames is 1 m)
Inspection  Detection limit: Activity Detection limit: Mass of Detector

system of -source, µCi nuclear materials, g mass, kg
241Am 137Cs 60Co 235U 238U 239Pu
“ISMA” 7 0.76 0.38 9 12 0.02 1.5

(Ukraine)
RМ-5000-07 60 0.8 0.8 30 125 0.6 70
(Belarus)
“YANTAR- – 1.1 1.5 12.5 100 0.36 200
1a”
(Russia)
NUCSAFE 200 7 3 10 – 0.3 –
(USA)
Gamma-radiation substantially contributes to the total detection

sensitivity, thus greatly increasing the detecting ability of small quantities

of nuclear material. To improve systems for the prevention of illegal

transportation of nuclear materials, this is a significant advantage.
Table 4. Comparative characteristics of “ISMA” neutron portal

monitor and other detection systems
(distance between portal frames is 6 m)
Inspection  Detection limit: Activity Detection limit: Mass of Detector

system of -source, µCi nuclear materials, g mass,
kg
241Am 137Cs 60Co 235U 238U 239Pu
“ISMA” 26 4.8 1.5 15 20 0.02 1.5

(Ukraine)
RМ-5000-07 150 10 4 250 2000 4.2 70
(Belarus)
“YANTAR-1a” 186 7.5 7.86 900 8 200
(Russia)
NUCSAFE – 8.1 4.0 374 6000 3.5 –
(USA)
At the same time, to suppress the accompanying gamma-radiation, we

may use different methods for the detection of fast neutrons against the
background of intense gamma-radiation. For example, neutron-gamma
separation was achieved using a specially developed algorithm (Ryzhikov
et al., 2017b) based on measured data by using the “2-windows” or “3-
windows” methods in different ranges of the energy spectrum. This
allowed the achievement of neutron-gamma separation with gamma
absolute rejection ratio for neutrons (GARRn) (see, for example, Kouzes,
2009) of up to 0.91 < GARRn < 1.09.
MULTI-LAYER COMPOSITE HEAVY-OXIDE

SCINTILLATORS FOR FAST NEUTRON DETECTION
In recent work (Ryzhikov et al., 2015a, 2016, 2017a, 2018), a design

of a multi-layer composite heavy-oxide scintillation structure (named

ZEBRA), which could detect mixed neutron and gamma radiation, was
proposed and tested. The ZEBRA scintillation detector (Figure 3-4)
consists of alternating and optically connected (i.e., glued) planar parallel
layers of two types: (i) 5-6 plates (films) of the scintillator material
dispersed in a transparent organic matrix (rubber glue), with a thickness of
~1-2 mm; (ii) 7-8 plates of a transparent plastic, with a thickness of ~5-7
mm, which act both as a moderator for neutrons and as light guides for all
scintillation photons.
Figure 3 is a schematic presentation showing the following
components: 1 – an internal reflector made of aluminized Mylar (it may be
absent in many ZEBRA detector variations); 2 – active layers of composite
scintillator material; 3 – passive layers of light-conducting plastic; 4 – a
photoreceiver (PMT or Si-PM).
Figure 3. Scheme of the multi-layer composite scintillator.
The first layer type (i.e., the thin layers containing the dispersed heavy
scintillator particles) required a transparent organic glue-like material with
low-molecular weight and thermal shock resistance. For this layer type, the
low molecular weight siloxane synthetic rubber SKTN-B, with a refractive

index of nglue  1.42 , was used. The average size of the heavy-oxide
crystalline scintillator fragment in these composite scintillator layers was
about 150-200 µm. The overall concentration of the small crystalline
fragments (granules) was chosen such that the volume fraction of the
active scintillator in the composite material was not less than 50-60%.
For the second layer type (i.e., the thicker light guides), the transparent
optical plastic polymethylmethacrylate (PMMA) with a refractive index of
n  1.49 (at light wavelength of 540 nm) and an absorption coefficient of
  0.03 cm1 was used.
The outer surface of the detector is covered with a diffuse light-
reflecting coating (except at the one face that is attached to the light
receiving device to provide optical contact and spectral matching). As an
outer coating, a polytetrafluoroethylene (PTFE) membrane with a diffuse
reflectivity coefficient of about 98% was used. The external reflector is
very important for good light collection and high detection efficiency.
An internal reflector as shown in Figure 3 (i.e., an aluminized Mylar
tape in the middle of the composite layers) was found not to be essential
and is omitted in some of the detector variants tested. Although it provides
a small increase in the scintillation output, it introduced production
difficulties that did not justify the small improvement in performance.
Nevertheless, detectors of both types were tested. The tested detectors
without internal reflectors in the composite layers were found to have
detection efficiencies approximately the same as those with reflectors.
A set of ZEBRA scintillators of large size (up to 100x100x41 mm3) on
the basis of different scintillators such as ZWO, BGO, GSO(Ce) were
prepared and tested. Each ZEBRA structure had 6 composite layers of
thickness 1 mm and 7 layers of transparent plastic with thickness 5 mm
(Figure 4). The sensitive detector area under irradiation by neutron flux
from the side (i.e., in the direction transverse to the plates) was 100 cm2. In
the general case, the multi-layer detector can be comprised of an arbitrary
number of plates, without any limitations on their area.

Figure 4. Multilayer ZEBRA scintillators on the basis of the composite scintillators

ZWO, BGO, GSO(Ce).
For the transparent light-guide layers, use of a scintillating plastic

transparent material was also considered. The neutron detection efficiency
for the detectors incorporating scintillating plastic as the light-guide
material was determined to be much better, but the neutron/gamma
rejection ratio was not as good. It is expected also that the production cost
of this alternate configuration would be somewhat higher.
The main difference between ZEBRA detectors and well-known
conventional “capture gated detectors” (Flaska, 2010; Paweczak, 2011;
Liu, 2016) is that the latter are based on thermalization and the use of
thermal neutron capture nuclei (such as 155Gd, 157Gd, 113Cd) with very large
thermal capture cross-sections for the (n, γ) reaction for neutrons. In
contrast, ZEBRA detectors include layers composed of composite heavy
oxide scintillators with heavy (Bi, W, Gd, Cd) and/or medium mass (Ge,
Zn, Cd) nuclei with high probabilities of both fast-neutron (above about ~1
MeV) inelastic scattering and resonance neutron interactions (mainly,
resonance capture with gamma quanta and conversion electron emission)
in an intermediate energy range from tens of eV to tens of keV. In addition
to inelastic scattering, the resonance neutron interaction (capture) reaction
is a key reaction for operation of ZEBRA detectors.

The ZEBRA detectors are designed for the direct detection of fast
neutrons and for the discovery of small quantities of transuranic elements
(by also detecting the accompanying gamma-radiation). Detectors of this
type are characterized by the following features:
 it is possible to prepare detectors of arbitrarily large working area

of the detecting plates, which allows a substantial (by many times)
increase in the sensitivity of such detectors in comparison with
detectors based on inorganic single crystals;
 the preparation of large area layers of composite scintillators (on
the basis of small-crystalline fractions of broken crystal fragments
or micro-crystalline powders obtained by solid-phase synthesis) is
much simpler and less expensive than the growth of costly large-
sized single crystals, the maximum size of which is essentially
limited by the growth technology;
 within the framework of a multi-layer design for such detectors,
engineering combinations using different scintillation materials are
possible, aiming at optimization of its productivity for different
tasks.
The principle of operation of ZEBRA detectors is as follows. The

incident neutrons interact with the layers of the composite heavy-oxide
scintillator and plastic. The composite scintillator layers contain heavy
nuclei with high cross sections for both inelastic scattering and radiative
capture in the region of resonant neutron scattering (the energy of
epithermal and intermediate neutrons). The alternating transparent plastic
layers serve as moderator of fast neutrons (from fast energies to
epithermal/intermediate energies) and simultaneously as optical light
guides through which the scintillation light transmitted. Fast neutrons
interact directly with the layers of the composite scintillator through an
inelastic scattering reaction if their energy is high enough for this, i.e.,
exceeding the energy threshold for inelastic neutron scattering (usually at
least several hundred keV). Additionally, incident neutrons also interact
with the heavy nuclei of the composite scintillator material as a result of

the resonance scattering reaction if their energy falls into the appropriate
energy interval after moderation in the plastic layers. The moderation of
the incident neutrons mainly occurs in the “thick” layers of hydrogen-
containing plastic as a result of the elastic neutron scattering reaction.
Elastic neutron scattering inside the “thin” layers of the composite can be
neglected, since the volume fraction of the organic filler is small, and the
energy loss due to scattering in the heavy oxide scintillator granules is
inversely proportional to the atomic mass of the heavy nuclei. Following
elastic scattering in the transparent plastic layers, moderated neutrons may
move in any direction, and most of them will reach the composite
scintillator layers except the small fraction that are scattered out of the
detector, primarily from the two outer plastic layers.
A feature of the ZEBRA scintillator is that the composite scintillator
material consists of heavy nuclei with a large value of the resonance
integral  res for resonance non-elastic scattering and/or concomitant
resonance capture reactions with emission of gamma rays and conversion
electrons. If the value  res reaches several hundred barns (e.g., W, Gd and
Cd; see Table 1), then it can be shown that each neutron slowed down to
the resonant energy region is highly likely to be absorbed and recorded as a
secondary gamma quantum in a rather small volume of the scintillator of
thickness of several hundred microns. Consequently, with high probability,
fast neutrons moderated to resonance energies may be registered in each
layer of the composite scintillator.
As a result of the reactions  n, n  and  n,   gamma quanta of
medium energies are produced which fall into the energy range of 20-300
keV, the energy range selected for signal registration in the ZEBRA
detector. In this case, gamma rays emitted in one active layer can be
registered both in the same and in several adjacent layers of the heavy-
oxide composite scintillator. Due to the small thickness of the transparent
plastic layers, there is no significant attenuation of the secondary gamma
radiation in them. The more likely energy of gammas released by inelastic
neutron scattering is from tens of keV to hundreds of keV. The energies of
gammas for resonant neutron capture (and/or energy of conversion
electrons by accompanying reactions) are mainly about tens of keV,

although they may reach 100s of keV or even MeVs for some nuclei. The
average energy of recoil protons released by fast neutrons (1-5 MeV) in the
transparent plastic layers is about hundreds of keV, an energy range too
small to produce many Compton electrons (much higher neutron energies
would be required for this to be a significant factor). The most probable
interaction of gammas with the heavy oxide scintillator is the photo-effect
because the energy of intrinsic gammas mainly lies in the range 20-300
keV as indicated by recent experiments.
The scintillation light obtained by the interaction of the secondary
gamma quanta (and/or conversion electrons) with the scintillator material,
at first passes from the composite layer to the transparent plastic layer, and
is transmitted to the photodetector (see Figure 3). The geometry of the
layers and the optical parameters of the multi-layer detectors (including
optical and spectral correspondence of scintillators and light-guides;
interface to the PMT; characteristics related to total internal reflection and
Fresnel losses; optical transparency of the composite scintillator and
transparent plastic media, etc.) have been chosen specifically to optimize
the light output.
Due to their design, ZEBRA detectors have gamma ray sensitivity in
addition to neutron sensitivity. But for fast neutron detection against
background gamma radiation, the high-energy gamma rays are rejected by
the choice of the special spectrometry range of 20-300 keV as previously
proposed in methods for heavy-oxide scintillator fast neutron detection
(see Ryzhikov et al., 2011, 2014, 2015a, 2015b, 2018). Lower energy
gamma rays from background are also rejected by detector calibration (i.e.,
the use of initial and/or real-time special algorithms and software designed
for neutron portal monitors based on our detectors), as well as the selected
spectrometry range. Moreover, Compton gamma rays may be rejected by
special separation methods including those developed previously and
referred to as the “spectrometry windows” method (Ryzhikov et al.,
2017b).
Unlike a homogeneous single-crystal detector in the ZEBRA
heterogeneous detector, in the ZEBRA scintillators, neutrons are detected
by each active layer with a sensitive area equal to the cross-sectional area
of the detector. Each active layer plays the role of an “internal” neutron
mono-detector. In fact, neutrons are simultaneously recorded not by one
but several such “internal” mono-detectors. The total area of all internal
active layers will be higher than the sensitive area of the detector itself.
Therefore, the sensitivity of the multilayer detector increases substantially,
as evidenced in recent experiments. With a total thickness of active layers
of 6-7 mm, the detection sensitivity of fast neutrons by a multilayer
ZEBRA detector is comparable to the sensitivity of a single crystal
scintillation detector in which the scintillator layer is ten times thicker in
the direction of transmission.
Table 5 presents, for comparison, the measured fast neutron intrinsic
detection efficiencies for multi-layer scintillators comprised of composite
heavy-oxide ZWO, PWO, BGO and GSO(Ce) materials. The
measurements were carried out using ZEBRA scintillators of dimension
40x40x41 mm each with the same number and thicknesses of layers (i.e.,
with the same total thickness of the detector). A 252Cf neutron source with a
neutron flux 2.35x106 nps (flux density at 100 cm from the source 1.7
nps/cm2) was used. The source was placed inside a lead sphere of 10 cm
diameter with a 10 mm opening. The lead shield ensured discrimination of
the accompanying gamma-radiation of the source. The distance between
the source and scintillator was changed from 50 to 200 см. The
measurements were carried under irradiation normal to (   ) and parallel
with (  ) the plates (layers) of multilayer scintillator. In each case, for
ZEBRA scintillators of cross-sectional dimensions 40x40 mm2 the
detection sensitivity was estimated according to Eq. (11) as   16
cps/nv.
Comparative analysis of the results presented in Table 5 leads to two
important conclusions. First, the intrinsic detection efficiency of fast
neutrons obtained with multi-layer scintillators with thickness comparable
to characteristic dimensions of large and expensive single crystal heavy
oxide scintillators (dimensions from ø40x80 and higher) is somewhat
lower reaching tens of percent. However, for ZEBRA detectors with
scintillating plastic layers (as moderator and light channel layers),

efficiencies are quite comparable to the corresponding single crystal
results, reaching 50-60%. Also, the sensitivity of these multi-layered
detectors will be sufficiently higher in comparison with detectors using
single crystals and can be increased even much more by enlarging the
sensitive area of the detecting plates.
Table 5. The detection efficiency of fast neutron scattering

by ZEBRA scintillators
# Sample Composite Moderator Efficiency Efficiency

Scintillator Material  (%)  (%)
1 ZWO PMMA 14.6 17.1
2 BGO PMMA 11.5 13.1
3 GSO+ZWO (1:1) PMMA 12.2 15.4
4 GSO+PWO (1:1) PMMA 17.2 22.1
5 GSO+BGO (1:1) PMMA 19.0 20.4
6 ZWO Plastic Scint* 50.7 60.2
7 BGO Plastic Scint* 55.7 59.1
* Plastic scintillator produced at ISMA (polystyrene with additives of POP and POPOP).
It should be noted that the measurements of the detection efficiency of

the ZEBRA detectors based on heavy oxide scintillation material are
dependent upon:
 chemical composition of composite scintillators, e.g., the presence

of nuclei with high cross-section of resonant neutron scattering;
 type of moderator, especially, if scintillating plastic or not;
 the choice of the direction of irradiation, which can fall onto the
multi-layer detector parallel or normal to the layers;
 the number and thickness of layers in the composite scintillator;
 the total thickness of the detector;
 the height of the detector in direction of the output window, i.e.,
the distance between the outer boundaries of the detector and the
photoreceiver.
The optimum detector design allows the avoidance of losses in

detection of neutrons.
CONCLUSION
A decisive step towards increasing the efficiency of fast neutron

detectors has been the search for new scintillation materials that have the
highest detection efficiency in a wide range of neutron energies (i.e., from
100 keV to 10 MeV) reaching values from several tens of percent to 50%
and higher, while allowing the possibility of scaling (i.e., the ability to be
produced in sizes and shapes that provide greater volume and sensitive
area).
The development of detectors based on heavy inorganic single crystal
heavy-oxide scintillators resulted in the achievement of the desired
capability for high-efficiency registration of fast neutrons based, in part, on
recognition of the signal from inelastic scattering interactions between fast
neutrons and the heavy atomic constituents of these single crystal
scintillators.
To achieve the additional objectives of enhanced sensitivity and
scalability, a new type of fast neutron detector (ZEBRA-detectors) based
on a new configuration of crystalline scintillation materials has been
proposed and developed. These detectors consist of sequentially alternating
layers of a transparent plastic moderator (passive layers) containing a large
concentration of hydrogen nuclei, and composite heavy oxide scintillator
layers (active layers) containing heavy and medium mass nuclei with a
large cross sections for inelastic scattering (for neutron energies above
100keV) and resonance absorption (for neutrons of intermediate energies
from 1 keV up to 100 keV). The moderator can be made from either
conventional or scintillation plastic materials. Different heavy oxide
scintillators, including CWO, ZWO, BGO, GSO (Ce), etc. were tested and
used as active components for these new fast neutron detectors. As part of
the proposed design, these multilayer scintillators can be made from any
number of layers of a sufficiently large area. They can also be joined to
each other (in two dimensions, along and across the layers), thereby
scaling the dimensions of the detecting system in an arbitrary way.
The registration efficiency of these new fast neutron detectors can
reach 50% or more, depending on the scintillator material and the
configuration of the device. The physical reasons for such high efficiencies
are associated with the simultaneous use of not one, but several
mechanisms of fast neutrons interaction with the material of a multilayer
composite scintillator when registering fast neutrons – inelastic scattering
of fast neutrons in a heavy oxide scintillator, resonance scattering and
capture of neutrons slowed down to resonant energies, as well as the
reaction of elastic scattering with the release of recoil protons in
scintillation plastic.
A substantial advantage of new approach, as compared with other
variants of solid-state detectors proposed to replace 3Не counters is that
most other technical solutions propose replacing 3Не detectors by other
detectors relying on registration of thermal neutrons, requiring the use of
moderators to thermalize the fast neutrons and with detection efficiencies
not exceeding 10%. In this new approach, a direct method of fast neutron
detection is proposed by using either a single crystal scintillator or a
multilayer composite scintillator with a high effective atomic number
(namely, heavy-oxide scintillators). This ensures high detection
efficiencies for fast neutrons and simultaneously high sensitivity, with
relatively small size and weight of the detector.
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BIOGRAPHICAL SKETCHES
Sergei V. Naydenov
Affiliation: Institute of Single Crystals (ISC), Kharkov, Ukraine
Education: DSc in Physics and Mathematics, ISC, 2008; PhD in

Physics and Mathematics, ISC, 1998; MSc in Physics and Engineering,
summa cum laude, Kharkov State University, 1993
Research and Professional Experience: Material Sciences,

Theoretical and Mathematical Physics, Condensed Matter Physics, Physics
of Complex Systems, Scintillator Physics, Radiation Detectors.
Professional Appointments: Leading Scientist, Department of Non-

Linear Optic Crystals
Honors: Award of the President of Ukraine in the field of Science and

Technology (2003). Member of Specialized Council for doctoral theses
(2009 – to present). Co-Author and authority responsible for 7
international projects from ISF, CRDF, INTAS, STCU, NATO.
 Ryzhikov, V.D., S.V. Naydenov, L.A. Piven, G.M. Onyshchenko,

C.F. Smith, T. Pochet, “Fast neutron detectors and portal monitors
based on solid-state heavy-oxide scintillators”, Radiation
Measurements 105, 17-25 (2017). https://doi.org/10.1016/j.
radmeas.2017.08.008.
 Ryzhikov, V.D., S.V. Naydenov, G.M. Onyshchenko, L.A. Piven,
T. Pochet, C.F. Smith, “Multi-layer fast neutron detectors based on
composite heavy-oxide scintillators for detection of illegal nuclear
materials”, Nuclear Inst. and Methods in Physics Research, A
903C (21 September 2018), 287-296 (2018). https://doi.org/

10.1016/j.nima.2018.06.074.
 Kovalenko, N.O., S.V. Naydenov, I.M. Pritula, S.N. Galkin, “II-
Sulfides and II-Selenides: Growth, Properties and Modern
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DOI:10.1016/B978-0-08-102096-8.00009-4.
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Vol. 5, No. 3. P. 45-52 (2018); DOI:10.26565/2312-4334-2018-3-
05.
 Naydenov, S.V., V.D. Ryzhikov, G.M. Onyshchenko, C.F. Smith,
“Advanced multi-layer composite structures for fast neutron
detection and shielding protection applications”, In book Micro
And Nanostructured Composite Materials For Neutron Shielding
Application (Editors: T. Sabu, A. Zakiah, T. Sajith), Chapter No.
12, P. 1-22. Elsevier Limited, United Kingdom, 2021. (will be
published in 2021).
Vladimir D. Ryzhikov
Affiliation: Institute of Scintillation Materials (ISMA), Kharkov,

Ukraine
Education: DSc in Physics and Mathematics, ISC, 1990; PhD in

Physics and Mathematics, ISC, 1973; MSc in Radio-Physics and
Electronics, Kharkov State University, 1967
Research and Professional Experience: Material Sciences, Radio-

Physics and Electronics, Radiation Detectors and Instruments for
Homeland Security, Neutron Detectors, Scintillation Crystals Growth.
Professional Appointments: Chief Scientist, Department of

Molecular and Heterostructured Materials
Honors: The State Award of Ukraine in the field of Science and

Technology (2000). Member of Ukrainian Council of Non-Destructive
Control Society (1997 – to present). Member of two Specialized Councils
for doctoral theses (1997 – to present). Honoured Inventor of Ukraine
(2010). Breastplate of State Customs Authority of Ukraine (2010).

radmeas.2017.08.008.
 Ryzhikov, V.D., S.V. Naydenov, T. Pochet, G.M. Onyshchenko,
L.A. Piven, C.F. Smith, “Advanced multilayer composite heavy-
oxide scintillator detectors for high efficiency fast neutron
detection”, Proceeding of the ANIMMA-2017 Conference, Liege,
Belgium, 2017.
903C (21 September 2018), 287-296 (2018). https://doi.org/10.
1016/j.nima.2018.06.074.
 Ryzhikov, V.D., B.V. Grinyov, S.V. Naydenov, G.M.
Onyshchenko, L.A. Piven, “Method of registration of fast neutrons
and combined detector based thereon”, Patent of Ukraine

#UA117862 C2 (published 10.10.2018).
12, P. 1-22. Elsevier Limited, United Kingdom, 2021. (will be
published in 2021)
Craig F. Smith
Affiliation: Naval Postgraduate School (NPS), Monterey, CA
Education: PhD, Nuclear Science and Engineering, UCLA, 1975. BS

Engineering, summa cum laude, UCLA, 1971
Research and Professional Experience: Advanced Nuclear Reactor

Technology. Radiation Detection for counter terrorism and special
applications. Explosives Detection using x-ray techniques. Nuclear
Forensics. Information Technology.
Professional Appointments: LLNL Chair Professor at NPS, 2004-

2010. Research Professor of Physics, NPS, 2010-Present. Associate Editor,
ASME Journal of Nuclear Engineering and Radiation Science. Adjunct
Professor, Monterey Institute of International Studies, 2006-10.
Honors: Visiting Research Fellow, Ecole Nationale Superieure

d’Ingenieurs, Bourges, France, 2001-2002. Fellow, American Nuclear
Society, 2001. Fellow, American Association for the Advancement of
Science (AAAS), 2002. UCLA Chancellor’s Intern/Teaching/ Dissertation
Fellowship, 1971-75. Member, Tau Beta Pi, Sigma Xi. Society of
American Military Engineers Award, 1972. UCLA Faculty Friends Award

for Outstanding Research, 1971.

radmeas.2017.08.008
903C (21 September 2018), 287-296 (2018). https://doi.org/10.
1016/j.nima.2018.06.074
12, P. 1-22. Elsevier Limited, United Kingdom, 2021. (to be
published in 2021)
 Glesmann, J.D., C.F. Smith, D.P. Heinrichs, “Neutron Protection
Factor Determination and Validation for a Vehicle Surrogate
Using a Californium Spontaneous Fission Source,” Radiation
Effects Research and Engineering, April 2019.
 Chiaverotti, D.J., C. F. Smith, A.G. Pollman, “Experimental
Verification and Military Employment of Centrifugally Tensioned
Metastable Fluid Detectors for Neutron Detection of Trace
Radiation Sources,” Radiation Effects Research and Engineering,
April 2018.
 Brewster, D., C. Smith et al., “A Feasibility Study for the Use of a

Continuous Wave Laser for Resonance Ionization Mass
Spectrometry Using Laser Ionization of Neutrals at Lawrence
Livermore National Laboratory,” Nuclear Materials, April 2018.
 Smith C., and L. Cinotti, “Lead-cooled Fast Reactor,” Chapter in
the Handbook of Generation IV Nuclear Reactors, Woodhead
Publishing, December 2016. (Revised Second Edition in
preparation). https://doi.org/10.1016/B978-0-08-100149-3.00006-
9.
Chapter 5
SCINTILLATION CRYSTALS OF THALLIUM

AND CERIUM DOPED POTASSIUM
DIHYDROGEN PHOSPHATE (KDP: TL AND
KDP: CE) FOR SELECTIVE DETECTION
OF FAST NEUTRONS
Sergei V. Naydenov1,*, Alexei P. Voronov1,

Igor M. Pritula1 and Craig F. Smith2
1
Department of Non-Linear Optic Crystals,
Institute for Single Crystals,
National Academy of Sciences of Ukraine, Kharkov, Ukraine
2
Department of Physics, Naval Postgraduate School, Monterey, CA, US
ABSTRACT
A new class of inorganic hydrogen-containing scintillators based on

potassium dihydrogen phosphate (KDP) and related compounds (i.e.,
*
Corresponding Author’s E-mail: sergei.naydenov@gmail.com.
144 Sergei V. Naydenov, Alexei P. Voronov, Igor M. Pritula et al.
KH2PO4, KD2PO4, NH4H2PO4, etc.) activated by ions of thallium (Tl+) or

cerium (Ce3+) (KDP:Tl and KDP:Ce) has been investigated and has been
found to provide high internal selectivity for the detection of fast neutrons
against the background of gamma radiation. These scintillation crystals
occupy an intermediate position between organic and inorganic
scintillators, and their fairly high concentration of hydrogen nuclei
enables the detection of fast neutrons based on proton recoil reactions. At
the same time, the entire crystalline matrix of the KDP crystal is not
overly sensitive to gamma radiation, since this crystalline material has a
low effective atomic number and density. Additionally, the specific
mechanism of luminescence by excitation of the internal hydrogen sub-
lattice occurs predominantly by heavy particles (i.e., neutron, protons,
alpha-particles, etc.), and less so by gamma rays or electrons. Theoretical
calculations and experiments show that the efficiency of fast neutron
detection by small (e.g., 10×10×10 mm3) KDP scintillator crystals can
reach 12% for KDP:Tl and 16% for KDP:Ce, levels that are as good or
better than for organic scintillators. However, the internal separation of
neutron/gamma signals (i.e., the ratio of detection efficiencies for
separate registration of fast neutrons versus gamma rays) for activated
KDP crystals is 70-80 times higher than for traditional plastic
scintillators.
Keywords: KDP crystals, inorganic scintillators, luminescence

mechanisms, fast neutrons detection, protons recoil, neutron/gamma
discrimination
INTRODUCTION
Despite the wide variety of fast neutron detectors developed so far

(see, for example, Marion and Fowler 1960; Harvey and Hill 1979; Klein
and Brooks 2006; Kouzes et al. 2015; Ryzhikov et al. 2017 and references
therein), based variously on solid, liquid or gaseous detection media, the
problem of separate detection of fast neutrons in mixed neutron/gamma
radiation fields (as produced by various nuclear sources), remains a very
relevant obstacle to be overcome. As a rule, many materials used to record
fast neutrons by detecting the elastic neutron scattering reaction and the
resultant formation of recoil protons (see Beckurts and Wirtz 1964), also
have an excessive sensitivity to accompanying and/or background gamma
Scintillation Crystals of Thallium and Cerium Doped Potassium … 145
radiation (see, for example, Birks 1964; Knoll 2010). Because of this, for
the separate detection of neutrons against a gamma background, it is
necessary to use complicated methods of discrimination by analyzing the
signals in form, amplitude and duration of the pulses. Therefore, the search
for new detection materials, which possess high internal selectivity to
neutrons (or other heavy particles, including protons, alpha-particles, etc.)
versus gamma radiation, is of particular interest for many radiation
detection applications.
The greatest previous success in the development of neutron detectors
has been associated with the detection of slow and thermal neutrons.
Detectors in which the detection medium contains nuclei with very high
probabilities of thermal neutron capture have achieved detection
efficiencies of 70% and higher for thermal neutrons. As a rule, these are
odd-even or even-odd nuclei with an “excess” or “deficiency” of neutrons
in comparison with highly stable isotopes. Such “neutron-capture” nuclei
include the isotopes 3He, 6Li, 10B, 113Cd, 155Gd, 157Gd and 135Xe, each with
a large cross section for radiative capture of thermal neutrons, ranging
from thousands of barns to tens and hundreds of thousands of barns (1 barn
= 10-24 cm2).
Scintillation detectors for slow neutrons based on 6LiI:Eu single
crystals (Carneiro 2011) or 6LiF/ZnS:Ag composite materials (Kojima et
al. 2004; Marin et al. 2015), enriched with the 6Li isotope up to 90-96%,
are widely used. Scintillating lithium- or boron-containing glasses and Gd
or Cd-containing capture-gated plastic scintillators (Flaska et al. 2010;
Fanchini 2016) are also used for such detectors. In gas discharge counters,
3
He or 10B (e.g., BF3 gas or B2O3 oxide sprayed on the inner surface of a
gas-filled tube) are also commonly used for neutron detection (Lacy et al.
2014). It is worth noting that gas-discharge counters based on 3He have
high sensitivity and selectivity for separate neutron detection. However,
the depletion, high cost and irreplaceability of the 3He isotope (Kouzes et
al. 2015) significantly limit its use in proportional neutron detectors. The
above-mentioned alternative detectors, using the neutron capture reaction,
can ideally record thermal or epithermal neutrons with energies below 1
eV. The cross section for the radiative capture of slow neutrons decreases
rapidly with increasing neutron velocity Vn (or the square root of energy,
Vn  En ) as  capt 1 Vn (see, for example, Beckurts and Wirtz 1964).
Additionally, in contrast with thermal neutron capture cross sections,
fast neutron capture cross sections decrease strongly with increasing mass
number of the target nuclei (see, for example, the known data from JENDL
2020). Therefore, the efficiency of direct detection of fast neutrons with
energies greater than 100 keV in such detectors usually does not exceed a
few percent. To efficiently register fast neutrons in such detectors, it is
necessary to use indirect methods that moderate (thermalize) the fast
neutrons using large amounts of organic moderator material. Paraffin or
high-density polyethylene can be used as such moderator material.
However, when detecting fast neutrons with energies of several MeV, the
detection efficiency in such detectors, even with the use of of a moderator,
does not exceed 5-10%.
Among the direct methods for detecting of fast neutrons without
moderation is the method of detecting recoil protons arising from the
elastic scattering of neutrons in hydrogen-containing media. For many
applications, the objective is to detect fast neutrons with energies from 100
keV to 10 MeV. Their detection can be carried out in solid (plastics, etc.)
or liquid (see, e.g., Paff et al. 2015) hydrogen-containing scintillators by
registering the recoil protons from scattering reactions.
Solid-state detectors based on organic (molecular) crystals of
anthracene, stilbene, etc. have been widely used (see, e.g., Hull et al. 2009;
Zaitseva et al. 2015; Inrad Optics 2020); and plastic scintillators based on
polystyrene, polyvinyltoluene, polymethymethacrylate, etc. with activators
and spectrum-shifting additives (PPO and POPOP1, etc.) have also been
used. However, all of these detectors have a high sensitivity to γ-radiation
of low and medium energies. Therefore, in mixed n/γ radiation fields, fast
neutron interactions (i.e., recoil protons and other light nuclei) and gamma
quanta are simultaneously registered. In order to exclude the influence of
the concomitant γ-radiation from radioactive sources and/or natural
radiation background, various methods of passive and active protection are
1
2,5-diphenyloxazole (PPO) and 1,4 di[2-(5phenyloxazolyl)]benzene (POPOP)
used in such detection systems, as well as methods of signal separation

such as pulse shape discrimination (PSD) (see, for example, Favalli et al.
2013).
It has been found that thallium activated crystals of ammonium halides
with high contents of hydrogen atoms (e.g., ammonium iodide (NH4I:Tl)
and ammonium bromide (NH4Br:Tl)) can be used to detect fast neutrons by
recoil protons (Czirr and Berrondo 1995). The traditional thallium
activated alkali-halide scintillation crystals of NaI: Tl or CsI: Tl can also be
used to detect fast and slow neutrons (Ryzhikov et al. 2014; Pereira et al.
2017), but the mechanisms for detecting neutrons are quite different:
inelastic scattering of neutrons by heavy nuclei (iodine and cesium) and/or
radiative capture (mainly on iodine nuclei). However, the efficiency of
detection of neutrons in alkali-halide crystals remains low, and the
efficiency of intrinsic separation of n/γ is very low, since these crystals are
highly sensitive to gamma radiation. There are indications that in detectors
based on alkali-halide crystals the PSD method can be used for the
separation of n/γ signals.
It is important to note that the PSD method involves somewhat
complicated approaches for discriminating between the pulses from
registered neutrons and those from γ-quanta in mixed radiation fields.
Therefore, it is important to search for and identify new scintillators that
can provide intrinsic selectivity in the detection of fast neutrons in mixed
n/γ fields. Such scintillators should have a high intrinsic selectivity to
different types of radiation.
An example of an ideally selective neutron detector is a gas-discharge
3
He counter (with a neutron moderator). In it, the parameters of the
detector (tube geometry, operating voltage, pressure and gas composition,
etc.) are selected in such a way that the efficiency of gamma-quanta
detection is extremely low. This allows the achievement of a n/γ signal
ratio of from 104 to 106. There are no materials with comparable selectivity
among liquid scintillators of an organic base, as well as among organic
solid scintillators. For crystalline inorganic scintillators, the capability of
intrinsic (i.e., without the use of hardware or software separation) selective
detection of fast neutrons can best be achieved by the presence of a high
concentration of hydrogen atoms in such a crystal, while, at the same time,

there is a relative absence of atoms with a high atomic number ( Z ) and
corresponding density to avoid the absorption and reemission of gamma-
quanta of low and medium energies by the photo-effect (with its
probability increasing by  Z 4 ). Consequently, the search for inorganic
crystalline scintillators with high selective sensitivity to fast neutrons
should primarily be conducted among materials with a low effective
atomic number and low density.
Recently, at the Institute of Single Crystals (ISC, Kharkov, Ukraine), it
has become possible to grow unique scintillation crystals from aqueous
solutions of KH2PO4 (i.e., potassium dihydrogen phosphate or KDP) doped
with thallium ions Tl+ (Voronov et al. 2006, 2007) or cerium ions Ce3+
(Voronov et al. 2008, 2009). The uniqueness of the obtained scintillation
crystals (KDP:Tl and KDP:Ce) is that they occupy an intermediate position
between organic and inorganic scintillators. On the one hand, each such
crystal from the KDP family is a typical inorganic dielectric with a wide-
band ( Eg = 8.8 eV ) electron structure and strong covalent bonds in the
anionic group H2PO4– bound by a weaker ionic bond to the cation
sublattice of K+ ions. On the other hand, this crystal contains a highly
mobile (at room temperatures) sublattice of hydrogen atoms, saturated with
numerous hydrogen bonds with nearby oxygen atoms. The concentration
of hydrogen nuclei in the KDP lattice is ~2.07 × 1022 cm–3. This is
substantially (approximately twice) lower than the concentration of
hydrogen atoms in plastic (e.g., polystyrene, etc.) or molecular organic
scintillators (e.g., anthracene, etc.). However, as follows from the
experiments presented below, the hydrogen concentration in KDP is still
sufficient for the effective detection of fast neutrons. It is important that the
effective atomic number of the activated KDP crystals is equal to that of
plastic and molecular organic scintillators, and its density is 2.34 g/cm3.
This is much lower than the effective atomic number and density of most
inorganic scintillators, and this suggests the potential for highly selective
detection of fast neutrons by this material.
DOPED KDP SCINTILLATION CRYSTAL GROWTH
Pure (i.e., not activated by various additives) inorganic KDP crystals

are traditionally grown from aqueous solutions by the method of
temperature reduction. This method can be used to grow very large KDP
crystals with an aperture up to 50x50 cm2 and weighing up to 500 kg
(Zaitseva and Carman 2001). Pure crystals have a wide band of optical
transparency (175-1500 nm), high structural perfection (dislocation density
< 102 см-2) and high radiation strength under exposure to various types of
ionizing radiation. The optical absorption coefficient of KDP crystals does
not change upon irradiation with powerful fluxes of protons with fluence
up to 1013 protons/cm2, fast neutrons up to 1010 neutrons/cm2 or gamma
radiation with a dose up to 105 Gy (107 rad) (Kolybayeva et al. 1997). It
should be noted that the extensive presence of hydrogen bonds in the KDP
structure makes it possible to easily incorporate various inorganic and
organic additives into the matrix of the crystal (Sugimotoy and Ikeda
1996).
KDP:Tl and KDP:Ce single crystals are also grown from an aqueous
solution (with supersaturation of at least 5%) by a temperature reduction
method in the range of 40-600°C. The salt KH2PO4 is synthesized from
KOH and H3PO4 reagents of high purity. The doping component Tl+, at a
concentration of 10-2, 10-1 and 1.0 wt.%, is introduced into the mother
liquor as an aqueous solution of the TlNO3 salt, and this enables Tl
concentrations in the resulting crystals ranging from 10-3 to 10-1 wt.%.
Direct doping with cerium in the form of an aqueous solution of Ce(NO3)3
is not possible due to the formation of water-insoluble cerium phosphate
(CePO4). Therefore, the Ce3+ doping component, at a concentration of 10-2
wt.%, can be introduced (Voronov et al. 2009) into the mother liquor in the
form of an aqueous solution of the organometallic alizarin-complex AC-Ce
of the form (C19H15NO8 – Ce3+), where C19H15NO8 is the organic ligand of
the alizarin-complex (AC).
Figure 1 shows a KDP:Tl crystal grown on an orientation primer (101)
in the form of a plate with cut edges. The seed plane was oriented with an
accuracy of at least 30´. The content of the Tl and Ce additives was
controlled by chemical and atomic emission spectroscopic analysis. The

thallium content in the prism and pyramid sectors turned out to be
approximately the same. Consequently, the doping additive is distributed
evenly over the growth sectors. The concentration of the thallium additive
in the KDP crystal turned out to be virtually the same as the concentration
in the aqueous solution.
Figure 2 shows a KDP: Ce crystal grown on a point seed with
orientation (001), a conventional approach achieved by a combination of a
prism (100) and a pyramid (101). The content of cerium in the growth
sectors of the prism and pyramid turned out to be different, 10-2 wt.%
versus 5 × 10-3 wt.%, respectively.
Figure 3 shows crystals of KDP:Tl and KDP:Ce cut from blanks and
processed to the desired dimensions for use in subsequent measurements.
Figure 1. Morphology of KDP:Tl crystals grown on a flat seed with orientation (101).
Figure 2. Morphology of KDP: Ce crystals grown on a point seed with

orientation (001).
Figure 3. Typical samples of finished KDP: Tl and KDP: Ce crystals. The left two
crystals are of KDP: Tl, while the one on the right is KDP: Ce.
OPTICAL AND LUMINESCENCE PROPERTIES OF

ACTIVATED KDP CRYSTALS
Absorption spectra (recorded by a Perkin Elmer Lambda 35
spectrophotometer) and photoluminescence (recorded by a Hitachi F4010
fluorescence spectrophotometer) were investigated on processed samples
with dimensions of 10x10x10 mm3 oriented and cut out in different
crystallographic directions X = (100), Y = (010), Z = (001). These crystals
were finished with optically polished planes, and measurements were made
when a light beam passed along the optical axis of the crystal in the
wavelength range from 200 to 800 nm, at room temperature.
In the absorption spectra of KDP:Tl, the maximum absorption band of
the activator (Tl+) corresponds to a wavelength of 220 nm and shifts
toward shorter wavelengths with increasing thallium concentration. In pure
KDP crystals, the optical absorption bands associated with the activator
thallium impurity are absent.
Figure 4 shows the excitation and photoluminescence spectra of
KDP:Tl crystals excited by UV light with a wavelength of 220 nm. The
excitation spectra of KDP:Tl consist of two bands, and the Figure shows
the impact of increases in the thallium concentration from 10-3 wt.% to 10-1
wt.%, where the maxima shift to the right toward increasing wavelength
with increasing concentration of Tl. The maximum of the emission band
corresponds to 275 nm. The Stokes shift is 55 nm.
Figure 4. Excitation and photoluminescence spectra of KDP: Tl crystals depending on

the thallium concentration: (1) 10-1 wt.%; (2) 10-2 wt.%; (3) 10-3 wt.%. Transmission of
light is along the optical axis of the crystal.
With increasing thallium concentration, the maximum of the radiation

band does not change its position, but the radiation intensity increases. It
has been established that the position of the thallium absorption band does
not depend on the acidity of the solution, on the growth rate, or on the
growth temperature. The main factors affecting the intensity of absorption
and luminescence are the concentration of the activator and the nature of
its entry into the pyramidal and prismatic crystal growth sectors.
In the absorption spectra of KDP:Ce crystals (more precisely, KDP:
(AC + Ce)), two absorption bands with maxima at 470 nm and 290 nm are
observed. The absorption band with λmax = 470 nm is associated with the
absorption of the ligand, and the band λmax = 290 nm is due to electron
transitions of 4f → 5d for Се3+ ions. Absorption spectra of samples cut
from different crystal growth sectors (prisms or pyramids), with different
concentrations of cerium ions, differ in the absorption intensity when the
corresponding band maxima coincide. Excitation of the crystal with UV
light λex = 290 nm leads to the appearance of luminescence at λmax = 350
nm, and excitation with light λex = 470 nm causes the appearance of long-
wavelength luminescence at λmax = 650 nm. The emission band with a
maximum λmax = 350 nm is due to interconfiguration transitions from the

lower level of the 5d-shell of Се3+ ions to the ground-state levels of the 4f-
shell. The longwave band λmax = 650 nm is a luminescence band of the
bound ligand and refers to the emission of the whole complex (AC+Ce).
Figures 5-6 show the photoluminescence decay kinetics in KDP:Tl and
KDP:Ce crystals obtained on tested samples by irradiation with a source of
synchrotron radiation at the experimental station SUPER-LUMI in the
laboratory of HASYLAB (Hamburg, Germany). The luminescence kinetics
at room temperature is well described by the curve of the mono-
exponential law with decay time constant τ = 300 ns for KDP: Tl (Figure
5) and τ = 50 ns for KDP:Ce (Figure 6). As it would be expected, by
analogy with activated alkali-halide scintillators, the luminescence for
thallium ions is much slower than for cerium ions with transitions from
deep-lying electronic shells. The time response of luminescence at the low
temperature of 10 K for KDP:Tl crystals (Figure 5, curve 1) looks like an
extended pedestal, showing the time constant of excitation of long-lived
excitations equal to τ ~ (0.3-1.0) ms.
In non-doped KDP crystals, photoluminescence is not observed.
Figure 5. Kinetics of photoluminescence decay in KDP:Tl crystals at excitation

wavelength λex = 220 nm: (1) at temperature T = 10 K; (2) at T = 293 K. Both curves
are normalized to the value of their maximum.
Figure 6. The photoluminescence decay kinetics in KDP:Ce crystals at temperature T =

300 K: (1) excitation wavelength λex = 161 nm, decay time τ = 200 nm; (2) excitation
λex = 290 nm, decay time τ = 50 ns.
Figure 7. The radioluminescence spectrum of KDP: Tl crystals at temperature 295 K

excited by X-rays with an energy Eex = 40 keV.
Figures 7-8 show the spectra of the radioluminescence of KDP:Tl and

KDP:Се crystals obtained by irradiation of X-rays with energy of 40 keV.
The peak of the emission band KDP:Tl corresponds to wavelength of 275
nm (Figure 7) as well as under UV excitation. In the radioluminescence
spectrum of KDP:(AC + Ce), two peaks of radiation with maxima at 350
nm (cerium ion radiation) and 600 nm (radiation from the entire
organometallic complex) are observed (Figure 8).
In undoped KDP crystals, there is no radioluminescence.
Figure 8. The radioluminescence spectrum of KDP: (АС+Се) crystals at temperature

295 K when excited by X-rays with energy Eex = 40 keV.
MECHANISMS OF RADIOLUMINESCENCE AND

SCINTILLATION RESPONSE IN KDP SCINTILLATORS
Let us consider the nature of radioluminescence in KDP:Tl crystals.

The thallium ion Tl+ is a well-known activator that forms electronic s2-
centers in cubic alkali-halide crystals (Zazubovich et al. 2002). The free
thallium ions in the ground state have a configuration of the outer electron
shell 6s2, see, e.g., (Kittel 2005), and in the excited state have 6s6p
configuration in KDP (Ogorodnikov et al. 2012). These configurations
correspond to the ground level 1S0 and the series of excited levels 1P1, 3P0,
3
P1, 3P2. The energy interval between neighboring states is ~1 eV. The
allowed electronic transitions in the crystal field of cubic symmetry are 1S0
→ 3P1 and 1S0 → 1P1 (absorption band bands A and C, respectively), and in
the tetragonal symmetry field – 1S0 → 3P1, 1S0 → 3P2 and 1S0 → 1P1
(absorption bands A, B and C, respectively). The transition 1S0 → 3P0 is
allowed only in a field of lower symmetry.
The Tl+ center in KDP:Tl crystals is the only confirmed s2 center in
the non-cubic intrinsic lattice, for which s2 → sp transitions corresponding
to A, B, and C absorption bands are possible as in ordinary alkali-halide
crystals (Fujita 1994). In the absorption spectra of KDP:Tl crystals, A-, B-,
and C-bands were observed (Fujita 1978), which are absent in the spectra
of pure KDP crystals. At low temperatures, five absorption bands (i.e., Az,
Axy, Bxy, Cxy, Cz) at wavelengths of 223 nm, 215 nm, 180 nm, 170 nm,
162 nm, respectively, were detected in KDP:Tl, with polarization of the
transmitted light along the optical axis of the crystal (z-axis) and in the
plane perpendicular to optical axis (xy-plane) (Fujita 1994). At room
temperature, two absorption bands are observed at photoexcitation at 223
nm (Az) and 215 nm (Axy) (Fujita 1997). Emission during photoexcitation
of KDP:Tl at room temperature is usually observed only for the A-band at
the reverse transition of 3P1 → 1S0 due to the absence of the optical
radiative transitions 1P1 → 3P1, 3P2 → 3P1 (Voronov et al. 2006; Ichimura et
al. 2006).
The excitation of luminescence under the influence of X-rays in KDP:
Tl crystals was previously considered (Ogorodnikov et al. 2017). Ionizing
radiation, as usual, leads to the generation of main charge carriers, i.e.,
band electrons and holes, and the formation of bound electron-hole pairs.
Under the influence of ionizing radiation in the hydrogen sub-lattice of
KDP:Tl crystals, pairs of opposite defects also appear in the form of
interstitial ion H+ (positively charged D-defect) and hydrogen vacancies
VH+ (negatively charged L-defect). After the capture of a band electron D-
defect is converted into an interstitial neutral hydrogen atom, the so-called
Н0-center, which has high mobility in the crystal. The L-defect is localized
on the anion (H2PO4)–; after trapping a hole it turns into another center, the
so-called A-radical. As a charge excitation, it is a hole localized on the
oxygen ion near the hydrogen vacancy VH+. Alternatively, an A-radical can
be represented as a composite radiation defect [HPO4]– = [(H2PO4)– + VH+
+ h+]. Both of these centers can later undergo diffusion through the lattice
and recombination with main charge carriers (the H0 center with a hole,
and the A-radical with an electron, respectively). As a result of
recombination of an electron and a hole, the charged center returns to the
initial state of the lattice defects. Under ordinary conditions in a wide
temperature interval, the recombination of an electron with an A-radical is
nonradioactive (Ogorodnikov et al. 2003, 2007). However, the transfer of
energy released during such recombination can lead to the excitation of the
Tl+ ion in the case that the A-radical is located in the immediate vicinity of
the ion. This is a feature of the model of the recombination mechanism of
luminescence in activated KDP crystals.
Similarly, in the case of nonradioactive recombination of H0-centers
with band holes near Tl+ ions, excitation and de-excitation of latter can
also occur. In addition, the excitation of the Tl+ ion can occur directly by
secondary ionizing particles, but the fraction of the radiation energy
transferred in this case will not be so significant, since the concentration of
the dopant is relatively low.
In addition to the H0-centers and A-radicals in activated KDP crystals,
other centers of nonradiative transfer of the electronic excitation energy
from the crystal matrix to the activator ions can also occur. They are so-
called B-radicals. Calculations of the band structure of KDP in para- and
ferroelectric phases were performed (Zhang et al. 2001). It was found that
there are no fundamental differences in the electronic structure of these
phases. At room temperature in the paraelectric phase, the ceiling of the
valence band of the crystal is formed mainly by 2рπ states of oxygen
atoms, and the bottom of the conduction band by the 3s states of
phosphorus atoms and 1s states of hydrogen atoms. The lowest inter-band
transition is due to an electron transfer between the levels of 2рπ-oxygen
and 1s-hydrogen. In this case, the electron is transferred to the conduction
band and simultaneously the A-radical [HPO4]– is formed. The capture of
another band hole by an A-radical leads to the formation of the B-radical
[H2PO4]0, which is an autolocalized hole. The trapping of a hole in the
formation of the B-radical is accompanied by the capture of an electron
(from an electron-hole pair) at a suitable nearby capture center. The most
likely electronic capture centers are the impurity ions of Tl+ activator, as
well as the interstitial ion H+ and some anionic and cationic impurities, for
example SO42-, Ni2+, Mn2+. If the electron is captured by the thallium ion
Tl+ + e– → Tl0, a composite radiation defect ([H2PO4]0 + [Tl]0) is formed.
The possible recombination of the electron-hole pair on the activator [Tl]0
takes it to the excited state Tl0* with a subsequent radiation pulse.
Thus, for the luminescence scheme of KDP:Tl with the participation of

radiation, defects of the hydrogen sub lattice can be described by three
main recombination transitions:
[H]0 + h+ + Tl+ → H+ + Tl+* → H+ + Tl+ + hν ;

– –
[HPO4] + e + Tl+ → (HPO4)2– + Tl+* → (HPO4)2– + Tl+ + hν ;
[HPO4]– + (h+ + e–) + Tl+ → [H2PO4]0 + Tl0* → [H2PO4]– + Tl+ + hν .
In all cases, the spectral composition of the radioluminescence of

KDP: Tl is determined by the radiative transition of thallium 3Р1 → 1S0 to
the ground level. The maximum radioluminescence corresponds to 275 nm
(hν = 4.5 eV). Cascade transitions from higher excited levels of thallium to
the lowest excited level remain nonradioactive.
The scintillation response of the KDP:Се crystal is due to the
analogous luminescence mechanism described above for KDP:Tl+ crystals.
The differences concern the transfer of excitation to the center of the
luminescence, which is the Се3+ ion of cerium, and the removal of
excitation from it with the emission of the radioluminescence pulse.
In the radioluminescence spectra of KDP: Се, a single luminescence
center associated with the Се3+ ion manifests itself. The effect of
successive charge exchange of an ion upon excitation of Се3+ can occur
according to the scheme:
Ce3+ + h+ → Ce4+; Ce4+ + e– → (Ce3+)*; (Ce3+)* → Ce3+ + hν (3.54 eV).
The radioluminescence pulse of KDP:Се crystals is due to

configuration transitions from the lower level of 5d-shell of Се3+ ions to
the levels of the ground state of 4f-shell. The maximum of the scintillation
spectrum corresponds to λem = 350 nm (3.54 eV). Unlike KDP:Tl crystals,
it is shifted to the long-wavelength region, which somewhat increases the
sensitivity of fast neutron detection using conventional bi-alkaline
photomultipliers.
Obviously, the features of the described recombination mechanism are
preserved when considering the luminescence of KDP:Tl or KDP:Ce under
irradiation by fast neutrons. Under elastic scattering of fast neutrons with
energies above 0.5 MeV, radiation ionization fluxes of light nuclei –

protons (produced in the scattering of neutrons by hydrogen nuclei) and
oxygen nuclei – arise in the KDP matrix. The contribution to the transfer of
energy of ionizing radiation resulting from the recoil of heavier potassium
nuclei and phosphorus can be neglected, since the total energy losses of the
neutron on these nuclei are proportional (i.e., En : En A ), and its amount
is less than 6% in comparison with losses due to the recoil protons.
In addition, the bremsstrahlung and ionization losses during
deceleration of recoil nuclei of potassium and phosphorus increase rapidly
with increasing nuclei charge, which leads to more significant radiative
quenching of luminescence (Birks 1964) than for ionization losses from
recoil hydrogen and oxygen nuclei. When recoil protons or light nuclei
decelerate in matter (with the formation of secondary fast δ-electrons),
ionization and excitation of the atoms of crystal matrix will ultimately
occur, similar to X-ray irradiation. The top of the valence band of the KDP
crystal is mainly filled with states of 2p orbitals of oxygen atoms, and the
conduction band bottom is formed by 1s states of hydrogen. Consequently,
the recoil and ionization of these atoms will lead to the main generation of
band carriers in the crystal. In addition, the secondary charged particles
will also generate defects in the hydrogen sublattice of KDP crystal. The
oxygen atoms in KDP lattice are connected by numerous hydrogen bonds
with hydrogen atoms. Therefore, it should be expected that the recoil of
oxygen nuclei would lead to comparable effect of ionization and excitation
of the hydrogen sublattice in comparing to influence of recoil protons.
Thus, the generation and transfer of charge excitations by elements of the
hydrogen sublattice of KDP:Tl or KDP:Ce crystals to Tl+ or Ce3+
luminescence centers will occur mainly as a result of ionization braking
losses for recoil protons and recoil of oxygen nuclei, which will lead to the
observed scintillation response of the crystal from fast neutrons.
DETECTION EFFICIENCY OF KDP SCINTILLATORS TO

FAST NEUTRONS AND GAMMA-RAYS
A weakening of the particle flux in matter occurs according to an

exponential law. In the elastic scattering reaction, each neutron can
repeatedly experience energy loss in collisions with the nuclei of the
medium. However, when light nuclei are scattered, the neutron rapidly
loses its energy and the recoil nuclei that arise after several collisions
receive much less energy from it and no longer contribute significantly to
the scintillation response in comparison with the contribution from single
scattering of fast neutrons. If we assume that, in the ideal case, each recoil
nucleus is recorded, and confine oneself to the contribution of single
scattering, then
el
 n   nrecoil  1  exp  el h  , (1)
tot 
where  el is the macroscopic cross-section for elastic scattering of

neutrons, tot  el   non  el is the total macroscopic section; h is the
thickness of the material in the direction of the neutron flux. The
macroscopic cross-section for the k -channel (reaction) of neutrons
k  i ni i , k is determined by the concentrations ni of the nuclei of i -sort
of the chemical composition of the substance and the microscopic nuclear
scattering cross sections  i , tot   i ,el   i ,non el , where  i ,el and  i ,non el are
partial cross-sections of elastic and non-elastic scattering.
For plastic scintillators and organic single crystals, the 1H1 recoil
protons make the main contribution to the scintillation pulse, since the
deceleration of 12C6 carbon recoil nuclei having a much higher charge in
such materials is accompanied by high specific ionization losses and leads
to strong radiation extinguishing within the framework of the Birks theory
(Birks 1964). In addition, as a rule, before scattering by hydrogen nuclei,
the neutron can be multiply scattered on carbon nuclei, which contributes
to the overall detection efficiency. As a result, instead of the pre-

exponential factor in formula (1), the following expression applies
H  
2
 el C  C 
 1      1, (2)
tot  H  C   H  C   H  C  

where tot  el   H  C is the total elastic scattering cross section,  H

and  C is the elastic scattering cross-section for hydrogen and carbon
nuclei, respectively. In the exponential factor, only the contribution of  H
should be retained, since the intrinsic recoil of the carbon nuclei gives a
negligibly small momentum to produce scintillations. Then, instead of the
formula (1), we obtain
 nORG  1  exp   Н h  , (3)
where  H is the macroscopic cross section for the elastic scattering of

neutrons by the hydrogen nuclei. In many cases, the efficiency of an
organic scintillator is well described by this formula.
For KDP scintillation crystals, the previously described features of the
luminescence and scintillation response to fast neutrons should be taken
into account, and the contribution to the elastic scattering cross section
should be retained in formula (1), not only for 1H1 recoil protons, but also
for recoil of light oxygen nuclei 16O8. Then we have
 Н  O
 nKDP  1  exp     Н  O  h  , (4)
 Н  O   P   K 
where  H and  O – are the elastic neutron scattering cross-sections for

hydrogen and oxygen nuclei in the KDP crystal,  P and  K are the elastic
scattering cross-section for the medium nuclei of phosphorus and
potassium which do not contribute significantly to the scintillation pulse.
Formula (4) also takes into account that the contribution of inelastic
neutron reactions in the energy range up to 10 MeV to the formation of

secondary charged particles and the scintillation momentum is extremely
small.
For purposes of calculations, known data for the averaged microscopic
cross sections for the interaction of neutrons with nuclei (JENDL 2020)
have been used. The neutron source spectrum corresponded to the 235U
fission spectrum, which is in many respects similar to the spectrum of the
239
PuBe source. The concentration of nuclei ni is calculated from the
formula
ni   N A  ai M  , (5)
where N A  6.022 1023 mol 1 Avogadro’s number,  is the density of the

substance, M is the molar weight, ai – number of atoms of the i -sort in
the molecule of the substance.
Table 1 presents the theoretical values of the fast neutron detection
efficiency calculated using the formulas (3)-(4) for: (i) a typical plastic
scintillator based on polystyrene, (ii) an organic anthracene crystal, and
(iii) KDP:Tl and KDP:Ce crystals. The thickness of the scintillator is
everywhere assumed equal to 10 mm. The mean free path of neutrons is
evaluated from the formula:
1
ln  tot , (5)
The obtained value  nKDP should be considered as a theoretical limit of

the maximum possible efficiency of neutron detection for a given type of
material of a certain thickness. The addition of thallium or cerium does not
change the calculated value, since the concentration of these additives is
negligible compared to the concentration of the main nuclei. However, the
scintillation efficiency of the crystal (which was not taken into account in
these calculations) depends on these dopants. Therefore, the experimental
value of efficiency may differ for KDP crystals with different compositions
and concentrations of the activator.
Table 1. Theoretical comparison of parameters and fast neutrons

detection efficiency of hydrogen-containing organic and
inorganic scintillators
Scintillator Effective Density, Concentration Mean Free Detection

atomic g/cm3 of 1H nuclei, Length, Efficiency,
number cm-3 cm %
Polystyrene 5.7 1.04 4.82 × 1022 3.30 17.25
Anthracene 5.8 1.25 4.23 × 1022 3.26 14.31
KDP: Tl, 14.3 2.34 2.07 × 1022 3.93 17.22
KDP: Ce
In summary, theoretical estimates (Table 1) show that KDP

scintillators can have fast neutron detection efficiencies comparable to
those of organic scintillators.
EXPERIMENTAL MEASUREMENTS OF THE RESPONSE

OF KDP SCINTILLATORS TO FAST NEUTRONS
AND GAMMA-RAYS
Experimental measurements of the efficiency of detection of fast

neutrons and gamma rays by KDP:Tl and KDP:Ce crystals were performed
and compared to the performance of standard plastic scintillators (Voronov
et al. 2018). For the measurements, the treated KDP:Tl and KDP:Ce
crystals measuring 10х10х10 mm3 with polished side faces were selected.
The concentration of the activator corresponded to the maximum light
output of the luminescence. A scintillator of the Ukraine polystyrene-based
scintillator (UPS) series was used as the plastic scintillator. The
composition of the UPS scintillator was as follows: polystyrene (C8H8)n),
98.5%; phosphor-terphenyl (PTP) 1.48% and 1,4 di[2-
(5phenyloxazolyl)]benzene (POPOP) 0.02% (luminophore additive). The
investigated scintillator was placed in a light-shielded body with a diameter
of 20 mm with a diffuse reflective Tetratek® (polytetrafluoroethylene)
film. Measurements of the amplitude spectra were performed by
scintillator-PMT assembly. The photomultiplier was PMT Hamamatsu
R7056 (photosensitivity spectrum from 185 to 650 nm, maximum

sensitivity at 420 nm). The voltage on the photomultiplier was chosen to
equal to 760 V. The pulses were recorded using a multichannel analog-to-
digital converter. The lower cutoff threshold was 20-25 keV. The
composition of the spectrometer included a fast charge-sensitive
preamplifier. The time constant of signal integration was chosen for all
scintillators to be equal to ~6 μs.
A 239Pu-Be source (the characteristic fission spectrum with neutron
energies from 0.1 to 10 MeV, and an average neutron energy En = 1.9
MeV) was used as a source of neutrons. The distance between the source
of neutrons and the center of the detector was 20 cm. To protect against
concomitant gamma radiation (i.e., photons with Eγ ~ 60 keV from the
241
Pu impurity in 239Pu decay products, as well as high-energy quanta with
Eγ from 0.1 to 4 MeV from other reactions), a 50 mm thick lead screen was
placed between the neutron source and the detector the flux of fast
neutrons was 45%). To protect against thermal neutrons, a screen of
cadmium foil 1 mm thick was used. The general scheme of the experiment
is shown in Figure 9.
Figure 9. Setup of the experiment: (1) 239Pu-Be source of neutrons; (2) scintillator in
the light-protective housing; (3) PMT; (4) Cd-screen from thermal neutrons; (5) Pb-
screen from gamma radiation.
Figure 10. Amplitude spectra from 239Pu-Be fast neutron source obtained for different
scintillators: (1) KDP:Tl; (2) KDP:Ce; (3) UPS (polystyrene); (4) background. Counts
from the background were not subtracted.
Figure 10 shows the hardware spectra of the investigated samples of

scintillators when irradiated with the neutron source. Figure 11 shows the
hardware spectra when the same samples are irradiated with a gamma
quantum source of 137Cs. Calibration of the energy scale of the
spectrometer was performed using this source. The maximum response Eγ
= 662 keV corresponds to the 3000 channel of the spectrometer. Channel
300 corresponds to Eγ = 60 keV.
As follows from Figure 10, the response to neutrons for the
scintillators KDP:Tl and KDP:Ce propagates up to energies of 300 keV
and corresponds to the continuous spectrum of the recoil protons. These
neutron spectra are similar to the spectrum for the UPS scintillator based
on polystyrene.
On the contrary, as can be seen from Figure 11, the response to gamma
quanta for KDP:Tl is concentrated only in the low-energy region (less than
50 keV) and is strongly cut off at high energies in contrast to the spectrum
of the plastic scintillator. In addition, the amplitude of the response to
gamma quanta for KDP scintillators in the low-energy region is
comparable to the background radiation contribution, and is about an order
of magnitude lower than that of plastic.
Figure 11. Amplitude spectra from 137Cs source of gamma rays obtained for
scintillators: (1) KDP: Tl; (2) KDP: Ce; (3) polystyrene UPS; (4) background. Counts
from the background were not subtracted.
Based on the measured amplitude spectra, the detection efficiency for

fast neutrons and gamma-rays is presented in Table 2. The detection
efficiency of the different particles was determined from the expression
  V  V0   F  F0   V  V0   I S  , (6)
where V is the pulse count rate in the presence of a corresponding neutron

or gamma-ray source, V0 is the counting rate in the absence of a source
(average count rate of a natural background), F is the particle flow into the
detector, I  k filter Fsource 4 r 2 is the particle flux density at a distance r
from the source; Fsource is the passport value of the neutron activity of the
source (for neutrons it is equal 1.06×105 neutron/s); k filter is the the
transmittance of the fast neutron flux by a lead filter, S is the the area of
the sensitive surface of the scintillator, F0 is the the background flow of
particles through the detector, and the relation F0 = I S was recognized.
To increase the accuracy of the measurements, the pulse counting time was
chosen sufficiently large (20-30 min).
Table 2. The efficiency of detection of fast neutrons and gamma-rays

by KDP: Tl and KDP: Ce scintillators 10х10х10 mm3 and a plastic
scintillator UPS (based on polystyrene) ø16x9 mm
Scintillator Fast neutron Gamma-ray Relation,

detection detection  n 
efficiency,  n efficiency,  
Plastic UPS 13.1% 32.8% 0.4
KDP:Tl (0.1 wt.% Tl) 12.4% 0.4% 31.0
KDP:Ce (0.01 wt.% Ce) 16.2% 0.6% 27.0
As can be seen from Table 2, the efficiency of detection of fast

neutrons by KDP: Tl and KDP: Ce scintillators varies from 12 to 16%,
comparable to the efficiency of a plastic scintillator. This is in good
agreement with the theoretical calculation (see Table 1). At the same time,
the ratios of the efficiency of detection of fast neutrons and gamma-ray
particles for KDP: Tl and KDP: Ce scintillators, respectively, are 78 and 68
times higher than for plastic. This confirms the high intrinsic selective
sensitivity of KDP scintillators to fast neutrons. With a suitable choice of
low-energy threshold for the spectrometer, the registration with these
scintillators of fast neutrons in mixed neutron/gamma radiation fields
practically does not require the use of passive protection against high-
energy gamma rays. Detectors based on KDP: Tl and KDP: Ce crystals can
achieve discrimination up to 102, which is comparable to the use of active
protection from Compton gamma-quanta (according to the anti-
coincidence scheme). Perhaps this will not be enough to achieve some
standards (Kouzes 2009) for the detection of fissile and radioactive
materials, where signal separation is sometimes required up to 105-106.
However, the important fact is the high intrinsic separation of fast neutrons
from gamma rays in detectors based on activated KDP crystals. This
property of KDP-based scintillators is unique and can be claimed in
various applications. The application of the PSD or other methods can
further improve this result.
The sensitivity and efficiency of neutron detectors based on KDP
scintillation materials can be significantly improved by increasing of
thickness (crystal volume) of the scintillator and light output. The growth
of large-sized activated KDP crystals is associated with considerable

difficulties and requires a long growing time. As an alternative, the design
can be suggested of a multilayer composite detector consisting of several
plates of a high-transparency KDP scintillator 5-10 mm thick separated by
thin layers (up to 1 mm thick) of another scintillator with “neutron-
capture” elements, for example, composite layers made from
microfragments of the scintillator Gd2SiO5:Ce (GSO: Ce), located in the
organic filler (glue). The presence of gadolinium allows detecting not only
fast, but also slow neutrons. This may increase the efficiency of neutron
detection. This design of multilayer detector has already proved itself in
fast neutron detectors based on heavy-oxide scintillators (Ryzhikov et al.
2018).
CONCLUSION
It turns out that there is a whole class of inorganic hydrogen-containing

scintillators that have high internal selectivity in the detection of fast
neutrons against the background of gamma radiation. These are wide-gap
single crystals of the KDP group (KH2PO4, NH4H2PO4, etc.) activated by
thallium ions Tl+ or cerium Ce3+, which are ordinarily grown from aqueous
solutions. They occupy an intermediate position between organic and
inorganic scintillators. On the one hand, these crystals contain a fairly large
number of hydrogen nuclei (~ 2.07 × 1022 cm–3 for KH2PO4), that makes
them similar to organic scintillators, which are often used for detection of
fast neutrons. On the other hand, the hydrogen nuclei here form an ordered
single-crystal sublattice, unlike in plastic scintillators. Therefore, a
significant scintillation response in KDP scintillators is formed only upon
excitation of their hydrogen sublattice as a whole by knocking out and
subsequent registration of recoil protons, which occurs only when heavy
particles interact, for example, as a result of elastic scattering of fast
neutrons.
This hydrogen sublattice is insensitive to light particles or gamma

radiation (i.e., the scintillation response is small). In addition, the entire
crystalline matrix of the KDP crystal as a whole is not too sensitive to
gamma radiation, since this material has a low effective atomic number
and density (i.e., the cross sections for the photoelectric and Compton
effects are small).
Photo-luminescence and radio-luminescence in KDP:Tl and KDP:Ce
crystals have been investigated. The luminescence upon irradiation by fast
neutrons is caused by secondary ionizing radiation, namely by recoil
protons and recoil oxygen nuclei. Secondary radiation leads to direct
excitation of the activator due to ionization losses or to the formation of
radiation defects of the hydrogen sublattice (Frenkel’s pairs), subsequent
processes of migration and recombination of ones, that lead to the transfer
of electronic excitations to the vicinity of the luminescence centers Tl+ or
Ce3+ ions. For KDP(Tl) and KDP(Ce) crystals with an optimal activator
concentration, a characteristic scintillation response was obtained upon
irradiation with 137Cs gamma radiation source and 239PuBe fast neutrons
source. As theoretical calculations and experiments show, the efficiency of
fast neutron detection for activated KDP scintillators is equal or better than
for organic scintillators. On treated crystals with 10×10×10 mm3 size, it
reaches 12% for KDP: Tl crystals and 16% for KDP: Ce crystals. At the
same time, a high internal selectivity of KDP scintillators to fast neutrons
or alpha particles was established. The internal separation of n/γ signals
(i.e., the ratio of detection efficiencies for separate registration of fast
neutrons or gamma rays) for activated KDP crystals is 70-80 times higher
than for traditional plastic scintillators.
The obtained results show that the newly identified activated KDP: Tl
and KDP: Ce crystals are selectively sensitive to fast neutrons and
significantly supplement the list of solid-state scintillators for detecting
neutrons. These crystals can be used in a variety of different applications,
including the detection and control of fissile nuclear materials and other
related anti-terrorist purposes.
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Chapter 6
THERMODYNAMIC EVALUATION
AND PROCESS SIMULATION OF
THE PRODUCTION OF HYDROGEN-SYNGAS
USING MIXED IRON-BASED OXIDES
WITH METHANE
V. Collins-Martinez2, J. F. Cazares-Marroquin1,2,
J. M. Salinas-Gutierrez2, M. J. Melendez-Zaragoza2
and A. Lopez-Ortiz2,
1
ESIQIE-Instituto Politécnico Nacional,
Unidad Profesional Adolfo López Mateos, Ciudad de México
2
Departamento de Ingeniería y Química de Materiales,
Centro de Investigación en Materiales Avanzados, México

Corresponding Author’s E-mail: alejandro.lopez@cimav.edu.mx.
176 V. Collins-Martinez et al.
ABSTRACT
Syngas production through partial oxidation of hydrocarbons is one

of the actual challenges in the petrochemical and petroleum refining
industry, where a process that exhibits an optimal industrial efficiency
and usage is needed. In this context, partial oxidation through a chemical
looping (CL) can be an option to face these challenges. In the present
research, the use of mixed metal oxides (FeMoO4, Fe2ZnO4, Fe2MnO4) as
oxygen carriers under the CL reaction scheme is proposed to overcome
the current disadvantages of the partial oxidation of methane process. The
objective of the present work is to identify potential metal oxides that are
aimed for the production of syngas and able to regenerate within
favorable conditions. This was accomplished by a thermodynamic
simulation of an arrangement of two reactors using the Aspen-Plus©
process simulator. Metal oxide reduction was carried out in the first
reactor: CH4 + Fe2MO4 = H2 + CO + Fe + M, while in the second reactor
the oxidation of the reduced metals was achieved: Fe + M + H2O =
Fe2MO4 + H2, where M = Mo, Zn or Mn. Results indicate that FeMoO4,
Fe2ZnO4 and Fe2MnO4 produced syngas gas at 750°C, 730°C and 600°C,
respectively. However, FeMoO4 was not fully regenerated at favorable
conditions. Otherwise, Fe2ZnO4 and Fe2MnO4 were completely
regenerated at 440°C and 640°C. Finally, Fe2MnO4 shown the more
favorable operating conditions among the studied oxygen carriers.
1. INTRODUCTION
Currently about 80% of the energy demand is supplied by fossil fuels

(natural gas and oil), 14% of different renewable energies and 6% by
nuclear energy. These demand proportions need to be changed so that less
dependence on fossil fuels can be achieved as the global energy demand
increases. For this purpose, the usage of renewable and nuclear energies
need to increase considerably and consequently the energy of fossil fuels
will eventually decrease. Hydrogen itself is not an energy source, but an
energy vector, and therefore, it can help in the transition for the industry
between the use of energy provided by hydrocarbons and energy from
renewable sources [1].
Hydrogen is a fundamental raw material for the petrochemical and oil
refining industries, it can be produced from fossil fuels and renewable
Thermodynamic Evaluation and Process Simulation … 177
energy sources. The most economical route to produce hydrogen is from

hydrocarbons, such as natural gas and methanol, through the steam
methane reforming process (SMR) [1, 6].
CH4 + H2O → CO + 3H2

ΔHRо = 49.2 Kcal/mol (1)
Currently, there are large capacity hydrogen generating plants, because

of the great demand within the oil refining industry. This is primarily due
to the new regulations that restrict fuels to a very low sulfur and aromatics
content, since the hydrodesulfurization process requires a large amount of
hydrogen [6].
The main advantage for this process resides in its relatively high
hydrogen yield. With SMR it is possible to achieve energy efficiencies of
13.1-14.6 GJ/1000 Nm3 resulting in a yield of 2.4-2.7 mol H2 per each
mole of CH4 fed [3].
Some disadvantages of this SMR process are its large energy demand,
consequence of its high endothermic reaction (ΔHо = 49.2 Kcal/mol), very
intense operating conditions (T = 900°C at 10 atm) and the amount of CO2
release to the atmosphere during normal operation. This last results in a
significant amount of CO2 released during the process (25 Tons of CO2/1
MMscf of H2 product). Other processes have been proposed, such as the
reforming of methane with CO2 (dry reforming) with the use of metal
catalysts [2-5]. The process consists in the reaction of reforming a
greenhouse gas with methane to produce a mixture of CO and H2
commonly called syngas as follows: CH4 + CO2 = CO + H2. One of the
main problems that occurs with the dry reforming catalysts is the sintering
that these suffer at operating conditions and their deactivation by the
formation of carbon, in the case of nickel-based catalysts [4].
The current focus on hydrogen and syngas production is to find ways
to obtain these from renewable sources of energy, for example; the
electrolysis of water, the gasification of biomass or even nuclear energy.
Currently the production of hydrogen by the above methods is not
economically viable. A possible bridge between the current hydrogen
production technologies and those based on renewables is to continue to

employ natural gas as a raw material, with the option of CO2 capture
during the process, thus making this more environmentally friendly, while
other technologies become more competitive and mature. Therefore, it
becomes necessary to find new ways to obtain hydrogen from
hydrocarbons that could reduce production costs, CO2 emissions and
increase their performance [3].
It has been reported that the of partial oxidation of methane process
(reaction 2, POX) exhibits better performance for the production of syngas
and other advantages such as being an exothermic reaction, thus requiring
less energy than the SMR, in addition to employ small reactors because of
a short residence time due to its fast kinetics, compared to the SMR. This
POX reaction has been studied using catalysts of different nature and
compositions. However, there are still some important disadvantages in its
actual reaction scheme such as: the operating temperature is very high,
typically in the order of 900-1000°C and the need for an onsite oxygen
plant, which increases the initial investment of the process, making it more
expensive.
2CH4 + O2 = 4H2+ 2CO

ΔHRо = -17.18 Kcal/mol (2)
Recently, an improvement to POX has been reported and this is based

on the partial oxidation reaction through a chemical looping process
(Chemical Looping Partial Oxidation, CLPO), which is a technology for
the production of syngas, from natural gas and light hydrocarbons [7]. This
process was originally proposed by Ryden and Lyngfelt [9] and continued
by Mattisson and Lyngfelt [8]. The most important advantage of this
process is that from the produced syngas, the production of pure hydrogen
is also feasible in a second stage of the process. Because heat transfer
occurs directly between the gas and the oxygen carrier, it is convenient to
reduce the size of the reactor and these factors presumably making the
CLPO a cheaper technology than the conventional POX process [7, 9].
Figure 1. CLPO process scheme.
The use of metal oxides as oxygen carriers is a strategy that avoids the
expense of an oxygen plant to carry out reaction 2. In this CLPO reaction
scheme in the fuel reactor the oxidation of the fuel is carried out using a
metal oxide (MeO), thus providing the necessary oxygen (reaction 3) so
that the partial oxidation of methane takes place producing syngas, in
addition to the reduced metal as a solid product. In the next step, the
reduced metal is fed to the second reactor (oxidation reactor) where reacts
with steam (reaction 4), thus producing pure hydrogen and the original
metal oxide, which is sent back to the fuel reactor to complete a chemical
loop. Figure 1 presents a basic outline of the CLPO process. In this
Figure It can be seen that the final gas product of the first reactor is syngas,
while in the second, pure hydrogen is obtained.
CH4 + MeO = 2H2 + CO + Me (3)
H2O + Me = MeO + H2 (4)
This process has also been called POX-MeO. The operation of this
process is essentially determined by the performance of the oxygen carrier
(MeO). Therefore, an ideal oxygen carrier should present a high oxygen
capacity and structural stability, while remaining active after an extensive

number of redox cycles [13].
Several metal oxides have been used been studied for their
performance as oxygen carriers. Since 2014 there were more than seven
hundred oxygen carriers that had been synthesized and studied to work in
this process [14]. Recent oxygen carrier designs are composed of two main
parts; the primary oxide and the inert support. Oxides of Fe, Ni, Cu, Mn,
Co and Ti have been proposed as candidates for primary oxides [7].
Furthermore, other processes have used the concept of CLPO and
examples of these are: Ni-and Co-based carriers for pure hydrogen
production developed by Svoboda et al. [18] the fluidized bed reactor using
NiO on α-Al2O3 as oxygen carrier proposed by Diego et al. [19] and the
three-reactor scheme (TRCL) projected by Kang et al. [20]. Examining
recent CLPO studies, the syngas chemical looping process research by Fan
et al. [21] using oxygen carriers based on Fe, Ni, and Ce is one of the most
significant research. Their results show a syngas (CO + H2) purity of more
than 90%, which was obtained with Ni and Fe based oxygen carriers.
However, at those conditions carbon formation over the surface of these
materials, as well as carbides (Fe3C) were found. Other proposed metals
have avoided carbon deposition during their cycle reaction operation, but
have limited the conversion of methane, thus reducing the production of
syngas.
There exist many drawbacks with use of single metals oxides, like
thermodynamics and reaction kinetics limitations. In order to solve these,
binary metal oxides were proposed to enhance the kinetics and
thermodynamics of the process, as well as the selectivity of the oxygen
carriers for syngas production. Several examples can be found in the
literature, like mixed metal ferrites studied by Aston et al. [22] who found
a 99% yield towards H2, while the re-oxidation of the oxygen carrier was
confirmed. Results were compared with a single iron oxide and the mixed
metal spinnels showed a higher extent of reduction under the same reaction
conditions, which produced more H2 than the single iron oxide material
(Fe2O3). The Fe-Mn oxides were studied by Lambert et al. [16] for the
chemical looping combustion process, showing a fast reduction of
(Mn,Fe)2O3 to MnO and Feo proving that the Fe-based binary oxides are an
excellent proposal for the POX-MeO process due to their re-oxidation
feasibility, while being a low-cost material. Because of these important
features, in the present research it was decided to study, from a
thermodynamics point of view, Fe-based binary oxides (FeMO4, M = Mn,
Mo, Zn) that are expected to provide high methane conversions towards
syngas production, while providing chemical activity and high temperature
stability as oxygen carriers for the CLPO of methane. Furthermore, the
proposed Fe-based oxygen carriers (FeMO4) are expected to follow the
following reactions:
4CH4 + FeMO4 → 8H2(g) + 4CO(g) + Fe + M (5)
CH4(g) + FeMO4 →2H2O(g) + CO2(g) + Fe +M (6)
CH4(g) →C + 2H2(g) (7a)
2CO(g) →C + CO2(g) (7b)
4H2O(g) + Fe + M →FeMO4 + 4H2(g) (8)
C + H2O (g) →H2(g) + CO(g) (9a)
C + 2H2O(g) →2H2(g) + CO2(g) (9b)
Reaction 5 produces syngas (H2 + CO) along with the reduced metallic
species Fe and M, while reaction 6 shows the complete oxidation of
methane to produce CO2 and H2O. Under these conditions other reactions
may arise such as methane decomposition and Boudard’s reactions,
reactions 7a and 7b, respectively. These reactions produce coal which is an
undesirable product. The re-oxidation of the reduced metallic species is
described by reaction 8 to produce the original FeMO4 and H2. Coal
gasification may simultaneously occur in the re-oxidation stage, which are
reactions 9a and 9b, leading to hydrogen production and carbon oxide
species (CO and CO2). Due to the reported reaction behavior of Ni and Co
ferrites as oxygen carriers during the syngas production and the re-
oxidation of their reduced species (Fe and Mn) it makes this reaction
concept very attractive to be evaluated using similar mixed metal oxides,
such as; Fe2MnO4, FeMoO4 and Fe2ZnO4 under a CLPO reaction scheme.
The aim of the present work is to evaluate the thermodynamic
feasibility of Fe2MnO4, FeMoO4 and Fe2ZnO4 metal oxides under the
CLPO reaction scheme. This will employ the use of thermodynamic
analyses and process simulation for the production of syngas. For the case
of the thermodynamic analyses, these will consist in calculations of every
possible reaction involved in the process to determine feasible operating
conditions being; temperature, CH4/FeMO4 molar feed ratio in the fuel
reactor, while for the oxidation reactor will be temperature and steam/Fe-
M feed molar ratio. Process simulations will employ the Aspen Plus©
process simulator, which will focus in determining process material and
energy balances as well as optimal operating conditions in both reactors
and in the entire process. Simulation results will be used to evaluate the
thermal efficiency of the overall process and H2 and syngas yields to
compare them with similar current CLPO processes previously reported in
the literature to evaluate the potential of the proposed oxygen carriers and
technology.
2. METHODOLOGY
2.1. Thermodynamic Analysis
Each reaction was studied in terms of the Gibbs free energy as a

function of temperature. Calculations of equilibrium concentrations in the
CLPO for FexMO4 oxygen carriers (M = Mn, Mo, Zn) were performed
using the RGIBBS reactor model of Aspen Plus©. Since this reactor makes
use of a method based on the Gibbs free energy minimization technique,
which includes all possible reactions that take place according to the
compounds and phases present in the reaction system. For this method it is
necessary to define all the compounds that will be involved in the reaction.
Therefore, the following gaseous compounds were defined: CH4(g), CO(g),
CO2(g), H2(g), Zn and H2O(g), while for the solid compounds were
included: C, Fe2MnO4, Fe2ZnO4, FeMoO4, MnO2, MnO, Mn, ZnO, Zn,
MoO3, MoO2, MoO, Mo and Fe. The aim of this thermodynamic analysis
is to evaluate the feasibility of the binary metal oxides in the reaction
scheme, using the process flowsheet shown in Figure 2.
Figure 2. Flowsheet for the thermodynamic analysis.
2.2. Process Simulation
The simulation was performed using Aspen Plus© and was

concentrated on determining the material and energy balance of the process
and finding the optimal operating conditions for each reactor. In this
process simulation, the variables studied were: reactor temperature, which
varied from 100-1000°C at 1 atm, the FeMO4 molar feed which varied
from 1 to 3 kmol/h. Whereas, in the oxidation reactor the molar flow of
H2O was studied from 2 to 9 kmol/h in a temperature range of 100-1000°C
at atmospheric conductions.
Simulation parameters employed were: a thermodynamic system based
on the Redlich-Kwong-Aspen equation of state (EOS) to calculate the
physical properties of the chemical compounds involved. The molar feed
flow of CH4 was fixed at 4 kmol/h, in addition to search for the conditions
where coal formation is not allowed.
Once the process units were established several sensitivity analyses
were performed to obtain the optimal operating conditions for the process,
while finding the highest yield towards syngas (fuel reactor) and hydrogen
(oxidation reactor) while simultaneously avoiding carbon formation in the
fuel reactor. The first sensitivity analysis was performed in the fuel reactor
aiming to find the CH4/FeMO4 molar feed ratio and the operating
temperature where the highest yield towards syngas while simultaneously
avoiding any carbon formation. The second sensitivity analysis was
performed in the oxidation reactor aiming the complete regeneration of
FeMO4 and the highest yield of pure hydrogen production.
2.3. Syngas Yield and Thermal Efficiency
The thermal energy efficiency was evaluated using equation (10)

proposed by Abbott et al. [23], which is based on the first law of
thermodynamics and is defined as the ratio between the energy produced
(H2 + CO) and the energy input (CH4).
𝑚̇𝑖 ×𝐿𝐻𝑉𝑖
𝜂= (10)
𝑚̇𝑖 ×𝐿𝐻𝑉𝑖 +𝑊𝑖 +𝑞𝑖
where mi and LHVi are the mass flow and the lower heating value of the “i”
species, respectively, while Wi and qi are the mechanical work and the
required heat of the components “i,” respectively. This latter refers mainly
to the mechanical work and energy requirements of the equipment
involved in the process to be evaluated. The mechanical work were not
taken into account because it is out of the scope of the present work and
the energy requirements are automatically calculated. Fuerthermore, the
thermal effienciency was calculated according to the following expression:
𝑚̇𝐻2 × 𝐿𝐻𝑉𝐻2 + 𝑚̇𝐶𝑂 × 𝐿𝐻𝑉𝐶𝑂

𝜂= (11)
𝑚̇𝐶𝐻4 × 𝐿𝐻𝑉𝐶𝐻4 +𝑞𝑖
Table 1. HHV and LHV of process species
Fuel HHV(MJ/kg) LHV(MJ/kg)

Hydrogen 142.2 121.2
Carbon monoxide 10.1 10.1
Methane 55.5 50.0
The thermal efficiency can be calculated using the high caloric value
(HHV) to obtain an suitable range of thermal efficiency. Table 1 shows the
LHV and HHV of the species of interest involved in the process.
Moreover, the yield to syngas was calculated from simulation results
as a the mean yield of H2 and CO, according to the following expression:
𝑌𝐻2 +𝑌𝐶𝑂
𝑌𝑠𝑦𝑛𝑔𝑎𝑠 = 2
∗ 100 (12)
Furthermore, to reduce energy costs a Pinch Analysis was performed

using heat exchangers from Aspen Plus©, in order to take advantage of the
temperature gradients between products and reactants involved in the
process.
Figure 3. Process Simulation Flowsheet.
The CLPO process for the oxygen carriers scheme is shown in

Figure 3. The aim of the pinch analysis was to optimize the thermal
efficiency of the process. In order to achieve this, heat exchangers were
strategically placed where product streams, GAS-1 and GAS-2, were
allowed to exchange heat with the feed streams (methane) to be preheated
and to generate steam (STEAM and CH4-PRH streams). Also, in Figure 3

details of the entire process streams, recirculations and heat generation by
burners to provide energy to reactors, stream splits and separation of gases
from solids (cyclone separators) are presented.
3. RESULTS AND DISCUSSION
3.1. Thermodynamic Analysis
Figure 4 presents the thermodynamic analysis of the process variables,

showing the process operating area where the target conditions are
achieved; no carbon formation and full oxygen carrier regeneration.
Results of the thermodynamic analyzes indicate that the widest area for
free carbon operation condition belongs to Fe2ZnO4 followed by FeMoO4
and Fe2MnO4. In the case of the regeneration area, the largest one belongs
to Fe2MnO4, followed by Fe2ZnO4, while complete oxidation for FeMoO4
is not possible when using this oxygen carrier for the process. Therefore,
according to results presented in Figure 4 it can be concluded that FeMoO4
can be discarded as a possible oxygen carrier for the proposed process,
since it cannot be completely oxidized under the studied conditions.
Although, Fe2ZnO4 presents the largest operating area of without carbon
formation, its regeneration area is very small, thus limiting the conditions
of the oxidation reactor to temperatures below 400°C and feed H2O ≤ 9
kmol/h. Furthermore, this temperature is too low for a relatively fast
desired reaction kinetics, whereas, a high amount of steam used increases
energy costs, not very convenient process conditions. On the other hand,
Fe2MnO4 shows a fairly good carbon-free operating area, with conditions
of temperatures greater than 620°C and feed Fe2MnO4 > 1.4 kmol/h, which
comply with a presumably fast desired reaction kinetics. For the case of the
oxidation reactor, there is a good range of temperatures and feed molar
flowrates of H2O where complete regeneration can be obtained, making it
possible to achieve suitable conditions for the entire process.
Figure 4. Free-carbon operation area in fuel reactor (a) and full oxygen carrier
oxidation area in oxidation reactor (b).
As a result of the thermodynamic analysis it can be concluded that the

only oxygen carrier that meets the previously established requirements for
the CLPO of methane process is Fe2MnO4. Therefore, the process
simulation was performed only for the Fe2MnO4 oxygen carrier, and this is
presented in the following section.
3.2. Process Simulation
Simulation of the process was performed in two stages. In the first

stage, the optimal parameters of each reactor were found by sensitivity
analyses and results of the previous thermodynamic analysis. In the second
stage, an optimal energy balance was achieved through an energy
sensitivity analysis (Pinch Analysis) by adding heat exchangers between
the input and output streams, thus obtaining the final simulation scheme
presented in Figure 3. Since, the avoidance of carbon formation in the fuel
reactor is one of the main objectives of the present simulation, a sensitivity
analysis was carried out to study the variations presented as a function of
the operating temperature and the molar feed to the POX-MeO reactor
(fuel reactor).
Figure 5. Surface response of H2(a) and C(b) formation in POX-MeO reactor.
Figure 5a presents results of the sensitivity analysis on the production

of hydrogen, which show a greater production of hydrogen at temperatures
greater than 600°C, and an increase of hydrogen generation as the feed of
Fe2MnO4 decreased towards values around 1-1.5 kmol/h), while the locus
of greatest hydrogen production (H2 = 7.89 kmol/h) occurs at conditions of
T = 1000°C and Fe2MnO4 = 1 kmol/h.
Furthermore, Figure 5b shows results of the sensitivity analysis on
carbon formation, where the stoichiometric methane feed of 4 kmol/h was
fixed according to the stoichiometric value in reaction 5. In this figure it
can be seen that within the POX-MeO reactor (fuel reactor) carbon free
operation can be achieved at conditions of temperatures greater than 620°C
and molar flowrates of Fe2MnO4 higher than 1.4 kmol/h.
Figure 6 presents the CO and CO2 generation as a function of
temperature and Fe2MnO4 molar feed to the fuel reactor. In Figure 6a it can
be observed that the formation of CO has a similar behavior to the
production of hydrogen, it is desirable that the molar H2/CO ratio to be
equal or greater than 2, (very convenient for the Fischer Tropsch process
feed), which can be achieved at temperatures higher than 620°C and molar
flowrates greater than 1.4 kmol/h. Results presented in Figure 6b also show
that reaction 6 is promoted at conditions of temperature equal to 620°C and
at higher oxygen carrier feed molar flowrates, while at higher temperatures
the CO2 generation decreases. Even though it is not one of the main
objectives of the present simulation, low CO2 production is encouraged.
Figure 7 presents the production of Fe and MnO as a function of
temperature and Fe2MnO4 molar feed to the fuel reactor. Figure 7a shows
the production of reduced Fe, where it is promoted at the same conditions
where no carbon formation is allowed, thus confirming that the operating
conditions for reaction 5 is to be carried out at temperatures higher than
620°C. Also, in Figure 7b the production of MnO is shown, which is a
product that does not agree with reaction 5, since at the thermodynamic
conditions studied the reduction of Fe2MnO4 was limited to the formation
of MnO because Mn generation is not favored. Here in this Figure it is also
evident that the behavior of MnO production is very similar to Fe
generation.
In order to find optimal operating conditions, a comparision of
different syngas production scenarios is presented in Table 2. In this Table
the production of H2, CO, Fe and MnO at temperatures of 650°C, 700°C,
750°C, 800°C, 850°C and 900°C were obtained at a fixed molar flowrate
of 1.63 kmol/h of Fe2MnO4. Similarly, this molar flowrate is proposed for
an operating window, where no carbon formation is possible.
Figure 6. Surface response of CO(a) and CO2 (b) formation in POX-MeO reactor.

Figure 7. Surface response of Fe(a) and MnO (b) formation in POX-MeO reactor.
Table 2. H2, CO, Fe and MnO production as a function

of temperature
Temperature (°C) H2 (kmol/hr) CO (kmol/hr) Fe (kmol/hr) MnO (kmol/hr)

650 5.31 1.61 3.2 1.6
700 6.17 2.54 3.2 1.6
750 6.84 3.33 3.2 1.6
800 7.21 3.62 3.2 1.6
850 7.36 3.69 3.2 1.6
900 7.39 3.75 3.2 1.6
When analyzing the production of hydrogen with respect to

temperature it can be noted that at 800°C and gretater temperatures there is
no considerable variation in terms of syngas generation since only a
marginal increase is presented. These extreme conditions (T > 800°C) will
ultilmately impact in the associated energy costs of the entire process.
Therefore, a temperature range of 750°C-800°C is very appropriate for the
present study. When evaluating this temperature range the temperature of
775°C was considered suitable due to the fact that the syngas generated
shows a H2/CO molar ratio of 2.03, which is very convenient for further
processsing of this gas, for example towards the Fischer Tropsch process.
Also, at these conditions Fe2MnO4 is completely reduced to Fe and MnO
according to reaction 5.

Furthermore, Figure 8 shows a contour plot of methane conversion as a

function of reactor temperature (°C) and Fe2MnO4 molar feed (kmol/h). By
analyzing these results under the proposed required conditions, a methane
conversion of 95.9% can be obtained. The 99% of methane conversion can
be achieved at higher temperatures than 800°C and higher Fe2MnO4 molar
flowrates than 2.0, but this results in a marginal increase in conversion,
compared with higher temperatures that would have to be reached at these
conditions.
Consequently, the optimal operating conditions for the fuel reactor
(POX-MeO) can be considered as T = 775°C and Fe2MnO4 = 1.6 kmol/h
feed. Finally, this is an important result since these are the conditions
where no carbon deposition is feasible and a complete reduction of
Fe2MnO4 also occurs, along with a high conversion of methane (95.9%)
and a high production of syngas (CO + H2 = 10.52 kmol/h) while
presenting a H2/CO molar ratio of 2.03, which is very convenient as
described above.
Figure 8. Contour plot of methane conversion as function of temperature

and Fe2MnO4.

Figure 9. Surface response of H2(a) and Fe2MnO4 (b) formation in REGEN reactor.
Figure 9 presents the production of H2 and Fe2MnO4 as a function of

temperature and H2O molar feed to the oxidation (regeneration) reactor.
Here, Fig 9a and 9b show the production of pure hydrogen and the
regeneration of the oxygen carrier, respectively, with respect to the molar
steam feed and the temperature of the oxidation reactor (REGEN) for the
selection of the more favorable operating conditions in the process.
In Figure 9b it can be observed that the oxidation of Fe and MnO is
feasible at very low temperatures (for example, 100°C) and a maximum H2
production of 5.19 kmol/h can be obtained. However, in order to favor the
kinetics of reaction (8), it is convenient to use temperatures above 500°C,
according to the results reported by Voldsund et al. [24]. Thus, the
optimum operating condition for the oxidation reactor can be established at
T = 500°C and a steam molar flowrate of 6.8 kmol/h resulting in a
production of Fe2MnO4 = 1.6 kmol/h and H2 = 5.19 kmol/h.
Furthermore, Table 3 presents the material and energy balance of the
process simulation where two methane burners (BURNER1 and
BURNER2) and two heat exchangers (HEATX1 and HEATEX2) were
used according to the process scheme of Figure 3. The heat exchangers
were used to preheat the methane and water feed to the process using the
product gas streams of each reactor (GAS-1 and GAS-2). Methane is
preheated and reaches a separator (S1) where it is divided into two streams,
one for the reactor feed of 4 kmol/h (CH4-RXN stream) and the other

stream for the burners, which will reach another separator (S2) to feed each
burner (streams B1 and B2).
In order to achieve a temperature of approximately 775°C in the POX-
MeO reactor, it is necessary that the BURNER1 generates a heat of 987.73
MJ/h (Q1). Similarly, for the REGEN reactor to reach a temperature of
approximately 500°C, the BURNER2 is required to generate a heat of
192.35 MJ/h (Q2).
Furthermore, methane was used as fuel combined with air to reach the
required temperature in both reactors, these parameters were established by
sensitivity analysis, once obtained for optimum parameters the results of
the mass balance was found and results are reported in Table 3.
Table 3 shows the products of the POX-MeO reactor, with a H2
production of 7.05 kmol/h, together with 3.47 kmol/h, 0.38 kmol/h and
0.65 kmol/h of CO, CO2 and H2O, respectively. Finally, it is observed 0.15
kmol/h of unreacted methane in the final syngas product stream. On the
other hand, in the solids stream, a complete reduction of Fe2MnO4 was
achieved where 1.63 kmol/h of MnO and 3.2 kmol/h of Fe were reached.
Otherwise, results of the REGEN reactor consisted of a complete
regeneration of Fe2MnO4, with a flowrate of 1.63 kmol/h, which was
recirculated back to the POX-MeO reactor. In the case of hydrogen, 4.89
kmol/h was obtained, together with 1.91 kmol/h of H2O (GAS-2).
Reported results of a typical steam methane reforming process (SMR)
are approximately 75% H2, 12% CO, 6% CO2, and 7% CH4, while results
obtained by the POX-MeO process of the present study are 60% H2, 30 %
CO, 6% H2O, 3% CO2 and 1% CH4. Although, the POX-MeO achieves a
lower mole fraction of H2 compared with steam reforming the POX
process is more oriented for the production of syngas, while the SMR
process is concentrated towards the production of hydrogen. Furthermore,
POX-MeO generates a greater conversion of methane and syngas with less
impurities than SMR. These results can also be compared with a similar
CLPO processes, but employing Ni-based oxygen carriers, which obtained
a dry gas product composition of 65% H2, 25% CO, 9% CO2 and 1% CH4
[19]. These results are similar, but it can be noticed that the H2/CO molar

ratio of the referenced process is less than 2, which is not a convenient

feature for a syngas.
Furthermore, a comparison with other reported studies, the use of a
binary oxides as oxygen carriers greatly helps to reduce the temperature
operating conditions, since reported operating temperatures for the POX-
MeO reactor using only Fe3O4 as oxygen carrier can reach temperatures
equal or greater than 1500°C [21]. Therefore, results reported in the
present work represent an important improvement for this process.
Table 3. Simulation results for the production of syngas

from CH4 and Fe2MnO4
3.3. Thermal Efficiency
The thermal efficiency was calculated as previously indicated in the

methodology section using the equation (10) and resulting in a theoretical
thermal efficiency that varied between 88.7% by using LHV and 92.8%
employing values of HHV.
In direct comparison with the efficiency of the SMR process (70-85%),
the current process of CLPO, the POX-MeO using Fe2MnO4 as oxygen
carrier, the efficiency of the process is between 3.7-22.8% higher and this
can be attributed entirely to the hydrogen generated in the regeneration

stage, which makes the H2/fuel molar ratio higher than 2.0, hence
producing a higher thermal efficiency.
3.4. Process Yield
According to the results of the mass balance, shown in Table 3. The

theoretical yield obtained towards the synthesis gas was calculated by the
procedure described above. In addition, the molar ratio of H2/fuel and
H2/CO were calculated and compared with other chemical looping
processes reported in literature. This comparison is shown in Table 4.
In this Table it is evident that the proposed POX-MeO process using
Fe2MnO4 as oxygen carrier is able to achieve greater thermal efficiencies
than the SMR [25], the autothermal reforming (ATR) [26] and the current
partial oxidation (POX) processes [19].
Table 4. Thermal Efficiency of the POX-MeO with other processes
Process Thermal efficiency

SMR [25] 70-85%
ATR [26] 60-75%
POX [19] 60-75%
POX-MeO (Fe2MnO4) 88.7-92.8%
Table 5. Comparison of the POX-MeO process

with respect other similar CL processes
Process H2/Fuel molar ratio YSyngas (%) H2/CO molar ratio

SMR [25] 1.47 86.7 3.0-5.0
ATR [26] 2.91 61 1.6-2.6
POX [19] 2.5 67 2.6
POX-MeO (Fe2MnO4) 2.98 87.4 2.03-3.44

Furthermore, Table 5 presents a comparison of the obtained results of

the POX-MeO process using Fe2MnO4 as oxygen carrier with respect to
other processes for syngas production reported in the literature. Here, in
this Table it is evident that the present CLPO (POX-MeO) compared to a
SMR process [25] produced twice more H2 for each mole of CH4 being
fed. This is mainly attributed to the H2 produced in the regeneration of
Fe2MnO4 with steam. Additionally, Fe2MnO4 has proven to be a
convenient oxygen carrier since, compared to the results reported by de
Diego et al. [19] Fe2MnO4 is able to achieve a 20% yield and a H2/fuel
molar ratio of 0.5, which is higher than those reported for Ni-based oxygen
carriers. The H2/fuel ratio obtained for the POX-MeO process obtained in
the present research is close to that reported for the autothermal methane
process (ATR) by De Souza et al. [26] with only a difference of 0.07,
whereas the POX-MeO process achieved a greater methane conversion.
CONCLUSION
FeMoO4, Fe2ZnO4, Fe2MnO4 as iron-based oxygen carriers were

evaluated by thermodynamic analyses and process simulations for the
production of hydrogen-synthesis gas (syngas) using Aspen Plus®.
According to the thermodynamic analysis, it can be concluded that
Fe2MnO4 is the best oxygen carrier among the Fe-based studied materials
for the production of H2 and syngas. Simulation results found optimal
reaction conditions to carry out the POX-MeO process. Optimum
temperature in the fuel reactor was 775°C and simultaneously obtaining a
methane conversion of 95.9% without carbon formation. While the
temperature for the oxidation reactor was established at 501°C for a
complete regeneration of the oxygen carrier, in addition to a production
stream of pure hydrogen. Furthermore, these results show a syngas stream
with a H2/CO molar ratio of 2.03 from the POX-MeO reactor and high
purity hydrogen stream from the REGEN reactor. The thermal efficiency
achieved under these conditions was in the range of 88.7-92.8% and a
syngas yield of 87.4%, which are higher compared to other conventional

syngas production processes reported in the literature. Finally, an

experimental evaluation of the present process is recommended, to assess
the results obtained and the viability of this process proposed in the present
research.
ACKNOWLEDGMENTS
The authors are thankful to Centro de Investigacion en Materiales

Avanzados, S. C., and Instituto Politecnico Nacional, ESIQIE for their
support in the use of the facilities. Furthermore, to the SMH and XVIII
International Congress of the Mexican Hydrogen Society for the
fellowship to present this research.
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[12] Sanusi, S. Y., M. A. Esmail Mokheimer, M. A. Habib., Thermo-
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[25] Sunny, P A., A. Solomon, K. Aparna., Syngas Production from

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Reviewed by:
Dra. Rosa de Guadalupe González Huerta

ESIQIE-IPN, México
Alternate Energy Laboratory
E-mail: rosgonzalez_h@yahoo.com.mx.
Dr. Miguel Escobedo Bretado

Universidad Juárez del Estado de Durango (UJED), México
Facultad de Ciencias Químicas
E-mail: miguel.escobedo@ujed.mx.

Chapter 7
DEVELOPMENT OF ROTATIONAL DEVICE

IN MAGNETRON SPUTTERING SYSTEM
FOR CIVIL CONSTRUCTION AND ELECTRIC
POWER DISTRIBUTION
SECTORS APPLICATION
Maurício Marlon Mazur1-3,*, Sidnei Antonio Pianaro2,

Kleber Franke Portella3,
Mariana d´Orey Gaivão Portella Bragança3,
Emerson Luís Alberti4 and Viviane Teleginski Mazur1
1
Federal University of Technology – Paraná – Guarapuava – Brazil
2
State University of Ponta Grossa – Ponta Grossa – Brazil
3
Lactec – Curitiba – Brazil
4
Elejor S.A. – Curitiba – Brazil
*
Corresponding Author’s E-mail: mzmauricio@hotmail.com.

202 Maurício Marlon Mazur, Sidnei Antonio Pianaro et al.
ABSTRACT
Contaminants from harmful gases and natural agents are the main
source of chloride ions and sulfates, which promote deleterious chemical
reactions to civil and energy sector structures. In the civil sector, the main
agent of degradation is the alkali-aggregate reaction (AAR), which
propagates micro cracks and reduces the lifetime of Portland cement
structures. Some papers present alternatives to reduce AAR deleterious
effects with additions of pozzolanic materials, nano-Fe3O4 and nano-
TiO2. In the electricity sector, the contaminants are responsible for
increasing the so-called surface leakage currents on the electrical
insulator, whose intensity may cause the device to fail in service. To
minimize the effects of leakage current, titanium, aluminum nitride and
hafnium oxide thin films were applied to ceramic electrical insulators to
promote surface self-cleaning properties. In this sense, a multifunction
rotational system was developed for deposition of titanium thin films.
The results obtained from the deposition process of nanostructured
titanium or thin films by the technique of magnetron sputtering plasma
proved to be favorable for both applications, namely, the reduction of the
AAR in concrete structures and reduction of the leakage current and
formation of hydrophobic films with self-cleaning characteristics in
porcelain electrical insulators.
Keywords: Alkali-Aggregate Reaction (AAR), contaminants, magnetron

sputtering, electrical ceramics insulators, rotational system
1. INTRODUCTION
This chapter of the book presents the development of a rotational

system and two innovative applications of pulsed plasma magnetron
sputtering technology (PMS). The PMS technology is widely used for
deposition of thin, micro and nanometric films, in laboratory assembled
systems as in industrial scale. The thin films deposited through the
technique have several benefits such as: deposition rate control as well as
crystallinity, roughness and adhesion [1]. The magnetron sputtering
systems that only have one target as a source, deposit films in a directional
way, making impossible the substrates of complex geometry deposition.

Development of Rotational Device in Magnetron Sputtering System … 203
Two alternatives to overcome this deficiency of the system were reported

in the literature, being able to increase the amount of magnetrons per
exposed area or to rotate the samples inside the reactor [2]. In this work,
two technological applications of PMS were performed by using a self-
developed rotational system. At first, thin films of titanium were deposited
in coarse aggregates of basaltic origin, used in civil construction for the
manufacture of concrete; secondly, the same film was deposited in
porcelain electrical insulators to be used in the energy transmission sector,
which are subject to deleterious effects by natural and/or artificial
contaminants.
1.1. Civil Construction Aggregates
The alkali-aggregate reactions (AAR) are formed by alkaline

hydroxides in the concrete, originating from silicates at certain rock types
or from aggregates with potential reactivity. Many of the pollutants are
responsible for the chemical process of AAR formation, mainly in which
Na+ and K+ participation is highlighted, causing, by their nature,
volumetric gaining reactions. The product of these reactions is an
amorphous silicate with the characteristics of a hygroscopic gel, whose
expansion disseminates cracks in the cementitious matrix and in the
aggregate, resulting in a surface and structural map-like form [3-5].
Sanchez [6] has his work commenting the need for development and
application of nanotechnology to alter the electrical, mechanical and
thermal characteristics in concrete, seeking to mitigate the degradation of
civil structures. According to Bragança [7], the addition of 1% nano-Fe3O4
in early stage concrete reduces water absorption as well as void indices,
conferring less susceptibility to corrosion and greater electrochemical
stability. In this line of research, the mitigation of the alkali-aggregate
reaction, from obtaining nanomaterials with the PMS technique, in the
form of continuous or discontinuous thin films, was previously published
by Portella et al. [8].

1.2. Electricity Sector Substrates
In the electricity sector, the insulators are elements of fundamental

importance to give mechanical and dielectric support to transmission
wiring at most diverse voltage ranges. These devices are installed in
regions subject to various contaminants, for example: sea air, responsible
for precipitating salts [9]; industries, with possible acidic or basic
pollutants, soot and alkaline ions; sand, which causes leaching and
accumulates on the insulator surface [10]; and organic material, derived
from bird excrements, microorganisms and marine microalgae [11-12].
The presence of contaminants leads to the formation of a layer of low
resistivity on the surface of the dielectric, causing an increase in leakage
current, the intensity of which may cause the isolator to fail in service,
interrupting power supply, increasing transmission cost and producing
ceramic residues from the insulator disposal [13].
Regardless of their nature, the above mentioned contaminants are the
main cause of failure in the power transmission system. One way to reduce
the deleterious effects of contaminants in the materials used by the
electrical sector is to obtain surfaces with a self-cleansing effect, with
hydrophobic characteristics.
Several techniques are used for the production of films and structures
on the surfaces, such as sol-gel, dip coating, laser, chemical vapor
deposition (CVD), physical vapor deposition (PVD) among others [14].
Ramalla et al. [15], inspired by the lotus flower effect, with the objective of
obtaining super-hydrophobic surfaces, coatered electrical insulators with
silicon-based films, using the sol-gel technique. The obtained hydrophobic
property reduced adhesion effects of several contaminants, when compared
to electrical insulators without the film. The nanostructured thin films of
hafnium oxide deposited by Dave et al. [16-17] also stands out, which used
the magnetron sputtering plasma technique as a way of generating a new
surface with hydrophobic and self-cleaning characteristics in glass
insulators. Mazur et al. [18] obtained thin films of aluminum nitride with
hydrophobic characteristics, deposited in porcelain electrical insulators by

the PMS technique. The films presented contact angle of 80° and electrical
resistivity of the same order of magnitude than original insulators.
1.3. The Plasma Technology
Technological plasmas, used in industries and laboratories, have high

power and energy density. Among the benefits of plasma processing are
the low energy consumption, the reduction or extinction of toxic gases
and/or byproducts, reduction of the raw material volume required in
surface treatments and reduction of end product price [19].
Diverse energy sources can be used in plasma processing such as
microwave, radio frequency (RF), hollow cathode, arc vapor, direct
current, alternate current, including the use of magnetron sputtering and the
possibilities which combine different sources. For the generation of
plasma, there is a need for the electrons to gain enough energy to generate
collisions in the atoms and molecules to ionize them. Of the reactions that
occur in plasma, the most important ones include ionization (e- + X → X+
+ e-); molecular dissociation (e- + XY → X + Y + e-); excitation (e- + X →
X * + e-); and recombination (X * + e- → X). These reactions provide ions
from working gases, such as inert gases (Ar, He) or reactive (O2), precursor
gases (SF6), by molecular and metal decomposition for the formation of
films or etching for surface cleaning. Magnetron sputtering systems are
widely used due to the possibility of forming films in large areas. The
generated ions are confined and accelerated against a target inside a
magnetic field from permanent magnets. The target is the material to be
deposited, generating derangement, ejection of its atoms and its consequent
deposition in specific conditions, in a directional way throughout the
reactor [20].
Due to the directionality of the deposition, in this work a rotational
system was developed for the adaptation of the magnetron sputtering
plasma technique for the application in the civil construction and electrical
power sectors. In the civil construction it was studied the deposition of
titanium thin films in reactive coarse aggregates, added to the Portland

cement in order to mitigate the AAR. In the electrical power sector the
application of the same film in porcelain electrical insulators, started from
the hypothesis of promoting the formation of self-cleaning surfaces, to
reduce the intensity of leakage current effects.
2. MATERIALS AND METHODS
In this item, it is presented the methodology for preparation of basaltic

aggregates for civil construction and ceramic electrical insulators, the
conditions for the deposition process of titanium thin films and the
characterization techniques.
2.1. Preparation of Basaltic Coarse Aggregates for

Civil Construction
Coarse aggregates of basaltic origin, from a deposit in southern Brazil,

in the city of Candói - PR, were used as substrates. For this, they were
crushed with an average diameter of 4.8 mm (± 0.5). The substrates, as
shown in Figure 1, were washed in running water, kept in a drying oven at
65 °C, until usage. This procedure ensured reduction of dust and moisture
particles, enhancing vacuum generation inside of the reactor [22]. 300 g of
substrates were used for each deposition.
Figure 1. Substrates of coarse aggregates of basaltic origin used for PMS coating with
titanium film.

Figure 2. (a) Trapezoidal substrate cut for parameterization of depositions and

(b) prototype of commercial ceramic electrical insulator.
2.2. Preparation of Ceramic Electrical Insulators
In order to carry out the parametrizations of the deposition process,

trapezoidal substrates (Figure 2, a) were cut from a pillar type ceramic
insulator (Figure 2, b) available commercially of the CST brand. After
defining suitable parameters, a full prototype was prepared for deposition,
using the developed rotational system. The trapezoidal substrates and the
prototype were cleaned with acetone and isopropyl alcohol, remaining in a
drying oven at 65 °C until usage.
2.3. Plasma System and Deposition Conditions
The plasma system consists of PIREX glass and aeronautical

aluminum, containing a total reactor volume of 28 l. The opening port of
the reactor is longitudinal drawer type, with VITON hermetic seals. The
vacuum is obtained by means of two pumps, one mechanic, responsible for

generating a pre-vacuum, and a diffusion pump for its completion, both of

the EDWARDS brand. The pump set reaches vacuum pressure below 10-5
mbar. After generating the vacuum up to 10-5 mbar, the pressure was
stabilized with the working gas at a pressure of 10-3 mbar, which is the
ideal pressure for deposition of titanium films [18, 22]. Argon was used as
inert working gas to produce high deposition rates, with constant flow of 2
sccm managed by a Emiatec SFM5000 precision measuring system. The
power supply employed was of pulsed continuous current type [18, 22].
The working voltage was 800 kV with 1.3 Apk current and duty cycle of
50%. The titanium target (purity 99.999%), with dimensions of 80 x 245
mm was placed in a balance magnetron sputtering system. The plasma
system can be visualized in Figure 3, where its main constituents are
indicated: plasma reactor (i); magnetron device (ii); substrates holders (iii);
pressure indicator (iv); work gas inlet valve (v); reactor opening door,
drawer type (vi).
Figure 3. Plasma reactor adapted for the rotational system (i); magnetron device (ii);
substrate holder (iii); pressure indicator (iv); work gas inlet valve (v); reactor opening
port (vi).

The exposition time of the basaltic aggregates to the Ar plasma with

titanium target was of 300 s. For the electric insulator trapezoidal
substrates, the deposition time was 10, 20, 30, 40, 50, 60, 120, 180, 240 e
300 s. After the deposition of the films on the substrates of electrical
insulators, annealing was performed at 400 °C for 30 min with a heating
rate of 10 °C.min-1.
2.4. Substrate Characterization
The wettability characteristics of the basaltic aggregate samples and

electrical insulators were evaluated according to the recommendations of
IEC 62073 and ASTM D7334 [24, 25]. The testing procedure was
performed at 23 °C (± 2) using a spray bottle to produce a fine spray of
distilled water, with a conductivity of 10 μS.cm-1. The spray was applied to
the sample surface at a distance of 25 cm (± 10) for 20 s. The region of
analysis was a rectangle with a length and width ratio of 1:3. The contact
angle of the droplets that formed on the surface were measured using an
optical zoom camera positioned parallel to the solid/liquid/air interfaces.
The morphological characteristics of the deposited films were analyzed
in a MIRA 3LM model, FEG-SEM, TESCAN electronic microscope. The
equipment has EDS and EBSD system, both of Oxford/HKL. For EDS and
EBSD data acquisition and processing, a suite of integrated applications
was used in the Oxford Aztec 3.1/Channel 5 platform. The Raman
scattering spectroscopy technique also was used, with Bruker Senterra
brand equipment, with wavelength laser of 532 nm and 20 mW of power.
For the ceramic electrical insulators deposited films, before and after
the annealing at 400 °C, the technique of four point probe sheet resistivity
analysis was performed with JANDEL equipment, universal model Probe,
in ambient conditions.

2.5. Aggregates Reactivity Characterization - Prototype Testing
Reactivity and expansion tests were performed, following the ABNT-

NBR 15577 standard [20]. Coarse basaltic aggregates with the titanium
film were used to shape prismatic bars adapted for this standardized
method. This procedure was also adopted for in natura samples, without
deposition, submitted to the same procedure of crushing, cleaning and oven
time, validating the employed technique and the results obtained, which
were the average of three prismatic specimens [8, 21].
2.6. Ceramic Electric Insulators Leakage Current

Characterization - Prototype Testing
The electric leakage current test was carried out at the prototype of a
ceramic electrical insulator, according to NBR 15122/2013 [23], in which
the test method is prescribed for nominal voltages above 1000 V. The
prototype was developed with the deposited titanium film in conditions
that presented less wettability and higher value of electrical resistivity,
when measured by the four points probe technique. The same trial was
performed on control electrical insulators, without film deposition,
subjected to the same cleaning and oven time procedure.
3. RESULTS
3.1. Development of the Rotational System

in Vacuum Environment
The rotational system was fabricated with commercial aluminum alloy

6351-T6. The rectangular base shown in Figure 4 (a) contains fittings for
four bearings, holding two rollers. The rollers are attached using smooth
belts at their ends. GBR-Z809 bearings were disassembled by removing

protective shields and the lubricant was replaced with vacuum grease. The
rectangular base was fixed to the reactor port using AISI 304 M6 x 10 mm
stainless steel screws. The screws were machined with a groove
perpendicular to the thread, preventing the formation of virtual leaks. The
drive motor was positioned outside the reactor. A pair of synchronized
pulleys drives the motion to one of the rollers. The shaft connecting the
drive pulley to the engine passes through a hole in the reactor port, where
an o-ring was used to prevent leaks.
The multifunctionality of the rotational system allowed deposition in
both the pillar or pin types electric insulator and the coarse basaltic
aggregates, which were placed inside a hollowed cylindrical support.
Figure 4 (c) shows the electric insulator and Figure 4 (d) shows the
hollowed cylindrical support, both positioned at the rotational system. The
hollowed cylindrical support was manufactured with a polymer frame with
dimensions of 295 x 220 mm. An aluminum screen with 5.5 mm aperture
was coupled to support another screen with 1 mm openings to ensure that
the substrates of coarse basaltic aggregates tipped over when the device
was activated, allowing full surface deposition on the aggregates. The
polymeric cylinder fitted below the magnetron isolates the anode from the
cathode avoiding undesired electrical discharges generation during the
deposition process.
3.2. Results Obtained with Titanium Deposition over

Aggregate - Reactivity
The reactivity results of plasma-treated basaltic aggregates were

reported by Portella et al. [8]. Expansion tests were carried out for 30 days
in accordance with NBR 15577 [21] with a maximum expansion limit of
0.19% (Figure 5). The substrates with titanium film presented (0.160 ±
0.001)%, whereas the in natura aggregates, without deposition, presented
an average expansion of (0,77 ± 0,03)%, that is, four times larger values
than presented for the substrates with titanium film. Comparing the
presented results, it was observed that the substrate in natura exceeded the

normalized limit of 0.2% in 4 days of testing, while the substrates with the
titanium film kept below this limit for 30 days [8].
Figure 4. System with rectangular support and rotational rollers (a); set fitted on the
door of the plasma reactor (b); assembly for the deposition in ceramic electrical
insulator (c) and a case for basaltic aggregates (d).
1,00
0,95
0,90
0,85
0,80
0,75
Expansion result (%)
0,70
0,65
0,60
0,55
0,50 In nature
0,45 Nano titanium
0,40
0,35
0,30
0,25 Normative limit value = 0,19 %
0,20
0,15
0,10
0,05
0,00
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
Time (days)
Figure 5. Expansion results from the accelerated AAR test [8, 21], for the reference
aggregate and treated aggregate with DC plasma magnetron sputtering with Ti targets.

3.3. Obtained Results with Deposition of Titanium over

Aggregate-Wettability
The wettability of basaltic aggregates substrates was altered due to the

deposition of titanium film. The substrates in natura solely with argon
treatment present a contact angle of (40 ± 2)° as the substrates with
titanium film had angles of (79 ± 2)° for the water droplets over the
aggregates. The possible mitigation of AAR by the employed technique
may also be a consequence of the preferential bonding of the deposited
titanium with silica or silicates of the aggregate surface. In addition, as
sustained by results of the wettability test, the films increased the
hydrophobicity degree of the interface, preventing the primary or
secondary chemical bonds between the mineral phases of the aggregates
with the alkali or hydroxyl present in the hydrated phase of the cement [8].
3.4. Obtained Results with Titanium over Aggregate Deposition -

Raman Spectroscopy
The Raman spectroscopy results for the in natura aggregate indicated

the anorthite mineral chemical phase [8, 26, 27], as shown in Figure 6. In
the broad band formed in 100 cm-1, indicated in the anorthite spectrum, the
vitreous phases were attributed to aluminosilicates within the feldspar
structure, with bonding vibrational modes of Si–Onb (Onb: atoms without
oxygen bridges) [8, 26]. This behavior is typical of less polymerized
silicates. For comparison, the spectrum for titanium anatase phase [28] was
shown in Figure 6 and the deposited film. Due to the wide bands obtained
in the spectrum and the absence of defined peaks, it was not possible to
determine the phases present in the deposited titanium film. With the
employed film deposition conditions, without the annealing process, the
production of amorphous films is indicated in the literature [29]. The
spectrum presented in Figure 6 refers to a directional deposition, where it
was possible to observe the absence of the typical anorthite bands in the
spectra, then the surface coverage of the aggregate with the thin film of

titanium was inferred. In the rotated aggregates the deposition results were
responsible for the AAR reduction [8].
3000
2500
2000 Titanium deposited

Intensity (a. u.)
1500
Titanium anatase [28]
1000
Aggregate innature
500
Anorthite [27]
0
0 100 200 300 400 500 600 700 800 900 1000 1100
-1
Raman shift (cm )
Figure 6. Raman spectroscopy for the substrates of aggregates in natura s and

deposited titanium films [8, 27-28].
Figure 7. Sheet resistivity with the four point probe technique for deposited films with
and without annealing at 400 °C, with deposition times between 10 and 300 s. Zero
deposition time indicates the commercial substrate resistivity.

3.5. Obtained Results with Deposition of Titanium on the

Trapezoidal Substrates of Ceramic Electrical Insulators
Results of four point probe sheet resistivity technique are shown in

Figure 7. Different film thicknesses were obtained by varying the exposure
time in plasma. All deposited films, without annealing, have metallic
characteristics due to reduced sheet resistivity. The gradual resistivity
reduction, observed in Figure 7, is related to the thickness and the
continuity of the films. Substrates with longer deposition time present
resistivity reduction and a consequent increase in electrical conductivity.
The films from 10 to 60 s, after annealing, presented dielectric
characteristic with resistivity higher than the equipment detection limit. For
films with times above 60 s, the sheet resistivity presented values from 20
to 800 Ω/. These results indicate that the annealing process for films with
thicknesses greater than 60 s remains conductive. Higher temperatures and
successive annealing processes may be accounted to alter the resistivity
and morphological characteristics of titanium [30]. Thus, the annealed
films with times between 10 and 60 s presented electric characteristics
compatible for the application in prototypes of commercial insulators
through the rotational system.
3.6. Morphological Results by FEG - SEM/EDS
Figure 8 (a) shows the cross section of the ceramic insulator substrate
with 40 s deposition time, annealed at 400 °C. This is a representative
substrate for all films deposited with times between 10 and 60 s and
annealed. In Figure 8 (a) it is possible to visualize the ceramic body and
the glaze, with the ceramic electrical insulator bubbles and manufacturing
process defects [31]. Figure 8 (b) presents a cross section higher
magnification, where it was possible to visualize a fracture region of the
glaze and to evaluate the film morphology with the indication of the
substrate/film interface formation. The pulsed magnetron sputtering (PMS)
deposited titanium films presented a homogeneous surface with few visible

defects. After annealing however, the structural and morphological

characteristics are altered, showing cracks resulting from films retraction,
as shown in Figure 8 (c), where the segmented film is observed.
Figure 8. FEG-SEM Micrograph, from the fracture region cross section of the titanium
films deposited with 40 s and annealed (a). Magnification of fracture region (b),
highlight of sample surface with indications of films and retractions (c).
Figure 9. Wettability result of the ceramic electrical insulator substrate (a) with contact
angles > 30°; and substrate with titanium film deposited at 20 s and annealed, with
contact angles higher than <80° [22, 31].

The wettability of a surface can be altered according to the chemical

and morphological properties, being the roughness, in nano or micrometric
scale, a fundamental factor to obtain hydrophobicity [14]. Figure 9 (a)
presents the wettability result for the original electrical insulator, where the
mean measured contact angles were less than (30 ± 3)°, indicating a
hydrophilic characteristic. All films with times up to 60 s showed contact
angle (θ) higher than 60°, indicating hydrophobic characteristics [24, 25].
Figure 9 (b) shows the wettability result for the 20 s time film, annealed at
400 °C, which is representative where the measured contact angle was (75
± 3)°. This increase in the contact angle due to the titanium film deposition
may be directly connected to the heterogeneous characteristics, these
related to the surface roughness [35], after annealing process, due to the
generation of porosity or segmented films. The combination of sheet
resistivity and wettability results, led to the time of 20 s being chosen for
application in the ceramic electrical insulator prototype.
3.7. Raman Spectroscopy Results for Titanium

Deposition on Ceramic Electrical Insulators
The Raman spectroscopy results of Figure 10 are indicated in

comparison to literature works and the deposited and annealed films.
Commercial ceramic electrical insulator EDS analisis have shown in its
chemical composition a predominance of SiO2, 58.35%; ZrO2, 24.69%;
Al2O3, 7.11%; CaO, 4.44% and other oxides below 2%. Thus, in the
Raman spectra, the vibrational modes of the zirconium silicate Zr(SiO4)
were observed in the regions of 200, 213, 224, 355, 415, 440, 975, 1006
cm-1 [32]. Zirconium is commonly used at production of glazes for
application in electrical insulators as an opacifying agent, which confers,
among other aspects, color stability [33]. Modes of anatase structure
vibration occur in approximately 144, 197, 400, 515, 519 and 640 cm-1 [28,
34]. The Raman spectroscopy analysis indicates bands both related to the
substrate material, and to the formation of titanium films. In addition, the
morphology of films containing retraction regions, where the film is

fragmented or not continuous, contributes to the overlap of bands, making

it difficult to analyze the phase composition of films. The 144 cm-1 band
was observed only for the titanium anatase phase and is also observed on
all substrates deposited and annealed. In the other bands, there is
overlapping of the anatase and zirconia silicate phases.
3.8. Commercial Electrical Insulators Leakage Current

Laboratory Analysis
For the leakage current test, prototypes of commercial electrical

insulators were used, with titanium thin films deposited through the
developed rotational system, with time of 20 s and annealed at 400 °C.
Figure 11 presents the leakage current results as a function of the
laboratory test time. In the condition of salt spray exposure, the insulator
with the titanium film presented an average reduction of 8.4% in
comparison with the insulator without deposition [34].
6000
5000
4000
60 s
Intensity (a. u.)
50 s
3000
40 s
Original
30 s
2000 20 s
10 s
1000 Anatase [28]

ZrSiO [32]
4
0
100 200 300 400 500 600 700 800 900 1000
-1
Raman shift (cm )
Figure 10. Raman spectroscopy results for the electrical insulators substrates deposited
with times between 10 and 60 s, annealed at 400 °C, compared to literature.

Figure 11. Electrical leakage current result in salt spray for ceramic electrical
insulators prototype without and with titanium thin film, deposited on time of 20 s and
annealed [18].
This reduction degree was significant in high and medium voltage

electrical networks, evidencing the importance of the hydrophobic
characteristics on the surface of ceramic electrical insulators [15-18, 22].
CONCLUSION
The development of the rotational system allowed deposition of

titanium thin films on the surface of granular and cylindrical substrates,
with complex geometry. The resulting experiments using this rotational
system made it possible to deposit films in a way to obtain hydrophobic
surfaces.
The AAR of reactive basaltic aggregates was mitigated with titanium
films, reducing the deleterious reaction by up to four times. This reduction
was attributed to the wettability and water absorption characteristics, also
due to a possible reaction barrier between Ti and silica or surface silicate.
For the electrical insulators, the titanium films presented the
hydrophobic characteristics, mainly due to the fragmented or non-

continuous films morphology, by retraction during the annealing stage.

The increase of contact angle provided a reduction of up to 8% in the
leakage current, in laboratory tests. Also, in this case, because the films
have been deposited on a glass layer of the insulators, there may have been
a reaction barrier similarity between the Ti and the silica or surface silicate
to it. However, for both cases, additional tests are being performed to
evidence the reaction mechanism or barrier proposed.
ACKNOWLEDGMENTS
The authors are grateful for the infrastructure and support in human
and financial resources to ELEJOR, project R & D 2945-0004 / 2013; to
ANEEL; to COELBA, project R & D 0047-0047/2011; to ANEEL; to
CNPq, Law 8010/90, mainly to LI 14/3445028-1 DI_14/2190047-7; to
CNPq PIBIT SCHOLARSHIPS and CAPES; to COPEL GeT project R &
D 6491-0301/2013, to CNPq Law 8010/90, LI 14/344508-1 DI 14/
2190047-7; the CNPq Scholarship PIBIT and DT, processes number
302672/2016-8; to the Lactec Institutes; to the Federal University of
Paraná/PIPE; to Ponta Grossa State University/DEMA - laboratory C-
LABMU and INCTMN.
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CONTENTS OF EARLIER VOLUMES
Advances in Materials Science Research. Volume 42
Chapter 1 Polyvinylidene Fluoride:

A Versatile Material Properties and Applications
Daniel A. Lowy and Bence Mátyás
Chapter 2 Boron Doping in Hydrogenated Amorphous
Silicon Based Materials and Devices
Aomar Hadjadj
Chapter 3 Application of Conductive Properties
of Graphene Oxide Films
Vyacheslav A. Smirnov and Vladimir P. Vasiliev
Chapter 4 Electron Transport Properties of Low-
Dimensional Nanomaterial
Field-Effect Transistors
Hui Li and Lishu Zhang

226 Contents of Earlier Volumes
Chapter 5 Design and Applications of Structured Catalytic

Supports Synthesized by Coating in Spherical
Geometry. A Review
Sergio de Miguel, Patricia Zgolicz,
Adriana Ballarini and Sonia Bocanegra
Chapter 6 Construction and Evaluation of Photovoltaic
Power Generation and Storage System using
Silicon Carbide Field-Effect Transistors
and Spherical Si Solar Cells
Takeo Oku, Taisuke Matsumoto, Masashi Yasuda,
Koichi Hiramatsu and Mikio Murozono
Chapter 7 Electrochemical Behavior of the 316L Stainless
Steel in Hypochlorite Sodium Bleaching Process
Omar Tanane
Chapter 8 Effective Stress due to Impurities in Alkali-Halide
Single Crystal on the Basis of the Method:
Strain-Rate Cycling Tests Associated
with Ultrasonic Oscillation
Y. Kohzuki
Chapter 1 Complementary Derivatization in Matrix-Assisted

Laser Desorption/Ionization Mass Spectrometry
Vladimir Zaikin and Roman Borisov
Chapter 2 Thermostability Analyses of Substrate-Geometry-
Associated Physical Models of
Heterogeneous Nucleation
Sanat K. Singha, Prasanta K. Das
and Biswajit Maiti

Chapter 3 Preparation and Phase Transitions in

Y-Type Magneto-Electric Hexaferrites
T. Koutzarova, S. Kolev, K. Krezhov, Ch. Ghelev,
B. Vertruyen, L. M. Tran and A. Zaleski
Chapter 4 Vanadium Oxide Thin Films: Metal-Insulator
Transition, Electrical Switching, and Modification
of the Properties by Ion Implantation
A. L. Pergament, O. Ya. Berezina, S. V. Burdyukh,
V. P. Zlomanov and E. A. Tutov
Chapter 5 Doping in Multiferroic BiFeO3
S. Mahalakshmi and Sharat Chandra
Chapter 1 Modern Applications of

Lignocellulosic Biomaterials
George Z. Kyzas and Antonios N. Papadopoulos
Chapter 2 Pullulan: A Versatile Polymer for
Casting Orodispersible Film
Rushiraj Jani
Chapter 3 Development of a Dip-Coating Instrument Based
on an Arduino Microcontroller for Deposition of
Cerium-Doped Titanium Dioxide
Semiconductor Thin Films
Bruno Viana de Almeida Pasquini Dias,
Sarah da Silva Rufino,
Lucas Amaral Correia Cunha,
Patrick Pires Conti, Mayara da Silva Santos,
Estevão Modolo de Souza and
Cleocir José Dalmaschio

Chapter 4 Silicone Oil Emulsions

Masami Kawaguchi
Chapter 5 Xanthine Sensor with ZnO-Conjugated
Carbon Materials
Mohammed Muzibur Rahman
Chapter 6 Effect of Laser Irradiation on the Structure of
Iron-Based Amorphous Alloys
Yulia S. Nykyruy and Stepan I. Mudry
Chapter 1 Nucleation in Electrodeposition

Alicia Prados and Rocío Ranchal
Chapter 2 Electrochemical Systems: Electrodes
and Double Layers
Asghar Aryanfar, Agustin J. Colussi,
Laleh M. Kasmaee and Michael R. Hoffmann
Chapter 3 Influence on the Lamellae Structual Formation
of Perfluorinated Copolymers Having Fluorinated
Ethylene Oxide as Side-Chain
Yoshinori Abiko, Shuhei Hirayama
and Atsuhiro Fujimori
Chapter 4 Conducting Polymer Coated Fabrics for EMI
Shielding Application
N. Muthukumar and G. Thilagavathi

Chapter 5 Correlation Between Mild Steel Composition

and Corrosion Inhibition in Industrial Pickling
Hydrochloric Acid
Younes El Kacimi, Khaoula Alaoui,
Mouhsine Galai, Rachid Touir, Nadia Dkhireche
and Mohamed Ebn Touhami
Chapter 1 Recent Recycling Technologies for Waste

Polyvinyl Chloride (PVC) Products
Sunil S. Suresh, K. Jaidev, Omdeo K. Gohatre,
Smita Mohanty, Manoranajan Biswal
and Sanjay K. Nayak
Chapter 2 The Significance of Polyvinyl Chloride
and Graphene-Based Materials
Ayesha Kausar
Chapter 3 Flux Growth of Highly Crystalline Particles
of Idiomorphic Mixed Metal Oxides
for Water Purifier Applications
Fumitaka Hayashi, Shuji Oishi
and Katsuya Teshima
Chapter 4 Multimodal Waveguides
for Material Characterization
Abbas Omar

Chapter 5 Magneto-Thermoelectric Effects

in Porous Semiconducting Materials
Roland H. Tarkhanyan
Chapter 6 Porosity Enhancement in Non-Cordierite
Honeycomb Monoliths
J. M. Gatica, J. C. Hernández-Garrido
and H. Vidal

INDEX
aluminum oxide, 7, 86
#
aluminum sulfate, viii, 55, 56, 57, 62, 63,
3He 64, 65, 68, 71, 76, 79, 82, 86, 90, 91
alternatives, 104
ammonium, 147, 173
amplitude, 145, 163, 165, 166
A anatase, 213, 217, 223
annealing, 209, 213, 214, 215, 216, 217,
absorption spectra, 151, 152, 156, 171 220
absorption spectroscopy, 172 antimony, 16
accelerator, 57, 61, 62, 63, 64, 65, 66, 68, aqueous solutions, viii, 55, 61, 62, 148, 149,
69, 70, 73, 74, 75, 76, 77, 78, 79, 81, 85, 168
86, 87, 89, 90 atomic orbitals, 109
acid, 17, 34, 42, 75, 87 atoms, 106, 148, 157, 159, 162, 205, 213
acidic, 16, 65, 204 avoidance, 131, 187
additives, 64, 78, 82, 130, 146, 149, 162
adhesion, 202, 204, 222
age, 15, 20, 21, 29, 30, 36, 61, 71, 72, 73, B
75, 80, 84, 88
background radiation, 165
alkali-aggregate reaction (AAR), xii, 87,
Belgium, 135, 136, 139
202, 203, 206, 212, 213, 214, 219, 221
beneficial effect, 42
alkali-free set accelerators, 56
benefits, 40, 95, 101, 202, 205
aluminum hydroxide, viii, 55, 56, 57, 62,
benzene, 146, 163
63, 64, 65, 70, 72, 85, 87
binary oxides, 181, 194
aluminum hydroxysulfate, 56, 64, 68, 71,
72, 73, 74, 81

232 Index
coal bottom ash, v, vii, viii, 1, 2, 3, 5, 6, 7,

C
9, 10, 11, 13, 14, 18, 19, 22, 23, 24, 28,
31, 33, 34, 36, 37, 41, 43, 44, 45, 47, 48,
cadmium, 16, 110, 117, 118, 119, 133, 164,
49, 50, 51, 52, 53, 54
170
combustion, 3, 4, 5, 6, 9, 180
calcium, viii, 6, 7, 10, 11, 12, 24, 40, 55, 59,
commercial, 69, 75, 76, 94, 100, 207, 210,
60, 62, 65, 66, 69, 74, 75, 76, 77, 80, 81,
214, 215, 218
89
composite scintillators, 104, 112, 125, 126,
calcium carbonate, 77
130, 133, 136
calibration, 114, 128
composites, 13
calorimetric method, 66
composition, viii, 6, 7, 8, 9, 16, 40, 41, 55,
carbon, ix, 2, 4, 5, 6, 9, 28, 93, 99, 102, 160,
58, 60, 64, 68, 69, 74, 77, 78, 79, 80, 84,
161, 177, 180, 181, 184, 186, 187, 188,
112, 130, 147, 158, 160, 163, 193, 217,
189, 191, 196
224
carbon dioxide, 2
compounds, vii, viii, x, 7, 16, 40, 55, 56, 57,
cement, v, vii, ix, 1, 2, 4, 7, 9, 12, 21, 24,
68, 72, 74, 75, 78, 79, 83, 84, 143, 182,
30, 37, 40, 41, 43, 45, 46, 48, 49, 50, 51,
183
53, 54, 56, 57, 58, 59, 60, 61, 62, 63, 65,
concrete, vii, viii, xii, 1, 2, 3, 4, 12, 16, 17,
66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76,
18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28,
77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87,
29, 30, 31, 33, 34, 35, 36, 37, 38, 40, 41,
88, 89, 90, 91, 93, 94, 95, 96, 97, 98,99,
42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52,
101, 102, 213
53, 54, 55, 56, 57, 58, 60, 62, 63, 65, 66,
ceramic, viii, xii, 202, 204, 206, 207, 209,
67, 74, 75, 76, 77, 78, 79, 80, 81, 82, 84,
210, 212, 215, 216, 217, 219, 222, 224
85, 86, 87, 88, 89, 90, 95, 98, 116, 202,
cerium, vii, x, 138, 144, 148, 149, 150, 152,
203, 221, 223
153, 154, 158, 162, 168
conduction, 157, 159
certification, ix, 93, 94
conductivity, 37, 38, 42, 209
cesium, 147
configuration, 125, 131, 132, 155, 158
challenges, xi, 105, 176
constituents, 5, 57, 62, 65, 74, 75, 77, 80,
chemical, vii, viii, ix, xi, 2, 6, 7, 9, 12, 14,
84, 131, 208
16, 40, 41, 56, 60, 65, 76, 80, 83, 84, 88,
construction, ix, 3, 4, 16, 40, 56, 57, 63, 93,
89, 90, 130, 150, 160, 176, 178, 179,
94, 95, 97, 101, 116, 203, 205, 206
180, 183, 195, 202, 203, 204, 213, 217,
consumers, 94, 95
224
consumption, 12, 68, 69, 71, 94, 95, 98, 99
chemical bonds, 213
contaminants, xi, 202, 203, 204, 222
chemical properties, 9, 14
corrosion, 31, 76, 78, 82, 203
chemical reactions, xi, 202
cost, ix, 42, 51, 84, 93, 94, 95, 105, 125,
chemical vapor deposition, 204
145, 181, 204
cleaning, viii, xii, 202, 204, 205, 206, 210,
cracks, xii, 26, 27, 78, 202, 203, 216
222
crystal growth, 152, 174
coal, vii, viii, 1, 2, 3, 5, 6, 10, 11, 12, 15, 16,
crystalline, x, 7, 10, 72, 107, 124, 126, 131,
33, 40, 41, 45, 54, 97, 98, 99, 181, 184
136, 144, 147, 169, 173

Index 233
crystallinity, 202
E
crystallization, 60, 65, 78
crystals, x, 25, 26, 27, 61, 76, 77, 103, 117,
ecosystem, 4, 101
144, 146, 147, 148, 149, 150, 151, 152,
electrical ceramics insulators, 202
153, 154, 155, 156, 157, 158, 159, 161,
electrical conductivity, 215
162, 163, 167, 168, 169, 170, 171, 172,
electricity, xii, 98, 202, 204
173, 174
electron, 26, 109, 113, 125, 148, 152, 155,
156, 157
D electron microscopy, 26
electronic structure, 157
decay, 74, 111, 120, 153, 154, 164 electrons, xi, 106, 109, 111, 112, 127, 128,
decomposition, 181, 205 144, 156, 159, 205
defects, 17, 156, 158, 159, 169, 215 emission, 99, 101, 102, 109, 110, 113, 117,
deficiency, 60, 65, 70, 145, 203 125, 127, 150, 151, 152, 154, 158
degradation, xii, 85, 202, 203 employment, ix, 81, 93, 95, 97, 98
deposition, xii, 76, 180, 191, 202, 204, 205, energy, ix, x, xi, 5, 37, 40, 46, 93, 97, 99,
206, 207, 208, 209, 210, 211, 212, 213, 104, 106, 108, 110, 111, 112, 113, 114,
214, 215, 217, 218, 219, 220 115, 118, 119, 122, 125, 126, 127, 128,
deposition rate, 202, 208 146, 154, 155, 157, 159, 160, 162, 164,
detection, vii, ix, x, 103, 105, 106, 107, 108, 165, 167, 172, 176, 177, 178, 182, 183,
110, 112, 113, 114, 115, 116, 117, 118, 184, 185, 186, 187, 190, 192, 202, 203,
119, 120, 121, 122, 124, 125, 126, 128, 205, 221
129, 130, 131, 132, 133, 134, 135, 136, energy consumption, 99, 205
137, 138, 139, 140, 141, 144, 145, 146, energy density, 205
147, 148, 158, 161, 162, 163, 166, 167, energy efficiency, 99
168, 169, 171, 172, 173, 215 energy input, 184
detection efficiency and sensitivity, x, 104 energy transfer, 110, 157, 172
detection of fast neutrons, ix, x, 103, 105, engineering, 40, 126, 221
106, 107, 119, 122, 126, 134, 138, 144, environment, 4, 16, 17, 61, 78, 79, 80, 101
146, 147, 148, 163, 167, 168 environmental impact, 42
detection system, 105, 108, 116, 117, 120, environmental protection, 7
121, 122, 135, 147 environments, 81, 82, 221
diffusion, 33, 80, 156, 208 excitation, xi, 108, 109, 112, 144, 151, 152,
discrimination, 115, 129, 133, 144, 145, 153, 154, 156, 157, 158, 159, 168, 169,
147, 167, 170, 171 172, 174, 205
distribution, 72, 76, 78, 95, 115, 221 exposure, 16, 31, 33, 80, 149, 215, 218
doping, 149, 150, 173
dosage, 23, 57, 63, 68, 69, 71, 72, 76, 81, 89
F
drying, 9, 36, 42, 206, 207
durability, vii, viii, ix, 1, 2, 4, 17, 19, 33, 36,
fast neutron detection, v, vii, ix, xi, 103,
40, 41, 42, 56, 58, 84, 87, 89
105, 106, 108, 110, 113, 114, 117, 118,

234 Index
120, 122, 128, 132, 135, 136, 138, 139, hardening process, 75
140, 141, 144, 158, 162, 163, 167, 169 heat release, 66, 67
fast neutrons, vi, x, 104, 105, 106, 107, 108, heat transfer, 178
109, 110, 111, 115, 116, 117, 119, 120, heating rate, 209
126, 127, 128, 129, 131, 132, 133, 134, heavy metals, 7, 9, 16, 17
136, 139, 143, 144, 146, 147, 148, 149, heavy particle, xi, 144, 145, 168
158, 159, 160, 161, 163, 164, 166, 167, heavy-oxide scintillators, v, x, 103, 104,
168, 169, 171, 174 108, 111, 112, 118, 119, 120, 122, 131,
fast neutrons detection, 144, 163 132, 136, 137, 139, 141, 168, 173
films, xii, 123, 202, 204, 205, 208, 209, 213, heavy-oxide single crystals, ix, 103
214, 215, 216, 217, 219, 224 height, 117, 120, 130
formation, viii, xii, 2, 6, 13, 20, 26, 27, 55, homeland security, vii, ix, 103, 104, 134,
58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 139, 172
69, 70, 71, 72, 73, 74, 75, 77, 78, 82, 86, hydration, vii, ix, 7, 20, 24, 25, 41, 42, 43,
89, 108, 120, 144, 149, 156, 157, 159, 56, 58, 59, 60, 65, 66, 67, 68, 69, 70, 71,
162, 169, 177, 180, 184, 186, 187, 188, 72, 74, 75, 76, 77, 80, 84, 85, 86, 87, 88,
189, 190, 192, 196, 202, 203, 204, 205, 89, 91
206, 211, 215, 217 hydrocarbon deposits, 104
formula, 64, 161, 162 hydrocarbons, xi, 176, 177, 178
fragments, 14, 72, 124, 126 hydrogen, vii, x, 37, 107, 110, 119, 127,
fusion, 22, 23, 30, 33, 41 131, 143, 146, 147, 148, 149, 156, 157,
158, 159, 160, 161, 163, 168, 169, 172,
173, 177, 178, 179, 180, 181, 184, 188,
G
190, 192, 193, 194, 196, 197
hydrogen atoms, 147, 148, 157, 159
gadolinium, 117, 118, 119, 168
hydrogen bonds, 148, 149, 159
gamma radiation, x, 104, 105, 106, 117,
hydroxide, 7, 11, 12, 56, 63, 64, 70, 72, 85,
123, 127, 128, 136, 144, 147, 149, 164,
87
167, 168, 169
gamma rays, xi, 127, 128, 144, 163, 166,
167, 169 I
gasification, 177, 181
gel, 13, 24, 25, 26, 27, 58, 59, 60, 70, 71, ideal, 114, 160, 179, 208
73, 78, 79, 203, 204, 220, 221 images, 9, 10, 26, 27, 41
geometry, 25, 41, 115, 116, 128, 147, 202, improvements, x, 20, 26, 104
219 induction, 58, 61, 66, 67, 68, 71
growth, ix, 58, 93, 94, 95, 96, 97, 98, 126, induction period, 58, 61, 66, 67, 68, 71
150, 152, 167, 173, 174 industrial wastes, 3
industry, vii, viii, xi, 1, 4, 16, 22, 40, 41, 56,
57, 94, 95, 96, 99, 101, 176, 177
H
infrastructure, 46, 94, 95, 96, 220
hafnium, viii, xii, 202, 204

Index 235
inorganic hydrogen-containing scintillators, light, x, 6, 37, 104, 105, 107, 115, 123, 124,
vii, x, 143, 168 125, 126, 128, 130, 146, 151, 152, 156,
inorganic scintillators, x, 136, 144, 147, 159, 160, 161, 163, 164, 167, 169, 178
148, 163, 168, 170, 173 light beam, 151
insulators, viii, xii, 202, 203, 204, 206, 209, limestone, 3, 77, 97, 98
210, 215, 217, 218, 219, 221, 222, 223, liquid phase, 58, 62, 63, 65, 68, 70, 73
224 low temperatures, 156, 192
interaction process, 106, 113 luminescence, xi, 144, 152, 153, 156, 158,
interface, 128, 213, 215 159, 161, 163, 169, 172, 173
investment, 94, 178 luminescence mechanisms, 144
ionization, 159, 160, 169, 205
ionizing radiation, 136, 149, 156, 159, 169
M
ions, vii, x, xi, 12, 33, 58, 60, 61, 62, 63, 65,
66, 68, 70, 72, 73, 74, 76, 77, 78, 79, 80,
magnetron sputtering, vi, xii, 201, 202, 204,
82, 144, 148, 152, 153, 155, 157, 158,
205, 208, 212, 215, 222, 223, 224
168, 169, 170, 171, 172, 202, 204, 205
manufacturing, vii, viii, ix, 1, 2, 4, 93, 94,
iron, 5, 6, 7, 10, 11, 40, 41, 74, 78, 79, 83,
215
95, 114, 115, 117, 180, 196
matrix, x, 26, 37, 65, 68, 77, 78, 83, 107,
irradiation, 114, 115, 116, 124, 129, 130,
123, 144, 149, 157, 159, 169, 203
149, 153, 154, 158, 159, 169
measurements, 114, 116, 118, 129, 130,
150, 151, 163, 166
K mechanical and durability properties, vii, 2,
19
KDP:Ce, x, 138, 144, 148, 149, 150, 152, mechanical properties, 22, 24, 40, 88
153, 154, 158, 159, 162, 163, 165, 167, metal oxides, viii, xi, 176, 179, 180, 182,
169, 174 183
KDP:Tl, x, 138, 144, 148, 149, 150, 151, 153, metals, xi, 9, 16, 17, 97, 176, 180
154, 155, 156, 158, 159, 162, 163, 165, microstructure, 2, 9, 17, 24, 25, 26, 40, 41,
167, 169, 174 51, 53, 54
KDP crystals, xi, 144, 148, 149, 151, 153, mixing, 18, 58, 62, 65, 66, 68, 71, 76
154, 156, 157, 162, 167, 168, 169 moisture, 100, 104, 206
kinetics, vii, ix, 56, 58, 87, 153, 154, 178, moisture capacity, 104
180, 186, 192 moisture content, 100
mole, 177, 193, 196
molecular weight, 123
L morphology, 60, 68, 70, 76, 77, 89, 215,
217, 220
laboratory studies, 81
multi-layer detectors, 104, 128
laboratory tests, 220
leakage, viii, xii, 202, 204, 206, 210, 218,
219, 220

236 Index
phosphate, vii, x, 7, 143, 148, 149, 173

N
phosphates, 10, 75
phosphorus, 157, 159, 161
nanomaterials, 203, 221
photodetector, 128
nanotechnology, 203
photoluminescence, 151, 152, 153, 154
national borders, 134
photons, 107, 123, 164
natural gas, 176, 177, 178
photovoltaic power generation, 226
natural resources, viii, 1, 2, 3, 4, 5, 40
physical characteristics, 80, 113
neutron/gamma discrimination, 144
physical properties, 14, 15, 41, 183
neutrons, ix, x, 103, 104, 105, 106, 107,
planetary exploration, 223
108, 109, 110, 111, 112, 113, 114, 115,
plants, ix, 3, 16, 93, 95, 96, 99, 101, 177
116, 117, 118, 119, 120, 122, 123, 125,
polystyrene, 107, 130, 146, 148, 162, 163,
126, 127, 128, 129, 131, 132, 134, 136,
165, 166, 167
138, 139, 144, 145, 146, 147, 148, 149,
porosity, 20, 23, 31, 37, 75, 80, 81, 217
158, 159, 160, 161, 162, 163, 164, 165,
Portland cement, v, vii, viii, xii, 1, 3, 43, 49,
166, 167, 168, 169, 171
50, 53, 55, 56, 58, 59, 60, 64, 65, 66, 67,
nuclear safeguards, vii, ix, 103, 104
69, 71, 72, 76, 85, 86, 87, 89, 91, 94, 95,
nuclear theory, 132
202, 206, 221
nucleation, 36, 58, 76, 77
potassium, vii, x, 63, 143, 148, 159, 161
nuclei, x, 104, 105, 106, 107, 108, 109, 110,
power plants, viii, 1, 3, 5, 6, 16, 104
112, 113, 115, 118, 119, 125, 126, 127,
preparation, iv, 59, 62, 64, 79, 87, 126, 142,
128, 130, 131, 144, 145, 146, 147, 148,
206
159, 160, 161, 162, 163, 168, 169
probability, 9, 16, 17, 31, 36, 105, 127, 148
nucleus, 108, 109, 111, 112, 120, 160
probe, 170, 209, 210, 214, 215
protection, 138, 140, 141, 146, 167
O protons, xi, 128, 132, 144, 146, 147, 149,
159, 160, 161, 165, 168, 169
optical parameters, 128 protons recoil, 144
optical properties, 173, 223 prototype, x, 104, 207, 210, 217, 219
organic compounds, 74, 77, 84 purity, 149, 180, 196, 208
organic polymers, 74
oxidation, viii, xi, 176, 178, 179, 180, 181,
182, 183, 184, 186, 187, 192, 195, 196 Q
oxygen, viii, xi, 110, 148, 156, 157, 159,
quanta, 106, 109, 110, 111, 112, 114, 115,
161, 169, 176, 178, 179, 180, 182, 185,
118, 120, 125, 127, 128, 146, 147, 164,
186, 187, 188, 192, 193, 194, 195, 196,
165, 167
213
quantification, 13
parallel, 123, 129, 130, 209

Index 237
silicon, 6, 7, 9, 10, 107, 204

R
silicon carbide, 226
simulation, xi, 106, 132, 135, 176, 182, 183,
radiation, x, 104, 105, 114, 116, 117, 120,
185, 187, 189, 192
122, 126, 129, 134, 136, 144, 145, 146,
simulations, 182, 196
147, 149, 152, 153, 154, 156, 157, 158,
single crystals, ix, 103, 106, 107, 118, 126,
159, 160, 169, 171, 172, 173
130, 145, 149, 160, 168, 170, 173, 174
radiation detectors, 104, 137, 139
sodium, 27, 57, 63, 78, 79, 88
Raman spectra, 217
sodium hydroxide, 88
Raman spectroscopy, 213, 214, 217, 218,
solution, 12, 27, 28, 42, 62, 63, 71, 73, 78,
223
79, 80, 81, 82, 149, 150, 152, 174
reactions, viii, x, 20, 55, 59, 76, 82, 85, 105,
specific gravity, 14, 15, 41
108, 110, 111, 116, 127, 144, 146, 162,
spectroscopy, ix, 56, 71, 72, 79, 133, 172,
164, 181, 182, 203, 205
209, 217, 221
reactivity, viii, 22, 55, 65, 203, 211, 222
spherical si solar cell(s), 226
recombination, 156, 157, 158, 169, 205
stability, vii, ix, 56, 61, 64, 89, 180, 181,
recommendations, iv, 9, 12, 40, 209
203, 217, 221
regeneration, 184, 186, 192, 193, 194, 196
structure, x, 2, 25, 33, 37, 64, 65, 71, 75, 79,
requirements, 41, 56, 87, 184, 187
82, 104, 107, 110, 122, 124, 148, 149,
resistance, 24, 31, 32, 34, 35, 42, 76, 77, 80,
157, 213, 217, 220
81, 85, 88, 123
substitution, 20, 28, 30, 37
response, 11, 132, 134, 153, 158, 159, 160,
sulfate, viii, 7, 27, 34, 35, 42, 55, 56, 57, 60,
161, 165, 168, 169, 188, 189, 190, 192
62, 63, 64, 65, 66, 68, 69, 70, 71, 73, 76,
room temperature, 148, 151, 153, 156, 157
77, 78, 79, 80, 81, 82, 84, 85, 86, 88, 89,
rotational system, xii, 202, 205, 207, 208,
90, 221
210, 211, 215, 218, 219
sulfur, 5, 15, 177
surface area, viii, 1, 12, 15, 17, 18
S surface treatment, 205
sustainability, viii, 1, 2, 101
scattering, x, 104, 106, 107, 108, 110, 112, sustainable development, 101
113, 115, 117, 119, 125, 126, 127, 130, symmetry, 114, 115, 155
131, 132, 144, 146, 147, 158, 160, 161, synthesis, 126, 195, 196
168, 209
selectivity, x, 144, 145, 147, 168, 169, 180
sensitivity, x, 104, 105, 106, 113, 115, 116, T
120, 126, 128, 129, 130, 131, 132, 144,
temperature, 9, 12, 14, 64, 88, 109, 149,
145, 146, 148, 158, 164, 167, 184, 187,
153, 154, 155, 156, 172, 178, 181, 182,
188, 193
183, 184, 185, 186, 187, 188, 189, 190,
separation of neutron/gamma, xi, 144
191, 192, 193, 194, 196
silica, viii, 3, 6, 7, 10, 12, 13, 40, 41, 55, 57,
testing, 104, 117, 209, 212
77, 81, 82, 83, 85, 86, 88, 89, 90, 97,
texture, 9, 11, 14, 15, 18
213, 219, 220, 221

238 Index
thallium, vii, x, 138, 144, 147, 148, 150,

W
151, 152, 153, 155, 157, 158, 162, 168,
173
water absorption, 15, 31, 42, 203, 219
thermal energy, 86, 184
weapons, 104, 105
thermal resistance, 6
weight gain, 35
thermalization, 125
weight loss, 34
thermodynamics, 180, 184
wettability, 209, 210, 213, 217, 219, 224
thin films, viii, xii, 202, 203, 204, 205, 206,
218, 219, 222, 223, 224
titanium, viii, xii, 202, 203, 205, 206, 208, Z
209, 210, 211, 213, 214, 215, 216, 217,
218, 219, 223, 224 ZEBRA detectors, x, 104, 125, 126, 128,
total energy, 159 129, 130
total internal reflection, 128 zinc, 16
toxic gases, 205 zirconia, 218
transportation, 16, 122, 135 zirconium, 217, 224


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ADVANCES IN MATERIALS SCIENCE RESEARCH

Additional books and e-books in this series can be found

NOTICE TO THE READER

Library of Congress Cataloging-in-Publication Data

ISBN: 978-1-53618-7 H%RRN

Published by Nova Science Publishers, Inc. † New York

Chapter 5 Scintillation Crystals of Thallium and Cerium

Advances in Materials Science Research. Volume 43 begins with a

experience has already been gained in the use of alkali-free accelerators,

(ZWO), PbWO4 (PWO), Bi4Ge3O12 (BGO), Gd2SiO5(Ce) (GSO(Ce)) have

luminescence by excitation of the internal hydrogen sub-lattice occurs

the main agent of degradation is the alkali-aggregate reaction (AAR),

REVIEWING THE ROLE OF COAL BOTTOM

Coal bottom ash (CBA) is a by-product of the coal industry and is

* Corresponding Author’s E-mail: navdeeps@nitj.ac.in.

CBA as partial replacement of PC whereas few of them have reported

Keywords: concrete, coal bottom ash, microstructure, mechanical and

Flexibility, robustness, sustainability, and inexpensiveness are some of

Table 1.1. Coal combustion products (CCPs) worldwide

Countries CCP’s production )Mt( CCP’s Utilisation )Mt(

The current chapter reviews some of the important investigations

2. COAL BOTTOM ASH

Across the globe, coal is one of the most recommendable natural

or scrubber ash. The obtained discharge from the scrubber is in form of

2.1. Chemical Composition of Coal Bottom Ash

2.2. Microstructure of Coal Bottom Ash

2.2.1. Mineralogical Characteristics

particles were observed in CBA which were mainly in the form of

Figure 1. Morphology images of coal bottom ash by SEM at 20 μm magnification (a)

The observations from Asokbunyarat et al. (Asokbunyarat et al. 2015)

Table 2.2. Elements in CBA from SEM-EDS analysis

Point Surface Morphology Element

2.3. Pozzolanic Activity and Reactivity of Coal Bottom Ash

In general, the pozzolanic response of the material is the capacity to

materials can associate governs on various aspects like, duration of curing,

The SEM and XRD results of different combinations indicate the

2.4. Physical Properties of Coal Bottom Ash

The physical properties of CBA depend on the variability of parent

Siddique 2014a; 2014b). The gradation also depicts that 80%-90%

Table 2.3. Physical properties of CBA (%) reported by various authors

Author(s) Physical Properties

following their parental source (Butalia, Wolfe, and Amaya 2017; M.

3. GENERAL ENVIRONMENTAL CONSIDERATIONS

The transportation of raw coal and the availability of cooling water

leads to the risk of permanent damage of lungs, respiratory systems,

4. PROPERTIES OF CONCRETE MADE WITH CBA AS

The following paragraphs summarize the influence of CBA used as

summarizes the mechanical behavior of CBA based mortars in which

4.1. Fresh Properties of Coal Bottom Ash Based Concrete

The behavior of freshly made concrete is of vital importance as it

prepared correspondingly with three combinations of ground CBA

Figure 4. Slump flow values of Grinded CBA based concrete mixes.

4.2. Compressive Strength of Coal Bottom Ash Based Concrete

The most reliable and hand to hand tests performed on concrete to

43.7) of percentage by-weight were adopted for studying the effect of

period of 90 days compared to that of control mortar. Likewise, in the

an increase in the content of Grinded CBA (with a fineness of 25 by

Table 4.1. Compressive strength of concrete at 28 days of

Author)s( Ground Coal Bottom Ash )%(

Kula et al. (Kula et al. 2002) have conducted his investigation in

incomparable values of compressive strength to that of control concrete

that comparable mechanical properties (compressive strength) with greater

4.2.1. Microstructural Analysis of Concrete with Incorporation of

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