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Calcined Clay as Supplementary Cementitious Material

Article  in  Materials · October 2020

DOI: 10.3390/ma13214734

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Review

Calcined Clay as Supplementary

Cementitious Material
Roman Jaskulski 1,*, Daria Jóźwiak-Niedźwiedzka 2 and Yaroslav Yakymechko 1
1 Faculty of Civil Engineering, Mechanics and Petrochemistry, Warsaw University of Technology,
Łukasiewicza 14, 09-400 Płock, Poland; [email protected]
2 Institute of Fundamental Technological Research, Polish Academy of Sciences, Pawińskiego 5b,

02-106 Warsaw, Poland; [email protected]

* Correspondence: [email protected]

Received: 3 October 2020; Accepted: 21 October 2020; Published: 23 October 2020

Abstract: Calcined clays are the only potential materials available in large quantities to meet the
requirements of eco-efficient cement-based materials by reducing the clinker content in blended
cements or reducing the cement content in concrete. More than 200 recent research papers on the
idea of replacing Portland cement with large amounts of calcined clay are presented and discussed
in detail. First, the fundamental information about the properties and structure of clay minerals is
described. Then, the process of activation and hydration of clays is discussed, including the methods
of pozzolanic activity assessment. Additionally, various testing methods of clays from different
worldwide deposits are presented. The application of calcined clay in cement and concrete
technology is then introduced. A separate chapter is devoted to lime calcined clay cement. Then an
influence of calcined clay on durability of concrete is summarized. Finally, conclusions are
formulated.

Keywords: calcined clay; binder; supplementary cementitious materials; cement-based materials

1. Introduction
Sustainable development, understood as progress that meet the needs of the present without
compromising the ability of future generations to meet their needs, is now the basic idea behind the
current paradigm of technological progress. The greatest threat to the achievement of the objectives
of sustainable development is the excessive emission of greenhouse gases, including, above all,
carbon dioxide, which results in global warming with many serious negative consequences for future
development and its prospects.
The building industry makes a significant contribution to increasing the carbon dioxide content
in the atmosphere, with cement production accounting for 5% of global carbon dioxide emissions [1]
being its largest source. This is due, on the one hand, to the high energy intensity of the Portland
clinker production process. The production of one ton of clinker requires the supply of 3.1–3.8 GJ of
heat, whereas in the older generation wet method kilns the demand may reach even 6 GJ/t [1]. On the
other hand, during cement production, carbon dioxide is emitted from raw materials, mainly
limestone. The amount of this emission is about 0.53 kg/kg of clinker [1].
The possibilities of reducing the energy intensity of cement production are limited, although it
is already possible to reduce heat consumption to 2.9 GJ/t of clinker. The use of alternative fuels
further reduces carbon dioxide emissions from fossil fuels. However, the use of limestone in clinker
production cannot be eliminated or reduced. Therefore, solutions to further reduce CO2 emissions to
the atmosphere by the cement and concrete industry are the production of blended cements that
reduce the amount of clinker and the use of supplementary cementitious materials (SCM), mainly

Materials 2020, 13, 4734; doi:10.3390/ma13214734 www.mdpi.com/journal/materials

Materials 2020, 13, 4734 2 of 36

pozzolans, in the concrete technology. A pozzolan, according to ASTM C125, is “a siliceous and
aluminous material which, in itself, possesses little or no cementitious value but which will, in finely
divided form in the presence of moisture, react chemically with calcium hydroxide at ordinary
temperature to form compounds possessing cementitious properties” [2].
The most commonly used SCM so far is fly ash from coal power plants. However, this additive,
which is used in the production of both cement and concrete, is slowly losing its primary importance
due to the progressive decommissioning of coal and lignite power plants. As a result, the supply of
fly ash will be significantly reduced in the near future. Another cement additive used to reduce
clinker content is a granulated blast furnace slag. However, it has no potential to replace fly ash, not
least because its global supply is far below potential demand. Additionally, it is only available in
countries where the steel industry exists. However, even where it is available, its share in blended
cements production is not large. In India, for example, Portland slag cement accounts for only about
8% of total cement production, while ordinary Portland cement accounts for 24% of production, and
Portland pozzolana cement accounts for 65%, where the main addition is fly ash [3,4].
The decreasing supply of fly ash from the power industry is encouraging the search for new
sources of pozzolan additives for cement and concrete production. One of the directions of this search
is ashes obtained from biomass combustion, [5]. Another is the use of natural and artificial pozzolana.
The former include, among others, volcanic tuffs already known in ancient times or zeolites. The best
known representative of the second group is the metakaolin formed by the calcination of kaolinite
from clays with its significant content.
Metakaolin was shown to be the best clay raw material for SCMs production, but in its pure
form it is only found in a limited number of deposits, so its availability is not sufficient to meet the
needs of the building materials industry. It is also in the focus of interest of other industries [6,7]. For
this reason, there has been interest in the possibility of producing SCMs from other locally available
natural clays containing, in addition to kaolinite, other minerals which have the potential to develop
pozzolanic activity upon appropriate activation. Research conducted in this direction led to the
separation of a new group of pozzolanic materials—calcined clay.
Clay is a widely spread material in the world, cheap and easily accessible [8]. At the same time,
it is a material with a great diversity in terms of mineralogical composition, hence numerous
literature items devoted to the analysis of the possibility of using clays from specific deposits for the
production of SCM in the calcination process [9–11].
In general, the literature on the activation of clay minerals and their use in civil engineering is
very rich and covers a wide range of issues. It would be very difficult to discuss this vast area of
research in one review article, so certain assumptions on the scope of this review were made First of
all, it focuses on calcined clays used as SCM in binders, where cement is the dominant component,
and in the cement-based concrete. Outside the scope of interest remain cement-free binders based on
calcined clays, which are the basis of geopolymers, as well as other alkaline-activated binders
(including clay minerals). Issues that do not fall within the assumed topics of the article are
mentioned where it was indicated for various reasons.
The paper is divided into eight thematic sections. The first section describes a fundamental
knowledge about clay minerals and publications on clays from various deposits in the world. In the
next section the topic of clay minerals activation with emphasis on calcination process and research
of hydration mechanisms and pozzolanic activity with factors influencing them are presented. A
separate section is devoted to the role of calcined clays in concrete technology (as SCM) and in
blended cements production. Due to the wealth of literature devoted to lime calcined clay cement
(LC3), a separate section is also devoted to it. The next chapter discusses the results of research on the
impact of calcined clays on concrete durability. Numerous publications on calcined clay, which
cannot be clearly classified as one of the above thematic areas, have been placed in a separate section
devoted to suitable aspects of the application of these materials. The summary presents the
conclusion of the literature review
Materials 2020, 13, 4734 3 of 36

2. Characteristic of Clay Minerals

Clay minerals, that are the subject of this review, belong to two main groups, which are often
referred to in the literature as 1:1 and 2:1 minerals. These two terms result from their structure, which
consists of repetitive tetrahedral (T) and octahedral (O) layers [12]. The T layer consists of corner-
contacting tetrahedral Si4+, Al3+, and Fe3+ cations, while the O layer consists of edge-contacting
octahedral Al3+, Fe3+, Mg2+, and Fe2+ cations, which are arranged alternately in cis and trans
configurations (see Figures 1 and 2).

Figure 1. The tetrahedral sheet. T, tetrahedral cations; Oxa, apical oxygen atoms; Oxb, basal oxygen
atoms. a and b refer to unit cell parameters. Reprinted from Brigatti, M.F.; Galán, E.; Theng, B.K.G.
Structure and Mineralogy of Clay Minerals. In Handbook of Clay Science; Bergaya, F., Lagaly, G., Eds.;
Elsevier Ltd: Amsterdam, The Netherlands, 2013; pp. 21–81. License number 4912071405833.

Figure 2. The octahedral sheet. O-trans, trans-oriented octahedra; O-cis, cis-oriented octahedra; Oxa,
apical oxygen atoms; Oxo, OH, F, Cl octahedral anion. a and b refer to unit cell parameters. Reprinted
from Brigatti, M.F.; Galán, E.; Theng, B.K.G. Structure and Mineralogy of Clay Minerals. In Handbook
of Clay Science; Bergaya, F., Lagaly, G., Eds.; Elsevier Ltd.: Amsterdam, The Netherlands, 2013; pp. 21–
81. License number 4912071405833.
Materials 2020, 13, 4734 4 of 36

At the contact of T and O layers there is a layer of oxygen atoms (so-called apical oxygen).
Additionally, the O layer contains oxygen atoms (non-apical oxygen) forming OH− groups and other
anions (F−, Cl−), which are located in the corners of octahedrons, but are not shared with the T layer
[12].
The division of minerals into 1:1 (TO) or 2:1 (TOT) groups results from the repetitive
arrangement of layers of the one or the other type (see Figure 3). This division is far from covering
the rich diversity of clay minerals, at least because 2:1 minerals may additionally contain anhydrous
interlayer cations, hydrated interlayer cations or octahedral interlayer sheet. In addition, clays also
contain complex minerals in which TO and TOT layers co-exist and can be distributed regularly or
randomly.

Figure 3. Models of 1:1 and in 2:1 layer structures. Oxb, basal oxygen atoms; T, tetrahedral cations; O,
octahedral cations; Oxa, apical oxygen atoms; Oxo, octahedral anions (OH, F, Cl). Reprinted from
Brigatti, M.F.; Galán, E.; Theng, B.K.G. Structure and Mineralogy of Clay Minerals. In Handbook of Clay
Science; Bergaya, F., Lagaly, G., Eds.; Elsevier Ltd.: Asmetdam, The Netherlands, 2013; pp. 21–81.
License number 4912071405833.

Minerals 1:1 include two groups: the kaolin group and the serpentine group. The first group
includes: kaolinite, dickite, nicrite, halloysite, hisingerite. To the second group belong, among others,
lizardite, antigorite, chrysotile, caryopilite, pyrosmalite, polygonal serpentines and polyhedral
serpentines.
Minerals 2:1 form a large group of which the following should be mentioned: pyrophyllite and
talc both of ideally layered structure; mica, more than 200 variants [13], of which muscovite and illites
will be discussed further on; and smectites, of which montmorillonite is discussed further on. The 2:1
structure also has vermiculite, chrorites and, finally, minerals with mixed layer structure, such as
illite-smectite [14,15], chlorite-smectite [16] or illitic-chlorite. The calcination of the former is devoted,
among others, in the publication of Garg and Skibsted [15].
A more detailed discussion of the properties and structure of clay minerals is beyond the scope
of this review. In the following section, the minerals which are part of calcined clays and which
Materials 2020, 13, 4734 5 of 36

determine their properties are discussed in more detail. The discussion is focused on their properties,
which are important in the activation process and determine their properties as pozzolan materials.
The article describes also factors influencing the optimization of activation process.
The most important clay minerals, which are subject to temperature activation and, therefore,
are discussed in more detail in this paper, are kaolinite and montmorillonite, which also occurs in the
form of variants called Ca-montmorillonite and Na-montmorillonite [17–19]. Additionally, illite,
being a poorly crystallised mica, and muscovite belonging to the same family, can be subjected to the
calcination process, although both show low pozzolan activity even after heat treatment (illite,
however, slightly higher than muscovite). Nevertheless, both are also included in this review of clay
minerals. Relatively little attention is paid to sepiolite, halloysite and mixed-layer minerals in the
research on pozzolan activity, therefore, due to a small number of publications, these minerals are
discussed more briefly in this paper.
Kaolinite and the product of its calcination, i.e., metakaolinite, are the most thoroughly tested of
the clay minerals that are part of the clays subjected to calcination in order to use them as SCMs due
to their pozzolanic activity. Part of this literature can be found in [20,21]. Other minerals are much
less popular so far, so Garg and Skibsted’s publications on montmorillonite are worth mentioning
here [22,23]. Garg and Skibsted [22] presented the result of investigation on the activity of calcined
pure montmorillonite due to the changes in the structure under the heating. The authors traced the
changes in the structure of montmorillonite heated up to 1100 °C using the NMR technique. The
results indicate that montmorillonite exhibits pozzolanic activity both in the raw state as well as
heated up to any temperature value it was subjected to in the mentioned studies, although above 800
°C a clear decrease in this activity is visible.
It is not only montmorillonite that exhibits pozzolanic activity in its raw state. Among such
minerals we can also include illite, kaolinite and muscovite [24–26]. However, it is montmorillonite
that is most active in the raw state. The least active of them is muscovite due to a small proportion of
amorphous phase, which is additionally accompanied by very high water content [27]. Nevertheless,
it is commonly accepted that the most active mineral of the pozzolanic is metakaolinite. The study of
He et al. [17] revealed that Ca-montmorillonite may show even higher pozzolanic activity after
calcination. It is associated with a high content of amorphous silica. Additionally, in [28] two types
of bentonite (containing mainly montmorillonite) were tested and obtained better results than most
of the five kaolinites, although it should be added that such results were obtained only in lime
consumption and electric conductivity tests.
To the group of kaolinites, i.e., minerals 1:1 belongs halloysite—a lesser known close “cousin”
of kaolinite. Both these minerals have identical chemical structure with the only one difference that
halloysite may contain two additional water molecules in the interlayer space. Halloysite is, therefore,
sometimes referred to as hydrated kaolinite. This small difference has significant consequences for
the structure of this mineral, which forms different forms such as tubes, spheres and laths [12,29].
Water in the interlayer space can be easily removed by thermal treatment and such dehydrated
halloysite is sometimes referred to as metahalloysite. The results of a study on the pozzolanic activity
of clays rich in halloysite are presented in papers of Tironi et al. [30,31]. Obtained results confirmed
the high pozzolanic activity of calcined clays containing halloysite, confirming their usefulness as a
raw material for SCM production.
Muscovite is also included among the clay minerals that show pozzolanic activity after
appropriate heat treatment, although in this case the results are ambiguous. Ambroise [24], by
examining the possibility of activation at 750 °C of, among others, muscovite and phlogopite,
obtained results indicating low effectiveness of this form of treatment. Samples of calcined muscovite
blended with calcium hydroxide after seven days of curing in the moulds disintegrated after placing
them in water, where they were to undergo further curing. On the other hand, [8] showed that
muscovite increases the hydration heat of the cement and its effect varies depending on the
temperature of thermal treatment (the raw material was tested, as well as heated at various
temperatures from 500–950 °C). Additionally, in [27] the calcined muscovite pozzolanic activity at
800 °C was shown, although it was relatively low compared to calcined illite and kaolinite.
Materials 2020, 13, 4734 6 of 36

Another clay mineral which has been studied due to its potentially pozzolanic properties is
sepiolite [17,32]. It is a 2:1 group mineral with an unusual structure due to discontinuity of TOT layers
[12]. Studies have shown that without heat treatment sepiolite is not a material that is active as a
pozzolan. Its additional disadvantage, from a technological point of view, is high water demand. The
use of sepiolite in raw form as a partial substitute for cement led to a significant decrease in the
strength of the mortar used to assess the hydraulic properties of potentially pozzolanic materials. On
the other hand, calcination carried out at the temperature of 830 °C allows to obtain a material with
distinct, although relatively low pozzolanic activity and significantly reduced water demand [32].
The low pozzolanic activity of sepiolite may result from low Al content (about 1%), which, together
with Si, is responsible for pozzolanic activity of clay minerals.
Illit is one of the minerals which show practically no pozzolanic properties in their raw state.
Heat treatment carried out at high temperatures (930–950 °C) both pure mineral with small
admixtures [33] as well as clays with a dominant share of illite [34] leads to a material with moderate
pozzolanic activity. The dehydroxylation process itself, occurring at a lower temperature, does not
lead to activation of the illite and formation of a material with a positive value of hydraulic index
whereas, at the temperature that causes the destruction of its structure, a partial recrystallization of
the resulting amorphous phase takes place at the same time, which reduces the potential pozzolanic
activity of this mineral.
Mixed-layer minerals, which are characterised by the presence of different types of layers, are
very common in clays. According to Weaver [35], it is estimated that out of 6000 tested samples of
clay minerals from all over the USA as much as 70% of them contain different varieties of mixed-
layer minerals. Such widespread minerals could not be omitted in studies on pozzolanic activity of
clays, although the number of publications on this topic is small. He et al. [14], investigated the
pozzolanic activity of synthetic clay consisting of layers of mica and smectite, used as a catalyst [36].
The share of illite (i.e., mica) in relation to montmorillonite (smectite) according to various studies of
this material is in the range from 3:1 to 2:1. His studies showed that this mineral, after calcination at
960 °C, showed good pozzolanic properties, achieving in the test mortar strength of 113% in relation
to mortar consisting only of OPC.
The study of natural mixed-layer mineral of similar composition (illite/smectite in the ratio
70/30) was conducted by Garg and Skibsted [15]. In this case, the optimal calcination temperature
was 900 °C and its exceeding led to crystallization of a part of amorphous phase and decrease of
pozzolanic activity. Apart from a slightly different mutual ratio of mica and smectite, the mineral
studied by Garg and Skibsted did not contain NH4+ ions, which may partially explain the discrepancy
in the value of the optimal calcination temperature in relation to the findings of He et al.
Lemma et al. [16] study of mixed-layer clay consisting mainly of illite (45%) and chlorite (14%)
containing also non-clay minerals, such as quartz (30%) and feldspar (10%), revealed high optimal
calcination temperature of the material. The highest value of strength activity index (SAI) of this clay
was observed after calcination at 1100 °C. More detailed analysis of the obtained results indicated
that an increase in the pozzolanic activity at this temperature, in relation to that observed at 900 °C
after total dehydroxylation of the illite, was caused by the transition of feldspar from a crystalline to
an amorphous form. Although this mineral is not typical for clay rocks, its occurrence in the
composition of clay intended for calcination may be a premise for carrying out this process at a higher
temperature.

3. Activation and Hydration of Clays

3.1. Activation Process and Its Conditionalities

Raw clays usually have a moderate or low pozzolanic activity. To increase it, they need to be
activated. As a result of activation, clay minerals undergo processes of dehydroxylation and
amorphisation and the accompanying change in coordination of Al ions. Those processes lead to,
among other things, greater solubility of Al and Si ions and their greater reactivity, which is a basic
condition for the demonstration of pozzolanic activity by clay minerals [37]. The activation process
Materials 2020, 13, 4734 7 of 36

can be carried out mechanically (by grinding) [38–40] or thermally by heating to a temperature high
enough to destroy the structure of the clay minerals, but low enough to avoid recrystallization and
the formation of chemically inert phases. Some publications indicate that kaolinitic clays should be
ground before they undergo calcination [41,42], i.e., their activation should have both mechanical and
thermal component. Processes occurring during thermal or mechanical activation can also be induced
chemically to some extent [37,43]. Sanchez et al. [44] studied the effects of thermal activation of kaolin
supported by an activator in the form of 1% ZnO admixture. The efficacy of the activation process of
acid treatment of clay before its calcination was also studied [45]. Due to the subject matter of this
article, only thermal activation, i.e., calcination, will be described in more detail.
The effectiveness of the thermal activation process, and consequently pozzolanic activity of the
obtained material, depends on many factors. These include: calcination temperature, particle size and
shape, time and others [24]. The most attention is paid to the analysis of the temperature influence.
According to Fernández et al. [18], the exposure of clay to too low or too high a temperature can
significantly affect the activation process. In the former case, due to incomplete dehydroxylation, in
the latter case, due to the melting of minerals and their subsequent recrystallization leading to the
formation of phases which do not react with the cement hydration products and do not exhibit any
pozzolanic activity.
The process of dehydroxylation, i.e., tearing off OH- groups [17], leads to serious damage in the
crystal structure of clay minerals. As a result, among other things, it leads to increased exposure of
Al ions on the surface of the mineral grains and increased solubility [18]. This effect is more
pronounced in the case of kaolinite than in the case of group 2:1 minerals, which is reflected in the
differentiation of pozzolanic activity of clay minerals. The structure of the minerals also affects the
dehydroxylation temperature, which occurs in a wide range from 350 °C to 900 °C, and for its full
effect in most cases the mineral must be heated to temperatures between 600 and 800 °C [46,47]. At
temperatures below 600 °C, this reaction takes place only with kaolinite [48,49]. Montmorillonites
undergo this process at temperatures between 550–850 °C. Illite is dehydroxylated in the temperature
range 600–900 °C [18]. Neißer-Deiters et al. [8] have studied the influence of temperature on the
properties of calcined mica consisting of muscovite with a small admixture of phengite. The
investigated material was subjected to calcination at different temperatures ranging from 500 °C to
950 °C. As the raw muscovite already exhibits pozzolanic properties, the aim of the study was to
determine whether and how the calcination influences its pozzolanic activity and water demand. The
results indicate that the calcination process, regardless of the temperature, leads to slight changes in
the above-mentioned parameters.
Another variable of importance in the thermal activation process is time. Its impact has been
studied by Chakchouk et al. [50]. They determined the optimal parameters of mortar with the use of
calcined clay. For this purpose a model with three variables was developed. In addition to the
calcination time, the temperature of the calcination and the exchange rate of cement to calcined clay
in the subsequently tested blended binder were also taken into account. In 23 individual experiments,
the time varied from 1.32 h to 4.68 h. In most cases, it was 3 h. They showed, that a longer calcination
time was beneficial in increasing the strength of the tested mortar if the temperature was lower than
700 °C, and above this temperature the effect was the opposite.
The duration of the thermal activation process is usually counted in hours or minutes when
using fluidized bed reactors [51]. This type of calcination is referred to as soak-calcination. This
process is most commonly used and most of the publications are devoted to it, however, in these
publications the time is sometimes given for the whole process, sometimes it is only the time of
keeping the material at the highest temperature, and sometimes it is not specified at all. This makes
it difficult an attempt to summarise and make clear recommendations. Especially since this time also
depends on the degree of material fragmentation, its pre-treatment (e.g., drying to constant mass) or
the type of device in which the activation is carried out (rotary kiln or fluidized bed reactor).
However, regardless of whether the process of soak-calcination takes several minutes or several
hours, the activation process known as flash-calcination, which lasts from fractions of a second to
several seconds, can be clearly distinguished from it [51–55]. The shortening of the process results
Materials 2020, 13, 4734 8 of 36

from a very large fineness of the processed material and from the high temperature in the calciner
reaching 1100 °C. The combination of high pulverization and high temperature causes the clay
subjected to calcination to be heated very quickly in its entire mass. The rise of temperature reaches
0.5–1.5 × 104 °C/s [52,54]. Such a rapid temperature increasing leads to a material with slightly
different characteristics from clay obtained from the soak-calcination process. In such clays in
particular, the dehydroxylation process is sometimes not complete. Moreover, due to the rapid
process, the obtained material has a lower density and higher porosity. This usually also translates
into increased reactivity [51,53,54]. Most of the research on flash-calcination concerns clays with high
kaolinite content, therefore, the work of Rasmussen et al. [53] is worth mentioning. They carried out
a study using clays with a composition dominated by minerals from the 2:1 group. They concluded
that, also in the case of this type of clays, flash-calcination can lead to the production of clays with a
high-level of pozzolanic activity, and the advantage as compared to soak-calcination procedure in
this case lies in the lower risk of melting and recrystallization of minerals, such as feldspar or spinel [53].
It is not only time, temperature or particle size that determine the success of the calcination
process. Bich et al. [56] studied the conditions of the dehydroxylation process depending on the
degree of ordering of the mineral structure. They used three clays with high kaolinite content and
different degree of order of this mineral defined by values of P0 coefficient (it is defined further in the
article). They showed, that in case of kaolinite with disordered structure (P0 = 0.68), that it was enough
to heat the material at 650 °C for 45 min for full dehydroxylation whereas, in the case of kaolinite
with well-ordered structure (P0 = 1.4), such time allowed dehydroxylation of 71–95% of kaolinite. The
relationship between kaolinite dehydroxylation degree and lime consumption from CaO saturated
solution after 28 days was also shown. Although the level of linear regression adjustment (R2 = 0.73)
indicates that the kaolinite dehydroxylation level is an important but not the only factor shaping the
calcined clay pozzolan activity even if it contains more than 75% of kaolinite.
The calcination process, due to its complexity resulting from a number of parameters regulating
it, as well as from various possible variants of its execution, has also gained mathematical models
describing it. Teklay et al. [54,57] developed two mathematical models of the calcination process. The
first one [57], with reference to the material itself, models the calcined mineral in the form of spherical
particles with specific physical parameters, which are affected by temperature, as a result of which
some changes in its properties occur. This model is independent of the form of the process (flash- or
soak-calcination). The other model [54] is an attempt to mathematically describe the flash-calcination
process itself, allowing to determine its key parameters in relation to specific input data referring to
the material subjected to heat treatment.
Among publications devoted to the activation of clays and clay minerals, there are also those
concerning the conduct of this process with the use of additional substrates aimed at changing certain
characteristics of the finished material. The primary purpose of such additives or admixtures is to
increase pozzolanic activity [58]. As an example of research on the influence of admixtures on
calcined clay, Taylor-Lange et al. [59,60] can be mentioned. The admixture in this case was zinc oxide,
which was added to clays containing kaolinite, montmorillonite and illite both before and after
calcination. The results were promising only in case of the clays containing kaolinite. The presence of
calcined clay significantly reduced the delaying effect of zinc oxide on the cement hydration process.
The increase in kaolinite pozzolanic activity was also obtained by Ghorbel and Samet [61], who
added iron nitrate solution to clay rich in this mineral. As a result of calcination of such additionally
enriched clay, hematite and goethite were formed. The authors came to the conclusion that the
presence of the former increases the kaolinite pozzolanic activity as long as it does not exceed 2.7%.
The presence of iron ions in clay subjected to calcination also has its less favourable effects. They are
responsible for its reddish hue, which is visible in cements blended with use of such clay. The reddish
shades of cement are sometimes improperly interpreted as a sign of poor quality of the material,
hence the idea to study the calcination process in a reducing atmosphere [62]. In this process, ground
petroleum coke was also added to the raw ground clay. As a result of such calcination, a product was
obtained whose red colouring was much less intense. The durability of the obtained effect remains
an issue to be investigated.
Materials 2020, 13, 4734 9 of 36

3.2. Activation of Various Clays and Clay Minerals

It is assumed that the largest pozzolanic activity characterizes kaolinite, which also has the
lowest activation temperature range. According to He et al. [17], calcination of this mineral can be
successfully carried out even at 450 °C, although full completion of the dehydroxylation process
requires a temperature of about 650 °C [63]. The high pozzolanic activity of calcined kaolinite results
from the high content of hydroxyl groups and their location, which favours the exposure of Al groups
on the surface of material grains after the dehydroxylation process [18]. Illite and montmorillonite
also lose hydroxyl groups under the influence of temperature, but Al atoms remain in the structure
of these minerals in places more difficult to access for cement hydration products, which may react
with them [18]. As a result, their pozzolanic activity is lower than that of calcined kaolinite [24].
Metakaolinite, which is a product of kaolinite calcination, is a transition phase during
the thermal transformation of kaolinite into mullite, which is an inactive pozzolanic mineral.
Sperinck et al. [63] presents the process of kaolinite calcination modelled using the molecular
dynamics (MD) simulations. The simulations were based on “heating” the simulated structure of the
mineral to 1000 K, removing 10% of the initial number of hydroxyl groups and then quickly “cooling”
it to 300 K in order to analyse the obtained results. The next steps of the simulation were carried out
until all OH− groups were removed. As a result of the simulation, a disordered mineral structure was
obtained, in which the silicon layers showed little disorder, while the aluminium layers were
significantly disordered and about 20% of the Al ions gained 5-fold coordination. It is less stable than
the original six-fold coordination and four-fold coordination, which was adopted by most Al ions
after calcination. This results in greater solubility and, as a consequence, also pozzolanic activity.
Interestingly, the Al ions only moved within their own layer, as they were held back from further
migration by a less affected silicon layer.
Minerals of the 2:1 group are characterised by a fairly wide range of temperatures at which
dehydroxylation occurs. As far as illite is concerned, the temperature required for this process is
650 °C, but further heating is possible (up to 930 °C), which leads to an increase in its pozzolanic
activity, probably due to the progressive amorphisation of the structure. According to He et al. [17],
Ca-montmorillonite and Na-montmorillonite undergo total dehydroxylation at temperatures of
730 °C and 740 °C, respectively. In the case of both these minerals, the pozzolanic activity increases
also after heating at higher temperature, but not exceeding 930 °C. Differences in decarboxylation
temperature between individual minerals of group 2:1, and even for the same mineral, were
explained by Drits et al. in [64]. They indicated the role of cis-vacant (cv) and trans-vacant (tv)
modified layers in determining this temperature. Both these variants of layers differ in the distance
between the nearest hydroxyl groups. In tv 2:1 layers the bond length is 2.45 Å ± 0.05 Å, whereas in
cv 2:1 layers it is considerably longer and is 2.85–2.88 Å. Hydrogen, which in the process of
dehydroxylation passes from one group OH- to another creating a water molecule, needs a little more
energy in the latter case. This explains well the difference in temperature required for full
hydroxylation between the 2:1 group minerals.
Studies on the process of montmorillonite calcination, using the NMR technique, were
conducted by Garg and Skibsted [23]. They showed that up to the temperature of 200 °C the
dehydration of the mineral takes place, then up to the temperature of 500 °C no significant changes
occur and then between 500 °C and 600 °C the dehydroxylation process begins. This process lasts
until the material reaches a temperature of 900 °C and is connected with the progressive
amorphisation of the mineral structure. Starting from the temperature of 1000 °C, another process of
changing the structure of the heated material begins, resulting in its recrystallization as a result of the
final destruction of the original layered mineral structure. In addition to NMR studies, Gard and
Skibsted [23] also studied the mineral’s pozzolanic activity by preparing mortars containing Portland
cement and calcined clay at a ratio of 70:30 and analysing the products of hydration at specific
intervals up to 1 year. The results indicated that 800 °C was the upper limit of the optimal calcination
temperature range. The lower limit of this range was 750 °C. Interestingly, montmorillonite heated
to a temperature above 850 °C showed significantly lower pozzolanic activity than in the raw state.
The presented results are consistent with the results of Al and Si solubility tests carried out by the
Materials 2020, 13, 4734 10 of 36

same authors [23]. Samples of calcined clay at two temperatures: 800 °C and 900 °C were subjected
to 24-h treatment with 0.1 M NaOH. The solubility of Si and Al, which is a good indicator of
pozzolanic activity, was about 4 times lower for clay activated at the higher of the given temperatures.
The less frequently occurring clay minerals, and thus slightly less popular among researchers,
include pyrophylite, whose dehydroxylation processes and effects of thermal treatment are presented
in papers [65,66]. Additionally, halloysite is not the subject of numerous publications [30,31], even
though it is a clay mineral showing high pozzolanic activity after calcination. Moreover, it is
interesting due to its differentiated structure. Its structure can form tubes or spheres, and these
differences manifest themselves to a large extent in the pozzolanic activity of the calcined mineral.
Halloysite in the spheroidal form is mainly active in the initial period due to more easily available
reactive alumina. In the tubular form alumina cations are not so easy available, therefore, this form
exhibits delayed activity [30].
Among the publications devoted to the study of clay activation, paper [67] should be mentioned,
which covers the subject of activation of pure clays, among others kaolinite, illite, etc. Activation of
clays containing smectites (bentonites) and kaolinite was studied by the authors of papers [68–70].
The analysis of activation process of clays containing illite and smectites (montmorillonite) in
comparison to those containing kaolinite is included in [71]. Heat treatment of clays containing about
40% kaolinite as well as about 40% illite and montmorillonite is described in [49].

3.3. Tests of Eligibility of Clays for Activation Procedure

Since deposits of pure clays containing only one type of clay mineral are not rich enough to meet
the growing demand of the construction industry for calcined clays as supplementary cementitious
materials, it is important to assess the clays from existing deposits in terms of the possibility of using
their resources as raw materials for the production of SCMs. The pozzolanic activity of clay is not a
simple sum of the activity of its individual constituent minerals. The co-occurrence of some of them
may give a synergy effect, but in other configurations the potential of any of the components may not
be fully exploited. Hence the need to develop a methodology for the assessment of specific deposits
arises in terms of their suitability for activation.
Diaz et al. [72] presented an idea for a method of initial assessment of clay based on its chemical
composition. This method is primarily intended for the assessment of clays containing minerals from
the kaolinite group, but its application is also possible for clays containing 2:1 minerals. In order to
assess the suitability of clays from a particular deposit using this method, first of all their chemical
composition should be determined, with the Al2O3 content, which should be more than 18%, then the
ratio of Al2O3 to SiO2 content, which should be higher than 0.3 and, finally, the loss on ignition, which
should not be less than 7%. Due to the deleterious effects of calcite and pyrite, the authors have added
two additional conditions: CaO < 3% and SO3 < 3%. The authors are of the opinion that first of all, the
exploitation should be carried out with the use of aluminium deposits containing over 40% of
kaolinite. However, in order to take into account the pozzolanic activity of 2:1 group clays, they
proposed a parameter defined as kaolinite equivalent calculated according to Equation (1):
%KEQ = {[m(350 °C) − m(850 °C)]/[m(200 °C) × 0.1396]} × 100, (1)

in which m(x) is the mass of the mineral after heat treatment at a given temperature x.
A promising tool for a preliminary assessment of potential clay minerals’ pozzolanic activity
may be cation exchange capacity, but not yet at this stage, as the author himself admits in his paper
[73]. The development of an effective and simple methodology for the assessment of clay deposits for
the cost-effectiveness of their exploitation as raw materials for SCMs production still remains an issue
to be resolved.
Materials 2020, 13, 4734 11 of 36

3.4. Methods of Assessment of Pozzolanic Activity

The pozzolan reaction occurs between Al2O3-2SiO2 and Ca(OH)2, which in the case of concrete
comes from the hydration of cement. The presence of water is also necessary for this reaction, as the
reaction products are hydrates. As a result of the pozzolan reaction, CSH gel (CaO·SiO2·H2O) and
hydrated calcium aluminates (e.g., C4AH13, C2AH8, C3AH6) are produced, as well as hydrated calcium
aluminosilicates of the hydrogehlenite type C2ASH and hydrogarnets (C3AS3-C3AH6).
Carboaluminates (e.g., calcium hemicarboaluminate hydroxide C4ACH11 which more detailed
formula is C3A·0.5CaCO3·0.5Ca(OH)2·10.5H2O) may also be formed in the presence of carbon dioxide
or limestone filler [47,74–77].
There are many different methods of determining pozzolanic activity. They are described among
others in [28,58,78,79]. According to [78] they can be divided into direct and indirect ones. Direct
methods include methods based on the analysis of Ca(OH)2 content and products of its reaction and
changes in the content of these compounds over time. These are methods using XRD, TGA and DTA
techniques, as well as methods based on solution titration, i.e., the Fratini test and its simplification,
also referred to as the saturated lime (SL) [78] test or lime consumption (LC) test [28]. Among the
indirect methods, the authors [78] include those that allow the determination of the pozzolanic
activity of the material on the basis of the study of the characteristic which is affected by this activity.
These features can be, e.g., the compressive strength of mortar specimens, the electrical conductivity
of a saturated solution of Ca(OH)2 in which the tested material is placed [80–83], or the determination
of the amount of heat released in calorimetric tests [84,85].
A wide review of methods of testing the pozzolanic activity is presented in paper of Tkaczewska
[79]. The methods described therein were divided into chemical and physical. Although some of them
come from currently withdrawn standards, it is worth quoting them here to show the richness and
diversity of approaches to this topic, which even with this review will not be exhausted.
One of the methods is the measurement of portlandite consumption by SCM using thermal
analysis methods, i.e., TGA in combination with DTA [86]. In this method, the measure of
pozzolanicity is the amount of calcium hydroxide bound by the tested material. It is defined as the
difference between the initial Ca(OH)2 mass and the remaining unbound mass. The latter is
determined in a thermal test from the loss in mass of the sample in the temperature range 490–510
°C, which corresponds to the decomposition of portlandite. This method has several weaknesses
which must be taken into account when using it. First of all, the temperature of calcium hydroxide
decomposition may vary depending on the alkali content or even grain size [87]. Another factor is
the possibility of loss of portlandite in the sample due to carbonation and mass loss of other hydration
products in the temperature range corresponding to calcium hydroxide. These problems were
identified by Kim and Olek [88] and they proposed an appropriate test procedure.
TGA/DTA testing requires expensive equipment, so it is not a method that can be used in many
laboratories that are less well equipped. To address such situations, Mendoza and Tobón [89] have
carried out a comparative study of the results of weight loss measurement of calcium hydroxide
mixture with potentially pozzolanic material using a moisture analyser. They succeeded in
demonstrating that if a sufficiently high sample heating temperature in the moisture analyser is
ensured (in the quoted article it was 230 °C), the mass loss at this temperature obtained using both
methods is characterised by a high correlation (R2 = 0.971), while the mass loss in the moisture
analyser is slightly higher. With appropriate assumptions, it is possible to test the pozzolanic activity
of the materials by determining the amount of water lost by the hydration products, which increases
with the progress of the pozzolanic reaction.
Fratini is identified with at least two different methods to test the activity of pozzolan. The first
one [90–92] consists in the determination of the amount of calcium ions bound by the tested material
mixed with cement. A sample of the ground test material is placed in a Ca(OH)2 suspension at 40 °C
for eight days [93]. During this time, the sample is shaken from time to time. The suspension is then
filtrated and the total alkalinity of the filtrate is determined by titration with 0.1 mol HCl solution.
The next step is to neutralise the filtrate with ammonia and to determine the amount of CaO in it by
complexometric method. The concentration of OH- ions (total alkalinity) and Ca2+ ions determined in
Materials 2020, 13, 4734 12 of 36

the test is compared with the calcium hydroxide solubility isotherm curve. The location of the result
below the curve means that the material is active pozzolan, the greater its activity, the greater the
distance of the result beneath the curve.
The second Fratini method is the strength method. It consists in testing the strength of two series
of mortar samples prepared with the use of cement and the tested material in the amount of 30–50%
of the hot water. One series of samples is stored for seven days in water at a temperature of 20 °C,
and the other only three days, after which it is transferred to water at 50 °C for another four days.
The difference in strength of both series of samples proves pozzolanic activity of the tested
material [94].
The method according to the PN-EN 450-1:2012 standard [95] is based on a similar methodology
as the Fratini strength method. It is designed to test the activity of fly ashes, however, it can also be
applied to other materials showing the pozzolanic activity. It is based on the determination of the
pozzolanic activity index (IAP), defined as the ratio, expressed as a percentage, of the compressive
strength of a mortar with a fixed proportion of binder, water and sand of a specific grain size made
in two versions. In the first version, 25% of cement is replaced by fly ash (or other pozzolanic
material), while in the second version, 100% cement is used. The standard requires that it is Portland
cement CEM I 42.5R. Pozzolanic activity index is calculated on the basis of the strength test after
28 and 90 days. After 28 days it should reach ≥75% and after 90 days it should be ≥85% for the test
material to be considered as active pozzolan. The method of measuring the pozzolanic activity index
gives results that closely correlate with the determination of lime concentration in saturated solution
with the test material [78,80,81,96]. This method is often referred to in the literature as SAI (strength
activity index) and varies, depending on the standard on which it is based, in the composition of the
tested mortar (the amount of cement exchanged for the tested material, e.g., 20% [97] or 30% [98]
instead of 25%) and the required minimum SAI value (e.g., it is 80% after 28 days [98] or 75% after
seven and 28 days [97]).
Apart from testing the strength of mortars containing cement, there are also methods based on
testing the strength of mortars prepared from slaked lime and the tested material. One such method
is contained in the Serbian standard SRPS B.C1.018:2015 [99]. A mixture of slaked lime, pozzolana,
sand and water with a mass ratio of 1:2:9:1.8 is prepared for testing. From this mixture samples of
40 × 40 × 160 mm are formed, which are stored for 24 h in temperature 20 ± 2 °C with a relative
humidity of 90%. Then they are placed in thermostat chamber at temperature 55 ± 2 °C for five days.
Before testing, specimens are stored again 24 h in temperature 20 ± 2 °C and relative humidity of at
least 90%. Compression and flexural strength of the specimens is the basis for the division into three
classes of pozzolanic activity. The requirements for each class are as follows: class I—bending strength
≥ 4.0 MPa, compressive strength ≥ 15.0 MPa; class II—bending strength ≥ 3.0 MPa, compressive
strength ≥ 10.0 MPa; class III—bending strength ≥ 2.0 MPa, compressive strength ≥ 5.0 MPa.
The method based on the study of the influence of pozzolanic material on the strength of cement
mortar is also Graff’s method [79]. In this method three series of mortars differing in binder are
prepared. In the first series it is Portland cement and in the second series it is a mixture of Portland
cement and the tested material, with the content of the latter in the samples: 15, 30, 50, 70 and 90%.
The third series is prepared just like the second series, but replacing the test material in the binder
with quartz sand in the same proportions. After seven, 28 and 90 days from the preparation the
sample is subjected to strength tests according to PN-EN 196-1:2006 [100] and the pozzolanity number
is calculated according to Equation (2):
P = (a − c)/(b − c), (2)
in which one: P is the pozzolanity number, a is the compressive strength after 28 days of the second
series of samples, b is the compressive strength after 28 days of the first series of samples and c is the
compressive strength after 28 days of the third series of specimens.
The method contained in the withdrawn Russian standard GOST 6269-54 [101] is similar to the
first of the Fratini methods described above. According to it, the measure of pozzolanic activity is the
total amount of calcium hydroxide bound by pozzolana during 30 days. A sample of the investigated
pozzolana (2 g) is placed in a container with 100 mL of saturated calcium hydroxide solution, which
Materials 2020, 13, 4734 13 of 36

is sealed and occasionally shaken vigorously. After two days, 50 mL of the solution is taken and is
titrated with HCl in the presence of methyl orange. Then 50 mL of saturated calcium hydroxide
solution is poured into the cylinder. This procedure is repeated every two days and the whole test
takes 30 days. A modification of this method is using barium hydroxide instead of calcium hydroxide
and determining its loss in time [79]. Barium hydroxide dissolves better in water but simultaneously
carbonates faster [102].
Chemical methods include the method contained in the withdrawn ASTM C379-65T [103]. It
assumes the determination of the pozzolanic activity of the material on the basis of the determination
of the amounts of soluble SiO2 and Al2O3 in it. The test material should be placed for 1.5 h in a 1-molar
solution of sodium hydroxide at 80 °C. The total content of dissolved SiO2 and Al2O3 above 20%
indicates that the material shows pozzolanic activity. The same standard also includes a method
based on testing the strength of the lime - pozzolanic mortar. Samples of such mortar should be stored
for seven days at 65 °C in a humid atmosphere, then cooled to 23 °C and kept at this temperature for
another 21 days, also in a humid atmosphere. The material exhibits adequate pozzolanic activity if
the samples reach compressive strength ≥4.1 MPa. ASTM C379-65T was withdrawn in 1966 and
replaced by ASTM C593-95 [104], which only contains the latter method.
Chapelle test consists in boiling the pozzolana sample in Ca(OH)2 solution for 16 h and then
determining the calcium hydroxide content in the filtrate [105]. A measure of the pozzolanic activity
of the material is the difference in Ca(OH)2 content in the initial solution and in the filtrate. Nino at
al. [106] have modified this method for their research. They used 300 mL of saturated calcium
hydroxide solution at 20 °C, when the solubility of this compound in water is 1.65g/L. They placed
0.5 g of kaolin, almost as much as Ca(OH)2 in the solution. After heating the solution to 100 °C, part
of the calcium hydroxide was precipitated, but during the test, as part of Ca(OH)2 reacted with kaolin,
the precipitate dissolved, keeping the solution saturated. The test was extended to 24 h and the
solution was mixed at 150 rpm.
Another chemical method is the Feret–Florentin method, about which Feret mentioned in [107]
and which he credited to Florentin [108]. The ground sample of test material is shaken for 10 min in
100 mL of HCl (30%) and then the amounts of SiO2, Al2O3 and Fe2O3 that have entered the solution
are determined. Then a further aliquot of the test material is mixed 1:1 with Ca(OH)2 adding enough
water to give the prepared mixture a plastic consistency. The prepared mixture is stored for three
days in a humid atmosphere and then it is placed in water at 15 °C. After one, four and 26 weeks
from the preparation of the mixture, part of the mixture is taken, dried, ground and the SiO2, Al2O3
and Fe2O3 content is determined in the same way as in the case of the test sample itself (shaking in
30% HCl). Pozzolan activity is measured by the increase in the amount of leached oxides in a sample
of test material with Ca(OH)2 compared to a reference sample containing the test material itself.
Feret himself is the author of the method in which pozzolanic activity is tested firstly by treating
the material with a 30% solution of HCl and then with a 25% solution of NaOH. The measure of
pozzolanicity is the amount of material tested, expressed as a percentage, which has migrated to the
solution. In order to consider that the material has a high pozzolanic activity, at least 60% of its mass
should be dissolved. The simplification of the Feret method is the Jarrige and Decreux method [109].
It consists in treating the tested material with HCl for five and 30 min. The measure of pozzolanic
activity is an increase in the amount of dissolved material with an increase in the leaching time.
Material characterized by good pozzolanic activity should have a difference in solubility of more than
10%.
The Guillaume method [110] consists in comparing the content of insoluble parts of two blended
cements, one of which contains 20% by weight of the tested material and the other 20% by weight of
quartz sand. Both cements are treated with HCl and the amount of insoluble residue is then
determined. In the next step the cements samples are heated at 1000 °C for 1 h, after which they are
treated with HCl as previously unheated samples. The pozzolan activity is determined by the
increase in solubility of the cements after heating. If active SiO2 is present in the test material, it reacts
with calcium oxide or alite to form HCl-soluble calcium silicates. Cement with added quartz sand
does not change significantly its solubility in HCl.
Materials 2020, 13, 4734 14 of 36

The method proposed by Battaglino and Schipp [111] is based on two criteria: the determination
of specific surface area of hardened cement paste prepared with the addition of 30% of tested material
and the determination of free Ca(OH)2 content. The tests are carried out after different hardening
periods. A sample of the paste should be ground and then the 30–60 μm fraction should be separated.
The specific surface area is determined by the BET method and the free Ca(OH)2 content by the
ethylacetylacetate method (Franke method) [112]. A material with good pozzolanic activity is
considered as one which reacts quite slowly with calcium hydroxide and leads to a large specific
surface area.
Another suggestion for the test of pozzolanic activity is the R3 method (rapid, relevant and
reliable). A detailed description of it and the underlying research can be found in [113,114]. This
method has two variants. The first one is based on a heat release test in an isothermal calorimeter, in
which the mixture is placed. It consists of the material tested, calcium hydroxide (additionally
calcium carbonate in the case of testing mixtures of LC3) and potassium hydroxide as well as
potassium sulphate both added in such quantities that the reaction environment has a similar
composition to a pore liquid in concrete. Detailed compositions of the mixtures are given in the above
mentioned publications. At the method development stage the prepared mixture was tested in a
calorimeter at 20 °C and 40 °C for seven days. Since the amount of heat released at the higher of these
temperatures after 1 day is equal to the amount released at the lower one after six days, further
analyses were based on the results obtained after one day at 40 °C. The second variant of this method
starts with the preparation of a mixture with the same composition as the first variant. This mixture
is placed in a sealed container and treated at 40 °C for one day. The sample is then dried at 110 °C
until its mass change per day becomes less than 0.5%. The sample so dried is exposed to a temperature
of 400 °C for two hours and then cooled to 110 °C. The sample is weighed before and after heating at
400 °C and the quantity of water bound in the hydration products is determined from Equation (3):
Wb = (ms − mc)/ms [%], (3)
In Equation (3) Wb is the quantity of water bound by the hydration products, ms is the mass of
the sample after drying to a constant mass but before exposure to 400 °C and mc is the mass of the
sample after heating and then cooling to 110 °C. According to [113], the results obtained show a high
correlation with the results of the strength tests and the Chapelle test. A quick test of pozzolanic
activity based on the conductivity test was proposed by Luxán et al. [115], developing an idea
presented by Raasek and Bhaskar [116]. The idea of this method is to test the conductivity of a
saturated solution of Ca(OH)2 kept at a constant temperature of 40 ± 1 °C, in which a sample of the
tested material, dried earlier at 105 ± 5 °C, is placed. Pozzolan activity is measured by the difference
of the compensated conductivity of the solution at the start of the test and after 120 s. According to
the classification proposal of [115], a material is considered as non-pozzolanic if the difference in
compensated conductivity is less than 0.4 mS/cm, and if it is greater than 1.2 mS/cm, the material is
considered as having good pozzolanicity. Between these two results there are materials which show
variable pozzolanicity. In its original form this test was not resistant to interference from soluble salts
increasing the conductivity of the solution. Payá et al. [80] proposed several modifications to this test,
such as extending its time, carrying it out at different temperatures or using unsaturated calcium
hydroxide solution. The most important amendment to the test methodology was the proposal to
additionally measure the conductivity of distilled water, in which the material sample was placed.
Both curves obtained in this way (conductivity of calcium hydroxide solution and distilled water)
should be subtracted from each other and analysed.
Each method has its strengths and weaknesses, so it is best to use more than one method to
obtain as complete a picture as possible of pozzolanic activity of the tested material. Danatello et al.
[78] comparing the saturated lime method, Fratini test and SAI concluded that the first method is the
most questionable. It did not show any correlation with two other methods, between which a high
correlation was found. Therefore, they recommend using the Fratini test together with SAI, and also
one of the direct methods. There is also a number of voices that suggest only direct methods should
be used in the determination of pozzolanic activity [117].
Materials 2020, 13, 4734 15 of 36

4. The Results of Investigations of Clays from Various Worldwide Deposits

Maier et al. [10] examined 11 clays from various deposits in Germany. The calcination
temperature of each clay was determined from the DTG results by adding 100 °C to the main peak
temperature of the dehydroxylation process. The mineralogical composition of the raw materials and
the proportion of amorphous phase after the calcination process were determined. Reactivity was
investigated using R3 calorimetry according to [114] (described in the previous section) and solubility
of Al and Si ions. The results showed a high agreement between the results of the last two tests. The
authors also came to a conclusion that in order to properly determine the suitability of clay as a raw
material for SCM production it is not enough to know the chemical composition, especially in case of
clays with low kaolinite content. In those cases other minerals play an important role, therefore, it is
necessary to determine the complete mineralogical composition. The R3 calorimetric test can also be
useful in the evaluation of this type of clays.
Tironi et al. [11,118] have studied five kaolinitic clays from various deposits located in Argentina
with kaolinite content between 16% and 94%. These clays were tested by X-ray diffraction (XRD) and
Fourier transformed infrared spectrometers (FTIR) before activation. These tests determined the
phase composition of the clays and the order or disorder of the kaolinite they contain. The latter
determination was performed in accordance with the methodology proposed by Bich [56], which
consists in calculating the P0 coefficient, which is the quotient of the intensity bands at 3620 cm−1 and
3700 cm−1 obtained in the FTIR test. If P0 > 1, then according to [56], kaolin has well-organised
structure and P0 < 1 indicates disordered structure. In the case of three clays with intermediate
kaolinite content the structure of this mineral was disordered. The clays were heated to 700 °C where
they stayed for 5 min (and the whole heating process took 1 h). An XRD study after calcination
showed that the time and temperature were sufficient to transform the kaolinite into metakaolinite.
After calcination, pozzolanic activity was also determined by the Fratini test and the electrical
conductivity test (previously described). The compressive strength of mortars in which 30% of
cement was replaced with ground calcined clay was also tested. On the basis of the results of the
latter test, a model was proposed in which the strength of the mortars (after seven, 28 and 90 days),
in which 30% OPC was replaced with ground calcined clay, depends on the content of kaolinite in
the clay, on the specific surface defined by the Blaine method and on the inverse of the P0 coefficient.
The authors proved that the results obtained from the application of the proposed model are highly
consistent with the test results. Thus, they showed that the calcined clays’ pozzolanic activity
depends not only on kaolinite content but also on the degree of order of its structure and specific
surface of the clays after calcination and grinding.
Huenger at al. [119] selected three clays from Lower Lusatia deposits and tested their pozzolanic
activity after burning. Among the selected clays, one was characterized by a high content of quartz
(about 60%) co-occurring with smaller amounts of kaolinite and illite, the second one consisted
mostly of kaolinite (about 60%) and quartz and a small amount of illite, and in the third one more
than half of the composition consisted of quartz, and the other clay minerals mentioned earlier were
present in smaller, similar amounts. Each clay was calcined separately, as well as their mixtures.
Three temperatures of heat treatment were applied: 600 °C, 650 °C and 700 °C. The study of
mineralogical composition of the calcined clays showed a slight decrease in the illite content and a
significant decrease in kaolinite content accompanied by a proportional increase in the amorphous
phase. The studies of pozzolanic activity allowed to formulate a conclusion that the mixture of
kaolinite-rich clay with quartz-rich clay in the proportion 60:40 allowed to obtain a material with
satisfactory parameters.
Beuntner and Thienel [120,121] presented the results of research on clays with clay content of
about 70% (with a predominance of illite) from deposits located in southern Germany. In [120] the
authors compared the material obtained by calcination of clay with kaolinite content of 25% in two
technological processes. One was carried out on a laboratory scale and the other on an industrial
scale. The comparison of research results showed that calcination in industrial conditions allowed to
obtain material with slightly lower pozzolanic activity, but still at a satisfactory level. It was also
shown that the mineralogical composition of clay subjected to heat treatment varies according to
Materials 2020, 13, 4734 16 of 36

grading. Whereas [121] was devoted to the study of selected technological, mechanical and durability
properties of concrete prepared from nine different types of cement with different exchange rate of
the cement with calcined clay, which was used as a Type II addition. Mixtures of clay with cement in
most cases showed slower development of strength in the initial period. However, later on, the
strength increase accelerated and in the case of mixes with 20–25% clay, the strength exceeded the
values obtained for concrete with sole cement. Moreover, it was found that the replacement of cement
parts with calcined clay reduces consistency, bleeding and shrinkage.
Papers [122–124] are devoted to research on the possibility of using kaolinite waste fraction from
Amazonian deposits for the production of calcined clays, which were an intermediate product for
further zeolite production. The research was carried out on waste fractions of kaolin from deposits of
the Brazilian Amazon calcined at various temperatures in the range 550–800 °C for 2 h. Results of the
tests showed that the wastes were composed primarily of coarse-grained kaolinite, which can be an
excellent starting material for pozzolana and zeolite production.
Akasha [125] presented the results of research on the use of clay obtained from five locations in
Libya and calcined as a partial substitute for cement. The studied clays contained from 30% to 90%
of kaolinite and, besides that, mainly quartz (and in one case additionally a small amount of illite).
The clays were calcined at 800 °C for two hours. Subsequently blended cements were prepared in
which the share of calcined clays was 10%, 15% and 20%. The obtained results do not show a clear
correlation between pozzolanic activity and kaolinite content in the raw material. In comparison with
the control mortar, in which pure cement was used, only the mortar containing calcined clay
containing initially 30% kaolinite (the least) and 70% quartz showed higher strength at all test dates
and at all exchange rates.
Chakchouk et al. [126] have selected six clays from five Tunisian deposits located in different
parts of the country. Samples of clays have been tested for basic properties such as plastic limit, liquid
limit and plasticity index. Blue methylene test and calcimetry were also carried out on them. The
chemical composition and qualitative mineralogical composition with XRD was determined. The
chemical composition was used to verify the criterion of pozzolan activity according to two
standards: ASTM C618 [97] and an unspecified Indian standard. The results showed that with the
exception of one of the clays, which did not meet the Indian standard of CaO < 10%, the others should
be a good material for the production of pozzolanic active materials. These five clays were subjected
to calcination at 600 °C, 700 °C or 800 °C, and then their pozzolan activity was determined by
examining the compressive strength of clay mixed with calcium hydroxide in two proportions
CC:CH = 1 and CC:CH = 3. The highest strength was obtained in case of two clays with the highest
content of kaolinite and at three times the mass prevalence of calcined clay to calcium hydroxide.
Their optimal calcination temperatures are 700 °C and 800 °C. In the case of two of the remaining
clays, the measured pozzolanic activity was moderate and the optimal temperature (among the
applied ones) was 800 °C. The fifth of the examined clays showed weak pozzolanic activity, which
the authors attribute to high quartz content.
The reported results of the research indicate that it is necessary and advisable to develop a
research protocol which could be used as a standard for examining clays from unexplored local
deposits. The diversity of clays from different deposits in the same country indicates the need to take
into account the specific mineral composition of a particular clay in developing and optimising its
calcination technology.

5. Calcined Clay in Cement and Concrete Technology

The issue of calcined clays as SCM cannot be considered in isolation from the technological
determinants related to the use of this active pozzolanic material in the production of blended
cements and concrete. In [41] Samet et al. applied the response surface methodology (RSM) [127,128]
to determine the value of: calcination temperature, specific surface of calcined clay and its share in
the blended cement to obtain optimal parameters of the blended cement. Normal consistency, setting
time, stability of expansion, mechanical properties and the specific surface of the calcined clay were
Materials 2020, 13, 4734 17 of 36

taken into account. The presented methodology is universal and can be used to determine the optimal
composition of cement blends with different types of calcined clay.
The issue of optimization of the composition of cement blends with calcined clays was also
considered by Pierkes et al. [129]. Due to a large number of variable parameters, they planned their
research using the DOE (design of experiments) with statistic tool MINITAB®. Four types of Portland
clinker and three types of clays (illitic, kaolinitic and chloritic) were used in the research. The clay
was added to the clinker in amounts of 20% and 40%. Additionally, the anhydrite was added in a
different amount (2% or 4%). The research included compressive strength after two, seven and 28
days and studies of hydration products after 3 h and two days. The authors came to the conclusion
that there is space to improve the strength parameters of calcined clay cements by selecting both the
appropriate chemical and mineralogical composition of the raw materials and adjusting the amount
of sulphates accordingly.
Siddique and Klaus [130] have reviewed widely the literature on the influence of metakaolin on
the properties of mortars and concrete. The analysis included fresh properties, properties of hardened
materials and durability properties of concrete. They stated, that the use of metakaolin had a positive
impact on both early age and long-term strength properties of cement paste, mortar cement and
concrete. It also reduced water absorption of concrete by capillary suction (i.e., its sorptivity [131]),
as well as other parameters that may reduce the durability of the material (e.g., permeability) due to
the refinement of pore structure. Moreover, mortars and concrete performed with metakaolin
replacing cement in the amount of 10% and 15% showed very good chemical resistance, including
sulphate corrosion.
Paiva et al. [132] have studied properties of fresh and hardened concrete prepared with
metakaolin with the pre-set workability. The influence of metakaolin particles dispersion achieved
with water and polycarboxylic acid based HRWRA on concrete structure was researched and
discussed. The results clearly favoured the use of HRWRA to control the workability of mixture with
such fine additions as metakaolin. The use of water alone had resulted in increased porosity and the
formation of agglomerates of calcined kaolin, which has had a negative impact on the strength
parameters of the hardened material.
Research on the compatibility of superplasticisers with cement mixes containing metakaolin and
limestone was undertaken by Zaribaf et al. [133]. They used cement type IL according to ASTM C595
[134], containing limestone and commercially available metakaolin. Four admixtures each with
different chemical base were used as superplasticisers. The results, which were discussed, included
flowability measured by the minislump size, compressive strength, hydration heat measured in
isothermal calorimeter and setting time. On the basis of the results obtained, the authors came to the
conclusion that admixtures based on polycarboxylate ether (PCE) and polymelamine sulfonate (PMS)
were the most compatible.
An extended analysis of the efficiency of superplasticizers depending on the mineralogical
composition of calcined clay and the type of cement (OPC or PLC) was conducted by Sposito et al.
[135]. Apart from the two types of cement mentioned above, they used four types of calcined clay in
their research, one of which was a typical clay with different mineralogical composition, one was
commercially available metakaolin and the other two contained in its raw form more than 90% of one
of the minerals: illite or muscovite. Quartz powder was also used to evaluate its impact on the
rheology. Three different admixtures were used as superplasticisers. The tests were carried out on
both clay and cement mixes as well as on clinker-free suspensions. The results and their analysis
allowed the conclusion that zeta potential, total surface area and water demand were reliable
predictors of superplasticizer demand with the exception of mixtures with calcined muscovite.
However, the latter reservation should be alleviated in the case of clays with different mineralogical
composition, in which muscovite content is a medium. The share of quartz powder in the tested
systems for the variety significantly improved workability.
Nied et al. [136] investigated the synergistic effect of the use of metakaolin and limestone on the
mechanical properties and phase assemblage of the blends composed in this way. For this purpose
they prepared 12 blends with a fixed OPC content of 60% and a variable content (10%, 20%, 30% and
Materials 2020, 13, 4734 18 of 36

40%) of metakaolin of two qualities, limestone (10–40%) and quartz instead of limestone (20%) in
reference blends. The authors concluded that part of metakaolin in binary blends with OPC could be
replaced with limestone, which positively affects both workability and 28-day compression strength,
with the exchange ratio depending on the quality of metakaolin. Moreover, it was observed that the
addition of limestone stabilises ettringite, refines pore structure and alters the hydration of
OPC/metakaolin blend at early age.
Beuntner et al. [137] presented the results of a study on the possibility of using calcined clay in
high-performance concrete. It is worth emphasizing that they used not only metakaolin, but also
mixed layer clays, which on the one hand occur in much larger quantities in world clay deposits, but
on the other hand are treated as “poorer sisters” of kaolinite. The results of the research, which
included, among other things, compressive strength, modulus of elasticity and porosity, showed that
calcined clays, including those obtained from raw mixed layer ones, can successfully replace silica
fume in HPC, although this may require doses of superplasticisers larger than those currently
recommended by their manufacturers.
The use of calcined clays as binder components can be combined with the simultaneous use of
other types of pozzolan. Mechti et al. [138] presented results of a study in which finely ground sand
was used as an additional component which, in spite of its crystalline structure, showed the pozzolan
activity. The aim of the study was to determine the optimal proportions of cement blend components
and, as additional parameters, fineness of ground sand as well as temperature of calcination of clay.
The plan of the experiment included 28 mixtures characterised by different values of the optimised
parameters. The analysis of the results showed that the optimum composition under the assumed
assumptions was the one containing 80% of cement, 15% of sand with fineness lower than 40 μm and
5% of clay calcined at temperature 750 °C.
Two different pozzolana (calcined clay and fly ash) in cement mixes were also used by Ng and
Østnor [139]. This combination had its justification in the different characteristics of both pozzolana
materials. Fly ash is a material which very slowly increases the strength of cement-based composites,
while calcined clays, especially when used with limestone, are significantly faster in the process of
pozzolan reaction. In the presented studies, 20% of OPC was exchanged for fly ash, clay or mixtures
of these two pozzolana in different proportions. The results showed that the simultaneous
application of fly ash and calcined clay improved the workability of the mixture, which is usually
impaired when using only calcined clays as a substitute for cement. It has also been shown that the
combination of these two pozzolanic materials allows strength values to be achieved after 28 days at
the level of mixtures using only OPC.
Workability and hydration of blended cements with calcined illitic clay have been studied by
Marchetti et al. [140]. They used two types of ground, calcined illitic clays and OPC, the content of
which was reduced in favour of each clay by 15%, 25% and 35% by weight. Cement mixtures were
tested for their packing density (according to [141]), heat release, flow, compressive strength and
some additional parameters related to the hydration course. The obtained results allowed to state
that with the increase of the share of calcined illitic clay in the mixture, its workability decreased. As
far as heat release is concerned, the clay caused a decrease in the amount of heat generated during
the first 48 h, but at the same time it did not cause any significant delay in the hydration process.
Machner et al. [142] have studied the possibility of using dolomite to replace limestone as a third
component in mixtures with OPC and metakaolin. The test mixtures were composed of Portland
clinker, dolomite, limestone, metakaolin and gypsum. A total of six blends were prepared, which
together with the cement gave seven different series. In all mixtures the ratio of OPC to metakaolin
was constant at 6:1 and the addition of limestone or dolomite was 5%, 10% or 20%. The results showed
that if the 90-day strength was taken as a determinant, there was no significant difference between
limestone and dolomite. The latter mineral, however, showed less reactivity, which was particularly
evident at low curing temperature.
As it can be seen that the addition of calcined clay reduces the early strength of cement
composites due to lower reactivity of pozzolana. Paper [143] presents the results of research on the
possibility of acceleration of cement strength development in the initial period by using CSH seeds.
Materials 2020, 13, 4734 19 of 36

The clay obtained from a deposit in southern Germany, which after calcination was mixed with OPC
in the proportion 20:80, was used in the study. Thus, the prepared cement, corresponding to type
CEM II-A/Q, was enriched with 1%, 2% and 3% of CSH seeds admixture. In another series 5%, 10%
and 20% of the cement mass was replaced with the microlimestone. There were performed calorimetric
tests, TGA and SEM investigations as well as flow and compressive strength tests on mortars. The
results allowed to recommend the addition of 3% of CSH seeds admixture or 10% microlimestone to
optimize the early strength development of cement with 20% addition of calcined clay.
There is a consensus among researchers that the replacement of part of cement with metakaolin
(up to 15%) reduces drying shrinkage of concrete compared to material without metakaolin or with
silica fume [144–146]. However, as far as autogenous shrinkage is concerned, the results are
divergent. Gleize et al. [147] investigated the influence of metakaolin on the autogenous shrinkage of
cement paste. They used CEM I 52.5 cement, which was replaced by metakaolin at 0%, 5%, 10%, 15%
and 20% rates. Mixtures were prepared with two water to binder ratios: 0.5 and 0.3. In the latter case
a superplasticizer was used. The results allowed to formulate a conclusion that long-term autogenous
shrinkage decreased with increasing proportion of metakaolin in the binder. The majority of this
effect was caused by the pozzolanic activity of the applied metakaolin, and not by the effect of
dilution of the cement with the addition.
A review of the studies on the use of calcined clays in cement and concrete technology shows an
overwhelming predominance of articles devoted to various aspects of application of metakaolin. It is
the best-researched calcined clay mineral, although even in its case the results obtained are far from
being generalised. Although kaolin is a grateful object both for testing and for subsequent use after
calcination, due to its limited availability, more extensive research into the properties and application
of clays with different mineralogical compositions is necessary.
In addition, many of the work presented is based on results obtained using pastes or mortars
cement. Concrete testing results are in a clear minority. This is probably due to the need to produce
larger amounts of calcined clay with homogeneous parameters, which can be difficult in laboratory
conditions. Nevertheless, this is an important direction of research that deserves more attention.

6. Lime Calcined Clay Cement (LC3)

The cement consisting of Portland clinker, calcined clay (preferably rich in kaolinite), calcium
carbonate and gypsum is described in literature as LC3 [148]. It is a solution for a demand for cement
that is more environmentally friendly, the production of which takes place with lower CO2 emissions
to the atmosphere, and which at the same time is not inferior to ordinary Portland cement with a
clinker content of at least 90%. The abundance of raw clays and limestone is also an important factor
in the development of LC3 production, in contrast to the shrinking resources of good quality fly ash
or even their unavailability in some countries.
The most common composition for the LC3 is 50% of ground Portland clinker, 30% of ground
calcined clay, 15% of ground limestone and 5% of ground gypsum. Such a mixture is sometimes
referred to in the literature as LC3-50. Other proportions of components are also possible [149], but it
is known that cement prepared according to the above composition, according to the research
[113,150], reaches mechanical parameters corresponding to OPC already after seven days of
hydration, provided that the clay contains at least 40% kaolin.
An important aspect of LC3 production is its cost and profitability. Papers [151,152] present the
results of economic analysis of production of this type of ternary blend in India. The authors
concluded that the production of LC3 is economically viable if the following conditions are met: the
cost of fly ash will be high, the quality of fly ash will be low, the acquisition of fly ash will require
longer transport than the acquisition of clay and the quality of the extracted clay will reduce the
amount of clinker in cement. Most of these conditions are already met, for example, in countries
which do not have sources of good quality fly ash. Given the restrictions on the use of fossil fuels in
energy production, these conditions may soon be met automatically.
Apart from the economic aspect, the durability and performance of concrete with LC3 is no less
important. Several publications have been devoted to this issue. In papers [153,154] the authors
Materials 2020, 13, 4734 20 of 36

assessed the pore structure in concrete made of three types of cement: OPC, Portland pozzolana
cement with 30% of Class F fly ash and LC3. The results of the study showed a much finer pore
structure in concrete with LC3, which was proved in the mercury intrusion porosimetry study.
Additionally, the conductivity of the concrete obtained in this way turned out to be lower, which
allows one to assume that it will have higher resistance to the penetration of harmful ions into its
structure. In short, its durability can be predicted to be significantly higher than that of other concrete
series compared in the work.
Khan et al. [155] discussed carbonation of LC3. The study covered investigation of concrete with
cement, in which 15%, 30% and 45% of the mass was replaced by a mixture of calcined clay
(containing about 50% metakaolin and 50% quartz) and limestone in a ratio of 2:1. For comparison,
two series of concrete with OPC were used. One of them had the same aggregate, water and binder
ratio as the LC3 concrete series, and the other modified proportions and quantities. The results
indicate that concrete with LC3 and 15% cement exchange rate showed higher carbonation resistance
than concrete with OPC. At 30% a slight advantage was gained by concrete with OPC, and at a 45%
cement exchange rate to a mixture of calcined clay and limestone, concrete with LC3 showed a high
carbonation rate. The same authors [156] presented the results of the same concretes according to
their fresh properties, strength, porosity and drying shrinkage. They showed that the concrete with
LC3 was characterized by worse workability. As far as strength was concerned, the highest was
reached by concrete with a 15% exchange rate of cement, which also had the lowest porosity. As far
as drying shrinkage is concerned, all series of LC3 concrete were lower than OPC concrete.
An interesting approach to the issue of carbonation is presented in paper of Joseph et al. [157].
The authors have been tempted to create the protocol of testing the durability of LC3 (although not
only) with respect to carbonation. This protocol included the determination of indicators of the
carbonation process, such as diffusivity of CO2, hydration and carbonation products, total possible
carbonation, and pH change due to the carbonation and rate of carbonation. The paper also contains
a suggestion to determine the above mentioned elements and the possibility to apply the presented
approach to other issues concerning concrete durability.
Nguyen and Castel [158] evaluated the resistance of concrete with LC3 to chloride diffusion.
Three series of concrete were made for research purposes. One contained only general purpose
cement corresponding to Type I cement according to ASTM C150/C150M [159]. In the remaining two
15% and 20% of the cement was replaced by a mixture of calcined clay and limestone in the ratio 2:1.
The results indicate that the use of LC3 in concrete significantly increased its resistance to chloride
diffusion. The continuation of the research on chloride diffusion resistance Nguyen et al. presented
in [160], where they compared concrete made with OPC with concrete containing calcined clay
obtained in two technological processes: flash calcination and calcination in rotary kiln. Due to
differences in activity of both types of calcined clay, the authors decided to apply different
proportions of general purpose cement (as per Australian Standard AS 3972 [161]) to calcined clay
(20% for flash calcined clay and 44% for clay calcined in rotary kiln). This variation was due to the
intention to obtain the appropriate compressive strength of the hardened concrete (>45 MPa). The
results indicated four times higher chloride diffusion resistance of concrete with LC3. The difference
between the results of concrete made with different types of calcined clay turned out to be
insignificant, which led the authors to conclude that it is crucial in this case to properly select the
proportion of cement exchanged for calcined clay to meet the requirements of specific strength of
concrete exposed to chloride ingressives.
A different approach to chloride diffusion research was applied by Yang et al. [162]; they
discussed the results of simulations of this phenomenon in LC3 concrete and concrete with fly ash
compared to it. The authors conducted extensive simulations taking into account many elements
affecting the course of chloride diffusion in hardened concrete. The results showed that both
concretes had comparable service life even though the LC3 concrete contained less clinker. The
conclusions also indicated important parameters that should be introduced to the simulation in order
for the results to be reliable.
Materials 2020, 13, 4734 21 of 36

Nguyen and Castel [163] presented the results of research on corrosion of reinforcing steel in
concrete made using LC3. This issue is important because of the lower alkalinity of this type of
concrete due to the lower amount of portlandite, which is consumed by calcined clay in the
pozzolanic reaction. The research, carried out over 500 days, allowed the conclusion to be drawn that
performance of reinforced concrete prepared with LC3 was comparable to that for concrete with OPC
in the propagation phase.
Rengaraju et al. [164] also investigated corrosion of steel in concrete with LC3. They presented
the results of corrosion testing of steel in three concrete mixes prepared with the use of: OPC, a blend
of 70% OPC with 30% of fly ash and a blend of 50% OPC with a 50% mixture of limestone and calcined
clay. In their previous work [165] they carried out tests according to AASHTO T 358 standard [166],
which showed that concrete with LC3 showed very high resistivity, which is a good predictor of
resistance to chloride ion penetration and, consequently, to corrosion of reinforcing steel. As a
continuation of the tests, corrosion tests of steel in concrete were carried out using the method
included in ASTM G109 [167] and the impressed current corrosion test method. In the conclusions,
apart from the statement that LC3 cement composites showed higher resistance to chloride ingress
and better protection of steel against corrosion, the authors also claimed that the corrosion products
of steel in concrete with LC3 were less expansive and thus less destructive to concrete.
The study of corrosion of reinforcement in concrete made with LC3 was also conducted by
Pillai et al. [168]. They determined such concrete parameters as chloride diffusion coefficient, ageing
coefficient and chloride threshold for seven mixtures containing OPC and blends of OPC with
pulverised fuel ash (PFA) or with calcined clay and limestone (i.e., LC3). Using these parameters they
determined the service life of the two construction elements. The results showed that a construction
made of LC3 or blended cement with PFA will had a significantly longer service life with a much
smaller carbon footprint.
The issue of carbon footprint is focusing our attention on the eco-efficiency of LC3. In [169] the
authors have undertaken the assessment of the sustainability of LC3 using two methods: life cycle
analysis and eco-efficiency. The first method was used to assess the environmental impact of LC3
production compared to OPC and Portland pozzolana cement (with 20% zeolite content). The second
method assessed how the use of LC3 in the construction of a model residential building will increase
its eco-efficiency. The calculations led to the conclusion that the use of LC3 may lead to a reduction of
cement production costs by 4–40% and CO2 emissions by 15–30%.
No less important are the technological aspects related to LC3 production. The authors of paper
[170] undertook the assessment of suitability of four clays from deposits located in Cuba for LC3
production. The results turned out to be promising as they indicated that all examined clays had the
potential to be used in ternary blend cement production. Additionally, the authors showed that the
pozzolan activity was directly proportional to kaolinite equivalent (KEQ), and that the specific
surface area of the obtained cements depended mainly on the calcination temperature of the clays
and their mineralogical composition.
Nair et al. [171] presented the results of rheological properties test of cement paste and mortar
prepared using LC3 in comparison with OPC and Portland-fly ash cement (containing 30% Class F
fly ash). The effectiveness of five superplasticising admixtures based on polycarboxylic ethers (PCE)
differing in chemical composition and one admixture based on sulphonated naphthalene
formaldehyde (SNF) were also compared. The studies carried out have led to the conclusion that
larger quantities of superplasticisers were required for blends with LC3, with PCE providing a lower
viscosity than SNF and the latter additive had to be dosed in larger quantities to not allow to reduce
the w/b ratio below 0.4.
Li, X. and Scrivener, K.L [172] devoted their paper to the comparison of three methods of
determination of reacted metakaolin in LC3. The authors compared: mass balance [173],
thermodynamic modelling with Gibbs Free Energy Minimization Software [174] and the Partial or
not Known Crystalline Structure method (PONKCS) [175]. Of the methods analysed, the mass
balance approach yielded the most reliable results, although the use of GEMS software was, on the
other hand, less time-consuming and required less labour-intensive input. The PONKCS method
Materials 2020, 13, 4734 22 of 36

proved to be reliable in the case of LC3-50 mixtures containing clays with metakaolin content
above 60%.
Papers [176,177] present the results of two approaches to the pilot production of LC3 in India.
The composition of blends in both cases was almost the same: 50% Portland clinker, 30% or 31%
calcined clay, 15% crushed limestone and 4% or 5% gypsum. In the first approach [176] several
problems of technological nature emerged, such as too little fineness of the cement due to the use of
ground limestone and calcination of only part of the used clay. This resulted in a large scattering of
results and lower strength values of LC3 concretes. In the second approach [177], the authors did not
report any technological complications concluding that it is possible to produce good quality LC3
even without the need to change technologies in existing cement plants.
The influence of the degree of fineness of LC3 components on its selected physical and
mechanical parameters was examined and presented in [178]. It was assumed that each of the three
binder components (Portland cement—55%, calcined clay—30% and limestone—15%) can be ground
to two degrees: coarse and fine. In addition, in part of the series, clay or limestone was replaced by
finely ground quartz. The results indicate that the greatest influence on the strength parameters of
concrete with LC3 had the degree of clinker fineness, and a slightly lesser calcined clay fineness.
Limestone fineness was important only in the initial period of concrete strength development (up to
three days).
Examples of practical application of LC3 were presented by Maity et al. in [179]. Four different
LC blends with two types of clay and two types of limestone and, for comparison, Portland Pozzolan
3

Cement were used to produce concrete and various structural elements. All these products have
undergone quality control and have been incorporated into the construction of residential buildings.
The obtained results showed that the mechanical parameters of LC3 concrete can be even higher than
those of PPC concrete. The resulting buildings are tangible proof that LC3 had moved from the
concept and research phase to the first practical application tests.
Dhandapani and Santhanam [180] analysed the impact of the mutual ratio of limestone and
calcined clay on the binding and strength development of LC3 and blends in which the calcined clay
was replaced by Class F fly ash. Binary blends without added limestone were used as a reference.
The research showed a clear influence of limestone on the setting of the concrete and much less on
the further development of its strength. In addition, concrete using calcined clay achieved a very
significantly higher strength after seven and 28 days of hardening.
Ferreiro et al. [181] analysed the influence of the clay calcination temperature in the flash
calcination process and the fineness of raw clay on the workability and strength performance of LC3.
They used two types of clay, which were calcined in two different installations (gas suspension
calciner and flash calciner) and at two different temperatures. The clays used consisted mainly of
minerals of group 2:1, which was an additional value of the work, as most of the research on LC3 was
based mainly on clays containing kaolin. The results obtained allowed to conclude that both the
calcination temperature and the degree of fragmentation of the material subjected to this process had
a significant impact on the workability of fresh LC3 mortars and their strength development.
The influence of the method of constituent grinding on rheology and early strength of LC3 tested
on mortars was examined by Perez et al. [182]. The constituent were ground both separately and
jointly. Clinker, limestone and calcined clay ground separately were divided into three fractions,
from which LC3 was then composed using different combinations of the degree of grinding of the
components. In the case of components ground jointly the grinding time varied (25, 45 and 65 min).
As far as the latter case is concerned, the results indicate that the longer the grinding time, the higher
the strength of the LC3 later reached, while the change of mini slump radius over 45 min of grinding
time was no longer significant. In the case of separated milling, the degree of grinding of the clinker
was crucial and the degree of grinding of limestone was of secondary importance. The influence of
the degree of milling calcined clay was not studied by the authors.
The suitability of LC3 as a material for 3D printing process has been investigated by Chen et al.
[183]. They prepared four mixtures containing different proportions of two calcined clay with lower
(49%) and higher (90%) metakaolinite content, and then conducted extrudability and earlier strength
Materials 2020, 13, 4734 23 of 36

tests on them. The results showed that as the amount of metakaolinite in LC3 blend increased, its
extrudability decreased but at the same time the early strength increased. Therefore, it is crucial to
find the optimal content of metakaolinite in LC3 used for blends in 3D printing. A referral to the same
topic is in [184], in which the authors analyse the influence of viscosity modifying admixture on
extrudability of LC3 based materials.
Avet and Scrivener [185,186] focused on the issue of hydration of LC3 depending on the content
of calcined kaolinite in the blend. The research was carried out on LC3-50 blends with different
metakaolinite content. The results showed that with calcined kaolinite above 65% hydration of clinker
was slowed down after three days due to refinement of the pore structure. However, despite this, the
strength was still increasing, which is connected with further reaction of metakaolinite and increase
of the C-A-S-H amount.
Zunino and Scrivener [187] dealt with reactivity and mechanical performance of three mixtures
containing Portland cement, Portland cement-limestone blend and LC3. The distinction of this
publication is that the prepared mixtures were cured at a lowered temperature of 10 °C. The same
mixtures cured at 20 °C were used as a reference. The research included determination of
compressive strength after 1, 7 and 28 days, isothermal calorimetry as well as XRD phase assemblage
assessment and MIP pore refinement assessment. They found that LC3 cured at lower temperature
achieved significantly higher compressive strength than the same cement paste cured at higher
temperature. The authors claim that this was an effect of, among others, a slightly different course of
hydration of this cement.
In the summary of this chapter, it would be appropriate to repeat the concluding statements of
the previous section which indicate the need to extend the interest in clays which may be active after
calcination and which do not contain kaolinite or contain small amounts of kaolinite. Another
interesting aspect that comes to mind after reading the above article on the practical application of
LC3 is the possibility to test the suitability of this type of binder as a base for concrete for road
construction.

7. Influence of Calcined Clay on the Durability of Concrete

Durability issues are important for each of the cement-based materials used nowadays. A studies
related to the durability of cement-based composites prepared with calcined clays are presented in
this chapter.
Trümer and Ludwig [188] put forward the thesis that one of the obstacles to the wider use of
calcined clays in cement and concrete technology is the lack of information on the long-time
behaviour of the concrete. They used clays of various mineralogical composition, which they
subjected to the process of thermal activation and used in concrete mixtures as a substitute for 30%
of the cement. The investigated concretes focused on the resistance to sulphate attack, alkali-silica
reaction, chloride ingress as well as freezing-thawing resistance and carbonation. They revealed that
calcined clays in concrete showed significantly lower pozzolanic activity than in other cement
systems, which had a direct impact on the durability of concrete. As far as resistance to chloride
ingress is concerned, all clays have passed the test. At the other extreme is freeze-thaw resistance,
where only concrete with metakaolin showed satisfactory performance. Carbonation of concrete with
calcined clay, due to the reduction of Ca(OH)2 consumed in the pozzolanic reaction, progressed faster
than in concrete with OPC. The confirmation of pozzolanic activity should not be synonymous with
the recognition that the tested clay is suitable for the production of cement or concrete, because
depending on its composition and quality its influence on durability parameters may be diametrically
different.
Slightly more optimistic conclusions about the durability of concrete with cement blended with
calcined clay were formulated by Pierkes et al. [189]. They prepared a series of concretes using
cements with 20% (CEM II/A-Q) and 40% (CEM IV/A-Q) of various calcined clays and determined
their durability parameters, i.e., resistance to carbonation, chloride migration, freezing-thawing and
frost-deicing salts. The first three tests were carried out on non-air-entrained concrete and the fourth
on air-entrained concrete. The results indicated that concrete with the addition of calcined clays was
Materials 2020, 13, 4734 24 of 36

able to achieve comparable values of durability parameters as concrete with the addition of other
pozzolanic additives, such as fly ash or silica fume.
Shah et al. [190] prepared a short literature review on the durability of concrete with low clinker
content, which is replaced by various mineral additives: fly ash, calcined clay, limestone and slag.
This review covered chloride migration/penetration, carbonation, sulphate attack and alkali-silica
reaction. The authors concluded that significant chloride resistance can be achieved by using a
combination of mineral additives and, after that, the resistance was higher than blended cements.
The influence of mineral additions on carbonation was summarised by the statement that above a
certain level of exchange rate resistance of cement with mineral additions this resistance started to
decrease. Calcined clays were found to cause the faster front of carbonation in the material. ASR
(alkali-silica reaction) could be mitigated by SCMs, of which metakaolin is directly named. When it
comes to resistance to sulphate attack, the authors are of the opinion that a combination of calcined
clay and limestone appears to deteriorate in a sulphate environment.
Castillo Lara et al. [191] have conducted tests of physical-mechanical and durability properties
on micro-concrete. From this work only the part concerning the tests of durability, which in this case
were water absorption and sorptivity, was discussed. The tests were carried out on a cement system
defined as micro-concrete, whose characteristic feature was a maximum aggregate grain size of 5
mm, i.e., more than for mortars and less than for ordinary concrete. Two kinds of calcined clay
obtained from raw clay soil were used as a substitute for 30% cement. The results showed a decrease
in both water absorption and sorptivity of the micro-concrete tested after using a cement blend with
calcined clay compared to the material with OPC only.
The issue of carbonation of binders with metakaolin has been investigated by Bucher et al. [192].
The authors have carried out the research using the cements of type CEM I, CEM II/A-LL and CEM
II/A-V as a reference. The depth of carbonation was determined on concrete specimens made with
cements without additives and with partial replacement of cement with metakaolin. The results
confirmed that the use of calcined clay accelerated the carbonation of concrete except when the
component of cement blend was limestone (i.e., in the case of CEM II/A-L cement). Concrete with this
blend containing 15% of metakaolin showed higher resistance to carbonation than concrete with
Portland cement itself.
Studies [193,194] were devoted to resistance of cement mortars, containing, e.g., calcined clays,
to chloride ingress. The first one discusses the results of tests carried out on mortar specimens
prepared using ten different binders. These binders were composed by replacing 35% of the cement
with pozzolanic active materials, including calcined clay. The research concerned concretes subjected
to an artificial marine environment for 270 days. The use of alternative binders allowed the obtaining
of a material with adequate resistance to chloride ingress while reducing CO2 emissions by 15%. In
the other paper the authors investigated, among others, the resistance to chloride ingress of mortar
prepared from cement with 35% content of calcined clay. In one of the mortar series, water was
replaced with 0.5 M Na2SO4 solution, which served as a chemical activator and precursor of ettringite
formation. The results of strength and resistance to chloride ingress revealed that the use of such a
chemical activator positively affected both parameters.
Calcined clay is a pozzolanic material which makes it possible to reduce the negative effects of
alkali-silica reaction, which has been demonstrated in a number of studies [188,195,196]. This is one
of the methods of preventing ASR, besides the use of low-reactivity aggregate [197]. Paper [195]
presents results of tests of mortars made with high alkali Portland limestone cement, in which 0%–
30% of cement binder was replaced with calcined clay. Cement used in the research was characterized
by 4.32% Na2Oeq. As the amount of calcined clay in cement increased, the expansion of mortar bars
decreased. The lowest expansion value was achieved by mortar with 25% content. The authors
attributed this to the formation of more CaSi2O5 and the associated reduction of sodium silicate,
which is the main product of the ASR reaction responsible for the damage caused by it. In [196] the
authors presented the results of research on effectiveness of calcined clays in ASR mitigation. Mortars
containing highly reactive aggregate and four different types of calcined clays (replacing cement in
the amount of 5%, 10%, 15% and 20%) were used in the research. The research showed that the
Materials 2020, 13, 4734 25 of 36

chemical and mineral composition of the clay was crucial for the effectiveness of ASR mitigation.
Trümer and Ludwig [188] tested the resistance of concrete with cement mixed with calcined clay to
both ASR and sulphate attack. Three calcined clays containing as basic minerals, respectively,
kaolinite, illite and montmorillonite after mixing with CEM I cement in a ratio of 30:70 significantly
reduced the expansion of mortars and increased their resistance to sulphate attack.
Studies [198–200] were devoted to research on the resistance of cement composites to sulphate
attack. Aramburo et al. [198] tested cement with a high content of calcined clay to show that it was
possible to produce CEM IV/A-SR and CEM IV/B-SR type cements, which complied with the
requirements of the current European standard UNE EN 197-1:2011 [201]. The specificity of this study
was the very high degree of cement exchange for calcined clay, which was 40%, 50%, 60% and 70%.
Apart from calcined clay, two different Portland cements were used in cement mixes, one with high
C3A content and the other with high C3S content. The research showed the required increase in
resistance to sulphate cements with calcined clay was accompanied by a decrease in compressive
strength. Al-Akhras [199] presented the results of a wide range of research, in which the influence of
the exchange of 5%, 10% and 15% of cement to metakaolin on the durability of concrete to sulphate
attack was analysed. Apart from various degrees of cement exchange to calcined kaolin, the w/c ratio,
initial moist curing period, curing type and air content were also variable parameters. The results
allowed to formulate a conclusion that 10% and 15% of the exchange of cement to metakaolin allowed
to achieve excellent durability to sulphate attack. Concrete with a lower w/c ratio achieved better
durability performances, the time of moist curing proved to be insignificant, autoclaving increased
the resistance to moist curing ratio as well as offer a higher air content in concrete. Shi et al. [200]
presented the results of a study on the influence of 35% of cement exchange on calcined clay
(metakaolin or calcined montmorillonite) or calcined clay and limestone in different proportions on
sulphate resistance of mortars. White Portland cement and ordinary Portland cement were used as
base cements. The results showed that all mixtures in which the ratio of calcined clay to the sum of
calcined clay and limestone was greater than 0.5 showed excellent resistance to sulphate attack.
Quite a large group of papers on durability are focused on cement systems with calcined kaolin.
Saillio et al. [202], as well as Yazıcı [203], have analysed various aspects of the durability of concrete
and mortars produced with metakaolin addition. Tafraoui et al. [204] gave a brief literature review
on the durability of ultra-high performance concrete containing metakaolin. Badogiannis and Tsivilis
[205] dedicated their article to the study of the effect of Greek low kaolinite on the durability of
concrete, and Shekarchi et al. [206] examined the transport properties (i.e., water penetration, gas
permeability, water absorption, electrical resistivity and chloride ingress) of metakaolin-blended
cement.
Shi et al. [207] analysed the results of a durability study of Portland cement blends containing,
apart from cement, the following additives: pure limestone, pure metakaolin, metakaolin and
limestone in 3:1 mass proportion, metakaolin and silica fume, and the three additions simultaneously.
The obtained results allowed to state that mortar with pure limestone showed the worst durability
parameters in all tests. Mortar with pure cement had the highest resistance to carbonation, but it did
not perform well in resistance tests to sulphate attack and chloride ingress, and mortar with pure
metakaolinite obtained exactly the opposite resistance parameters.
The issues of concrete durability with calcined clay have also been addressed in two review
articles on calcined clays [47] and SCMs in general [58].
A review of studies on the durability of concrete with calcined clay makes it clear that the subject
is by no means exhausted. There are relatively few studies on frost resistance and resistance to surface
scaling. These issues are important for countries where, during the colder seasons, the temperature
can repeatedly pass through zero, while relatively fewer articles come from these countries. When
studying these durability properties, it also seems appropriate to determine the compatibility of
binders containing calcined clay with air-entraining agents.
Due to the confirmed effectiveness of the addition of calcined clay in limiting the alkali-silica
reaction, it is worth considering the simultaneous use of these co-binders with waste glass, either as
an aggregate in concrete or as an additional material exhibiting pozzolanic activity. The use of waste
Materials 2020, 13, 4734 26 of 36

glass has so far been limited by concerns about the durability of concrete. Among the studies on the
durability aspects of concrete with calcined clays, it is also difficult to find those concerning air
permeability. It can be assumed that in this aspect of concrete with the addition of calcined clay will
be superior to concrete based on traditional cements, but there is a great deal of room for research
between the conjecture and hard evidence.

8. Conclusions
This review paper presents the idea of the replacement of Portland cement by addition of
calcined clays. Such application of this kind of pozzolanic materials, as clinker/cement replacement
or as supplementary cementitious materials, can be an ecological and economically justified way to
meet the global need to reduce CO2 emissions in concrete technology. Although clay is a material
with a very diverse mineralogical composition, its low price, availability and, above all, its
distribution in the world make it a valuable supplementary cementitious material in concrete
technology.
Several studies have shown that the thermal treatment is necessary to activate the clay’s minerals
or to increase their pozzolanic activity. To determine the conditions of success of the calcination
process, the effects of time, temperature and particle size were investigated.
It was shown that mixing various clays in appropriate proportions with cement allowed to
obtain a concrete with satisfactory mechanical parameters, much better than the reference one
without calcined clay. It was described that the use of calcined clay increased both early age and long-
term mechanical properties of cement paste, mortar and concrete. Moreover, it was found that the
replacement of cement content by calcined clay influenced the reduction of the bleeding and
shrinkage. The simultaneous use of calcined clays as binder components with other types of pozzolan
was also shown.
Research on various aspects of a new binder type—lime calcined clay cement, LC3—was
thoroughly described. Its composition (Portland clinker, calcined clay, calcium carbonate and
gypsum) and as well as fresh mix properties and concrete resistance against aggressive liquid and
gaseous media were presented.
It is confirmed that cement systems containing calcined clay, also with the addition of limestone,
showed better durability and increased resistance to most of the aggressive actions to which concrete
was exposed. The exception was carbonation, but satisfactory results have also been achieved in this area.
Most of the discussed papers were carried out on mortar or cement paste, and clearly less on
concrete. It seems that the application of calcined clay as a supplementary cementitious material in
concrete technology requires more research, as not all the findings performed on a smaller scale (i.e.,
on mortars and cement paste) can be directly transferred to the parameters and performance of
concrete.
Future research aimed at improving the long-term durability of cement-based composites
containing calcined clays is needed. It is suggested to optimize the composition of calcined clay
cements by selecting the appropriate chemical and mineral components of raw materials to obtain
the required mechanical parameters. Additionally, more research should be carried out on the
practical application in the cement and concrete production of calcined clays of group 2:1. While there
is a great deal of basic research on clays and minerals themselves, application research in this field is
dominated by clays containing mainly kaolinite.

Author Contributions: Conceptualization: R.J. and D.J.-N.; methodology: R.J., D.J.-N. and Y.Y.; formal analysis:
R.J. and D.J.-N.; resources: R.J. and Y.Y.; writing—original draft preparation: R.J. and D.J.-N.; writing—review
and editing: R.J. and D.J.-N.; supervision: D.J.-N. and R.J. All authors have read and agreed to the published
version of the manuscript.

Funding: This research received no external funding.

Conflicts of Interest: The authors declare no conflict of interest.

Materials 2020, 13, 4734 27 of 36

References
1. Damtoft, J.S.; Lukasik, J.; Herfort, D.; Sorrentino, D.M.; Gartner, E.M. Sustainable development and climate
change initiatives. Cem. Concr. Res. 2008, 38, 115–127.
2. ASTM. ASTM C125-20 Standard Terminology Relating to Concrete and Concrete Aggregates; ASTM Standard;
ASTM International: West Conshohocken, PA, USA, 2020; p. 9.
3. Emmanuel, A.C.; Parashar, A.; Bishnoi, S. The Role of Calcined Clay Cement vis a vis Construction
Practices in India and Their Effects on Sustainability. In Calcined Clays for Sustainable Concrete; RILEM
Bookseries; Springer Science and Business Media LLC: Dordrecht, The Netherlands, 2015; pp. 411–417.
ISBN 9789401799393.
4. WBCSD-IEA. Low-Carbon Technology for the Indian Cement Industry; IEA Technology Roadmaps; OECD:
Paris, France, 2013; ISBN 9789264197008.
5. Kosior-Kazberuk, M.; Józwiak-Niedzwiedzka, D. Influence of Fly Ash From Co-Combustion of Coal and
Biomass on Scaling Resistance of Concrete. Arch. Civ. Eng. 2010, 56, 239–254.
6. Murray, H.H. Industrial Applications of Kaolin. Clays Clay Miner. 1961, 10, 291–298.
7. Murray, H.H. Traditional and new applications for kaolin, smectite, and palygorskite: A general overview.
Appl. Clay Sci. 2000, 17, 207–221.
8. Neißer-Deiters, A.; Scherb, S.; Beuntner, N.; Thienel, K.-C. Influence of the calcination temperature on the
properties of a mica mineral as a suitability study for the use as SCM. Appl. Clay Sci. 2019, 179, 105168.
9. Nawel, S.; Mounir, L.; Hedi, H. Effect of temperature on pozzolanic reaction of Tunisian clays calcined in
laboratory. SN Appl. Sci. 2020, 2, 157.
10. Maier, M.; Beuntner, N.; Thienel, K.-C. An Approach for the Evaluation of Local Raw Material Potential for
Calcined Clay as SCM, Based on Geological and Mineralogical Data: Examples from German Clay
Deposits. In Calcined Clays for Sustainable Concrete; RILEM Bookseries: Dordrecht, The Netherlands, 2020;
Volume 25, pp. 37–47.
11. Tironi, A.; Trezza, M.A.; Scian, A.N.; Irassar, E.F. Kaolinitic calcined clays: Factors affecting its performance
as pozzolans. Constr. Build. Mater. 2012, 28, 276–281.
12. Brigatti, M.F.; Galán, E.; Theng, B.K.G. Structure and Mineralogy of Clay Minerals. In Handbook of Clay
Science; Bergaya, F., Lagaly, G., Eds.; Elsevier Ltd: Amsterdam, The Netherlands, 2013; pp. 21–81.
13. Brigatti, M.F.; Guggenheim, S. Mica Crystal Chemistry and the Influence of Pressure, Temperature, and
Solid Solution on Atomistic Models. Rev. Mineral. Geochem. 2002, 46, 1–97.
14. He, C.; Makovicky, E.; Øsbæck, B. Thermal stability and pozzolanic activity of raw and calcined mixed-
layer mica/smectite. Appl. Clay Sci. 2000, 17, 141–161.
15. Garg, N.; Skibsted, J. Pozzolanic reactivity of a calcined interstratified illite/smectite (70/30) clay. Cem.
Concr. Res. 2016, 79, 101–111.
16. Lemma, R.; Castellano, C.C.; Bonavetti, V.L.; Trezza, M.A.; Rahhal, V.F.; Irassar, E.F. Thermal
Transformation of Illitic-Chlorite Clay and Its Pozzolanic Activity. In Calciner Clays for Sustainable Concrete;
RILEM Bookseries: Dordrecht, The Netherlands, 2018; Volume 16, pp. 266–272. ISBN 9789402412062.
17. He, C.; Øsbæck, B.; Makovicky, E. Pozzolanic reactions of six principal clay minerals: Activation, reactivity
assessments and technological effects. Cem. Concr. Res. 1995, 25, 1691–1702.
18. Fernández, R.; Martirena-Hernández, J.F.; Scrivener, K.L. The origin of the pozzolanic activity of calcined
clay minerals: A comparison between kaolinite, illite and montmorillonite. Cem. Concr. Res. 2011, 41,
113–122.
19. Brown, I.W.M.; MacKenzie, K.J.D.; Meinhold, R.H. The thermal reactions of montmorillonite studied by
high-resolution solid-state 29Si and 27Al NMR. J. Mater. Sci. 1987, 22, 3265–3275.
20. Rashad, A.M. Metakaolin as cementitious material: History, scours, production and composition–A
comprehensive overview. Constr. Build. Mater. 2013, 41, 303–318.
21. Garg, N.; Wang, K. Comparing the performance of different commercial clays in fly ash-modified mortars.
J. Sustain. Cem.Based Mater. 2012, 1, 111–125.
22. Garg, N.; Skibsted, J. Thermal Activation of a Pure Montmorillonite Clay and Its Reactivity in Cementitious
Systems. J. Phys. Chem. C 2014, 118, 11464–11477.
23. Garg, N.; Skibsted, J. Heated Montmorillonite: Structure, Reactivity, and Dissolution. In Calcined Clays for
Sustainable Concrete; RILEM Bookseries; Springer: Dordrecht, The Netherlands, 2015; pp. 117–124,
ISBN 9789401799393.
Materials 2020, 13, 4734 28 of 36

24. Ambroise, J.; Murât, M.M.; Péra, J. Hydration reaction and hardening of calcined clays and related minerals
V. Extension of the research and general conclusions. Cem. Concr. Res. 1985, 15, 261–268.
25. He, C.; Makovicky, E.; Øsbæck, B. Thermal treatment and pozzolanic activity of Na- and Ca-
montmorillonite. Appl. Clay Sci. 1996, 10, 351–368.
26. Pomakhina, E.; Deneele, D.; Gaillot, A.-C.; Paris, M.; Ouvrard, G. 29Si solid state NMR investigation of
pozzolanic reaction occurring in lime-treated Ca-bentonite. Cem. Concr. Res. 2012, 42, 626–632.
27. Scherb, S.; Beuntner, N.; Thienel, K.-C. Reaction Kinetics of Basic Clay Components Present in Natural
Mixed Clays. In Calcined Clays for Sustainable Concrete; RILEM Bookseries; Springer: Dordrecht,
The Netherlands, 2018; Volume 16, pp. 427–433. ISBN 9789402412062.
28. Tironi, A.; Trezza, M.A.; Scian, A.N.; Irassar, E.F. Assessment of pozzolanic activity of different calcined
clays. Cem. Concr. Compos. 2013, 37, 319–327.
29. Joussein, E.; Petit, S.; Churchman, J.; Theng, B.; Righi, D.; Delvaux, B. Halloysite clay minerals—A review.
Clay Miner. 2005, 40, 383–426.
30. Tironi, A.; Cravero, F.; Scian, A.N.; Irassar, E.F. Pozzolanic activity of calcined halloysite-rich kaolinitic
clays. Appl. Clay Sci. 2017, 147, 11–18.
31. Tironi, A.; Cravero, F.; Scian, A.N.; Irassar, E.F. Hydration of Blended Cement with Halloysite Calcined
Clay. In Calcined Clays for Sustainable Concrete; RILEM Bookseries; Springer: Dordrecht, The Netherlands,
2018; Volume 16, pp. 455–460. ISBN 9789402412062.
32. He, C.; Makovicky, E.; Øsbæck, B. Thermal treatment and pozzolanic activity of sepiolite. Appl. Clay Sci.
1996, 10, 337–349.
33. He, C.; Makovicky, E.; Øsbæck, B. Thermal stability and pozzolanic activity of calcined illite. Appl. Clay Sci.
1995, 9, 337–354.
34. Lemma, R.; Irassar, E.F.; Rahhal, V. Calcined Illitic Clays as Portland Cement Replacements. In Calcined
Clays for Sustainable Concrete; Springer: Dordrecht, The Netherlands, 2015; pp. 269–276.
ISBN 9789401799393.
35. Weaver, C.E. The Distribution and Identification of Mixed-layer Clays in Sedimentary Rocks. Am. Mineral.
1956, 41, 202–221.
36. Wright, A. Catalysis by layer lattice silicates. I. The structure and thermal modification of a synthetic
ammonium dioctahedral clay. J. Catal. 1972, 25, 65–80.
37. Khalifa, A.Z.; Cizer, Ö.; Pontikes, Y.; Heath, A.; Patureau, P.; Bernal, S.A.; Marsh, A.T.M. Advances in
alkali-activation of clay minerals. Cem. Concr. Res. 2020, 132, 106050.
38. Frost, R.L.; Makó, É.; Kristóf, J.; Horváth, E.; Kloprogge, J.T. Mechanochemical Treatment of Kaolinite.
J. Colloid Interface Sci. 2001, 239, 458–466.
39. Frost, R.L.; Makó, É.; Kristóf, J.; Horváth, E.; Kloprogge, J.T. Modification of Kaolinite Surfaces by
Mechanochemical Treatment. Langmuir 2001, 17, 4731–4738.
40. Vizcayno, C.; de Gutiérrez, R.M.; Castello, R.; Rodriguez, E.; Guerrero, C.E. Pozzolan obtained by
mechanochemical and thermal treatments of kaolin. Appl. Clay Sci. 2010, 49, 405–413.
41. Samet, B.; Mnif, T.; Chaabouni, M. Use of a kaolinitic clay as a pozzolanic material for cements: Formulation
of blended cement. Cem. Concr. Compos. 2007, 29, 741–749.
42. Morsy, M.S.; El-Enein, S.A.A.; Hanna, G.B. Microstructure and hydration characteristics of artificial
pozzolana-cement pastes containing burnt kaolinite clay. Cem. Concr. Res 1997, 27, 1307–1312.
43. Komadel, P. Chemically modified smectites. Clay Miner. 2003, 38, 127–138.
44. Sánchez, I.; de Soto, I.S.; Casas, M.; Vigil de la Villa, R.; García-Giménez, R. Evolution of Metakaolin
Thermal and Chemical Activation from Natural Kaolin. Minerals 2020, 10, 534.
45. Belviso, C.; Cavalcante, F.; Niceforo, G.; Lettino, A. Sodalite, faujasite and A-type zeolite from 2:1
dioctahedral and 2:1:1 trioctahedral clay minerals. A singular review of synthesis methods through
laboratory trials at a low incubation temperature. Powder Technol. 2017, 320, 483–497.
46. Ambroise, J.; Murât, M.M.; Péra, J. Investigations on synthetic binders obtained by middle-temperature
thermal dissociation of clay minerals. Silic. Ind. 1996, 7, 99–107.
47. Sabir, B.B.; Wild, S.; Bai, J. Metakaolin and calcined clays as pozzolans for concrete: A review. Cem. Concr.
Compos. 2001, 23, 441–454.
48. Todor, D.N. Thermal Analysis of Minerals; Abacus Press: Tunbridge Wells, UK, 1976; ISBN 978-0856261015.
Materials 2020, 13, 4734 29 of 36

49. Alujas Díaz, A.; Martirena-Hernández, J.F. Influence of Calcination Temperature on the Pozzolanic
Reactivity of a Low Grade Kaolinitic Clay. In Calcined Clays for Sustainable Concrete; RILEM Bookseries 10;
Scrivener, K.L., Favier, A.R., Eds.; RILEM: Dordrecht, The Netherlands, 2015; pp. 331–338.
50. Chakchouk, A.; Trifi, L.; Samet, B.; Bouaziz, S. Formulation of blended cement: Effect of process variables
on clay pozzolanic activity. Constr. Build. Mater. 2009, 23, 1365–1373.
51. Salvador, S. Pozzolanic properties of flash-calcined kaolinite: A comparative study with soak-calcined
products. Cem. Concr. Res 1995, 25, 102–112.
52. Slade, R.C.T.; Davies, T.W.; Atakül, H.; Hooper, R.M.; Jones, D.J. Flash calcines of kaolinite: Effect of process
variables on physical characteristics. J. Mater. Sci. 1992, 27, 2490–2500.
53. Rasmussen, K.E.; Moesgaard, M.; Køhler, L.L.; Tran, T.T.; Skibsted, J. Comparison of the Pozzolanic
Reactivity for Flash and Soak Calcined Clays in Portland Cement Blends. In Calcined Clays for Sustainable
Concrete; RILEM Bookseries; Springer: Dordrecht, The Netherlands, 2015; pp. 151–157. ISBN 9789401799393.
54. Teklay, A.; Yin, C.; Rosendahl, L.; Køhler, L.L. Experimental and modeling study of flash calcination of
kaolinite rich clay particles in a gas suspension calciner. Appl. Clay Sci. 2015, 103, 10–19.
55. Salvador, S.; Davies, T.W. Modelling of combined heating and dehydroxylation of kaolinite particles
during flash calcination; production of metakaolin. Process. Adv. Mater. 1994, 4, 128–135.
56. Bich, C.; Ambroise, J.; Péra, J. Influence of degree of dehydroxylation on the pozzolanic activity of
metakaolin. Appl. Clay Sci. 2009, 44, 194–200.
57. Teklay, A.; Yin, C.; Rosendahl, L.; Bøjer, M. Calcination of kaolinite clay particles for cement production: A
modeling study. Cem. Concr. Res 2014, 61–62, 11–19.
58. Juenger, M.C.G.; Siddique, R. Recent advances in understanding the role of supplementary cementitious
materials in concrete. Cem. Concr. Res 2015, 78, 71–80.
59. Taylor-Lange, S.C.; Riding, K.A.; Juenger, M.C.G. Increasing the reactivity of metakaolin-cement blends
using zinc oxide. Cem. Concr. Compos. 2012, 34, 835–847.
60. Taylor-Lange, S.C.; Rajabali, F.; Holsomback, N.A.; Riding, K.; Juenger, M.C.G. The effect of zinc oxide
additions on the performance of calcined sodium montmorillonite and illite shale supplementary
cementitious materials. Cem. Concr. Compos. 2014, 53, 127–135.
61. Ghorbel, H.; Samet, B. Effect of iron on pozzolanic activity of kaolin. Constr. Build. Mater. 2013, 44, 185–191.
62. Chotoli, F.F.; Quarcioni, V.A.; Lima, S.S.; Ferreira, J.C.; Ferreira, G.M. Clay Activation and Color
Modification in Reducing Calcination Process: Development in Lab and Industrial Scale. In Calcined Clays
for Sustainable Concrete; RILEM Bookseries; Springer: Dordrecht, The Netherlands, 2015; pp. 479–486 ISBN
9789401799393.
63. Sperinck, S.; Raiteri, P.; Marks, N.; Wright, K. Dehydroxylation of kaolinite to metakaolin—A molecular
dynamics study. J. Mater. Chem. 2011, 21, 2118–2125.
64. Drits, V.A. An Improved Model for Structural Transformations of Heat-Treated Aluminous Dioctahedral
2:1 Layer Silicates. Clays Clay Miner. 1995, 43, 718–731.
65. Fitzgerald, J.J.; Hamza, A.I.; Dec, S.F.; Bronnimann, C.E. Solid-State 27 Al and 29 Si NMR and 1 H CRAMPS
Studies of the Thermal Transformations of the 2:1 Phyllosilicate Pyrophyllite. J. Phys. Chem. 1996, 100,
17351–17360.
66. Frost, R.L.; Barron, P.F. Solid-state silicon-29 and aluminum-27 nuclear magnetic resonance investigation
of the dehydroxylation of pyrophyllite. J. Phys. Chem. 1984, 88, 6206–6209.
67. Hollanders, S.; Adriaens, R.; Skibsted, J.; Cizer, Ö.; Elsen, J. Pozzolanic reactivity of pure calcined clays.
Appl. Clay Sci. 2016, 132, 552–560.
68. Muñoz-Santiburcio, D.; Kosa, M.; Hernández-Laguna, A.; Sainz-Díaz, C.I.; Parrinello, M. Ab Initio
Molecular Dynamics Study of the Dehydroxylation Reaction in a Smectite Model. J. Phys. Chem. C 2012,
116, 12203–12211.
69. Drachman, S.R.; Roch, G.E.; Smith, M.E. Solid state NMR characterisation of the thermal transformation of
Fuller’s Earth. Solid State Nucl. Magn. Reson. 1997, 9, 257–267.
70. Taylor-Lange, S.C.; Lamon, E.L.; Riding, K.A.; Juenger, M.C.G. Calcined kaolinite–bentonite clay blends as
supplementary cementitious materials. Appl. Clay Sci. 2015, 108, 84–93.
71. McConville, C.J.; Lee, W.E. Microstructural Development on Firing Illite and Smectite Clays Compared
with that in Kaolinite. J. Am. Ceram. Soc. 2005, 88, 2267–2276.
Materials 2020, 13, 4734 30 of 36

72. Alujas Díaz, A.; Almenares Reyes, R.S.; Carratalá, F.A.; Martirena-Hernández, J.F. Proposal of a
Methodology for the Preliminary Assessment of Kaolinitic Clay Deposits as a Source of SCMs. In Calcined
Clays for Sustainable Concrete; RILEM Bookseries; Springer: Dordrecht, The Netherlands, 2018; Volume 16,
pp. 29–34. ISBN 9789402412062.
73. Chatterjee, A.K. Pozzolanicity of Calcined Clay. In Calcined Clays for Sustainable Concrete; RILEM
Bookseries; Springer: Dordrecht, The Netherlands, 2015; pp. 83–89 ISBN 9789401799393.
74. de Silva, P.S.; Glasser, F.P. Hydration of cements based on metakaolin: Thermochemistry. Adv. Cem. Res.
1990, 3, 167–177.
75. Dunster, A.M.; Parsonage, J.R.; Thomas, M.J.K. The pozzolanic reaction of metakaolinite and its effects on
Portland cement hydration. J. Mater. Sci. 1993, 28, 1345–1350.
76. Dron, R. L’activite Pouzzolanique. Bulletin de liaison des laboratoires des ponts et chaussées. Spécial 1978,
93, 66–69.
77. Bonavetti, V.; Donza, H.; Rahhal, V.F.; Irassar, E.F. Influence of initial curing on the properties of concrete
containing limestone blended cement. Cem. Concr. Res 2000, 30, 703–708.
78. Donatello, S.; Tyrer, M.; Cheeseman, C.R. Comparison of test methods to assess pozzolanic activity.
Cem. Concr. Compos. 2010, 32, 121–127.
79. Tkaczewska, E. Methods of testing pozzolanic actvity of mineral additives. Mater. Ceram. Ceram. Mater.
2011, 63, 536–541. (In Polish)
80. Payá, J.; Borrachero, M..; Monzó, J.; Peris-Mora, E.; Amahjour, F. Enhanced conductivity measurement
techniques for evaluation of fly ash pozzolanic activity. Cem. Concr. Res 2001, 31, 41–49.
81. McCarter, W.J.; Tran, D. Monitoring pozzolanic activity by direct activation with calcium hydroxide.
Constr. Build. Mater. 1996, 10, 179–184.
82. Sinthaworn, S.; Nimityongskul, P. Effects of temperature and alkaline solution on electrical conductivity
measurements of pozzolanic activity. Cem. Concr. Compos. 2011, 33, 622–627.
83. Velázquez, S.; Monzó, J.; Borrachero, M.; Payá, J. Assessment of Pozzolanic Activity Using Methods Based
on the Measurement of Electrical Conductivity of Suspensions of Portland Cement and Pozzolan. Materials
2014, 7, 7533–7547.
84. Mostafa, N.Y.; El-Hemaly, S.A.S.; Al-Wakeel, E.I.; El-Korashy, S.A.; Brown, P.W. Activity of silica fume and
dealuminated kaolin at different temperatures. Cem. Concr. Res 2001, 31, 905–911.
85. Mostafa, N.Y.; Brown, P.W. Heat of hydration of high reactive pozzolans in blended cements: Isothermal
conduction calorimetry. Thermochim. Acta 2005, 435, 162–167.
86. Tironi, A.; Trezza, M.A.; Scian, A.N.; Irassar, E.F. Thermal analysis to assess pozzolanic activity of calcined
kaolinitic clays. J. Therm. Anal. Calorim. 2014, 117, 547–556.
87. Federico, L.M.; Chidiac, S.E.; Raki, L. Reactivity of cement mixtures containing waste glass using thermal
analysis. J. Therm. Anal. Calorim. 2011, 104, 849–858.
88. Kim, T.; Olek, J. Effects of Sample Preparation and Interpretation of Thermogravimetric Curves on Calcium
Hydroxide in Hydrated Pastes and Mortars. Transp. Res. Rec. J. Transp. Res. Board 2012, 2290, 10–18.
89. Mendoza, O.; Tobón, J.I. An alternative thermal method for identification of pozzolanic activity in
Ca(OH)2/pozzolan pastes. J. Therm. Anal. Calorim. 2013, 114, 589–596.
90. Fratini, N. Hydrated lime solubility in the presence of potassium hydroxide and sodium hydroxide.
Ann. Chim. Appl. 1949, 39, 616. (In Italian)
91. Fratini, N. Research of hydrolysis lime in cement pastes. Note II. Proposal test for the chemical evaluate of
pozzolanic cement. Ann. Chim. Appl. 1950, 40, 461–469. (In Italian)
92. Rio, A.; Fratini, N. Researches on the control and manufacture of pozzolan cements. Ann. Chim. Appl. 1952,
42, 526. (In Italian)
93. ISO 863:2008 Cement—Test Methods—Pozzolanicity test for Pozzolanic Cements; ISO Standard; International
Organization for Standardization: Geneva, Switzerland, 2008; p. 9.
94. Odler, I.; Skalny, J. Hydration of tricalcium silicate at elevated temperatures. J. Appl. Chem. Biotechnol. 2007,
23, 661–667.
95. PN-EN 450-1:2012 Fly Ash for Concrete; Definition, Specifications and Conformity Criteria; Polish Standard;
Polish Committee for Standardization: Warsaw, Poland, 2012; p. 30.
96. Frías, M.; Villar-Cociña, E.; Sánchez de Rojas, M.I.; Valencia-Morales, E. The effect that different pozzolanic
activity methods has on the kinetic constants of the pozzolanic reaction in sugar cane straw-clay ash/lime
systems: Application of a kinetic–diffusive model. Cem. Concr. Res 2005, 35, 2137–2142.
Materials 2020, 13, 4734 31 of 36

97. ASTM C618-19 Standard Specification for Coal Fly Ash and Raw or Calcined Natural Pozzolan for Use in Concrete;
ASTM Standand; ASTM International: West Conshohocken, PA, USA, 2019; p.5.
98. BS 3892:1997 Pulverised-Fuel Ash; Part 1: Specification forpulverised fuel ash for use with Portland cement;
British Standard; ASTM International: West Conshohocken, PA, USA, 1997; p. 23.
99. SRPS B.C1.018:2015 Non-Metallic Mineral Raws-Puzzolanic Materials-Constituents for Cement Production-
Classification, Technical Conditions and Test Methods; Serbian; Standard; Institute for Standardization of
Serbia: Beograd, Serbia, 2015.
100. PN-EN 196-1:2016-07 Methods of Testing Cement; Determination of Strength; Polish Standard; Polish
Committee for Standardization: Warsaw, Poland, 2016; p. 35.
101. GOST Active Mineral Additives to Binders. Russian Standard; Federal Agency on Technical Regulating and
Metrology: Moscow, Russia, 1963. (In Russian)
102. Slížková, Z.; Drdácký, M.; Viani, A. Consolidation of weak lime mortars by means of saturated solution of
calcium hydroxide or barium hydroxide. J. Cult. Herit. 2015, 16, 452–460.
103. ASTM C379-65T Specification for Fly Ash for Use as a Pozzolanic Material with Lime. ASTM Standard;
ASTM International: West Conshohocken, PA, USA, 1965.
104. ASTM C593-19 Standard Specification for Fly Ash and Other Pozzolans for Use With Lime for Soil
Stabilization. ASTM Standard; ASTM International: West Conshohocken, PA, USA, 2019; p. 5.
105. Chapelle, J. Sulpho-calcic attack of slags and pozzolans. Rev. Matériaux Constr. Trav. Publics. Ed. C Chaux
Cim. Plâtre Agglomérés 1958, 511–513, 187–100, 136–151, 159–170, 514–515. (In French)
106. Ninov, J.; Donchev, I.; Dimova, L. On the kinetics of pozzolanic reaction in the system kaolin–lime–water.
J. Therm. Anal. Calorim. 2010, 101, 107–112.
107. Feret, R. Researches into the Nature of Pozzolanic Reaction and Materials. La Rev. Matériaux Constr. Trav.
Publics 1933, 281–281, 41–44, 85–92.
108. Moran, W.; Gilliland, J. Summary of Methods for Determining Pozzolanic Activity. In Symposium on Use of
Pozzolanic Materials in Mortars and Concretes; ASTM International: West Conshohocken, PA, USA, 1950;
pp. 109–130.
109. Jarrige, A.; Ducreux, R. Quelques résultats d’expériences de laboratoire sur les cendres volantes et les
ciments aux cendres. Rev. Matériaux Constr. Trav. Publics 1958, 518, 300–305.
110. Guillaume, L. L’activité pouzzolanique des cendres volantes dans les ciments portland et les ciments au
laitier. Silic. Ind. 1962, 28, 297–300.
111. Battaglino, G.; Schippa, G. Su un nuovo methodo di valutazione dei materiali pozzolanicici. L’Industria Ital.
Cem. 1968, 38, 175–178.
112. Pressler, E.E.; Brunauer, S.; Kantro, D.L. Investigation of Franke Method of Determining Free Calcium
Hydroxide and Free Calcium Oxide. Anal. Chem. 1956, 28, 896–902.
113. Avet, F.; Snellings, R.; Alujas Díaz, A.; Ben Haha, M.; Scrivener, K.L. Development of a new rapid, relevant
and reliable (R3) test method to evaluate the pozzolanic reactivity of calcined kaolinitic clays. Cem. Concr.
Res 2016, 85, 1–11.
114. Li, X.; Snellings, R.; Antoni, M.G.; Alderete, N.M.; Ben Haha, M.; Bishnoi, S.; Cizer, Ö.; Cyr, M.;
De Weerdt, K.; Dhandapani, Y.; et al. Reactivity tests for supplementary cementitious materials: RILEM TC
267-TRM phase 1. Mater. Struct. 2018, 51, 151.
115. Luxán, M.P.; Madruga, F.; Saavedra, J. Rapid evaluation of pozzolanic activity of natural products by
conductivity measurement. Cem. Concr. Res 1989, 19, 63–68.
116. Raask, E.; Bhaskar, M.C. Pozzolanic activity of pulverized fuel ash. Cem. Concr. Res 1975, 5, 363–375.
117. Cara, S.; Carcangiu, G.; Massidda, L.; Meloni, P.; Sanna, U.; Tamanini, M. Assessment of pozzolanic
potential in lime–water systems of raw and calcined kaolinic clays from the Donnigazza Mine
(Sardinia–Italy). Appl. Clay Sci. 2006, 33, 66–72.
118. Tironi, A.; Trezza, M.A.; Scian, A.N.; Irassar, E.F. Potential use of Argentine kaolinitic clays as pozzolanic
material. Appl. Clay Sci. 2014, 101, 468–476.
119. Huenger, K.-J.; Gerasch, R.; Sander, I.; Brigzinsky, M. On the Reactivity of Calcined Clays from Lower
Lusatia for the Production of Durable Concrete Structures. In Calcined Clays for Sustainable Concrete; RILEM
Bookseries; Springer: Dordrecht, The Netherlands, 2018; Volume 16, pp. 205–211. ISBN 9789402412062.
120. Beuntner, N.; Thienel, K.-C. Properties of Calcined Lias Delta Clay—Technological Effects, Physical
Characteristics and Reactivity in Cement. In Calcined Clays for Sustainable Concrete; RILEM Bookseries;
Springer: Dordrecht, The Netherlands, 2015; pp. 43–50. ISBN 9789401799393.
Materials 2020, 13, 4734 32 of 36

121. Beuntner, N.; Thienel, K.-C. Effects of Calcined Clay as Low Carbon Cementing Materials on the Properties
of Concrete. In Proceedings of the Concrete in the Low Carbon Era, Dundee, UK, 9–11 July 2012;
pp. 504–517.
122. Pöllmann, H.; da Costa, M.L.; Angélica, R.S. Sustainable Secondary Resources from Brazilian Kaolin
Deposits for the Production of Calcined Clays. In Calcined Clays for Sustainable Concrete; RILEM Bookseries;
Springer: Dordrecht, The Netherland 2015; pp. 21–26. ISBN 9789401799393.
123. Maia, A.Á.B.; Saldanha, E.; Angélica, R.S.; Souza, C.A.G.; Neves, R.F. Utilização de rejeito de caulim da
Amazônia na síntese da zeólita A. Cerâmica 2007, 53, 319–324.
124. Maia, A.Á.B.; Angélica, R.S.; de Freitas Neves, R.; Pöllmann, H.; Straub, C.; Saalwächter, K. Use of 29Si and
27Al MAS NMR to study thermal activation of kaolinites from Brazilian Amazon kaolin wastes. Appl. Clay
Sci. 2014, 87, 189–196.
125. Akasha, A.M. Using of Libyan Calcined Clay in Concrete. In Calcined Clays for Sustainable Concrete; RILEM
Bookseries; Springer: Dordrecht, The Netherlands, 2015; pp. 555–561. ISBN 9789401799393.
126. Chakchouk, A.; Samet, B.; Mnif, T. Study on the potential use of Tunisian clays as pozzolanic material.
Appl. Clay Sci. 2006, 33, 79–88.
127. Box, G.E.P.; Hunter, J.S.; Hunter, W.J. Statistics for Experimenters: Design, Innovation, and Discovery, 2nd ed.;
John Wiley & Sons, Inc.: Hoboken, NJ, USA, 2005.
128. Montgomery, D.C. Design and Analysis of Experiments, 9th ed.; John Wiley & Sons, Inc.: Hoboken, NJ, USA,
2017; ISBN 9781119113478.
129. Pierkes, R.; Schulze, S.E.; Rickert, J. Optimization of Cements with Calcined Clays as Supplementary
Cementitious Materials. In Calcined Clays for Sustainable Concrete; RILEM Bookseries; Springer: Dordrecht,
The Netherlands, 2015; pp. 59–66 ISBN 9789401799393.
130. Siddique, R.; Klaus, J. Influence of metakaolin on the properties of mortar and concrete: A review.
Appl. Clay Sci. 2009, 43, 392–400.
131. Kubissa, W.; Jaskulski, R. Measuring and Time Variability of The Sorptivity of Concrete. Procedia Eng. 2013,
57, 634–641.
132. Paiva, H.; Velosa, A.; Cachim, P.; Ferreira, V.M. Effect of metakaolin dispersion on the fresh and hardened
state properties of concrete. Cem. Concr. Res 2012, 42, 607–612.
133. Zaribaf, B.H.; Uzal, B.; Kurtis, K.E. Compatibility of Superplasticizers with Limestone-Metakaolin Blended
Cementitious System. In Calcined Clays for Sustainable Concrete; RILEM Bookseries; Springer: Dordrecht,
The Netherlands, 2015; pp. 427–434 ISBN 9789401799393.
134. ASTM C595/C595M-20 Standard Specification for Blended Hydraulic Cements; ASTM Standard; ASTM
International: West Conshohocken, PA, USA, 2020; p. 8.
135. Sposito, R.; Beuntner, N.; Thienel, K.-C. Characteristics of components in calcined clays and their influence
on the efficiency of superplasticizers. Cem. Concr. Compos. 2020, 110, 103594.
136. Nied, D.; Stabler, C.; Zajac, M. Assessing the Synergistic Effect of Limestone and Metakaolin. In Calcined
Clays for Sustainable Concrete; RILEM Bookseries; Springer: Dordrecht, The Netherlands, 2015; pp. 245–251
ISBN 9789401799393.
137. Beuntner, N.; Kustermann, A.; Thienel, K.-C. Pozzolanic Potential of Calcined Clay in High- Performance
Concrete. In Proceedings of the International Conference on Sustainable Materials, Systems and Structures
(SMSS 2019) New Generation of Construction Materials, Rovinj, Croatia, 20–22 March 2019; pp. 470–477.
138. Mechti, W.; Mnif, T.; Chaabouni, M.; Rouis, J. Formulation of blended cement by the combination of two
pozzolans: Calcined clay and finely ground sand. Constr. Build. Mater. 2014, 50, 609–616.
139. Ng, S.; Østnor, T. Ternary cement blends with Fly ash-Calcined clay-OPC: An evaluation on their early age
and mechanical properties as binders. In Proceedings of the XXIII Nordic Concrete Research Symposium,
Aalborg, Danmark,21-23 August 2017; pp. 19–22.
140. Marchetti, G.; Pokorny, J.; Tironi, A.; Trezza, M.A.; Rahhal, V.F.; Pavlík, Z.; Černý, R.; Irassar, E.F. Blended
Cements with Calcined Illitic Clay: Workability and Hydration. In Calcined Clays for Sustainable Concrete;
RILEM Bookseries; Springer: Dordrecht, The Netherlands, 2018; Volume 16, pp. 310–317.
ISBN 9789402412062.
141. Wong, H.H.C.; Kwan, A.K.H. Packing density of cementitious materials: Part 1-measurement using a wet
packing method. Mater. Struct. 2008, 41, 689–701.
Materials 2020, 13, 4734 33 of 36

142. Machner, A.; Zajac, M.; Ben Haha, M.; Kjellsen, K.O.; Geiker, M.R.; De Weerdt, K. Portland metakaolin
cement containing dolomite or limestone–Similarities and differences in phase assemblage and
compressive strength. Constr. Build. Mater. 2017, 157, 214–225.
143. Ouellet-Plamondon, C.; Scherb, S.; Köberl, M.; Thienel, K.-C. Acceleration of cement blended with calcined
clays. Constr. Build. Mater. 2020, 245, 118439.
144. Ding, J.; Li, Z. Effects of Metakaolin and Silica Fume on Properties of Concrete. ACI Mater. J. 2002, 99,
393–398.
145. Zhang, M.H.; Malhotra, V.M. Characteristics of a thermally activated alumino-silicate pozzolanic material
and its use in concrete. Cem. Concr. Res 1995, 25, 1713–1725.
146. Brooks, J..; Megat Johari, M. Effect of metakaolin on creep and shrinkage of concrete. Cem. Concr. Compos.
2001, 23, 495–502.
147. Gleize, P.J.P.; Cyr, M.; Escadeillas, G. Effects of metakaolin on autogenous shrinkage of cement pastes. Cem.
Concr. Compos. 2007, 29, 80–87.
148. Scrivener, K.L.; Martirena-Hernández, J.F.; Bishnoi, S.; Maity, S. Calcined clay limestone cements (LC3).
Cem. Concr. Res 2018, 114, 49–56.
149. Krishnan, S.; Emmanuel, A.C.; Bishnoi, S. Effective Clinker Replacement Using SCM in Low Clinker
Cements. In Calcined Clays for Sustainable Concrete; RILEM Bookseries; Springer: Dordrecht,
The Netherlands, 2015; pp. 517–521, ISBN 9789401799393.
150. Alujas Díaz, A.; Fernández, R.; Quintana, R.; Scrivener, K.L.; Martirena-Hernández, J.F. Pozzolanic
reactivity of low grade kaolinitic clays: Influence of calcination temperature and impact of calcination
products on OPC hydration. Appl. Clay Sci. 2015, 108, 94–101.
151. Joseph, S.; Bishnoi, S.; Maity, S. An economic analysis of the production of limestone calcined clay cement
in India. Indian Concr. J. 2016, 90, 22–27.
152. Joseph, S.; Joseph, A.M.; Bishnoi, S. Economic Implications of Limestone Clinker Calcined Clay Cement
(LC3) in India. In Calcined Clays for Sustainable Concrete; RILEM Bookseries; Springer: Dordrecht,
The Netherlands, 2015; pp. 501–507. ISBN 9789401799393.
153. Dhandapani, Y.; Santhanam, M. Assessment of pore structure evolution in the limestone calcined clay
cementitious system and its implications for performance. Cem. Concr. Compos. 2017, 84, 36–47.
154. Dhandapani, Y.; Vignesh, K.; Raja, T.; Santhanam, M. Development of the Microstructure in LC3 Systems
and Its Effect on Concrete Properties. In Calcined Clays for Sustainable Concrete; RILEM Bookseries; Springer:
Dordrecht, The Netherlands, 2018; pp. 131–140. ISBN 9789402412062.
155. Khan, M.S.H.; Nguyen, Q.D.; Castel, A. Carbonation of Limestone Calcined Clay Cement Concrete.
In Calcined Clays for Sustainable Concrete; RILEM Bookseries; Springer: Dordrecht, The Netherlands, 2018;
Volume 16, pp. 238–243. ISBN 9789402412062.
156. Nguyen, Q.D.; Khan, M.S.H.; Castel, A. Engineering Properties of Limestone Calcined Clay Concrete.
J. Adv. Concr. Technol. 2018, 16, 343–357.
157. Joseph, A.M.; Shah, V.; Bishnoi, S. Protocol for Prediction of Durability of New Cements: Application to
LC3. In Calcined Clays for Sustainable Concrete; RILEM Bookseries; Springer: Dordrecht, The Netherlands,
2015; pp. 403–409. ISBN 9789401799393.
158. Nguyen, Q.D.; Castel, A. Chloride Diffusion Resistance of Limestone Calcined Clay Cement (LC3)
Concrete. In Proceedings of the SynerCrete’18: Interdisciplinary Approaches for Cement-based Materials
and Structural Concrete: Synergizing Expertise and Bridging Scales of Space and Time, Funchal, Portugal,
24–26 October 2018; pp. 129–134.
159. ASTM C150/C150M-20 Standard Specification for Portland Cement; ASTM Standard; ASTM International:
West Conshohocken, PA, USA, 2020; p. 9.
160. Nguyen, Q.D.; Afroz, S.; Castel, A. Influence of Calcined Clay Reactivity on the Mechanical Properties and
Chloride Diffusion Resistance of Limestone Calcined Clay Cement (LC3) Concrete. J. Mar. Sci. Eng. 2020, 8,
301.
161. AS 3972-2010 General Purpose and Blended Cements; Standards Australia: Sydney, Australia, 2010; p. 19.
162. Yang, P.; Dhandapani, Y.; Santhanam, M.; Neithalath, N. Simulation of chloride diffusion in fly ash and
limestone-calcined clay cement (LC3) concretes and the influence of damage on service-life. Cem. Concr. Res
2020, 130, 106010.
163. Nguyen, Q.D.; Castel, A. Reinforcement corrosion in limestone flash calcined clay cement-based concrete.
Cem. Concr. Res 2020, 132, 106051.
Materials 2020, 13, 4734 34 of 36

164. Rengaraju, S.; Pillai, R.G.; Neelakantan, L.; Gettu, R.; Santhanam, M. Chloride-Induced Corrosion
Resistance of Steel Embedded in Limestone Calcined Clay Cement Systems. In Calcined Clays for Sustainable
Concrete; RILEM Bookseries; Springer: Singapore, 2020; Volume 25, pp. 613–619.
165. Rengaraju, S.; Neelakantan, L.; Pillai, R.G. Investigation on the polarization resistance of steel embedded
in highly resistive cementitious systems–An attempt and challenges. Electrochim. Acta 2019, 308, 131–141.
166. AASHTO T 358 Standard Method of Test for Surface Resistivity Indication of Concrete’s Ability to Resist
Chloride Ion Penetration; AASHTO Standard; American Association of State Highway and
Transportation Officials: Washingtion, DC, USA, 2019; p.10.
167. ASTM G109-07(2013) Standard Test Method for Determining Effects of Chemical Admixtures on Corrosion of
Embedded Steel Reinforcement in Concrete Exposed to Chloride Environments; ASTM Standard; ASTM
International: West Conshohocken, PA, USA, 2013; p. 6.
168. Pillai, R.G.; Gettu, R.; Santhanam, M.; Rengaraju, S.; Dhandapani, Y.; Rathnarajan, S.; Basavaraj, A.S. Service
life and life cycle assessment of reinforced concrete systems with limestone calcined clay cement (LC3).
Cem. Concr. Res 2019, 118, 111–119.
169. Berriel, S.S.; Díaz, Y.C.; Martirena-Hernández, J.F.; Habert, G. Assessment of Sustainability of Low Carbon
Cement in Cuba. Cement Pilot Production and Prospective Case. In Calcined Clays for Sustainable Concrete;
RILEM Bookseries; Springer: Dordrecht, The Netherlands, 2015; pp. 189–194. ISBN 9789401799393.
170. Almenares Reyes, R.S.; Alujas Díaz, A.; Rodríguez, S.B.; Rodríguez, C.A.L.; Martirena-Hernández, J.F.
Assessment of Cuban Kaolinitic Clays as Source of Supplementary Cementitious Materials to Production
of Cement Based on Clinker–Calcined Clay–Limestone. In Calcined Clays for Sustainable Concrete; RILEM
Bookseries; Springer: Dordrecht, The Netherlands, 2018; Volume 16, pp. 21–28. ISBN 9789402412062.
171. Nair, N.; Mohammed Haneefa, K.; Santhanam, M.; Gettu, R. A study on fresh properties of limestone
calcined clay blended cementitious systems. Constr. Build. Mater. 2020, 254, 119326.
172. Li, X.; Scrivener, K.L. Determination of the amount of reacted metakaolin in calcined clay blends.
Cem. Concr. Res 2018, 106, 40–48.
173. Durdziński, P.T.; Ben Haha, M.; Zajac, M.; Scrivener, K.L. Phase assemblage of composite cements.
Cem. Concr. Res 2017, 99, 172–182.
174. GEMS Development Team. GEM Software (GEMS) Home. Available online: http://gems.web.psi.ch/
(accessed on 20 September 2020).
175. Snellings, R.; Salze, A.; Scrivener, K.L. Use of X-ray diffraction to quantify amorphous supplementary
cementitious materials in anhydrous and hydrated blended cements. Cem. Concr. Res 2014, 64, 89–98.
176. Bishnoi, S.; Maity, S.; Mallik, A.; Joseph, S.; Krishnan, S. Pilot scale manufacture of limestone calcined clay
cement : The Indian experience. Indian Concr. J. 2014, 88, 22–28.
177. Emmanuel, A.C.; Haldar, P.; Maity, S.; Bishnoi, S. Second pilot production of limestone calcined clay
cement in India: The experience. Indian Concr. J. 2016, 90, 57–63.
178. Vizcaíno-Andrés, L.M.; Antoni, M.G.; Alujas Díaz, A.; Martirena-Hernández, J.F.; Scrivener, K.L. Effect of
fineness in clinker-calcined clays-limestone cements. Adv. Cem. Res. 2015, 27, 546–556.
179. Maity, S.; Bishnoi, S.; Kumar, A. Field Application of Limestone-Calcined Clay Cement in India. In Calcined
Clays for Sustainable Concrete; RILEM Bookseries; Springer: Dordrecht, The Netherlands, 2015; pp. 435–441.
ISBN 9789401799393.
180. Dhandapani, Y.; Santhanam, M. Influence of Calcined Clay-Limestone Ratio on Properties of Concrete with
Limestone Calcined Clay Cement (LC3). In Calcined Clays for Sustainable Concrete; RILEMBookseries 25;
Springer: Singapore, 2020; pp. 731–738ISBN 9789811528064.
181. Ferreiro, S.; Canut, M.M.C.; Lund, J.; Herfort, D. Influence of fineness of raw clay and calcination
temperature on the performance of calcined clay-limestone blended cements. Appl. Clay Sci. 2019, 169,
81–90.
182. Perez, A.; Favier, A.R.; Martirena-Hernández, J.F.; Scrivener, K.L. Influence of the Manufacturing Process
on the Performance of Low Clinker, Calcined Clay-Limestone Portland Cement. In Calcined Clays for
Sustainable Concrete; RILEM Bookseries; Springer: Dordrecht, The Netherlands, 2015; pp. 283–289.
ISBN 9789401799393.
183. Chen, Y.; Li, Z.; Chaves Figueiredo, S.; Çopuroğlu, O.; Veer, F.; Schlangen, E. Limestone and Calcined Clay-
Based Sustainable Cementitious Materials for 3D Concrete Printing: A Fundamental Study of Extrudability
and Early-Age Strength Development. Appl. Sci. 2019, 9, 1809.
Materials 2020, 13, 4734 35 of 36

184. Chen, Y.; Chaves Figueiredo, S.; Yalçinkaya, Ç.; Çopuroğlu, O.; Veer, F.; Schlangen, E. The Effect of
Viscosity-Modifying Admixture on the Extrudability of Limestone and Calcined Clay-Based Cementitious
Material for Extrusion-Based 3D Concrete Printing. Materials 2019, 12, 1374.
185. Avet, F.; Scrivener, K.L. Hydration Study of Limestone Calcined Clay Cement (LC3) Using Various Grades
of Calcined Kaolinitic Clays. In Calcined Clays for Sustainable Concrete; RILEM Bookseries; Springer:
Dordrecht, The Netherlands, 2018; Volume 16, pp. 35–40. ISBN 9789402412062.
186. Avet, F.; Scrivener, K.L. Investigation of the calcined kaolinite content on the hydration of Limestone
Calcined Clay Cement (LC3). Cem. Concr. Res 2018, 107, 124–135.
187. Zunino Sommariva, F.A.; Scrivener, K.L. Reactivity and Performance of Limestone Calcined-Clay Cement
(LC3) Cured at Low Temperature. In Calcined Clays for Sustainable Concrete; RILEM Bookseries; Springer:
Dordrecht, The Netherlands, 2018; Volume 16, pp. 514–520. ISBN 9789402412062.
188. Trümer, A.; Ludwig, H.-M. Sulphate and ASR Resistance of Concrete Made with Calcined Clay Blended
Cements. In Calcined Clays for Sustainable Concrete; RILEM Bookseries; Springer: Dordrecht,
The Netherlands, 2015; pp. 3–9. ISBN 9789401799393.
189. Pierkes, R.; Schulze, S.E.; Rickert, J. Durability of Concretes Made with Calcined Clay Composite Cements.
In Calcined Clays for Sustainable Concrete; RILEM Bookseries; Springer: Dordrecht, The Netherlands, 2018;
Volume 16, pp. 366–371ISBN 9789402412062.
190. Shah, V.; Joseph, A.M.; Bishnoi, S. Durability Characteristics of Sustainable Low Clinker Cements: A
Review. In Calcined Clays for Sustainable Concrete; RILEM Bookseries; Springer: Dordrecht, The Netherlands,
2015; pp. 523–530. ISBN 9789401799393.
191. Castillo Lara, R.; Antoni, M.G.; Alujas Díaz, A.; Scrivener, K.L.; Martirena-Hernández, J.F. Study of the
addition of calcined clays in the durability of concrete Rancés. Rev. Ing. Construcción 2011, 26, 25–40.
192. Bucher, R.; Cyr, M.; Escadeillas, G. Carbonation of Blended Binders Containing Metakaolin. In Calcined
Clays for Sustainable Concrete; RILEM Bookseries; Springer: Dordrecht, The Netherlands, 2015; pp. 27–33
ISBN 9789401799393.
193. Geiker, M.R.; Weerdt, K. De; Garzón, S.F.; Jensen, M.M.; Johannesson, B.; Michel, A. Durability testing of
low clinker blends-chloride ingress in similar strength mortar exposed to seawater. In Proceedings of the
XXIII Nordic Concrete Research Symposium, Aalborg, Danmark, 21-23 August 2017; pp. 97–100.
194. Marangu, J.M.; Thiong’o, J.K.; Wachira, J.M. Chloride Ingress in Chemically Activated Calcined Clay-Based
Cement. J. Chem. 2018, 2018, 1–8.
195. Sarfo-Ansah, J.; Atiemo, E.; Boakye, K.A.; Adjei, D.; Adjaottor, A.A. Calcined Clay Pozzolan as an
Admixture to Mitigate the Alkali-Silica Reaction in Concrete. J. Mater. Sci. Chem. Eng. 2014, 2, 20–26.
196. Li, C.; Ideker, J.H.; Drimalas, T. The Efficacy of Calcined Clays on Mitigating Alakli-Silica Reaction (ASR)
in Mortar and Its Influence on Microstructure. In Calcined Clays for Sustainable Concrete; RILEM Bookseries;
Springer: Dordrecht, The Netherlands, 2015; pp. 211–217ISBN 9789401799393.
197. Jóźwiak-Niedźwiedzka, D.; Jaskulski, R.; Glinicki, M.A. Application of Image Analysis to Identify Quartz
Grains in Heavy Aggregates Susceptible to ASR in Radiation Shielding Concrete. Materials 2016, 9, 224.
198. Aramburo, C.H.; Pedrajas, C.; Talero, R. Portland Cements with High Content of Calcined Clay: Mechanical
Strength Behaviour and Sulfate Durability. Materials 2020, 13, 4206.
199. Al-Akhras, N.M. Durability of metakaolin concrete to sulfate attack. Cem. Concr. Res 2006, 36, 1727–1734.
200. Shi, Z.; Ferreiro, S.; Lothenbach, B.; Geiker, M.R.; Kunther, W.; Kaufmann, J.; Herfort, D.; Skibsted, J. Sulfate
resistance of calcined clay–Limestone–Portland cements. Cem. Concr. Res 2019, 116, 238–251.
201. EN 197-1. Cement-Part 1: Composition, Specifications and Conformity Criteria for Common Cements;
European Committee for Standardization: Brussels, Belgium, 2002; pp. 1–25.
202. Saillio, M.; Baroghel-Bouny, V.; Pradelle, S. Various Durability Aspects of Calcined Kaolin-Blended
Portland Cement Pastes and Concretes. In Calcined Clays for Sustainable Concrete; RILEM Bookseries;
Springer: Dordrecht, The Netherlands, 2015; pp. 491–499ISBN 9789401799393.
203. Yazıcı, Ş.; Arel, H.Ş.; Anuk, D. Influences of Metakaolin on the Durability and Mechanical Properties of
Mortars. Arab. J. Sci. Eng. 2014, 39, 8585–8592.
204. Tafraoui, A.; Escadeillas, G.; Vidal, T. Durability of the Ultra High Performances Concrete containing
metakaolin. Constr. Build. Mater. 2016, 112, 980–987.
205. Badogiannis, E.; Tsivilis, S. Exploitation of poor Greek kaolins: Durability of metakaolin concrete. Cem.
Concr. Compos. 2009, 31, 128–133.
 Materials 2020, 13, 4734 36 of 36

206. Shekarchi, M.; Bonakdar, A.; Bakhshi, M.; Mirdamadi, A.; Mobasher, B. Transport properties in metakaolin
blended concrete. Constr. Build. Mater. 2010, 24, 2217–2223.
207. Shi, Z.; Geiker, M.R.; De Weerdt, K.; Lothenbach, B.; Kaufmann, J.; Kunther, W.; Ferreiro, S.; Herfort, D.;
Skibsted, J. Durability of Portland Cement Blends Including Calcined Clay and Limestone: Interactions
with Sulfate, Chloride and Carbonate Ions. In Calcined Clays for Sustainable Concrete; RILEM Bookseries;
Springer: Dordrecht, The Netherlands, 2015; pp. 133–141. ISBN 9789401799393.

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