Cement and Concrete Research 149 (2021) 106564

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Cement and Concrete Research

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Limestone calcined clay cement and concrete: A state-of-the-art review

Meenakshi Sharma a, Shashank Bishnoi a, *, Fernando Martirena b, Karen Scrivener c
a
Department of Civil Engineering, Indian Institute of Technology Delhi, India
b
Department of Civil Engineering, Universidad Centrale de Las Villas, Cuba
c
Institute of Materials, Ecole Polytechnique Fédérale de Lausanne, Switzerland

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

Keywords: This article reviews the rapidly developing state-of-the-art literature available on the subject of the recently
Limestone calcined clay cement developed limestone calcined clay cement (LC3). An introduction to the background leading to the development
Production of LC3 is first discussed. The chemistry of LC3 hydration and its production are detailed. The influence of the
Hydration
properties of the raw materials and production conditions are discussed. The mixture design of concrete using
Workability
Durability
LC3 and the mechanical and durability properties of LC3 cement and concrete are then compared with other
cements. At the end the economic and environmental aspects of the production and use of LC3 are discussed. The
paper ends with suggestions on subjects on which further research is required.

1. Introduction: the need for new cements
With a service record of over 200 years, Portland cement has proven
to be a reliable material for construction throughout a wide range of
working and environmental conditions. The success of this cement is
attested to the fact that Portland cement concrete is the most produced
material in the world. Although during these 200 years, the production
process and the applications of cement have gone through many
changes, the robustness and the versatility of the cement has ensured
that its basic chemistry has remained unchanged. It is, therefore, no
surprise that most of the modern practically viable improvements to
cement involve a partial replacement of Portland clinker and not the
introduction of a completely new chemical process.
Concerns regarding the sustainability of cement production have led
to the development of many technologies that are widely used around
the world. While the first set of developments focused on reducing the
energy required for the production of clinker, most modern clinker kilns
today are close to the maximum thermodynamically possible efficiency.
The partial replacement of clinker with supplementary cementitious
materials (SCMs) allows a reduction of the environmental impact of
cement production without reducing the ease of use and versatility of
cement. Most cements available in most countries today are blended
with SCMs such as fly ash, slag and limestone. Although excellent ce­
ments can be produced using these SCMs, each of them changes the
performance of the cement under various conditions. With the devel­
opment of a wide variety of blended cements, no single type of cement is
known to be the most suitable one for all possible applications.
In the early 2000s, it was noticed that the clinker content in cement
was no longer decreasing and further reductions with the available SCMs
appeared to be improbable. For example, in the case of fly ash, despite a
wide availability of the material, it can only replace clinker up to a
limited extent due to its lower reactivity and in the case of slag, even
though higher replacement levels are possible, it is available in limited
quantities. Ternary blended cements offered the benefit of higher clinker
replacement levels, reducing the undesirable effects that one particular
SCM may have on the performance of the cement [1–3].
Limestone calcined clay cement (LC3) is one such recently developed
ternary blended cement in which the alumina from the calcined clay and
the carbonate from the limestone also react with each other, along with
the traditional pozzolanic reaction of calcined clay and the filler effect of
limestone, creating a synergy between the three primary components
(clinker, calcined clay and limestone) [2]. This allows a higher clinker
replacement and leads to the development of a finer and less connected
microstructure that gives the cement an excellent mechanical and
durability-related performance [2]. While the replacement of clinker
with limestone is usually limited to 15%, a maximum of 25% replace­
ment with calcined clay is usual. LC3 blends with as low as 40% clinker
have been produced in the laboratory [2]. At the same time, since clays
and limestone are widely available throughout the world, the produc­
tion of LC3 is practically feasible. Clays from different countries with
different sources of origin like from weathering of rocks, marine clays,
etc. and limestone from marble dust, stone waste, etc. have been used to

* Corresponding author.
E-mail address: bishnoi@iitd.ac.in (S. Bishnoi).

https://doi.org/10.1016/j.cemconres.2021.106564
Received 9 March 2021; Received in revised form 10 July 2021; Accepted 1 August 2021
Available online 11 August 2021
0008-8846/© 2021 Elsevier Ltd. All rights reserved.
M. Sharma et al. Cement and Concrete Research 149 (2021) 106564

produce LC3 [4–10]. Additionally, the cement can be produced using

technologies that are widely available and familiar to the cement in­
dustry, while its use does not require any special training [11,12]. This
gives the cement a distinct advantage against products that require
special handling and production.
Due to all of the above, LC3 has been identified as the most promising
technology that can help the cement industry to achieve its emission
targets [13]. Within a decade of the original ideas that led to its devel­
opment, the cement is already commercially available in several coun­
tries. The knowledge on this cement has also increased exponentially at
the same time. This article reviews the current knowledge on the pro­
duction, characteristics, and performance of LC3, also identifying the
key areas where more research is needed.

2. Composition and chemistry of LC3

The idea of LC3 is based on the observation that cements containing Fig. 2. Influence of replacement level of LC2 on the heat of hydration of pastes
alumina react with carbonate phases to produce carboaluminate phases adapted from [21].
that are hard and crystalline, and contribute to the development of the
microstructure. While calcined clays have been well-established as
pozzolanic materials and limestone is also widely used as a filler in ce­
ments [14,15], the idea of combining the two to achieve higher clinker
replacement levels was first reported in 2012 [2]. The composition of
LC3 in comparison to ordinary Portland cement (OPC) is shown in Fig. 1.
A significant increase in the formation of the carboaluminate phases was
reported with this combination as the basis for a comparable perfor­
mance to Portland cement. The production of a lower density C-A-S-H
has also been suggested to be the cause for the comparable performance
[16], although results from NMR have shown that the water content in
the C-A-S-H in LC3 is similar to that in other cements and that there is no
such difference in density [17,18].
Fig. 2 shows the typical heat of hydration of LC3 observed during the
first 24 h, compared with that of an OPC produced using the same
clinker. In Fig. 2, LC3 was made by partially replacing OPC with a blend
of limestone and calcined clay (LC2). The figure shows that the accel­
eration after the induction period is more rapid in the case of LC3 and an
additional sharp peak, that resembles that of C3A in OPC, is seen after
the first peak. In addition, it has also been shown that the heat released
during the first 72 h is lower than OPC [20]. The first, more gentle, peak
of hydration is generally agreed to be that of the silicate phases in the
clinker, while the second peak is attributed to the alumina originating
from either the clinker or the calcined clay [21,22]. While Zunino and
Scrivener [23] has suggested that this second peak is due to the hydra­
tion of aluminate phase in the clinker, studies of lime-calcined clay- Fig. 3. Comparison of the heat of hydration of OPC with LC3, having different
gypsum systems that did not have the aluminate phases have shown also amount of gypsum [23].

Fig. 1. Comparison of composition of OPC and LC3 [19].

2
M. Sharma et al.
similar peaks at similar ages [24]. The position of the second peak has
been reported to depend on the gypsum content in the cement and the
kaolinite content in the clay (Fig. 3). The early occurrence of the
aluminate peak has been associated with lower long-term strength
development, so it is desirable to adjust the amount of sulphate so that
this peak occurs at least 1 h after the silicate peak. An additional third
peak, after the aluminate peak at approximately 34 h, associated with
the formation of carboaluminates has also been reported [25].
While a large majority of the studies reported in the literature are
based on a blend of LC3 that contained 50% clinker, with a calcined clay
to limestone ratio of 2:1 by mass, it has been suggested that the optimal
ratios would depend on the physical and chemical properties of clinker
[26]. Since both, the reaction of calcined clay and limestone depend on
the availability of lime (CH) in the system [2], the alite and belite
content in the clinker would influence the amount of calcined clay that
can react. Krishnan et al. have suggested that the quantity of calcined
kaolinite that can react in LC3 depends linearly on the alite and belite
content [26]. In addition to the low CH content, the reduced reactivity of
clays at later ages has also been attributed to low internal relative hu­
midity of LC3 [27]. It has been suggested that the reduced internal
relative humidity in LC3 results in a reduction of pore solution in the
capillary pores above a certain pore size [27]. Since hydration in
cementitious systems occurs through pore solution, the growth of hy­
dration products is possible only in the saturated small size pores
limiting the space available for growth and thus limiting the hydration
of clay.
It has been widely reported that only a small fraction of the limestone
in LC3 reacts with the alumina phases in cement and calcined clay to
produce carboaluminate phases, leaving a significant fraction of the
limestone to act as an unreacted filler (e.g. Fig. 4) [28]. The use of lower-
purity carbonates and other waste materials has, therefore, been justi­
fied [9]. Other studies have shown that other carbonates, such as
dolomite, can also react in a manner similar to calcite, albeit with
different kinetics [29]. The required amount of carbonate to efficiently
react with the available aluminates has also been related with the clinker
composition [26].
While the dissolution and reaction of the alumina has been suggested
to depend on the availability of sulphates, much like the reaction of the
aluminate phase in clinker, the reaction of the silicates depends more on
the availability of portlandite. The availability of alkalis has also been
shown to influence the rate of hydration, especially at the early age [30].
The silicate in the calcined clay reacts with portlandite to produce cal­
cium alumino-silicate hydrate (C-A-S-H). The composition of C-A-S-H
has been shown to depend on the calcined kaolinite content in the clay
Fig. 4. Phase assemblage in LC3 using the hydration model proposed by
Krishnan and Bishnoi [26]. The hydration model is based on the phase
assemblage measured using X-ray diffraction and scanning electron micro­
scopy [26].
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Cement and Concrete Research 149 (2021) 106564
and the temperature of hydration [18,31]. While some of the alumina in
the clay is seen to get incorporated in this product, the remaining
alumina reacts with the carbonate phases to form carboaluminates. It
has been shown that the carboaoluminate phases start to form only after
the exhaustion of sulphates in the pore-solution. Afterwards, the pres­
ence of any additional aluminates in the pore-solution leads to the for­
mation of the carboaluminate phases, preventing the conversion of
ettringite to monosulphate [32–34]. Some of the sulphate added to LC3
has been suggested to get adsorbed on C-A-S-H, especially at higher
curing temperatures, influencing the amount of aluminate that remains
available for the formation of carboaluminates [31]. A similar adsorp­
tion of sulphates in C-S-H has been reported for other cements as well
[35]. Due to the relatively slower dissolution of the carbonates, while
the hemicarboaluminate phase forms first, its conversion to mono­
carboaluminate is thermodynamically preferred in the long-term
[20,36].
Simple stoichiometric calculations have shown that ettringite and
carboaluminates have a similar role in reducing porosity [37]. It has
been reported that in a system with 50% clinker, these phases can
together occupy up to 25% of the volume of the hydrated cement paste.
Additionally, calcium alumino silicate hydrate (C-A-S-H) continues to
occupy around 50% of the paste volume, despite the lower clinker
content [16,37].
As is usual in blended cements, while the total porosity of LC3 paste
has been reported to be higher than Portland cement, a significant
refinement of the porosity has been reported [32]. This has been re­
ported to result in a more filled microstructure compared to OPC (Fig. 5)
and provide benefits both in terms of strength and durability [32]. It has
been reported that the combined physical and chemical effects allow LC3
mortars and concretes with 50% clinker content to reach similar
compressive strengths and durability indices as specimens prepared
using OPC at 28 days [38].
3. The production of LC3: raw materials and quality control
LC3 is produced either by co-grinding or blending together its com­
ponents to a homogeneous blend. Most studies on LC3 have been carried
out using clays having kaolinite as the main mineral. Although studies
using illite and montmorillonite have also been reported, the reactivity
of these minerals has been reported to be lower than kaolinite [39].
Initial results have shown that there is little to no additional benefit of
improving the kaolinite content in clays above 60% in terms of
compressive strength (Fig. 6). Although more detailed studies, taking
Fig. 5. Comparison of microstructure of hydrated plain grey cement (PC) and
white cement pastes (WPC) to the hydrated LC3 prepared using corresponding
cement (LC3-50 and WLC3-50) [18].
M. Sharma et al.
Fig. 6. Influence of kaolinite content of calcined clay (27%, 56.5% and 80%)
on the compressive strength evolution of LC3. LC3-55(Q:L) contains quartz in
place of clay while LC3-55(x%) contains calcined clay having x% kaolinite
content [41].
into account the effect of other factors, such as particle size and calci­
nation conditions is required, some results show that the hydration of
clinker phases, belite in particular, is reduced when clays with higher
kaolinite content are used [8,40–42]. Before addition to the cement, the
clays are calcined by removing water molecules from their structure
[39,43]. The structure and formulae of different clay minerals are shown
in Fig. 7. The higher reactivity of kaolinitic clays has been attributed to
the easier removal of the water molecules in its structure compared to
illite and montmorillonite [39]. The removal of this water breaks the
crystalline structure of the clay, making it amenable to dissolution in
alkaline conditions. This water is usually removed by heating the clay to
temperatures above 700 ◦ C, although other physical and chemical
activation techniques have also been reported [44]. While there is
disagreement on the temperature required for complete calcination,
possibly due to different heat-transfer conditions in various types of
equipment, it is generally agreed that increasing the temperature of the
solid above 900 ◦ C reduces its reactivity, first due to sintering and then
due to recrystallisation into spinel, mullite and cristobalite [45]. Rotary
kilns and flash calciners have been reported to be effective for clay
calcination [46–48]. Static calcination techniques have also been used
[11]. Higher calcination temperatures have been shown to be tolerable
when flash calcination is used [46]. It has also been shown that flash
Fig. 7. Structures and ideal formulas of a) kaolinite, b) illite and c) montmorillonite [39].
4
Cement and Concrete Research 149 (2021) 106564
calcination results in lower amorphous content compared to calcination
in rotary kilns [48]. A limited understanding of the influence of the other
phases present in the clay on the properties of cement is available since
most studies available in the literature have focused on clays with quartz
and hematite being the major impurities [20,49,50]. The presence of
calcite impurities in clays has been seen to reduce their reactivity due to
the formation of a calcium-rich phase on metakaolin particles, which
reduces their specific surface area and reactivity [51]. A reduction in the
calcination temperature and increase in the residence time is seen to
reduce this effect.
During the initial trials, the colour of the calcined clay was seen to
vary from grey to various shades of red [52], depending on the iron
content in the raw clay. This imparted a reddish colour to the cement as
well. Given the widespread image of cement as a dark powder, this was
initially seen as a barrier to the acceptance of LC3. Later studies showed
that the calcination of clays with iron as impurity in reducing conditions
leads to the formation of magnetite in place of hematite. This gives the
clay, and the cement, a grey colour that is more usual for cements
(Fig. 8) [53]. The colour of clay has been shown to have little influence
on the compressive strength of LC3 [53]. More detailed studies are
required to understand the influence of the colour of the clay on the
hydration kinetics, mechanical and durability performance of LC3.
The effectiveness of calcination can be measured either by a char­
acterisation of the clay or by measuring its reactivity. X-ray diffraction
has been reported to be the most suitable method to ensure that the clay
is properly calcined, but no recrystallisation has occurred [45]. It must,
however, be noted that a loss in the reactivity of clays occurs even before
recrystallisation occurs [45]. This has been reported to be due to the
sintering of clay particles [45]. However, given the limited availability
of the equipment, relatively more crude techniques like the measure­
ment of loss on ignition have also been reported to be useful [54,55]. Li
et al. [56] recently compared several test methods that can be used to
assess the effectiveness of calcination by measuring the reactivity of
SCMs, including calcined clay. It was shown that the recently stand­
ardised R3 method [40] and the Lime Reactivity test, which is a standard
test in the Indian standards [55], provide reliable results [57]. However,
since both these tests methods are time-consuming, their utility for real-
time quality monitoring is limited. Other test methods were not found to
be very reliable. There is, therefore, a need to develop test methods that
may be more suitable for quality control at calcination plants.
As discussed earlier, it has been reported that there is very little in­
fluence of the purity of limestone on the performance of LC3. The R3 and
M. Sharma et al.
Fig. 8. Images of clays: (a) original raw clay, (b) calcined clay without colour control calcination and (c) calcined clay with colour control calcination [52].
lime reactivity tests have been shown to be suitable to assess the reac­
tivity and compatibility of blends of limestone and calcined clay [57].
Trials of intergrinding of clinker, limestone, calcined clay and gypsum
have shown that the softer nature of limestone and clay and the harder
nature of clinker lead to a bi-modal particle size distribution of the
cement [29,58]. While the clay and limestone particles may be ground
too fine, the clinker particles remain coarse. A coating of the grinding
media with the particles of fine powders such as calcined clays during
grinding has also been reported to be a possible cause for the less
effective inter-grinding of cements [59,60]. There are some studies that
show benefits of the use of grinding aids (GA), such as diethylene glycol
(DEG), poly-carboxylate ether (PCE) and triethanolamine (TEA), for
inter-grinding by the reduction in coating of grinding media by calcined
clays, as can be observed in Fig. 9. Alkanolamine grinding aids, trie­
thanolamine (TEA), triiso-propanolamine (TIPA) and dieth­
ylisopropanolamine (DEIPA), have been shown to be effective in
enhancing the hydration of ferrite and aluminate phases during inter-
grinding of LC3 [61]. Since the hydration of the clay and limestone
also requires the presence of CH, which is produced from the hydration
of the clinker phases, finer particles of clinker are required for a
reasonable rate of hydration of all the constituents [28]. It has been
suggested that a separate grinding of clay and limestone and a later
blending with ground gypsum and clinker may provide a better alter­
native to inter-grinding as the performance of the individual compo­
nents can be optimized more easily [50]. Extensive work has also shown
the viability of the production of LC3 concrete by mixing OPC with a
ground blend of limestone and calcined clay (LC2), in a concrete mixer
[21].
Although some limited studies at other clinker contents are avail­
able, most of the results in the literature are available on LC3 blends with
50% clinker and a 2:1 gravimetric ratio of calcined clay to limestone.
Blends of this or similar proportion, therefore make the basis of most of
the results presented in this paper.
4. Physical and chemical properties of LC3 in comparison with
other cements
The physical and chemical properties of LC3, in comparison with
Fig. 9. Influence of increasing dosage of PCE-based grinding aids on the coating of calcined clay on the griding media. Left to Right – no GA and PCE-based grinding
aid at 0.15%, 0.75% and 1.5% addition by mass of powder [62].
5
Cement and Concrete Research 149 (2021) 106564
other cements, have been widely studied. Primarily due to fineness of
the calcined clay particles, LC3 has been reported to have a higher
specific surface area than other cements [12]. A direct comparison may
not be possible since it has been seen that while the Blaine measure­
ments for LC3 may be twice those of other cements, the water to cement
ratio to achieve a standard consistency does not increase as much. Also
Blaine fineness measurements of LC3 have been shown to be outside the
ranges for which the technique is considered to be valid [63]. This is due
to a large difference between morphologies of clay particles from clinker
particles, the former being more platy than bulky. For example, it has
been reported that while the Blaine fineness of an LC3 was more than
600 m2/kg compared to around 300 m2/kg for an OPC prepared using
the same clinker at the same plant, the water to cement ratio required for
normal consistency increased from around 0.28 to around 0.31 [11].
When ground together, most of the particles of blend of limestone and
calcined clay pass through a 45 μm sieve, whereas around 20% of clinker
particles are retained.
The setting time of LC3 has been reported to be shorter than OPC and
fly ash blended cements [38]. As seen earlier in Fig. 2, the acceleration at
the end of the induction period is faster in LC3 than in OPC and the
alumina peak is higher. The faster hydration, of LC3 and the higher
alumina content lead to the earlier setting [11]. Despite the earlier
setting, the one-day strength of LC3 is usually slightly lower than that of
OPC, although the strength development is more rapid by 3 days and the
28-day strength of LC3 with 50% clinker content is similar to that of an
OPC produced using the same clinker. The quantity of alkalis in the
cement has been seen to strongly influence the early and long-term
strength development. While higher alkali contents are seen to in­
crease the early strength, long-term strengths are seen to reduce [30].
Unlike most other blended cements, the rate of hydration of LC3 does not
reduce dramatically upon the reduction of temperature. An influence of
the early curing temperature is also seen on the long-term strength
development of the system [31]. However, the reasons for this were not
found in the literature.
5. Mixture design and workability of LC3 concrete
It has been seen that despite the significantly different structure of
M. Sharma et al.
the clay particles, no significant changes to the traditional approach to
mixture design are required to produce workable concretes using LC3.
Although some of the studies have shown the need for lower water to
binder ratios with LC3 compared to OPC so as to achieve similar
compressive strengths [64], other studies have reported similar 28-day
strengths in mixes having the same water to binder ratios with OPC
and LC3 [38,65]. It has been reported that despite the lower coarse
aggregate contents, self-compacting concretes produced using LC3 have
higher compressive strengths than vibrated concretes produced at the
same water to binder ratios [65]. This is probably due to the better
compaction and more uniform distribution of clay particles achieved at
the higher admixtures doses. The higher water retention and reduction
in bleeding of concrete mixes with calcined clays also plays a role in this.
The admixture demand is seen to increase with the clinker replacement
level [65].
Contradictory results on the segregation resistance and bleeding of
LC3 concrete mixes have been reported. While one of the studies has
reported more stable concrete even at higher dosages of super­
plasticizers and in self-compacting concretes [65], another study has
reported a high amount of bleeding in such mixes [64]. The more
thixotropic nature of LC3 paste has been attributed more to the floccu­
lation of clay particles resulting from the higher negative surface charge
on the surface of calcined clay particles, than to a structural build-up due
to hydration [43,66]. The higher water and admixture demand of LC3
has also been attributed to the flocculation of the finer particles and the
trapping of water between these flocs and between the sheets of clay
[43,66]. Conversely, the presence of limestone particles in LC3 is seen to
reduce flow resistance and improve workability. As mentioned above,
the specific surface area of LC3 measured using air permeability or
particle size distribution methods must be used with caution while
determining the water demand of these cements. Also, if approaches to
optimise the packing and water demand, similar to those that have been
reported in the literature for other systems [69], are applied to LC3, care
must be taken to account for the different morphologies of the three
main components. Since gypsum is also reported to play a role in water
demand, workability and admixture demand of cements [70], it is also
likely to impact workability and setting of LC3 concrete. Due to its
shorter setting time, the use of retarders may be useful to prolong the
workable duration of concrete.
6. Compatibility of admixtures with LC3
While studies on the suitability of chemical admixtures with LC3 are
limited, some work on water reducing admixtures is available in the
literature. While more detailed studies are available on pastes, limited
results are available with concretes. It is understood that since the sur­
face of the particles play the most important role in the adsorption and
functioning of most types of admixtures, the difference in the
morphology and surface charge of the clay particles when compared to
the clinker particles, can significantly alter the efficacy of the admix­
tures. Water reducing and air-entraining admixtures that rely on elec­
trostatic forces are likely to be influenced by the presence of clay
particles.
Studies on the compatibility of LC3 with various types of commer­
cially available water reducing admixtures has shown that while LC3 is
more compatible with admixtures with polycarboxylate ether (PCE)
based active components, compared to sulphonated naphthalene form­
aldehyde (SNF) based ones, the saturation dosage is higher than other
cements [64]. The slump retention was also seen to be reduced in con­
cretes with PCE based admixtures, highlighting the need for the devel­
opment of more suitable admixtures for LC3 [71,72]. The slump
retention was seen to marginally improve with the use of a retarder. The
effect was seen to be higher in cements with a higher clinker replace­
ment level.
The kaolinite content in the clay has been reported to significantly
influence the performance of admixtures [71]. This is expected due to
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Cement and Concrete Research 149 (2021) 106564
the high internal and external surface area of calcined kaolinite parti­
cles. The interaction between clay particles and high-range water re­
ducers enhances the structural build-up and yield stress of LC3 making it
a suitable candidate for 3D-printable concrete [73,74]. Despite the
altered rheology of LC3, it has been shown that a sprayable and pump­
able engineered cementitious composite (ECC) can be made by opti­
mally designing concrete mixes [75]. An optimisation, rather than a
maximisation, of the kaolinite content in the clays is, therefore, desir­
able to improve the performance of LC3. Similar to the approach to
optimise the kaolinite content based on reaction stoichiometry [26], an
integrated approach to optimise both the strength and the workability
could be developed. In a similar study, an optimized particle packing of
LC3 with silica fume was shown to improve the structural recovery,
dynamic and static yield stress of 3D-prinable concrete [76].
7. Mechanical properties of LC3 concrete
The main advantage of LC3 is that it can be produced with clinker
factors as low as 40% to 50% without a reduction in the mechanical
performance from a few days onwards. Since compressive strength is the
key parameter for all structural design, a large volume of work on the
influence of various parameters is available in the literature. While most
results show that the 28-day compressive strength of LC3 is similar to
that of an OPC produced using a similar clinker, there is some variation
in the results at other ages. Most results show that the 3-day strength of
LC3 and its concretes is slightly lower than that of OPC and it is higher
than that of slag or fly ash blended cements [38]. By 7 days, the strength
of LC3 has been reported to be similar to or higher than that of OPC.
Some studies have reported a minimal increase in the compressive
strength after 28 days (Fig. 10) [16,20,62], while others have reported
an increase [38]. Initial results show that parameters such as the particle
sizes of the individual components and the composition of the clinker,
temperature and alkali content play an important role on strength
development [26,30,31,77].
The fineness of the individual components is seen to influence
strength development more than the overall fineness of the cement. It
has been reported that while the presence of finer clinker grains im­
proves strength, there is little influence of the fineness of the clay and
limestone particles beyond a certain level. It has been shown that this is
mainly due to the availability of portlandite being the limiting factor for
the hydration of the calcined clay and limestone [41]. This is especially
the case when clinkers with a lower alite content are used. A faster
hydration of finer clinker particles ensures that the demand for calcium
ions by the other two components is met. The rapid consumption of
calcium ions in the secondary hydration reactions increases the early
rate of clinker hydration, reducing the availability of unhydrated clinker
phases, and strength development, at later ages. The reason for the
continued increase in strength after 28 days, despite the lack of any
evidence of further hydration, needs further investigation.
The gel-space ratio is often used to represent the state of develop­
ment of cementitious microstructures and the parameter is shown to be
related to compressive strength. The gel-space ratio is calculated as the
volume of the hydrates formed as a ratio of the total volume available for
their growth. A comparison of the compressive strength of LC3 mortars
with the gel-space ratio shows significantly lower gel-space ratios in the
LC3 blends despite similar strengths as OPC, even at early ages. This
could either indicate insufficient information about the hydration
products that are included in the calculation of the ratio, or the forma­
tion of significantly different microstructure than OPC [16,37]. It has
been suggested that supplementary cementitious materials can be
included in the gel volume in these calculations for better results [37].
The chemical composition of limestone appears to have limited in­
fluence on strength development. When limestone is replaced with
dolomite, the strength development is seen to be slightly slower,
although the 28-day strength is similar to when a pure calcite is used
[9,10,29]. Even at 90 days, only a small fraction of the limestone is
M. Sharma et al.
Fig. 10. Compressive strength development in LC3 compared to other cement [62].
estimated to have reacted. Despite the small volume of carbonates
reacting, the contribution to the volume of hydration products is large,
since the carbonate only makes around 5% of the weight of the car­
boaluminate phases. For this reason, low grade limestones, which are
often stockpiled after separation from more pure material, can also be
suitable for use in LC3. The influence of the impurities in limestone on
the development of mechanical properties has not been studied in detail.
The fineness of limestone, however, does influence strength develop­
ment and the heat of hydration during the early age, mainly because of
the filler effect and its influence on the sulphate balance of aluminate
hydration [23].
Although the influence of the kaolinite content in the clay has been
studied in quite detail and an optimum kaolinite content has been sug­
gested from the point of view of strength and workability at a clinker
replacement level of 50% [41], very little on the influence of the clinker
replacement level on strength has been reported. While some studies
show slightly higher strengths at replacement levels of 20% to 30%, the
results appear to depend on several factors such as the fineness and
reactivity of the calcined clay and clinker [21].
Apart from compressive strength, little data on other mechanical
properties of LC3 is available. Some initial studies show that the rela­
tionship between the elastic modulus and compressive strength of LC3
concrete is similar to other concretes [38,78]. Engineering cementitious
composites (ECC) made using LC3 were shown to have higher strain
capacity and lower crack width compared to the OPC based ECC [79].
LC3-ECC having as low as 20% clinker content can achieve approxi­
mately 5 MPa tensile strength that is found to decrease with increase w/
b ratio [80]. The fineness of limestone influences the tensile ductility,
crack width and crack density of LC3-ECC [81]. LC3 has been shown to
have higher flexural strength compared to OPC due to the higher frac­
tion of crystalline aluminates and C-A-S-H gel in LC3 [82,83]. Limited
studies were found on the tensile and flexural behaviour of unreinforced
LC3 concrete. Autogenous shrinkage of LC3 concretes has been reported
to be similar to that with OPC and fly ash blended cement [38,84]. Creep
has been reported to be lower in LC3 concretes compared to other con­
cretes [84]. This has been attributed to the intermixing of clay particles
in the C-S-H structure that might influence the viscous behaviour of the
C-S-H gel. The proportion of limestone to the clay and the clay purity is
also seen to have an influence, with cements containing higher calcined
kaolinite contents showing lower basic creep compliance (Fig. 11) [84].
This can be especially useful in prestressed applications, although
studies on the subject were not found. LC3 has also been shown to in­
crease the bond strength between the polyethylene fibers and matrix
[83].
8. Durability and service-life design of LC3 concrete
The pore-structure of LC3 has been reported to be more refined that
of OPC and fly ash blended cements (Fig. 12) [32]. Since a greater
intermixing of the hydration products is also observed, it is possible that
the refinement of the pores is due to a more uniform distribution of
hydration products throughout the microstructure as a result of pre­
cipitation of the products on the significantly larger surface of calcined
7
Cement and Concrete Research 149 (2021) 106564
Fig. 11. Influence of kaolinite content of calcined clays (15%, 25%, 45%, 50%,
60% and 95%) on the creep compliance of LC3 in comparison to the plain
cement (PC) [85].
clay and limestone. The finer porosity may also be a result of the higher
volume fraction of low-density crystalline phases such as ettringite and
carboaluminates. This refined pore-structure has been shown to result in
a lower permeability and therefore more durable concrete in many
exposure conditions. The reduced permeability has also been charac­
terised as a reduction in capillary sorption, chloride ingress and an in­
crease in the resistivity of the concrete [32,87]. It has also been shown
that the finer pore-structure in LC3 develops earlier than in other ce­
ments [32]. This makes the cement less susceptible to a reduced service
life due to poor curing.
Since the corrosion of reinforcing steel is the predominant cause of
deterioration in reinforced concrete structures, a significant effort has
gone into understanding the mechanisms of the ingress of chlorides and
carbon dioxide in LC3 concrete, which are the main causes of this
corrosion. Studies have shown that the refined and more tortuous pore-
structure significantly reduces the ingress of chloride ions in concrete.
While some studies have indicated that cements with a higher alumina
content, as is the case for LC3, also tend to bind more chlorides, leaving
fewer ions in a free condition to react with the reinforcement, some
results on LC3 show that there is only a small increase in the binding of
chlorides [88]. It has also been reported that the conversion of mono­
carboaluminate and stratlingite to Friedel's salt leads to a higher
chemical than a physical binding of the chlorides, reducing the revers­
ibility of the binding [89,90]. The purity of clay is shown to have a
significant influence on the resistance against chloride ion transport, as
shown in Fig. 13 [88].
Since the pH of the pore solution in LC3 has been shown to be
marginally lower than other cements (approximately 13.8 for OPC and
approximately 13.2 for LC3 [91]), the initiation of chloride induced
corrosion is expected to start at lower chloride concentrations [92]. The
slower migration of moisture and the higher resistivity of LC3 concrete
indicate that the rate of corrosion may be slower even after initiation
[92]. However, initial results have shown that reduction in the pH may
M. Sharma et al.
Fig. 12. Evolution of pore sizes in OPC paste, fly ash-blended paste and LC3 paste with curing age, measured using mercury intrusion porosimetry [32].
Fig. 13. Chloride profile comparison of plain cement (PC) and LC3 mixes,
consisting clays of different kaolinite content (17.0%, 50.3%, 79.4%, 95.0%),
subjected to 3% NaCl ponding solution [88].
Fig. 14. Estimated service life of a RC bridge girder subjected to chloride
environment [92].
8
Cement and Concrete Research 149 (2021) 106564
lead to a higher rate of corrosion in LC3 concrete in saturated conditions
[92]. Initial studies show a significant increase in the service life when
LC3 is compared to OPC, as shown in Fig. 14 [92], although more
detailed studies are needed on the subject. It must be noted here that
most service-life models do not include the corrosion propagation period
in the estimation of service life in the case of chloride exposure.
In the case of carbonation, the lower carbonatable content in LC3
increases the rate at which the carbonation front progresses in concrete
[93]. This is despite the reduction in the gas permeability that occurs
due to a refinement of the pore-structure, indicating that the reserve
alkalinity is the key controlling parameter in carbonation. It has also
been shown that the carbonation of the aluminates leads to a reduction
in the solid volume that is coupled with a release of water into the
microstructure. Although, initially, this water reduces the rate of ingress
of carbon dioxide, once dried, the gas-permeability increases [94]. This
is contrary to what has been traditionally reported for OPC, where most
of the carbon dioxide reacts with calcium hydroxide, leading to an in­
crease in the solid volume (Fig. 15). A detailed study on the influence of
carbonation on the microstructure of LC3 has shown that a migration of
calcium ions from unhydrated cement grains, which is also expected to
lead to an increase in the solid volume, also occurs in LC3 [94]. Recent
results have shown that despite this increase in porosity, the sorptivity of
carbonated LC3 concrete is lower than that of carbonated OPC and
Fig. 15. Relative change in solid volume of OPC, PPC and LC3 on exposure to
carbon dioxide [94]. The relative change was calculated using thermody­
namic modelling.
M. Sharma et al.
Portland pozzolana cement (PPC) concrete [95]. This is most likely due
to the finer capillary pores and the lower pore-entry diameter that has
been reported in LC3 pastes [96]. Therefore, while the lower pH in the
case of LC3 is likely to support faster rates of corrosion, the slower
transport of moisture and ions through the concrete may reduce the
corrosion current, especially when a good quality cover concrete is
provided. Detailed studies on the subject are required to study the in­
fluence of the changes in the microstructure due to carbonation on the
service life of structures subjected to corrosion due to carbonation.
The resistance of LC3 to alkali silica reaction has been measured in
terms of expansion of mortar bars submerged in alkaline solutions.
These measurements have shown that LC3 mortars do not suffer from
alkali silica reaction (ASR) expansion, even with reactive aggregates
[97,98]. This is expected since not only is the alkalinity in LC3 lower
than other cements, but also the release of alumina in the pore solution
from calcined clay can significantly reduce the rate of aggregate disso­
lution [99]. Exposure to sodium sulphate has also been shown to lead to
lower expansion and cracking risk in the case of LC3 compared to other
cements [97,100,101]. The resistance against sulphates has been seen to
increase as replacement of clinker with limestone and calcined clay is
increased. While this could be due to the relatively more harmless nature
of the conversion of carboaluminates to ettringite, this needs further
investigation. Although accelerated tests using MgSO4 have been re­
ported to be harsher than usual practical conditions, further studies on
its influence on LC3 are required. Studies on service life modelling of LC3
concrete exposed to sulphates were not found.
The performance of LC3 subjected to fire/elevated temperature has
not been studied in detail. One study found in the literature on the
performance against elevated temperatures shows that the residual
compressive strength ratios of LC3 are quite similar to OPC, after being
subjected to different elevated temperatures (300 ◦ C, 550 ◦ C and 900 ◦ C)
[102]. The reduction in residual compressive strength has been shown to
increase with increase in the replacement ratio of limestone and calcined
clay.
No study on the influence of cyclic freezing and thawing on LC3
concrete are available. Although, it is expected that the freeze-thaw
resistance of LC3 will be higher compared to OPC due to the finer and
less connected pores in LC3, similar to other composite cements detailed
studies on the subject are required [103,104].
9. Economics and sustainability
LC3 has been shown to effectively address all three major pillars of
sustainability –environment, economy and society, which in the case of
engineering materials can be characterised by safety and serviceability
(including engineering performance). The economic viability of LC3 has
been established in many scenarios around the world [105–108]. Since
the economic viability of any product has to be compared against that of
other products that it can replace, the analysis varies from location to
location, depending on the materials in use locally. Parameters such as
the availability and cost of raw materials, the cost of processing and
transportation and the perceived market value play a role. The pro­
duction of LC3 can be carried out in various scenarios where the indi­
vidual steps of clinker production, clay calcination, grinding and
blending can be carried out either at the same location or at different
locations. The transportation mode and distance to the market also plays
a role. The methodology and constraints to carrying out such analysis
have been reported in the literature [107,109,110]. It has been seen that
LC3 is viable especially at locations where the cost of other SCMs is high
or their low quality does not allow a high enough clinker replacement.
The economic viability is also seen to depend on the cost of production
of clinker and the availability of fuels [105–107]. It has also been shown
that the capital investment required for the setting up of a new plant of
LC3 is lower than the cost of setting up a plant of OPC of similar capacity.
Similarly, the cost of increasing the capacity of a cement plant by con­
verting the production to LC3 has been reported to be lower that of the
9
Cement and Concrete Research 149 (2021) 106564
addition of a new clinker production line. This has been shown to be
especially beneficial in the case of countries where an increase in the
demand of cement is being experienced [105–107]. Economic benefits
of converting an old clinker kiln to a clay calciner have also been re­
ported. The return on capital has also been compared using various
calcination technologies [111]. Data on financial investment and returns
from actual cement plants producing LC3 is, however, not available.
The energy consumption and the CO2 emissions from the production
of LC3 have also been compared with those of other cements as the key
indicators of environmental impact [105–107]. While these calculations
have been shown to be more complex with the requirement of large
amounts of data, reliable databases and tools are easily available. It has
been shown that while the absolute results depend highly on the chosen
scenarios and the system boundaries in the chosen approach, the relative
differences are similar. Several approaches, such as “cradle-to-gate”,
“gate-to-gate”, “cradle-to-grave”, etc. are available. For example, the
total energy consumed and the emissions depend on whether or not the
impact of the production of the fuel is included. The relative benefit of
producing LC3 vs. other cements still remains similar, irrespective of the
chosen scenario and approach.
Clinker being the most energy-intensive constituent of cement, the
reduction in its content that is possible through the use of LC3 was seen
to significantly reduce the energy consumptions and the emissions
related to cement consumption. While SCMs like fly ash and slag are
assumed to have zero additional emissions and energy consumption,
since clay requires calcination, it also makes a contribution. However,
the temperature of calcination is significantly lower than the tempera­
ture of the production of clinker and there is no CO2 emitted from the
decomposition of the clay. It has been reported that the energy required
for the calcination of clays is only around 60% of the energy required for
the production of clinker [112] and that the CO2 emissions are around
30% of those from clinker production. However, a direct comparison
between different cement types is difficult since factors such as trans­
portation of raw materials, fuel used, etc. also make a significant
contribution to the overall energy and emissions. An economic analysis
of the production of LC3 in India has shown the commercial viability of
LC3 compared to Portland pozzolana cement (PPC) in most scenarios
(Fig. 16) [106]. A similar study conducted for the Cuban market has
shown potential benefits of using LC3 to reduce CO2 emission and
monetary cost associated with the production of cement (Fig. 17).
In usual situations, it has been reported that, overall, the energy
emissions from the production of LC3 are around 15% lower than those
from OPC and the CO2 emissions are around 30%–40% lower [112].
However, when compared to PPC, the energy consumed in production
may be higher, even though the emissions may be lower [112]. The
studies have shown the importance of preparing a detailed inventory of
Fig. 16. Estimated cost of production of LC3 with respect of PPC (having 30%
fly ash). X-axis represents the difference of the distance from the source of fly
ash from the distance to the source of usable clay. Y-axis represents the ratio of
the estimated cost of production of PPC to the cost of production of LC3. The
legends represent the purchase cost of fly ash [106].
M. Sharma et al.
Fig. 17. Comparison between (left) CO2 emission and (right) cost of production of OPC vs. LC3 considering a massive investment in the best available technology for
production of both, OPC and LC3 [105].
the elements in the production that contribute to the environmental
impact [112]. The influence of the chosen methodology, such as cradle-
to-gate or gate-to-gate, has also been reported [112]. Since a high level
of clinker replacement is possible using blast furnace slags, which are
also assumed to be a zero energy and emissions raw material for the
cement industry, the energy and emissions from LC3 are calculated to be
higher than slag cements in most scenarios. It may be, however, noted
that slag is available in limited amounts in most countries and there is a
reduction in the early strength development at higher replacement with
slag, while LC3 does not suffer from these drawbacks.
A comparison of the environmental impact at the scale of concrete
has shown a higher benefit of replacement of OPC with LC3 in concretes
of higher strength due to the higher cement content in these concretes. It
has been argued that since most of the cement is used in the production
of concrete, a comparison at this scale is more relevant.
Studies at the level of individual dwelling units have quantified the
financial and environmental benefits through the use of LC3 in masonry
mortar and the additional benefits of using LC3 for the production of
hollow concrete blocks for the walls. The comparison has been carried
out at the same strength and functionality level [108]. In order to sup­
port decision-making based on the combined influence of environmental
impact, safety and serviceability, two factors called the A-index and
energy intensity (eics, 365) have been suggested [109]. A-index combines
the carbon footprint and durability of concrete and the energy intensity
is the energy consumed in the production of one cubic metre of concrete
per MPa compressive strength attained at 1 year. Example calculations
Fig. 18. Energy intensity and A-index of concrete under chloride exposure. The
two sustainability parameter, A-index and energy intensity, are low for LC3
making it a suitable choice for sustainable concrete [109].
10
Cement and Concrete Research 149 (2021) 106564
for reinforced concrete exposed to carbon dioxide and chloride exposure
have been reported (Fig. 18) [109].
Overall, it is seen that although the environmental benefits of
replacing other cements with LC3 depend on several factors in the sce­
nario being analysed, a significant reduction in the environmental
footprint is achieved in comparison with other contemporary cements
[107,108,113]. It is interesting to note here that despite the significant
differences in the approaches and parameters used in the two cases, the
savings in energy and emissions that have been reported for Cuba are
similar to those reported for India.
10. Potential areas of research on LC3
Potential areas of further research on LC3 that have been identified
from the above review are listed below.
1. Test methods that can rapidly quantify the quality of a calcined
clay for the purpose of quality control on a plant.
2. The influence of various impurities in limestone and clay on the
performance of LC3.
3. The influence of calcination conditions, including colour control,
on the performance of LC3.
4. Although the existing admixtures also work, those that are more
suitable for use with LC3 should be developed. This includes ad­
mixtures for water reduction, air entertainment, retardation and
early-strength activation and corrosion inhibition due to
carbonation.
5. Studies on the tensile and flexural strength of LC3 concretes.
6. More detailed work on creep and shrinkage of LC3 concrete.
7. Studies of mechanical performance, creep and shrinkage in pre­
stressed concrete.
8. Influence of carbonation on microstructural parameters that can
influence corrosion. Further, the rate of corrosion in carbonated
LC3 concrete under various conditions.
9. More detailed studies on the resistance of LC3 concretes to
various deterioration mechanisms, such as sulphate attack, alkali
silica reaction, freeze-thaw, etc.
10. More detailed studies on identifying the mechanism of the in­
fluence of curing temperature on hydration, strength develop­
ment and microstructural development.
11. The resistance of LC3 concretes to high temperature and fire.
12. Service life analysis of LC3 concretes exposed to various deteri­
oration mechanisms.
M. Sharma et al.
CRediT authorship contribution statement
Meenakshi Sharma: Conceptualization, Methodology, Data Cura­
tion, Resources, Discussion, Writing - original draft, Writing - review &
editing
Shanshank Bishnoi: Conceptualization, Discussion, Writing - orig­
inal draft, Writing - review & editing
Fernando Martirena: Discussion, Writing - review & editing
Karen Scrivener: Discussion, Writing - review & editing
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
The authors would like to acknowledge Swiss Agency for Develop­
ment and Cooperation (SDC) for providing the financial support for the
Low Carbon Cement project.
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