buildings
Article
Mechanical Performance and Physico-Chemical Properties of
Limestone Calcined Clay Cement (LC3) in Malawi
Innocent Kafodya 1 , Debojyoti Basuroy 2 , Joseph Mwiti Marangu 3 , Grant Kululanga 1 , Riccardo Maddalena 4
and Viviana Iris Novelli 4, *
Citation: Kafodya, I.; Basuroy, D.;
Marangu, J.M.; Kululanga, G.;
Maddalena, R.; Novelli, V.I.
Mechanical Performance and
Physico-Chemical Properties of
Limestone Calcined Clay Cement
(LC3) in Malawi. Buildings 2023, 13,
740. https://doi.org/10.3390/
buildings13030740
Academic Editor: Antonio
Caggiano
Received: 15 February 2023
Revised: 3 March 2023
Accepted: 6 March 2023
Published: 11 March 2023
Copyright: © 2023 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Buildings 2023, 13, 740. https://doi.org/10.3390/buildings13030740
1 Civil Engineering Department, Malawi University of Business and Applied Sciences, Blantyre 312225, Malawi;
ikafodya@poly.ac.mw (I.K.); gkululanga@poly.ac.mw (G.K.)
2 Society for Technology and Action for Rural Advancement (TARA), New Delhi 110016, India;
dbasuroy@devalt.org
3 Department of Physical Sciences, Meru University of Science & Technology, Meru 60200, Kenya;
jmarangu@must.ac.ke
4 School of Engineering, Cardiff University, Cardiff CF24 3AA, UK; maddalenar@cardiff.ac.uk
* Correspondence: novelliv@cardiff.ac.uk
Abstract: Malawi is one of the least-developed countries in Sub-Saharan Africa with disaster-prone
housing infrastructure characterized by poor construction materials. Therefore, there is a need to
provide resilient and cost-effective materials, such as limestone calcined clay cement (LC3). However,
the exploitation of LC3 in Malawi is limited due to a lack of mineralogical information about the
clays and limestone and related strength and durability when used as a cementitious material. In
this study, the strength and physico-chemical properties of LC3 systems with 50% and 40% clinker
contents (LC3-50 and LC3-40) were investigated. Cement mortar specimens were prepared at water
to cement (w/c) ratios of 0.45, 0.5, and 0.6 with varying calcined clay (CC) to limestone (CC/LS)
ratios (1:1, 2:1, and 3:1). The effects of CC/LS ratio on the fresh properties, strength, and durability
were investigated. The results showed that specimens with 40% Portland cement replacement levels
(LC3-40) exhibited higher standard consistency (up to 45%) than LC3-50, porosity in the range of
8.3–13.3%, and maximum water uptake in the range of 3.8–10.9%. On the other hand, LC3-50 samples
offered the highest strength of approximately 40 MPa, complying with requirements for pozzolanic
cementitious materials, whereas LC3-40 conforms to the strength requirements for masonry cements.
This work shows that LC3 systems can be manufactured with local clays and limestone available in
Malawi, and used as a sustainable construction material to mitigate carbon emissions as well as boost
the local economy.
Keywords: calcined clay; limestone; cement; hydration; porosity; LC3
1. Introduction
Malawi is a developing country in Sub-Saharan Africa. It is situated within the East
Africa lift system where natural hazards such as tropical cyclones and earthquakes are
common. The prevailing poor socio-economic conditions in Malawi result in poor housing
infrastructure, especially in informal settlements [1]. Ordinary Portland Cement (OPC)
produced from clinker is commonly used in the Malawi construction industry. The records
show that annual cement consumption exceeds 370,000 tons [2]. The poor economic status
of the country forces the majority of locals to use mud mortar in place of cement, resulting
in weak housing infrastructure that is vulnerable to natural disasters. Statistics from
past earthquake events indicate that 4000 households were damaged mainly due to the
poor quality of the construction materials [1]. The report of the recent series of tropical
cyclones shows that more than 193,558 households were affected and 22,000 households
were completely damaged, a situation that called for an improvement in the housing
infrastructure in Malawi [3]. Whilst cement is expensive in Malawi, its properties improve
https://www.mdpi.com/journal/buildings
Buildings 2023, 13, 740 2 of 17

infrastructures’ durability and strength and it remains a vital construction material to build
resilient housing infrastructures.
For decades cement production has been a major contributor to the global carbon
footprint and initiatives have been recommended to reduce carbon dioxide (CO2 ) emission
and energy consumption in cement production in a quest to combat the impact of climate
change as stipulated in the UN Sustainable Development Goal 13 [4–6]. The incorporation
of supplementary cementitious materials (SCMs) as a partial replacement for OPC has been
shown to produce blended cements with better strength and durability performances than
conventional Portland cement [4,7,8]. It is reported that about 20% of SCMs such as fly ash,
natural pozzolana, ground granulated blast-furnace slag (GGBS), and limestone are used
as additives in cement. However, the quality of fly ash and the availability of GGBS are the
major drawbacks in their application for cement production [9]. Other notable alternatives
are geopolymers that have high prospects for carbon reduction and resource consumption,
however, their practical use is foreseen in the medium to long term [10,11]. Limestone
calcined clay cement (LC3) is the recent alternative, which is a ternary blended cement
based on the combination of Portland cement clinker with calcined clay and limestone. It
can be produced with low-grade clay and dolomite-rich limestone [7]. When kaolinitic
clays are calcined at temperatures in the range of 500–800 ◦ C, metakaolin (MK) is obtained,
which exhibits excellent pozzolanic reactivity when combined with limestone filler [12–14].
The performance of LC3 is comparable to or better than ordinary Portland cement (OPC)
at a clinker factor of 0.5, making it a low-cost and environmentally friendly solution for
construction material.
In addition to its environmental benefits, LC3 systems have been shown to be eco-
nomically viable compared to conventional Portland cement. Joseph et al. performed
an economic analysis of the production of LC3 from raw materials locally sourced in In-
dia [15,16]. Results showed that LC3 concrete provides a more economical alternative to the
rising cost of fly ash, due to its transportation, and better-controlled mineralogical quality.
There is low production of fly ash in Malawi since the country does not depend on fossil
fuels for power generation, making LC3 production a cost-effective alternative to OPC and
other blended cements.
Other researchers studied the effects of limestone calcined clay pozzolana (LCCP) on
the engineering properties of mortar and concrete, focusing on variations in initial setting
times and compressive strength [17]. They concluded that the induction duration and
initial setting time of cement paste reduce with an increased cement replacement level.
Higher or similar compressive strength could be registered for all the LCCP blends as
compared to ordinary Portland cement. Although these results were insightful, it should
be acknowledged that the quality of clay and limestone has a bearing on the performance
of LC3 and might be even better for Malawian-based samples.
Ez-zaki et al. (2021) assessed factors that control fresh state properties of limestone-
calcined clay cement in comparison with Portland and binary cements, by combining
rheological measurements with setting time determination and the evaluation of plastic
shrinkage [18]. It was concluded that plastic shrinkage occurs from the mixing to the setting
of fresh paste and governs microstructural changes due to settlement and evaporation.
Several studies reported that low-grade clays with kaolinite content of about 40% may be
used for LC3 with good mechanical and durability performance of concrete [7,16,19,20].
On the other hand, other investigations concluded that calcined clays may increase water
demand due to the fineness and large specific surface area of the particles, owing to the
amorphous structure of kaolinite that results in a loss in workability [19,21].
The durability properties of cementitious materials are critical for the design of con-
crete structures. Durability issues of LC3 concrete such as porosity, carbonation, chloride
diffusion, and steel reinforcement corrosion have been pursued by various researchers.
Dhandapani et al. assessed the pore structure of concrete with LC3, OPC, and fly ash
cements using mercury intrusion porosimetry [22,23]. Compared to Portland cement-based
binders, it was observed that LC3-based materials offer a much-refined microstructure,
Buildings 2023, 13, 740 3 of 17

further confirmed by low conductivity results. Khan et al. (2018) focused on address-
ing issues related to carbonation when calcined clay dosages of 15%, 30%, and 45% at a
calcined-clay-to-limestone ratio of 2:1 were used [21]. The results indicated that concrete
with LC3 and 15% dosage showed higher carbonation resistance than concrete with OPC.
Nguyen et al. (2020) [24] and Rengaraju et al. (2019) [25] evaluated the chloride diffusion
resistance of concrete with LC3 using three series of concrete batches. Two dosages with
15% and 20% of the cement were replaced by a mixture of calcined clay and limestone in a
ratio of 2:1. The results revealed that the use of LC3 in concrete significantly increases its
resistance to chloride diffusion and provides better protection of steel against corrosion.
Pillai et al. (2019) have reported concrete parameters such as chloride diffusion
coefficient, aging coefficient, and chloride threshold for cement mixtures containing OPC
and blends of OPC with pulverized fuel ash (PFA) or LC3 [26]. The parameters were used
to establish the service life of the two construction elements. The results showed that
construction with LC3 possesses longer service life with a much smaller carbon footprint.
Although the literature indicates the good performance of LC3-based cementitious
materials, there are variations in the properties of raw materials used for various studies.
The raw materials are mainly country-specific whose characteristics depend on the geo-
logical formations. It is anticipated that Malawian-based raw materials will produce LC3
systems with specific characteristics owing to the unique geological nature of the country.
There are significant quantities of natural raw materials such as limestone and kaoli-
nite clays to produce cost-effective and sustainable limestone calcined clay cement (LC3)
in Malawi [2]. The limestone and dolomite resources in Malawi are estimated to be over
800 million tons in the form of metamorphic marble in the southern region. The kaolinite
clay and gypsum are estimated to be over 14 million tons and 8000 tons, respectively, in
the central region. Irrespective of abundant resources, LC3 production in Malawi is not
yet explored due to the unavailability of substantive information about the characteristics
of clays and limestone, guidelines on LC3 system formulations, strength, and durability.
However, attempts have been made to characterize some clays and limestone in Malawi
for potential application in LC3 production [27]. It is therefore imperative to investigate
the properties of LC3 with mineral constituents sourced in Malawi in order to establish
a potential replacement of OPC to manufacture low-cost, sustainable, durable, and re-
silient construction. It should be acknowledged that the highest percentage of housing
stock in Malawi is unreinforced masonry with fired bricks [28]. LC3 is a potential binder
for soil-stabilized blocks that can replace fired bricks thereby promoting environmental
conservation. It is anticipated that LC3 production could foster the creation of small to
medium business enterprises in the mining sector, which is a pillar in Malawi’s Vision 2063
agenda [29].
In this study, the strength and physico-chemical properties of LC3 blends with raw
materials sourced in Malawi were investigated. The LC3 constituents were characterized
using thermogravimetric (TGA), X-ray fluorescence (XRF), and X-ray diffraction (XRD)
analyses. Two types of ternary cement systems namely, LC3-50 (50% clinker content) and
LC3-40 (40% clinker content) were investigated. The fresh properties were determined by
standard consistency and setting time tests. The strength at 28 days strength was measured
at varying calcined clay-to-limestone and water-to-cement ratios. Finally, the porosity of
the better-performing LC3 system was determined and a strength-porosity relationship
was established.

2. Materials and Methods

2.1. Materials
The raw materials for manufacturing LC3 systems were clay, limestone, clinker,
and gypsum. The clay soil was sampled from Lithipe in Central Malawi, (−14.172479,
34.114961). Limestone was obtained from the mining site in Balaka, Southern Malawi
(−15.042424, 35.050234). The map showing the location of the raw materials source is
shown in Figure 1. Clinker was obtained from a local Lafarge cement manufacturing
Buildings 2023, 13, x FOR PEER REVIEW 4 of 17

Buildings 2023, 13, 740 4 of 17

Limestone was obtained from the mining site in Balaka, Southern Malawi (−15.042424
35.050234). The map showing the location of the raw materials source is shown in Figure 1
Clinker was
distributor in obtained
Blantyre, from a local to
conforming Lafarge cement manufacturing
the international requirements distributor
for Portlandince-
Blantyre
conforming to the international requirements for Portland cement. Natural
ment. Natural gypsum was collected from the deposit in the Dowa district located in gypsum was
collected
Central from the deposit in the Dowa district located in Central Malawi.
Malawi.

Figure 1. Geographical locations of sampled clay and limestone in Malawi. Image adapted from
Figure 1. Geographical
Maduekwe locations
and de Vries (2019) [30]. of sampled clay and limestone in Malawi. Image adapted from
Maduekwe and de Vries (2019) [30].
2.2. Methods
2.2.1. Materials Preparation
2.2. Methods
Limestone, gypsum, and clinker were ground separately to produce a fine powder.
2.2.1. Materials Preparation
The clay soil was initially pulverized and sieved using a 75 µm sieve. Only volumes finer
than 75Limestone, gypsum,
µm were used and clinker
for preparing LC3 were ground
systems. separately
Calcined clay was toproduced
produce using
a fineapowder
static calcination process, where a 50 g clay sample was heated at 800 ◦
The clay soil was initially pulverized and sieved using a 75 µm sieve. Only volumes fine
C in a muffle furnace
for
than30 75
min.
µmThe loss used
were on ignition (L.O.I.) index
for preparing LC3and the mineralogical
systems. Calcined claycomposition of LC3 using a
was produced
constituents obtained by means of X-ray fluorescence (XRF) are shown in Table 1.
static calcination process, where a 50 g clay sample was heated at 800 °C in a muffle fur
nace for 30 min. The loss on ignition (L.O.I.) index and the mineralogical composition o
Table 1. XRF analysis of LC3 constituents and L.O.I. index.
LC3 constituents obtained by means of X-ray fluorescence (XRF) are shown in Table 1.
Chemical Composition (Oxides, %)
Compound
Table 1. XRF analysis of LC3 constituents
Clinker Clay and Calcined
L.O.I. index.
Clay Limestone Gypsum
Na2 O 0.03 0.009 0.003
Chemical Composition 0.003 %)
(Oxides, 0.003
Compound
MgO 4.00 0.12 0.20 9.20 4.80
Al2 O3 Clinker
7.35 Clay29.44 Calcined Clay
36.03 Limestone
1.65 1.90Gypsum
NaSiO
2O 2 34.07
0.03 48.15
0.009 46.71
0.003 6.45
0.003 1.50 0.003
P2 O5 0.36 0.06 0.06 0.034 0.00
MgO
SO3
4.00
1.19
0.120.06 0.20
0.83
9.20
0.34 52.5
4.80
Al2ClO3 7.35
0.03 29.44
0.007 36.03
0.004 1.65
0.002 0.005 1.90
K
SiO22 O 0.65
34.07 48.150.3 0.35
46.71 0.05
6.45 0.01 1.50
CaO 52.17 0.44 0.71 47.26 32.01
PTiO
2O5 0.360.3 0.060.40 0.06
0.43 0.034
0.057 0.02 0.00
2
SO
MnO 3 1.19
0.004 0.060.02 0.83
0.022 0.34
0.018 0.004 52.5
Fe
Cl2 O 3 2.58
0.03 0.007 2.9 3.35
0.004 0.61
0.002 0.07 0.005
L.O.I. 0 18.09 11.30 34.32 7.17
K2O 0.65 0.3 0.35 0.05 0.01
CaO 52.17 0.44 0.71 47.26 32.01
The limestone used sampled in Balaka (Malawi) contained a significant amount of
TiO2 oxides 0.3
magnesium 0.40which might affect
(MgO) at 9.2%, 0.43 the strength development
0.057 0.02
of cement
MnO 0.004 0.02 0.022 0.018 0.004
Fe2O3 2.58 2.9 3.35 0.61 0.07
L.O.I. 0 18.09 11.30 34.32 7.17
 pastes due to the formation of brucite during hydration [31], [32]. The calcination temper-
ature and kaolinite content of clay were determined by means of TGA and XRD analyses,
respectively. The results are shown in Figure 2.
The TGA results showed that dehydroxylation of kaolinite to metakaolin occurred in
the region of 400–600 °C with a weight loss of approximately 9%, indicating an initial
Buildings 2023, 13, 740
kaolinite content of 63%. The calcination temperature was therefore determined at5800 of 17
±
10 °C to ensure the full dehydroxylation of kaolinite, in agreement with previous studies
[7], [33]. The XRD patterns for the raw clay showed the presence of kaolinite as a dominant
pastes
mineraldue to theThe
phase. formation of brucite
peak at around 12°during hydration
2θ associated with[31,32]. Thefurther
kaolinite calcination tempera-
confirmed high
ture and from
content kaolinite
TGAcontent of whilst
analysis, clay were determined
no kaolinite by means
phases of TGA
are visible and
in the XRD analyses,
calcined clay pat-
respectively. The results are shown in Figure 2.
tern after calcination.

(a) (b)
Figure2.2.(a)
Figure (a)TGA
TGAprofiles
profilesand
and(b)
(b)XRD
XRDpatterns
patternsofofraw
rawclay
clayand
andcalcined
calcinedclay.
clay.

TwoTGA
The ternary cement
results showedsystems, LC3-50 and LC3-40,
that dehydroxylation were prepared
of kaolinite with a occurred
to metakaolin Portland in ce-
ment replacement at◦ 50% and 40% by mass, respectively. For both
the region of 400–600 C with a weight loss of approximately 9%, indicating an initial kaoli-systems, three series
were
nite designed
content withThe
of 63%. varying calcined
calcination clay to limestone
temperature (CC/LS)determined
was therefore at 800 ± 10 ◦1:1,
ratios of, respectively, C
to2:1, and 3:1.
ensure the For
full each series, the water
dehydroxylation to cement
of kaolinite, in (w/c) ratio was
agreement withkept at 0.45,
previous 0.5, and
studies 0.6.
[7,33].
TheXRD
The gypsum content
patterns wasraw
for the chosen at 5% bythe
clay showed mass in bothofseries
presence to ensure
kaolinite suitable mechan-
as a dominant mineral
ical strength
phase. development
The peak at around 12 ◦ 2θThe
[19]. series mix
associated withdesigns
kaolinitearefurther
summarized
confirmedin Table
high2. content
from TGA The workability of the
analysis, whilst no cement
kaolinite systems,
phases are andvisible
the effect ofcalcined
in the the calcined clay content,
clay pattern after
were measured by determining standard consistency, and initial and final setting times,
calcination.
Two ternary
following cement systems,
the methodology reportedLC3-50
in ASTMand LC3-40,
C187 and were
ASTM prepared with a Portland
C191, respectively [34],
cement
[35]. Thereplacement at 50%
paste for both and and
initial 40% final
by mass,
settingrespectively.
times wasFor both systems,
prepared using the three series
predeter-
were
mined designed
normalwith varyingof
consistency calcined clay tosystem.
each cement limestone (CC/LS) ratios of, respectively, 1:1,
2:1, and 3:1. For each series, the water to cement (w/c) ratio was kept at 0.45, 0.5, and 0.6.
Table
The 2. Mixcontent
gypsum design for
wasLC3-50
chosen and LC3-40
at 5% series,inatboth
by mass varying calcined
series clay-to-limestone
to ensure (CC/LS)
suitable mechanical
ratios bydevelopment
strength mass and water-to-cement
[19]. The series(w/c)mixratios by mass.
designs The relative content
are summarized in Table (%wt.)
2. of clinker,
calcined
The clay, limestone,ofand
workability thegypsum
cementissystems,
also reported.
and the effect of the calcined clay content,
were measured by determining standard LC3-50 consistency, and initial and final setting times,
following the methodology reported in ASTM C187 and ASTM C191, respectively [34,35].
Calcined Clay to Water to
The paste for both initialClinker
and final setting
Calcined times
ClaywasLimestone
prepared using the predetermined
Gypsum
Limestone (CC/LS) Cement
normal consistency of each cement % system.% % %
Ratio (w/c) Ratio
1:1 Preparation50.0
2.2.2. Specimen for LC3 Mortars 22.50 22.50 5.0 0.45
1:1 50.0 22.50 22.50
Three mortar prismatic specimens for compressive strength and water absorption 5.0 0.5rate
1:1 50.0 22.50 22.50
were measurements were prepared in accordance with BS EN 196-1:2016 using standard 5.0 0.6
2:1 mixing and50.0
sand [36]. After 30.00
casting, the specimens were15.00 5.0
kept in a temperature-controlled 0.45
environmental 2:1 chamber at 50.0 21 ◦ C and relative
30.00 humidity 15.00 of 90% for 24 h. 5.0Specimens0.5 were
then demolded 2:1 and placed in 50.0a water-curing 30.00tank for 27 days. 15.00 After curing,
5.0 mortar prisms0.6
from each cement system and series were air-dried and tested for mechanical strength
following the standard BS EN 196-1:2016 [36].

2.2.3. Pore Size Distribution and Electron Microscopy Imaging

Mercury Intrusion Porosimetry (MIP) was used to measure the pore size distribution
of the mortar samples cured for 28 days. Prior to MIP measurements, the hydration was
halted by isopropanol exchange for three days [37]. The pore diameters were measured in
the range between 0.65 mm and 0.003 µm. A micromeritics AutoPore V9600 porosimeter
(Micromeritics Instrument Corporation, Norcross—GA, USA) was used. The pressure
applied by the porosimeter was in the range of 0–420 MPa with a constant contact angle
Buildings 2023, 13, 740 6 of 17

of 140◦ . Scanning electron microscopy (SEM) imaging and chemical analysis was carried
out on selected samples using a Zeiss Sigma HD FEG-SEM (Zeiss, Oberkochen, Germany).
Secondary electron (SE) imaging and energy dispersive spectroscopy (EDS) X-ray analysis
was performed under high vacuum conditions with a beam energy of 20 kV, and a 60 um
diameter final aperture, with a resulting beam current of 1.5 nA.

Table 2. Mix design for LC3-50 and LC3-40 series, at varying calcined clay-to-limestone (CC/LS)
ratios by mass and water-to-cement (w/c) ratios by mass. The relative content (%wt.) of clinker,
calcined clay, limestone, and gypsum is also reported.

LC3-50
Calcined Clay to Clinker Calcined Clay Limestone Gypsum Water to Cement
Limestone (CC/LS) Ratio % % % % (w/c) Ratio
1:1 50.0 22.50 22.50 5.0 0.45
1:1 50.0 22.50 22.50 5.0 0.5
1:1 50.0 22.50 22.50 5.0 0.6
2:1 50.0 30.00 15.00 5.0 0.45
2:1 50.0 30.00 15.00 5.0 0.5
2:1 50.0 30.00 15.00 5.0 0.6
3:1 50.0 33.75 11.25 5.0 0.45
3:1 50.0 33.75 11.25 5.0 0.5
3:1 50.0 33.75 11.25 5.0 0.6
LC3-40
Calcined Clay to Clinker Calcined Clay Limestone Gypsum Water to Cement
Limestone (CC/LS) Ratio % % % % (w/c) Ratio
1:1 40.0 27.50 27.50 5.0 0.45
1:1 40.0 27.50 27.50 5.0 0.5
1:1 40.0 27.50 27.50 5.0 0.6
2:1 40.0 36.67 18.33 5.0 0.45
2:1 40.0 36.67 18.33 5.0 0.5
2:1 40.0 36.67 18.33 5.0 0.6
3:1 40.0 41.25 13.75 5.0 0.45
3:1 40.0 41.25 13.75 5.0 0.5
3:1 40.0 41.25 13.75 5.0 0.6

2.2.4. Specimen Preparation for Water Absorption Measurements

The specimens for water uptake characteristics were prepared in the same manner as
those prepared for the compression test in Section 2.2.2. From the water uptake test, two
properties were measured, namely the surface rate of water absorption and the saturation
water absorption. The specimens were initially oven dried for 24 h at 60 ◦ C. The water
absorption rate of absorption was performed following the methodology outlined in ASTM
C1403-15 [38] by placing oven-dried specimens into contact with water and the capillary
absorption rate was measured after 2 h, 72 h, and 120 h.

3. Results and Discussions

3.1. Effect of Limestone on Calcined Clay Ratio Standard Consistency and Setting Time
The effects of the calcined clay to limestone (CC/LS) ratio on the standard consistency
of LC3-50 and LC3-40 are summarized in Figure 3.
The results showed that the standard consistency (%) of both LC3-50 and LC3-40
systems increased with an increasing CC/LS ratio. The standard consistency of LC3-50
varied between 37.5% and 42.5%, whilst LC3-40 ranged between 38.8% and 45%, with
consistency values increasingly proportional to the calcined clay content. In comparison,
LC3-40 exhibited a standard consistency of 1.9% higher than LC3-50. This is due to the
nature of calcined clay, mainly composed of amorphous metakaolin. Amorphous phases
provide a large surface area for water absorption due to their disordered arrangement
Buildings 2023, 13, 740 7 of 17

of molecules that allows penetration and dissolution of the water. Therefore, the higher
Buildings 2023, 13, x FOR PEER REVIEW 7 of 17
the metakaolin content, the higher the quantity of water required to achieve cement paste
consistency [19,39]. The effect of the (CC/LS) ratio on the setting times is shown in Figure 4.

Figure 3. Variation of standard consistency with calcined clay to limestone ratio.

The results showed that the standard consistency (%) of both LC3-50 and LC3-40 sys-
tems increased with an increasing CC/LS ratio. The standard consistency of LC3-50 varied
between 37.5% and 42.5%, whilst LC3-40 ranged between 38.8% and 45%, with con-
sistency values increasingly proportional to the calcined clay content. In comparison, LC3-
40 exhibited a standard consistency of 1.9% higher than LC3-50. This is due to the nature
of calcined clay, mainly composed of amorphous metakaolin. Amorphous phases provide
a large surface area for water absorption due to their disordered arrangement of molecules
that allows penetration and dissolution of the water. Therefore, the higher the metakaolin
content, the higher the quantity of water required to achieve cement paste consistency
Figure
Figure 3. Variation
3. Variation
[19], [39]. ofstandard
of
The effect standard consistency
consistency
of the (CC/LS) with
with
ratio calcined
on calcined
the claytimes
clay
setting tolimestone
to limestone ratio.
ratio.
is shown in Figure 4.

The results showed that the standard consistency (%) of both LC3-50 and LC3-40 sys-
tems increased with an increasing CC/LS ratio. The standard consistency of LC3-50 varied
between 37.5% and 42.5%, whilst LC3-40 ranged between 38.8% and 45%, with con-
sistency values increasingly proportional to the calcined clay content. In comparison, LC3-
40 exhibited a standard consistency of 1.9% higher than LC3-50. This is due to the nature
of calcined clay, mainly composed of amorphous metakaolin. Amorphous phases provide
a large surface area for water absorption due to their disordered arrangement of molecules
that allows penetration and dissolution of the water. Therefore, the higher the metakaolin
content, the higher the quantity of water required to achieve cement paste consistency
[19], [39]. The effect of the (CC/LS) ratio on the setting times is shown in Figure 4.

(a) (b)
Figure4.4.Variation
Figure Variationofofsetting
settingtimes
times(a)
(a)Initial
Initialsetting
settingtime
time(b)
(b)final
finalsetting
settingtime.
time.

Initialand
Initial andfinal
finalsetting
settingtimes
timeswere were reduced
reduced with
with anan increase
increase in calcined
in calcined clayclay content
content in
in both cement systems. LC3-50 showed delayed initial and
both cement systems. LC3-50 showed delayed initial and final setting times compared to final setting times compared
to LC3-40,
LC3-40, withwith initial
initial setting
setting timetimevaryingvarying between
between 210 at
210 min min1:1atCC/LS
1:1 CC/LSratio ratio
and 120andmin120
atmin
3:1 at 3:1 CC/LS
CC/LS ratio.ratio.
On the Onother
the other
hand,hand, the initial
the initial setting setting
time for time for LC3-40
LC3-40 variedvaried
between be-
90tween
min at90themin1:1atCC/LS
the 1:1 ratio
CC/LS and ratio and at
40 min 40themin 3:1atCC/LS
the 3:1ratio.
CC/LS Anratio. An increase
increase in clinker in
clinkerinfactor
factor in the cement
the cement systemsystemfrom 0.4 from 0.4 to
to 0.5 0.5 resulted
resulted in a delayed
in a delayed initialinitial setting
setting timetimeby
two-fold.
by two-fold. Final setting
Final settingtimes
times showed
showed similar
similartrends
trends with
withthe thevalues
valuesofofLC3-50
LC3-50ranging
ranging
between 336 min at 1:1 CC/LS ratio and 275 min at 3:1 CC/LS ratio. In the case of LC3-40,
(a)between 336 min at 1:1 CC/LS ratio and 275 min at 3:1 CC/LS (b) ratio. the case of LC3-40,
the
thefinal
finalsetting
settingtime
timewas wasrecorded
recordedbetweenbetween255 255minminatataa1:11:1CC/LS
CC/LSratio ratioand
and135135min
minat ataa
Figure
3:1
3:1CC/LS4. Variation
CC/LSratio.
ratio.The of setting
Thefinal times
finalsetting
setting(a) Initial
times
times setting
forfor
LC3-50 time
LC3-50 (b)
andand final
LC3-40 setting
LC3-40 wereweretime.
reduced
reducedby 61bymin61 and
min
120 min, respectively. Reducing the clinker factor from 0.5 to 0.4 resulted in an accelerated
settingInitial
timeand final setting
of almost 100 min.timesBS were
EN reduced
197-1:2011 with an increase initial
recommends in calcined clay
setting content
times for
in both cement systems. LC3-50 showed delayed initial and
conventional cements (strength class 32.5 MPa) should be greater than 75 min, thus all final setting times compared
to LC3-40,
LC3-50 withsystems
cement initial and
setting timeatvarying
LC3-40 1:1 CC/LS between
comply 210 minthe
with atrequired
1:1 CC/LS ratiotime
setting and[40].
120
min at 3:1the
However, CC/LS ratio.in
reduction On the other
setting time hand,
could be theattributed
initial setting
to a hightimeratefor of
LC3-40 varied
hydration be-
in the
tween 90ofmin
presence at themetakaolin
reactive 1:1 CC/LSinratio and 40
calcined min
clay, at theto3:1
leading CC/LS
faster ratio.silicate
calcium An increase
hydrates in
clinker factor in the cement system from 0.4 to 0.5 resulted in a
(C-S-H) nucleation that resulted in a build-up of bridges between cement particles [18]. On delayed initial setting time
by two-fold. Final setting times showed similar trends with the values of LC3-50 ranging
between 336 min at 1:1 CC/LS ratio and 275 min at 3:1 CC/LS ratio. In the case of LC3-40,
the final setting time was recorded between 255 min at a 1:1 CC/LS ratio and 135 min at a
3:1 CC/LS ratio. The final setting times for LC3-50 and LC3-40 were reduced by 61 min
 and 120 min, respectively. Reducing the clinker factor from 0.5 to 0.4 resulted in an accel-
erated setting time of almost 100 min. BS EN 197-1:2011 recommends initial setting times
for conventional cements (strength class 32.5 MPa) should be greater than 75 min, thus all
LC3-50 cement systems and LC3-40 at 1:1 CC/LS comply with the required setting time
Buildings 2023, 13, 740 [40]. However, the reduction in setting time could be attributed to a high rate of hydration8 of 17
in the presence of reactive metakaolin in calcined clay, leading to faster calcium silicate
hydrates (C-S-H) nucleation that resulted in a build-up of bridges between cement parti-
thecles [18].
other On the
hand, theother
delayhand, the delay
in setting in setting
time with time with
the reduced the reduced
clinker clinker
factor could factor could
be attributed
to be
theattributed to theofmodifications
modifications the chemicalofequilibria
the chemical equilibria
of the cement inof the cement
presenceinof
the presence
calcined
of calcined
clay, coupled clay,
with coupled with lower
lower hydration hydration
rate, rate, thus
thus retarding retarding
portlandite portlandite and
precipitation precipita-
the
subsequent setting
tion and the [18,41,42].
subsequent setting [18], [41], [42].

3.2. Compressive
3.2. Strength
Compressive and
Strength SEM
and SEM Images of LC3
Images Systems
of LC3 Systems
The 2828
The day
daycompressive
compressivestrength of of
strength systems LC3-50
systems and
LC3-50 LC3-40
and at varying
LC3-40 CC/LS
at varying CC/LS
ratios at w/c ratios are shown in Figure 5.
ratios at w/c ratios are shown in Figure 5.

(a) (b)

(c)
Figure
Figure 5. 28-day
5. 28-day compressive
compressive strength
strength of LC3-50
of LC3-50 andand LC3-40
LC3-40 at (a)
at (a) 0.450.45
w/cw/c ratio,
ratio, (b)(b)
0.5 0.5
w/c w/c ratio
ratio
and (c) 0.6 w/c ratio.
and (c) 0.6 w/c ratio.

TheThe compressive
compressive strength
strength reduced
reduced with
with anan increase
increase in in calcined
calcined clay
clay content
content forfor both
both
LC3-50
LC3-50 andand LC3-40
LC3-40 at 0.45
at 0.45 w/cw/c ratio.
ratio. TheThe maximum
maximum compressive
compressive strength
strength valuesvalues of LC3-
of LC3-50
50 were 36.8 MPa, 39.2 MPa, and 30.6 MPa for 0.45, 0.5, and 0.6 w/c ratio,
were 36.8 MPa, 39.2 MPa, and 30.6 MPa for 0.45, 0.5, and 0.6 w/c ratio, respectively. For respectively. For
LC3-40, the maximum strength values were 22.3 MPa, 31.9 MPa 29.1
LC3-40, the maximum strength values were 22.3 MPa, 31.9 MPa 29.1 MPa for 0.45, 0.5, MPa for 0.45, 0.5, and
and0.60.6
w/c ratios,
w/c respectively.
ratios, TheThe
respectively. lowest strength
lowest (5.1 (5.1
strength MPaMPaat 0.45 w/c w/c
at 0.45 ratio ratio
and 3:1
andCC/LS
3:1
ratio) was attributed to the low workability of the cement mixture. Low
CC/LS ratio) was attributed to the low workability of the cement mixture. Low compaction compaction of the
of fresh mortar
the fresh resulted
mortar in an increase
resulted in the pore
in an increase in thevolume of hardened
pore volume mortar and
of hardened ultimately
mortar and
low strength
ultimately low [43], [44].[43,44].
strength Additionally, the highthe
Additionally, calcined clay content
high calcined and subsequent
clay content and subse-high
quent high pozzolanic reactivity resulted in reduced levels of dissolved portlandite in the
liquid phase, inhibiting the full hydration of metakaolin phases and, in turn, hindering the
final strength [45]. Segregation of aggregate in the cement mortar due to water in excess
of the amount required for hydration is also a possible cause of low-strength develop-
ment [44,46,47]. LC3-40 was expected to have lower strength than LC3-50 systems due to
the reduced initial amount of Portland cement clinker.
 pozzolanic reactivity resulted in reduced levels of dissolved portlandite in the liquid
phase, inhibiting the full hydration of metakaolin phases and, in turn, hindering the final
strength [45]. Segregation of aggregate in the cement mortar due to water in excess of the
Buildings 2023, 13, 740 amount required for hydration is also a possible cause of low-strength development [44], 9 of 17
[46], [47]. LC3-40 was expected to have lower strength than LC3-50 systems due to the
reduced initial amount of Portland cement clinker.
According
Accordingto to BS EN 197-1:2011
BS EN 197-1:2011[40]
[40]and
andBSBSENEN 413-1:2011
413-1:2011 [48][48] specifications,
specifications, speci-
specimens
mens in series LC3-50 with CC/LS ratio of 1:1 complied with the strength
in series LC3-50 with CC/LS ratio of 1:1 complied with the strength requirements for requirements
for conventional
conventional Portland
Portland pozzolana
pozzolana cement
cement (PPC)
(PPC) whilst
whilst LC3-40
LC3-40 seriesseries
met met the require-
the requirements
ments for masonry cement. Furthermore, samples in series LC3-50
for masonry cement. Furthermore, samples in series LC3-50 with 0.5 w/c ratio also with 0.5 w/c ratio also
showed
showed the strength
the strength requirements
requirements for standard
for standard PortlandPortland
cement for cement for allratios.
all CC/LS CC/LS Atratios.
a w/cAt a
ratio
w/c ratio
of 0.6, forofall0.6, for all
CC/LS CC/LS
ratios, ratios,
both LC3-50bothandLC3-50
LC3-40 and LC3-40
series serieswith
complied complied
masonry with ma-
cement
sonry cement
strength strength requirements.
requirements. Based onstrength
Based on the standard the standard strength for
requirements requirements
PPC, LC3-50 forat
PPC, LC3-50 at 0.5 w/c ratios can potentially replace standard
0.5 w/c ratios can potentially replace standard Portland cement [27]. Portland cement [27].

3.3.Pore
3.3. PoreSize
SizeDistribution
Distributionand
andSEM
SEMImages
Images
Basedon
Based onthe
thestrong
strongperformance,
performance,the
thepore
poresize
sizedistribution
distributionofofselected
selectedsamples
samplesfrom
from
the LC3-50 system series was measured, and the results are shown in Figure
the LC3-50 system series was measured, and the results are shown in Figure 6. 6.

(a) (b)

(c)
Figure
Figure6.6.Pore
Poresize
sizedistribution
distributionofofLC3-50
LC3-50system
systematat(a)
(a)1:1
1:1CC/L
CC/L(b)
(b)2:1
2:1CC/L
CC/L(c)(c)
3:13:1
CC/L.
CC/L.

The
Thecumulative
cumulativepore porevolume
volumeranges
rangesbetween
betweenapproximately
approximately0.08 0.08and
and 0.13
0.13 mL/g
mL/gfor for
all
allLC3-50
LC3-50series.
series.Samples
Samplesatataaw/cw/cratio
ratioofof0.6
0.6showed
showedthethehighest
highestcumulative
cumulativeporeporevolume
volume
forseries
for seriesatatCC/LS
CC/LS ratios
ratios of 1:1
of 1:1 andand
2:1.2:1. However,
However, at highest
at the the highest calcined
calcined clay content
clay content (3:1
(3:1 CC/LS)
CC/LS) samples samples
at a w/catratio
a w/c ratioshowed
of 0.45 of 0.45 ashowed a higher cumulative
higher cumulative poresuggest-
pore volume, volume,
suggesting
ing that the water-to-cement
that the water-to-cement ratio influences
ratio influences the hardened
the hardened pore structure
pore structure [49].
[49]. This This
effect
iseffect is more
in fact in factevident
more evident in thesize
in the pore pore size region
region of capillary
of capillary pores; pores; the higher
the higher the w/cthe w/c
ratios
ratios
for for 1:1 CC/LS
1:1 CC/LS and 2:1 and 2:1 CC/LS,
CC/LS, the largerthethelarger theAll
pores. pores. All cumulative
cumulative pore volume
pore volume curves
curves present a generalized lognormal with sigmoidal distribution except for samples at a
w/c ratio of 0.45 with the highest clay content (3:1 CC/LS), which exhibits two inflection
points. This is indicative of two-phased volume intrusion; the first phase could be due to
an intrusion into the micro-cracks or air pockets at the sand-cement interfaces, whereas the
second phase could be attributed to intrusions into interconnected pores of the hydrated
 present a generalized lognormal with sigmoidal distribution except for samples at a w/c
ratio of 0.45 with the highest clay content (3:1 CC/LS), which exhibits two inflection points.
Buildings 2023, 13, 740 This is indicative of two-phased volume intrusion; the first phase could be due to10an of 17
in-
trusion into the micro-cracks or air pockets at the sand-cement interfaces, whereas the
second phase could be attributed to intrusions into interconnected pores of the hydrated
cement.The
cement. Thecritical
critical pore
pore entry sizes
sizes at
at various
variousw/c
w/c ratios
ratiosand
andCC/LS
CC/LSratios
ratiosare
areshown
showninin
Figure7.7.
Figure

(a) (b)

(c)
Figure
Figure7.7.Differential intruded
Differential volume
intruded forfor
volume LC3-50 system
LC3-50 at (a)
system 1:1 1:1
at (a) CC/LS (b) 2:1
CC/LS (b) CC/LS (c) 3:1
2:1 CC/LS
CC/LS.
(c) 3:1 CC/LS.

The
Thebimodal
bimodaldifferential
differential intruded
intruded volume curves curves are
are shown
shownfor forall
allmortar
mortarseries
seriesinin
theLC3-50
the LC3-50system.
system. The Thecurves
curves indicate
indicate the coexistence of of both
both coarse
coarseandandfine
finepores
poresinin
thehardened
the hardenedmortar
mortar microstructure.
microstructure. The critical
critical pore
poreentry
entrysizes
sizesrange
rangebetween
between0.019
0.019µm µm
and 0.08 µm and the total porosity is between 2.6% and 10.6%, respectively.
and 0.08 µm and the total porosity is between 2.6% and 10.6%, respectively. The values The values are
consistent
are with
consistent the the
with findings reported
findings in previous
reported workwork
in previous [49–51].
[49]–[51].
The morphological images of LC3-50 that exhibitedsuperior
The morphological images of LC3-50 that exhibited superiorstrength
strengthproperties
propertiesare are
shown in Figure 8. The SEM images showed variations in the composition
shown in Figure 8. The SEM images showed variations in the composition of elements of elements
fromdifferent
from differentpoints
pointsofofanalysis.
analysis.For
For site
site 1 (2:1
1 (2:1 CC/LS
CC/LS series
series at w/c
at w/c ratioratio of 0.45),
of 0.45), the
the three
three elements with relatively high percentages are O, Ca, and Si, suggesting the pres-
elements with relatively high percentages are O, Ca, and Si, suggesting the presence of
ence of calcium silicate hydrate (C-S-H) phases. For site 2 (2:1 CC/LS series at w/c ratio
calcium silicate hydrate (C-S-H) phases. For site 2 (2:1 CC/LS series at w/c ratio of 0.5), the
of 0.5), the dominant elements (composition > 10%) are O, Si, C, and Ca indicating the
dominant elements (composition > 10%) are O, Si, C, and Ca indicating the presence of C-
presence of C-S-H phases and carbo-aluminates. The latter contributes to space-filling,
S-H phases and carbo-aluminates. The latter contributes to space-filling, thus reducing
thus reducing porosity, and resulting in enhanced overall strength. The positive effects
porosity, and resulting
of carbo-aluminates in enhanced
precipitation onoverall strength. properties
the mechanical The positive effects
have beenof carbo-alumi-
reported else-
nates
where precipitation on the mechanical
[41,52,53], confirming the higherproperties
compressive have been reported
strength exhibitedelsewhere
by LC3-50 [41],
systems[52],
[53], confirming the higher compressive strength exhibited by LC3-50
at a 2:1 CC/LS ratio with w/c ratio of 0.5 (approximately 40 MPa). For site 3 (3:1 CC/LS systems at a 2:1
CC/LS
series at w/c ratio of 0.6), the dominant elements are O, Fe, Si, C, and Ca. The site isat
ratio with w/c ratio of 0.5 (approximately 40 MPa). For site 3 (3:1 CC/LS series
w/c ratio of 0.6),
considered to havethe intermixing
dominant elements are O, Fe,
of compounds, Si, C,C-S-H,
namely and Ca. The site is considered
tetra-calcium ferrite (C4F)to
and carbo-aluminates.
Buildings 2023, 13, x FOR PEER REVIEW 11 of 17

Buildings 2023, 13, 740 11 of 17

have intermixing of compounds, namely C-S-H, tetra-calcium ferrite (C4F) and carbo-alu-
minates.

(a)

(b)

(c)
Figure
Figure8.8.Selected
SelectedSEM
SEMimages
imagesandandchemical
chemicalmapping
mappingfor forLC3-50
LC3-50system
systemseries
serieswith
withthe
thehighest
highest
strength.
strength. (a) 2:1 CC/LS ratio at w/c ratio of 0.45; (b) 2:1 CC/LS ratio at w/c ratio of 0.5; and(c)
(a) 2:1 CC/LS ratio at w/c ratio of 0.45; (b) 2:1 CC/LS ratio at w/c ratio of 0.5; and (c)2:1
2:1
CC/LS ratio at w/c ratio of 0.6.
CC/LS ratio at w/c ratio of 0.6.

The
TheBogue–Lerch strengthvalues
Bogue–Lerch strength valuesasasreported
reported in in Beaudoin
Beaudoin andand Odler
Odler (2019)
(2019) ranksranks
tetra-
tetra-calcium alumino-ferrite (C4AF) phases as lowest during the early stages
calcium alumino-ferrite (C4AF) phases as lowest during the early stages of hydration [54]. of hydration
[54]. Hence,
Hence, the the
lowerlower strength
strength exhibited
exhibited by by LC3-50
LC3-50 with
with 3:13:1 CC/LSatataa w/c
CC/LS w/c ratio
ratio ofof 0.6
0.6
(approximately
(approximately 31 MPa) could be attributed to the formation of C4AF, counteractingthe
31 MPa) could be attributed to the formation of C4AF, counteracting the
strength-enhancing
strength-enhancingeffectseffectsofofcarbo
carboaluminates
aluminatesphases.
phases.The
Themicrostructural
microstructuraldevelopment
development
ofofLC3
LC3systems
systemsfromfrom21 21randomly
randomlyselected
selectedpoints
pointsof ofthe
thecement
cementmortar
mortarusing
usingSEM-EDS
SEM-EDSisis
presented
presentedby bythe
the Si/Ca
Si/CaandandAl/Ca
Al/Caratios
ratiosshown
shownininFigure
Figure9.9.The
Thescatter
scatterofofthe
thecomposition
composition
isisrelatively
relatively high, indicating
indicating aanon-uniform
non-uniformconsumption
consumptionofof silicate
silicate and
and alumina
alumina in cal-
in calcium
cium aluminate silicate hydrate (C-A-S-H) phases and also greater inter-mixing
aluminate silicate hydrate (C-A-S-H) phases and also greater inter-mixing of the aluminates of the alu-
minates
with thewith
finalthe final product,
product, as reported
as reported in literature
in literature [55,56]. [55], [56].
Buildings 2023, 13, x FOR PEER REVIEW
Buildings 2023, 13, 740 12 of 17

Figure9.9.Si/Ca
Figure vs.vs.
Si/Ca Al/Ca scatter
Al/Ca plot ratio
scatter plotvalues
ratio for LC3-50
values forsamples
LC3-50with higher strength.
samples with higher strength.
3.4. Relationship between Compressive Strength and Porosity
3.4. Several
Relationship
modelsbetween Compressive
have been proposed to Strength
predict theand Porosity
strength of the cement mortar as a
function of its porosity
Several models[57–61], summarize
have been in Table
proposed to3.predict the strength of the cement mo
function of its porosity [57]–[61], summarize in Table 3.
Table 3. Prediction models of porous materials.

Model Table 3. Prediction

Equation models of porousParameters
materials. Material
Balshin [57] σ = σo (1 − p)b 1 σo , b Ceramic materials
Model Equation Parameters
Mortar containing Al2 O3 and
Mater
Ryshkevitch [58] σ = σo e−kp σo , k
Balshin [57]   𝜎 𝜎 1 𝑝 ZrO𝜎2 , b
1 Ceramic m
Schiller [59] po N Sulfate plasters
σ = n In p Mortar con
Hasselman [60] Ryshkevitch
σ = σo [58]
− cp σ𝜎
o, c
𝜎 𝑒 Refractory𝜎materials
,k
Xudong-Chen modified Ordinary Portland cement
Al2O3 and
𝑝
h m  i0.5 2
pc − p 2
σo , pc , m
σ = σo 1− p 3
Zheng model [61]
Schiller [59] pc
𝜎 𝑛 𝐼𝑛 mortar
N Sulfate pl
o c
𝑝 threshold.
1 σ is Strength at zero porosity, 2 p is the percolation porosity at failure

Refractory
Hasselman [60] 𝜎 𝜎 𝑐𝑝 𝜎 ,c
The regression analysis of all LC3-50 system series irrespective of their w/c ratios als
.
and CC/LS ratios
Xudong-Chen modifiedwere used in prediction 𝑝
models,𝑝 and results are shown in Figure 10a.
2 σ , 𝑝 ,from
A
Ordinary P
𝜎 𝜎 strength and 1
linear relationship between compressive total 𝑝porosity, obtained 𝑚 MIP
Zheng modelhas
measurements, [61] 𝑝 of correlation of 0.66. This indicates that
been found, with a coefficient cement m
the𝜎 strength
is Strength
of theat zero porosity, 𝑝 is
is influenced
the percolation porosityThe at failure threshold.
1 2
cementitious materials by porosity. regression analysis
was then compared with the prediction models (Figure 10b). Whilst the measured strength
valuesThevaryregression
considerably as opposed
analysis of alltoLC3-50
the predicted
system ones, the models
series however
irrespective were w/c ra
of their
developed for specific cementitious materials, and the effects of the water-cement ratio are
CC/LS ratios were used in prediction models, and results are shown in Figure 10a.
not incorporated in the model parameters. The strength is also dependent on other factors,
relationship
such between
as age, curing compressive
conditions, strengthcomposition
and mineralogical and total porosity, obtained
of the starting from
materials, as MIP m
ments, has been
demonstrated found, with
in the previous a Therefore,
section. coefficient of correlation
adequately choosingof 0.66.parameters
model This indicates
strength
must of the cementitious
be carefully materials
considered for the prediction is influenced byofporosity.
of the strength The materials.
cement-based regression anal
However, the general trends are consistent for both predicted and measured
then compared with the prediction models (Figure 10b). Whilst the measured stren values.
ues vary considerably as opposed to the predicted ones, the models however wer
oped for specific cementitious materials, and the effects of the water-cement ratio
incorporated in the model parameters. The strength is also dependent on other facto
as age, curing conditions, and mineralogical composition of the starting mate
demonstrated in the previous section. Therefore, adequately choosing model par
must be carefully considered for the prediction of the strength of cement-based m
However, the general trends are consistent for both predicted and measured valu
ildings 2023, 13, x FOR
Buildings PEER REVIEW
13, 740 13 of 17 13 of
2023,
Buildings 2023, 13, x FOR PEER REVIEW 13 17
of 17

(a) (b)
(a) (b)
Figure 10. Relationship between compressive
10. Relationship between strength and
compressive total porosity
strength andand (a)porosity
total for experimental
(a) for data;
Figure
Figure 10. Relationship between compressive strength total porosity (a) experimental data;
for experimental data;
and (b) comparison with values obtained from strength prediction models.
andand (b) comparison
(b) comparison withwith values
values obtained
obtained fromfrom strength
strength prediction
prediction models.
models.

3.5. Capillary
3.5.Water
3.5. Absorption
Capillary Water
Capillary Absorption
Water Absorption
The capillary surface
TheThecapillarywater
capillary absorption
surface water
surface test was performed
absorption
water test was
absorption test was onperformed
selected
performed on specimens
selected at specimens
specimens
on selected at a at
a w/c ratiow/c
ofa0.5,
ratiobased
of 0.5, on
basedthe compressive
on the compressive strength results.
strength The
results. results
The for
results
w/c ratio of 0.5, based on the compressive strength results. The results for both LC3 both
for LC3
both LC3 systems
systems (LC3-50
(LC3-50 and
systemsandLC3-40)
LC3-40)
(LC3-50 are
and shown
are shown
LC3-40) in inFigure
are 11.11.
Figure
shown Specimens
Specimens
in Figure 11.exhibited a high
exhibited
Specimens initial
aexhibited
high initial water
a high initial
water absorption rate
absorption (0
rateto(060tomin)
60 for
min) both
for bothLC3-50 and
LC3-50 andLC3-40
LC3-40system
systemseries. After
series.
water absorption rate (0 to 60 min) for both LC3-50 and LC3-40 system series. After 24 h, 24
After h,
24 h, LC3-50
samples
LC3-50 samples LC3-50 with
with 1:1,1:1,
2:1,2:1,
samples andand
with 3:1 3:1
CC/LS
1:1, CC/LS
2:1, and ratios
ratios
3:1 showed
showed
CC/LS ratesrates
ratios of surface
of surface
showed ofwater
water
rates absorption
absorp-
surface of
water absorp-
66.07 g/100 cm 2 , 67.85 g/100 cm 2 , and 74.92 g/100 cm 2 , respectively.
tion of 66.07 g/100 cm66.07
tion of
2, 67.85 g/100
g/100 cmcm
2 , andg/100
2, 67.85 74.92cmg/100
2, andcm74.92
2 , respectively.
g/100 cm2, respectively.

(a) (b)
(a) (b)

(c)
(c)
Figure 11. Surface water absorption rates of LC3 systems at (a) 1:1 CC/LS ratio (b) 2:1 CC/LS ratio
Figure 11. Surface water absorption rates of LC3 systems at (a) 1:1 CC/LS ratio (b) 2:1 CC/LS ratio
ratio.11. Surface water absorption rates of LC3 systems at (a) 1:1 CC/LS ratio (b) 2:1 CC/LS ratio
Figure
(c) 3:1 CC/LS
(c) 3:1 CC/LS ratio.
(c) 3:1 CC/LS ratio.
On the other hand, LC3-40 with 1:1, 2:1, and 3:1 CC/LS ratios
3:1 indicated a rate of sur- a rate of sur-
On On
the the
face water absorption
other
other
after hand,
24 h
hand,
of
LC3-40
LC3-40
66.84 withwith
g/100 1:1,
cm
1:1,
2:1, 2:1,3:1
and
2, 75.93
and
g/100CC/LS
cm
CC/LS ratios
ratios80.23
2, and
indicated
indicated
g/100 acm
rate
2, of surface
faceabsorption
water water absorption
after 24after
h of 24 h ofg/100
66.84 66.84 g/100 cm2, 75.93
cm2 , 75.93 g/100g/100
cm2 ,cm
2, and
and 80.23
80.23 g/100g/100
cm2cm
, ,
2
respectively, respectively,
slightly higher than higher
slightly specimensthaninspecimens
LC3-50 series.
in LC3-50The reduced water
series. The reduced water
Buildings 2023, 13, 740 14 of 17
Buildings 2023, 13, x FOR PEER REVIEW 14 of 17

respectively, slightly higher than specimens in LC3-50 series. The reduced water absorption
absorption
for for LC3-50could
LC3-50 specimens specimens
be duecould
to thebehigher
due toratetheofhigher rate ofresulting
hydration, hydration,
in aresulting
refined
in a structure
pore refined pore structure
[62,63]. [62], [63].
Conversely, Conversely,
an increased an increased
surface surface water
water absorption absorption
for samples with
for higher
the samples with the
calcined higher
clay contentcalcined
for bothclayLC3
content
systemsfor is
both LC3 systems
attributed is attributed
to a higher amounttoofa
higher amount
unreacted of unreacted
metakaolin; its largemetakaolin;
surface area its favors
large surface area favors
water uptake water
[18,19]. Theuptake
maximum [18],
[19]. The
water maximum
uptake water
values (%) uptake
after values
24 h for (%) LC3
the two aftersystems
24 h foratthe tworatio
a w/c LC3 of
systems
0.5 areat a w/c
shown
ratio
in of 0.5
Figure 12.are shown in Figure 12.

Figure12.
Figure 12.Maximum
Maximumwater
wateruptake
uptakeatat24
24hhfor
forthe
theLC3-50
LC3-50and
andLC3-40
LC3-40systems
systemsatataaw/c
w/cratio
ratioof
of0.5
0.5
and varying calcined clay/limestone (CC/LS) ratios.
and varying calcined clay/limestone (CC/LS) ratios.

BothLC3
Both LC3systems
systemsshowed
showedsimilar
similarvalues
valuesof ofmaximum
maximumwaterwateruptake,
uptake,approximately
approximately
an average of 4.0% and 10.5% for the LC3-50 and LC3-40 series,
an average of 4.0% and 10.5% for the LC3-50 and LC3-40 series, respectively. The respectively. Thehigher
higher
absorption for LC3-40 is proportional to the total porosity at critical pore entry
absorption for LC3-40 is proportional to the total porosity at critical pore entry sizes. Thus,sizes. Thus,
the higher water uptake is attributed to the combined effect of the high volume
the higher water uptake is attributed to the combined effect of the high volume of pores, of pores,
otherwisefilled
otherwise filledwith
withhydration
hydrationproducts
products inin
thethe LC3-50
LC3-50 series,
series, andandthethe amorphous
amorphous nature
nature of
of the
the unreacted
unreacted metakaolin.
metakaolin. Higher
Higher water
water uptake
uptake might
might alsoalso facilitate
facilitate chloride
chloride transport
transport in
in cement
cement mortar,
mortar, a phenomenon
a phenomenon thatthat affects
affects its long-term
its long-term durability.
durability.

4.4.Conclusions
Conclusions
In
Inthis
thisstudy,
study,thethestrength
strengthandandphysico-chemical
physico-chemicalproperties
propertiesof ofLC3
LC3systems
systemsin inMalawi
Malawi
were
wereinvestigated. Cement mortar
investigated. Cement mortarspecimens
specimenswere wereprepared
preparedatatwater-to-cement
water-to-cement (w/c)
(w/c) ra-
ratios of 0.45, 0.5, and 0.6 and calcined clay-to-limestone (CC/LS) ratios of 1:1,
tios of 0.45, 0.5, and 0.6 and calcined clay-to-limestone (CC/LS) ratios of 1:1, 2:1, and 3:1, 2:1, and 3:1,
respectively.
respectively.The Theeffects
effectsofof(CC/LS)
(CC/LS) ratios
ratios on
on standard
standard consistency
consistency andandsetting
settingtime,
time,and
and
the
the effects of w/c and CC/LS ratios on compressive strength and porosity were studied.
effects of w/c and CC/LS ratios on compressive strength and porosity were studied.
The
Theresults
resultspresented
presentedininthis thiswork
workallowed
allowedfor forthe
thefollowing
followingconclusions
conclusionstotobe bedrawn:
drawn:
1.1. Increasing the calcined clay to limestone ratio resulted in an
Increasing the calcined clay to limestone ratio resulted in an increased standardincreased standard
con-
consistency of LC3-50 specimens, varying between 37.5% at 1:1
sistency of LC3-50 specimens, varying between 37.5% at 1:1 CC/LS ratio and 42.5% CC/LS ratio and
42.5%
at 3:1 at 3:1 CC/LS
CC/LS ratio whilst
ratio whilst for LC3-40
for LC3-40 rangedranged
betweenbetween
38.75%38.75% at CC/LS
at 1:1 1:1 CC/LSratioratio
and
and 45% at 3:1 CC/LS ratio. This is attributed to an increased amount
45% at 3:1 CC/LS ratio. This is attributed to an increased amount of amorphous me- of amorphous
metakaolin
takaolin in inthethe clay-rich
clay-rich systems,implying
systems, implyingthat
thatLC3-40
LC3-40samples
samples require
require more
more water
water
than LC3-50 to achieve suitable workability for maximum
than LC3-50 to achieve suitable workability for maximum hydration. hydration.
2.2. LC3-50
LC3-50 samples
samples showed
showed delayed
delayed initial
initial and
and final
final setting
setting times
times compared
comparedto tothose
thoseinin
LC3-40. The lower clinker factor and high calcined clay content in the LC3 systems
LC3-40. The lower clinker factor and high calcined clay content in the LC3 systems
are associated with accelerated setting time. Conversely, the presence of more reactive
are associated with accelerated setting time. Conversely, the presence of more reac-
phases such as metakaolin is responsible for the accelerated setting time.
tive phases such as metakaolin is responsible for the accelerated setting time.
3. Both LC3 systems complied with the strength requirements outlined in international
3. Both LC3 systems complied with the strength requirements outlined in international
standards. LC3-50 samples with a CC/LS ratio of 2:1 can achieve strength values com-
standards. LC3-50 samples with a CC/LS ratio of 2:1 can achieve strength values com-
parable with standard Portland Pozzolana Cement, whilst the strength of the LC3-40
parable with standard Portland Pozzolana Cement, whilst the strength of the LC3-40
system is comparable with one of the masonry cements. It is therefore recommended
system is comparable with one of the masonry cements. It is therefore recommended
Buildings 2023, 13, 740 15 of 17

to use LC3-50 systems in order to realize a significant reduction in carbon footprint

with acceptable strength.
4. The critical pore entry sizes of LC3-50 systems at w/c of 0.45, 0.5, and 0.6 range
between 0.019 µm and 0.08 µm with total porosity values between 2.6% and 10.6%,
indicating a well-refined microstructure.
5. Specimens in the LC3-50 system with high calcined clay content (3:1 CC/LS ratio)
and low w/c ratio (0.45) exhibited a bimodal pore distribution due to the coexistence
of air pockets and hydrated cement compounds in the microstructure.
6. LC3-50 specimens showed values of maximum surface water absorption up to 60%
lower than LC3-40, in line with porosity measurements.
7. The LC3-50 series provides a better environmental performance; the amount of CO2
emission is expected to reduce by almost 50% owing to the reduced amount of clinker
required to produce LC3-50.
Based on the findings abovementioned, further work will be conducted on LC3-
50 systems, focusing on their microstructure development and heath of hydration, and
the influence of accelerated aging and damage on the mineralogical composition and
overall durability.

Author Contributions: Conceptualization, I.K. and V.I.N.; methodology, I.K. and D.B.; validation,
formal analysis, I.K., D.B., G.K. and V.I.N.; investigation, I.K. and D.B.; writing—original draft prepa-
ration, I.K. and D.B.; writing—review and editing, I.K., D.B., V.I.N., J.M.M. and R.M.; supervision,
I.K.; project administration, I.K. and V.I.N.; funding acquisition, V.I.N. All authors have read and
agreed to the published version of the manuscript.
Funding: This work was funded by the HEFCW-GCRF via Cardiff University (HEFCW GCRF
Fellowship Award: Limestone Calcined Clay Cement: a low-cost construction material to realize a
resilient and sustainable built environment in Malawi). The APC was funded by Cardiff University.
Data Availability Statement: Data associated with the findings presented in this work are available
at the Cardiff University data repository under http://doi.org/10.17035/d.2023.0244558110.
Acknowledgments: The authors wish to acknowledge: Duncan Muir, School of Earth and Environ-
mental Sciences, Cardiff University, UK for the support with the SEM images, and Julian Steer, School
of Engineering, Cardiff University, UK for the support in acquiring thermogravimetric data.
Conflicts of Interest: The authors declare no conflict of interest.

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