A Step by Step Methodology For Building Sustainabl

applied
sciences
Article
A Step by Step Methodology for Building Sustainable
Cementitious Matrices
Styliani Papatzani 1,2, * and Kevin Paine 3
1 Department of Mathematics and Engineering Sciences, Hellenic Army Academy, Evelpidon Avenue,
166 72 Vari Attika, Greece
2 Directorate for the Restoration of Byzantine & Post-Byzantine Monuments, Hellenic Ministry of Culture,
Tzireon 8-10, 11742 Athens, Greece
3 BRE Centre for Innovative Construction Materials, University of Bath, Bath BA2 7AY, UK; k.paine@bath.ac.uk
* Correspondence: spapatzani@sse.gr

Received: 30 March 2020; Accepted: 20 April 2020; Published: 24 April 2020
Featured Application: A formulation and testing protocol for the development of low Portland
cement content cementitious binders.
Abstract: In an effort to produce cost-effective and environmentally friendly cementitious binders.

mainly ternary (Portland cement + limestone + pozzolanas) formulations have been investigated
so far. Various proportions of constituents have been suggested, all, however, employing typical
Portland cement (PC) substitution rates, as prescribed by the current codes. With the current paper
a step by step methodology on developing low carbon footprint binary, ternary and quaternary
cementitious binders is presented (PC replacement up to 57%). Best performing binary (60% PC and
40% LS (limestone)) and ternary formulations (60% PC, 20% LS, 20% FA (fly ash) or 43% PC, 20% LS
37% FA) were selected on the grounds of sustainability and strength development and were further
optimized with the addition of silica fume. For the first time a protocol for successfully selecting
and testing binders was discussed and the combined effect of highly pozzolanic constituents in low
PC content formulations was assessed and a number of successful matrices were recommended.
The present paper enriched the current state of the art in composite low carbon footprint cementitious
binders and can serve as a basis for further enhancements by other researchers in the field.
Keywords: low PC clinker; Portland cement; limestone; fly ash; silica fume; compressive strength;
TGA/dTG; PSD; SEM/EDX
1. Introduction
Concrete, and subsequently Portland cement, is one of the commodities whose demand is ever
increasing. According to the 2050 projections of CEMBUREAU, developing countries and emerging
markets such as India and China are expected to need almost six billion tonnes of cement by the year
2050 [1]. Taking into consideration that production of cement is a major cause for carbon dioxide
emissions, accountable for about 5–8% of anthropogenic CO2 emissions worldwide, concrete and
cement research has been focusing on the production of low Portland cement formulations using
supplementary cementitious materials, such as limestone, fly ash, ground granulated blast furnace
slag and silica fume.
Although the present research is focused and based on European Standards it should be noted
that a global shift towards performance based rather than prescriptive specifications (composition
based formulations) can be observed. In fact, particularly with respect to fly ash addition, the American
Concrete Institute suggests a maximum limit of 35% of fly ash addition in binary compositions while
Appl. Sci. 2020, 10, 2955; doi:10.3390/app10082955 www.mdpi.com/journal/applsci

Appl. Sci. 2020, 10, 2955 2 of 25
the need for admixtures is stressed [2]. Still, this limitation can be considered very conservative
according to the National Ready Mixed Concrete Association, claiming that prescriptive specifications
limit the opportunities to reduce the environmental impact of concrete. According to research carried
out the greatest occurrence in specifications is the restriction to the quantities of Supplementary
Cementitious Materials (SCMs) (85% occurrence) [3]. The general consensus, therefore is to aim
at specific performance, e.g., to limit the cement content, maximize the use of SCM, target specific
strengths, curing time, slump, water-to-cementitious materials ratio in order to design the desired
cement blend and concrete mix. This will effectively extend the allowable limits of the “code prescribed
permissible” amounts of SCMs in concrete mixes, creating a gap in the current knowledge on low
carbon footprint formulations containing more than two constituents.
Furthermore, the evolution of nanotechnology, has not only rendered monitoring of matter, at a
scale marginally above the atomic, possible, but has also revolutionized cement science, producing
novel cements and concretes of superior strength and durability [4,5]. Under the European Union
FP7 project (FIBCEM), various nanoparticles (commercially available or produced by the project
partners) were tested in cementitious matrices at the University of Bath, in an effort to produce low
carbon footprint cements [6–10]. For this, the amount of Portland cement (PC) had to be limited and
supplementary cementitious materials had to be added, forming blended cementitious matrices.
Although the value of hybrid binders is greatly appreciated [11] and an extensive number of studies
have been carried out in an effort to understand possible synergies between constituent materials such
as fly ash and limestone in ternary blends [12] or to determine the reactivity of pozzolanic materials [13]
in blended cements, there is still limited research on the synergies and material reactivities in very low
PC content cementitious matrices. That is to say, research presented to date, investigates the synergistic
effect of constituent materials for up to 20% PC replacement [14] or even higher PC replacement rates
(55% PC and 35% fly ash and silica fume) but having a very low water to binder ratio (0.17) [15].
Qualitative characteristics of the hydration products resulting from the binary combinations of PC
with either fly ash (FA) or silica fume (µS) or limestone (LS) have been studied in greater detail by
Lothenbach et al. [16]. Although there are many publications on binary systems, i.e., studies on various
contents of FA or µS or LS Portland cements, there is limited published research on ternary and above
systems. It has been found that in ternary cements containing PC, FA and LS, LS played a dual role;
LS (i) contributed as a filler and (ii) participated in chemical reactions with the aluminate hydrates
from the PC hydration [12,17]. In addition, following a study of eight different combinations of FA and
LS content combined with PC, this team of researchers concluded that the consumption of Ca(OH)2
was more pronounced for the 30%FA 5%LS and 65%PC blend rather than the 35%FA and 65%PC
blend and was related to the carboaluminates formation and consequently LS appears to interfere with
pozzolanic reactions. Consequently, with respect to compressive and flexural strength they inferred
that although a 5% replacement of cement by LS reduced the strength of the formulation, a 5% addition
of LS to 30%FA and 65%PC blend, will not cause strength reduction.
Furthermore, several research papers have reported a number of benefits of the combined effect
of FA and µS on Portland cement blends such as increased early age compressive strength and slump
of concretes [18]. Moreover, the C/S ratio decreased with increasing µS content, which effectively
caused an increase in compressive strength. Lastly, the maximum strength was obtained for the
PC50FA40µS10 formulation.
It is interesting to note that although very few studies have been reported on ternary cement
blends, no studies have been found on quaternary cement blends containing all the above-mentioned
elements, that is to say PC, FA, LS and µS. In fact, recently published reviews recognize the need for
research on ternary and quaternary cementitious composites and on optimization of cement binders
containing various pozzolanic materials at different proportions [19].
This gap is bridged by the current research. In fact a step by step methodology for the development
of cementitious matrices is presented, based on strength and sustainability criteria. In greater detail,
the following items were pursued in this study:
This gap is bridged by the current research. In fact a step by step methodology for the
development of cementitious matrices is presented, based on strength and sustainability criteria. In
greater detail, the following items were pursued in this study:
•Appl.Low
Sci. 2020, 10, 2955
carbon footprint binary and ternary cementitious matrices (Figure 1) suitable for further 3 of 25
modifications with the addition of silica fume were identified

• Best performing cementitious matrices were selected in terms of embodied energy and
• Low carbon footprint binary and ternary cementitious matrices (Figure 1) suitable for further
compressive strength
modifications with the addition of silica fume were identified
• Divergent results on the effect of the addition of limestone in composite cement binders were
• Best performing cementitious matrices were selected in terms of embodied energy and
clarified
• The pozzolanic reactivity in ternary and quaternary cement paste formulations was investigated
• Divergent results on the effect of the addition of limestone in composite cement binders
• The combined effect of highly pozzolanic constituents in low PC content formulations was
were clarified
assessed
• The pozzolanic reactivity in ternary and quaternary cement paste formulations was investigated
• The current knowledge on cement binder optimization was broadened.
• The combined effect of highly pozzolanic constituents in low PC content formulations was assessed
• In Thegreater
current detail, apart from
knowledge the industrial
on cement cement CEMwas
binder optimization II/A-L42.5 conforming to BS EN 197-1
broadened.
[20] which was studied on its own, given the name B1 in the binary combinations (Figure 1) three
more In greater
binary detail, apart from the
limestone—cement industrial cement
combinations were CEMcreated II/A-L42.5 conforming
with reduced to BS cement
Portland EN 197-1(PC) [20]
which was
content in a studied
gradual on its own,
manner (B2given the name
contained 80%PC, B1 inB3the binary combinations
contained 70%PC and B10 (Figure 1) three
contained more
60%PC.
binary
At limestone—cement
the same combinations
time, ternary blended cementswerewere
created with at
studied reduced
various Portland
fly ashcement
contents (PC) content
starting in a
from
gradual
20%. Thenmanner
a 35% FA (B2content
contained 80%PC, B3
formulation wascontained
studied in 70%PC and B10pastes
two different contained
(B5 and60%PC. At the
B8). The same
specific
time, ternary
amount is theblended cements
upper limit were studied
according to ACI at various fly ash contents
[2] for normal other thanstarting
massfrom 20%. Then
concretes a 35%
in binary
FA content formulation
combinations was studied
and with respect in two different
to the European Standardspastesused(B5inand
thisB8). The specific
research, amount
according to BSisENthe
upper[20],
197-1 limit theaccording
Portlandtocement
ACI [2](PC)
for normal
clinker other
content than massnot
should concretes
be lessin binary
than 65%combinations
in pozzolanicand with
blends
respect to the European Standards used in this research, according to BS
containing limestone. Therefore, the ternary ones pose a significant challenge due to the further EN 197-1 [20], the Portland
cement (PC)
reduction of PC clinker content should not be less than 65% in pozzolanic blends containing limestone.
content.
Therefore,
Next, the ternary ones pose a significant
performance-based concept was challenge due tousing
adopted, the further
as key reduction
indicatorsof PCthecontent.
28 day
Next, the performance-based concept was adopted, using as key indicators
compressive strength of the ten formulations, the hydration reactivity at 7 and 28 days of curing and the 28 day compressive
strength
the embodied of theCO ten
2, formulations, thereduction
as a result of the hydrationofreactivity
PC content at 7and
andincrease
28 daysin ofthe
curing and the
limestone embodied
and fly ash
CO2 , as aOf
content. result of the
the ten reduction of three
formulations, PC content
were and increase
selected for in the limestone
scanning electronandimages
fly ash in
content.
order to Ofdetect
the ten
formulations, three were selected for scanning electron images in order to detect
durability issues in the forms of microcracks, which were taken into consideration for the additional durability issues in the
forms of microcracks,
quaternary formulations. which were taken into consideration for the additional quaternary formulations.
Cementitious Selected
Nano-modified
matrices Cementitious
cementitious matrices
(current matrices
(published research)
research) (current research)
B B1: PC86LS14
i
B2: PC80LS20 Ternary formulations:
n
PC60LS40
a B3: PC70LS30 PC = 60%
r LS + nC2/nC3/nC4 = 40%
B10: PC60LS40
y
B4: PC66LS14FA20 Quaternary formulations: Quaternary formulations:
PC60LS20FA20
T
e B5: PC51LS14FA35 PC = 60% PC = 43%
PC43LS20FA37
r B6: PC36LS14FA50 FA + LS + nanoparticles= 40% FA + LS + nanoparticles= 57%
n
B7: PC60LS20FA20 Quaternary
a
r PC55LS20FA20μS5 Quinary formulations:
B8: PC45LS20FA35
y PC50LS20FA20μS10 PC = 43%
B9: PC30LS20FA50
FA+LS +µS+nanoparticles= 57%
PC43LS17FA37μS3
PC43LS14FA37μS6
Figure
Figure 1. Development ofofbinary,
1. Development binary, ternary
ternary andand quaternary
quaternary cementitious
matrices in the current
in the current research
research
and theirand their enhancement
enhancement with thewith the incorporation
incorporation of nanoparticles
of nanoparticles in published
in published research.research.
The last step included fine tuning of the selected formulations by increasing the FA content to 37%
for one of the ternary formulations, yielding; PC60LS40, PC60LS20FA20 and PC43LS20FA37. The latter
two formulations were further investigated after the addition of two different proportions of silica
fume (formulations typed in red in Figure 1).
Appl. Sci. 2020, 10, 2955 4 of 25
The resulting matrices were analyzed again against the key indicators determined above;
compressive strength 7, 28 and 56 days of curing, the hydration reactivity at 7, 28 and 56 days
of curing, the embodied CO2 and scanning electron imaging for microstructural defects, which could
undermine durability. All the above, have been studied and analyzed in the subsequent sections,
which paved the way for further modifications with the use of various nanoparticles (Figure 1).
2. Materials and Methods
2.1. Materials
The following materials and any commercially available data are listed below. These materials
were characterized with a selection of the techniques, before implemented in the various cement paste
combinations:
• Portland limestone cement: CEM II/A-L42.5 conforming to BS EN 197-1, Blaine density = 525 kg/m2 ,
absolute density = 3060 kg/m2 , bulk density = 1100 kg/m2 , clinker composition: 70% C3 S, 4% C2 S,
9% C3 A, 12% C4 AF. CEM II/A-L42.5 contained 14% by mass limestone to which additional
limestone was added
• Limestone (LS) (additional), conforming to BS EN 197-1
• Fly ash (FA), (siliceous) conforming to BS EN 450. The oxide composition provided by the material
data sheet was: 53.5% SiO2 , 34.3% Al2 O3 , 3,6% Fe2 O3 , 4.4% CaO
• Silica fume (µS), in undensified dry form conforming to BS EN 13263. According to the material
data sheet: specific surface area = 15–30 m2 /g, mean particle size = 0.15 µm.
2.2. Preparation of Paste Combinations: Mixing, Casting, Demoulding, Curing

The following methodology was adopted for the mixing procedure:
• Dry mixing of all powders with a spatula by hand.

• With the addition of water, the paste was mixed by a with an automatic dual shaft mixer at
1150 rpm for 3 min for pastes up to 300 g, time increasing with amounts of paste.
• Cylindrical specimens of 60 mm height and 30 mm diameter were prepared according to BS EN
196-1 [21].
• The cylindrical specimens of the initial cementitious matrices (B1-B10) were air-cured. However,
when the final selection of binary and ternary matrices was made, the three selected cementitious
matrices were reproduced, air-cured for 1 day, demoulded and then water cured until the day
of testing.
2.3. Step 1: Design of Cementitous Matrices

The design of the cementitious matrices was carried out in a step-by-step manner and was aimed at
designing and testing a low carbon dioxide footprint cement, which, at the same time, would have the
highest possible compressive strength. As shown in Figure 2, according to BS EN 197-1 [20], for binary
cements, containing clinker and limestone, only two types are allowed, CEM II/A-L and CEM II/B-L.
In the former, the limestone content should not exceed 20%, whereas in the latter, the limestone content
should not exceed 35%. Starting with B1, which was the as-received-cement by the industrial partner
of the project FIBCEM, the amount of clinker was gradually reduced in the subsequent formulations
(B2, B3 and B10).
Similarly, for ternary cementitious matrices containing clinker, fly ash and limestone, according to
BS EN 197-1, the Portland cement (PC) clinker content should not be less than 65%. Therefore, ternary
combinations (B4, B5, B6, B7, B8 and B9) where designed with a PC clinker upper bound content of
65%.
Appl. Sci. 2020, 10, 2955 5 of 25
Appl. Sci. 2020, 10, x FOR PEER REVIEW 5 of 26
Best performing pastes were identified and selected ternary formulations were subsequently
Best performing pastes were identified and selected ternary formulations were subsequently
optimized with the addition of silica fume, as the last step of the current research. The exact procedure
optimized with the addition of silica fume, as the last step of the current research. The exact procedure
is described in Sections 2.3.1 and 2.3.2, which is completed in Section 3, with the analysis of the results.
is described in Sections 2.3.1 and 2.3.2, which is completed in Section 3, with the analysis of the results.
Binary & Ternary Quaternary

cementitious cementitious Non-permissible according to EN 197 – 1
matrices matrices
B B1: PC86LS14 PC < 80%
i CEM II/A-L
n B2: PC80LS20 LS > 20%
a B3: PC70LS30 PC < 65%
r CEM II/B-L
B10: PC60LS40 LS > 35%
y
Based on PC60LS20FA20
T B4: PC66LS14FA20
e
r B5: PC51LS14FA35
P C 5 5 L S 2 0 FA 2 0 μ S 5 PC < 80%
n B6: PC36LS14FA50 CEM II/A-M
a P C 5 0 L S 2 0 FA 2 0 μ S 1 0 LS++ > 20%
r B 7 : P C 6 0 L S 2 0 FA 2 0
Based on PC45LS20FA35
y B 8 : P C 4 5 L S 2 0 FA 3 5 PC < 65%
CEM II/B-M
B9: PC30LS20FA50
P C 4 3 L S 1 7 FA 3 7 μ S 3 LS++ > 35%
P C 4 3 L S 1 4 FA 3 7 μ S 6
Figure 2. Binary,
Figure2. Binary,ternary
ternaryand
andquaternary
quaternarymatrices
matricesdeveloped
developed for
for the
the current
current research
researchcompared
comparedwith
with
the limitations posed by Eurocode BS EN 197-1.
the limitations posed by Eurocode BS EN 197-1.
2.3.1. Binary & Ternary Cement Formulations
2.3.1. Binary & Ternary Cement Formulations
The primary constituent is Portland limestone cement, CEMII/A-L42.5, which is a binary
The primary constituent is Portland limestone cement, CEMII/A-L42.5, which is a binary
combination on its own, since it contains 86% of PC and 14% of LS, as verified by TGA/dTG,
combination on its own, since it contains 86% of PC and 14% of LS, as verified by TGA/dTG, shown
shown in Section 3.1.2. The first specimen produced, then, was named B1 and contained only CEMII.
in Section 3.1.2. The first specimen produced, then, was named B1 and contained only CEMII. Eight
Eight more samples were produced next. B2 and B3 contained LS at 20% and 30%, respectively. B4 to
more samples were produced next. B2 and B3 contained LS at 20% and 30%, respectively. B4 to B9
B9 represented ternary formulations of PC, LS and FA. All 9 initial bases were mixed at a water to
represented ternary formulations of PC, LS and FA. All 9 initial bases were mixed at a water to binder
binder (w/b) ratio of 0.3. The exact proportions are shown in Table 1 that follows:
(w/b) ratio of 0.3. The exact proportions are shown in Table 1 that follows:
Table 1. Binary and ternary initial cement paste formulations—Mix Proportions % by total mass
Table 1. Binary and ternary initial cement paste formulations—Mix Proportions % by total mass of
of binder.
binder.
Sample PC (%) LS (%) FA (%) w/b
Sample PC (%) LS (%) FA (%) w/b
B1-PC86LS14
B1-PC86LS14 86 86 14 14 0.0
0.0 0.30.3
B2-PC80LS20
B2-PC80LS20 80 80 20 20 0.0
0.0 0.30.3
B3-PC70LS30 70 30 0.0 0.3
B3-PC70LS30 70 30 0.0 0.3
B4-PC66LS14FA20 66 14 20 0.3
B4-PC66LS14FA20 66 14 20 0.3
B5-PC51LS14FA35 51 14 35 0.3
B5-PC51LS14FA35 36 51
B6-PC36LS14FA50 14 14 35
50 0.30.3
B6-PC36LS14FA50 60 36
B7-PC60LS20FA20 20 14 50
20 0.30.3
B7-PC60LS20FA20
B8-PC45LS20FA35 45 60 20 20 20
35 0.30.3
B8-PC45LS20FA35
B9-PC30LS20FA50 30 45 20 20 35
50 0.30.3
B9-PC30LS20FA50
B10-PC60LS40 60 30 40 20 50
0.0 0.30.3
B10-PC60LS40 60 40 0.0 0.3
2.3.2. Quaternary Cement Formulations
2.3.2. Quaternary Cement Formulations
B7 and B8 were found to perform best as will be discussed they were further enhanced by the
B7 and B8 were found to perform best as will be discussed they were further enhanced by the
addition of µS. Initially, two quaternary formulations, having 60% PC by mass, in which the µS content
addition of μS. Initially, two quaternary formulations, having 60% PC by mass, in which the μS
was subtracted by the PC content, were designed as shown in Table 2.
content was subtracted by the PC content, were designed as shown in Table 2.
Appl. Sci. 2020, 10, 2955 6 of 25
Table 2. Quaternary µS enhanced cement paste formulations—Mix Proportions % by total mass

of binder.
Sample PC (%) LS (%) FA (%) µS (%) w/b

PC60LS20FA20 60 20 20 0.0 0.3
PC55LS20FA20+5%µS 55 20 20 5.0 0.3
PC50LS20FA20+10%µS 50 20 20 10 0.3
Then, a lower PC content paste was designed, containing 43% PC, 20%LS and 37% FA by mass as
a reference paste, which was further enhanced by the addition of µS, subtracted by the LS content, this
time, in order to maintain a w/b ratio of 0.3, as shown in Table 3.
Table 3. Quaternary µS enhanced cement paste formulations—low PC—Mix Proportions % by total

mass of binder.
Sample PC (%) LS (%) FA (%) µS (%) w/b

PC43LS20FA37 43 20 37 0.0 0.3
PC43LS17FA37+3% µS 43 17 37 3.0 0.3
PC43LS14FA37+6% µS 43 14 37 6.0 0.3
2.4. Preparation of Pastes for Characterization

For the characterization of the pastes, arrest of hydration was performed following two different
methodologies. In brief, if images were to be generated and the microstructure to be evaluated, such
as SEM/FESEM and MIP, solvent exchange was the technique employed for the arrest of hydration.
For experiments in which chemical reactions would occur or where the chemical composition had
to be evaluated, such as TGA, XRD, the oven drying technique was adopted as explained in detail
in [22]. For the SEM/FESEM and MIP studies, the samples were crashed and immersed in isopropanol
for 48 h. Isopropanol was selected as the most appropriate solvent according [23,24]. The samples
were, then, vacuum dried for 24 h. The cement paste samples were uncoated when examined at the
SEM. For the chemical analyses studies the samples were crushed and placed in the oven at 60 ◦ C for
up to 24 h. Then, they were ground and sieved through a 125 µm sieve and placed back in the oven
at 60 ◦ C for another 24 h. All samples were placed in the desiccator in a labelled air-tight container
until they were analyzed. For the compressive strength tests, the three samples prepared for each
paste formulation were removed from the curing tank a few minutes before being tested. Any uneven
surfaces were levelled with a diamond saw, avoiding capping. Consecutively, the specimens were
weighed and measured.
2.5. Experimental Techniques

The entire experimental program carried out in this research paper is summarized in Figure 3.
2.5.1. Thermogravimetric Analyses and Differential Thermogravimetry (TGA/dTG)

Thermogravimetric analyses were carried out using a TGA92 instrument (Setaram, Caluire,
France). Approximately 20 mg of each sample were placed in an alumina crucible and heated at a
rate of 10 ◦ C/min from 20 ◦ C to 1000 ◦ C under 100 mL/min flow of inert nitrogen gas. Mass change,
differential mass change and heat flow measurements were recorded and analyzed using the built-in
software. The differential thermogravimetric curve (dTG) was derived by the TG curve. The first
derivative curve was produced for the various samples tested and was used for comparisons instead
of the mass loss curve, as it yields sharp distinctive peaks.
Appl. Sci. 2020, 10, 2955 7 of 25
A) Constituent materials B) Binary and ternary cementitious matrices

Thermogravimetric analyses and differential thermogravimetry (TGA/dTG) on all Compressive strength tests on 3 specimens of each formulation (all formulations were
constituent materials (CEM II/LS/FA/ condensed μS) tested) at 7, 28 and 56 days of curing
Particle size distribution analysis (PSD) on all raw materials (CEM II/LS/FA/ condensed μS) Embodied CO 2 calculations for binary and ternary cementitious matrices (B1-B10)
Thermogravimetric analyses and differential thermogravimetry (TGA/dTG) (all

X-ray diffraction (XRD) on the fly ash sample
formulations were tested) at 7 and 28 days of curing
Scanning electron microscopy (SEM) / X-ray energy dispersive spectroscopy (SEM/EDX) for Scanning electron microscopy (SEM) imaging was carried out for; PC86LS14, PC60LS20FA20
the fly ash sample and PC60LS40 at 28 days of curing. PC60LS40 images at 1 day of curing were also taken.
C) Quaternary cementitious matrices

Compressive strength tests on 3 specimens of each optimized formulation at 7, 28 and 56 days of curing for matrices
based on PC60LS20FA20, while 1, 7, 28 and 56 days of curing for matrices based on PC43LS20FA37
Embodied CO2 calculations for all optimized formulations
Thermogravimetric analyses and differential thermogravimetry (TGA/dTG) (all optimized formulations were tested) at 7,
28 and 56 days of curing
Scanning electron microscopy (SEM) imaging was carried out for selected pastes; PC55LS20FA20+5%μS,
PC50LS20FA20+10%μS and PC43LS20FA37 at 28 days of curing
Figure
Figure 3. Overviewof
3. Overview ofthe
theexperimental
experimentalprogram.
program.
TGA/dTG
TGA/dTGwas wascarried
carried out
out for
for both
both constituent materialsand
constituent materials andcement
cementpastes.pastes. With
With respect
respect to to
hardened
hardened cement pastes, three broad areas, can be distinguished by the TGA; the first one is related to
cement pastes, three broad areas, can be distinguished by the TGA; the first one is related
the
todehydration
the dehydration of C–S–H ettringite
of C–S–H and monosulfate,
ettringite between
and monosulfate, 100 ◦ C100
between and°C ◦ C. It can be postulated
200and 200 °C. It can be
that the greater
postulated thatthe
theloss measured
greater themeasured
the loss greater thethe
amount
greaterofthe
C–S–H
amountandofettringite
C–S–H and was ettringite
producedwas by the
hydration
producedofbythe thepaste.
hydration of the paste.
Thesecond
The secondarea areaof ofinterest
interest is
is associated
associated with
with the
the dehydroxylation
dehydroxylationofofCa(OH) Ca(OH) 2 between
2 between °C ◦ C
400400
and510
and ◦
510 C. °C.TheTheamount
amount of of Ca(OH)
Ca(OH)22 present
presentin inthe
thepaste
pasteatatdifferent
differentages
ages can bebe
can computed
computed by by
thethe
stoichiometric elaboration of the mass loss results within the specific temperature
stoichiometric elaboration of the mass loss results within the specific temperature range [25]. range [25].
Thethird
The thirdareaareaofofinterest
interestisisthe
the decomposition
decomposition of of CaCO
CaCO3 3known
knownasasdecarboxylation,
decarboxylation, occurring
occurring
between610
between 610◦ C°Cand and 810
810 ◦°C. The amount
C. The amount of of CaCO
CaCO3 3present
presentininthethepaste
paste at at
different
different agesagescancan
be be
computed by the stoichiometric elaboration of the mass loss results within
computed by the stoichiometric elaboration of the mass loss results within the specific temperaturethe specific temperature
range.IfIfititisisgreater
range. greaterthan
than the
the limestone
limestone content
contentof ofthe
thereference
referencepaste,
paste,it itconstitutes
constitutes ananindication
indication of of
sample carbonation. Particularly for the quantification of Ca(OH)2, TGA is considered a very accurate
sample carbonation. Particularly for the quantification of Ca(OH)2 , TGA is considered a very accurate
technique [26], especially if coupled with XRD [27–30].
technique [26], especially if coupled with XRD [27–30].
2.5.2. Scanning Electron Microscopy (SEM)/X-Ray Energy Dispersive Spectroscopy (SEM/EDX)
2.5.2. Scanning Electron Microscopy (SEM)/X-Ray Energy Dispersive Spectroscopy (SEM/EDX)
The surface morphology was observed with SEM. Back scattered micrographs of uncoated
The surface morphology was observed with SEM. Back scattered micrographs of uncoated samples
samples at various magnifications and beam currents were obtained using a Jeol 6480 LV scanning
at various magnifications and beam currents were obtained using a Jeol 6480 LV scanning electron
electron microscope. For SEM/EDX elemental composition analyses sample was placed uncoated on
microscope. For SEM/EDX elemental composition analyses sample was placed uncoated on a sheet of
a sheet of molybdenum for unbiased elemental analyses. A matrix of 5 × 5 spectra was acquired and
molybdenum
the median offorthe
unbiased elemental
elemental analyses.
composition A matrix of 5 × 5 spectra was acquired and the median
was presented.
of the elemental composition was presented.
2.5.3. Particle Size Distribution Analysis (PSD)
2.5.3. Particle Size Distribution Analysis (PSD)
Particle size distribution analysis with optical system can provide the PSD of a wide range of
Particle
scales size distribution
of particles from 10 nm analysis with
to 3 mm. optical
Particle system
size can provide
distribution thewas
analysis PSDcarried
of a wide range
out at the of
scales of particles from 10 nm to 3 mm. Particle size distribution analysis was carried
MANIT laboratory, Bhopal, India, using an LA950 Laser Scattering Particle Size Distributionout at the MANIT
laboratory,
Analyzer Bhopal,
(Horiba,India, using India).
New Delhi, an LA950 Laser Scattering Particle Size Distribution Analyzer (Horiba,
New Delhi, India).
Appl. Sci. 2020, 10, 2955 8 of 25
2.5.4. X-Ray Diffraction (XRD)

2.5.4.XRD
X-Ray Diffraction (XRD)
measurements were performed for the FA using a D8 ADVANCE X-ray diffractometer
(Bruker,
XRD measurements wereCuKα
Coventry, U.K.) with radiation.
performed Spectra
for the were obtained
FA using in the range
a D8 ADVANCE 4° <diffractometer
X-ray 2θ < 20° at an
angular step-size of 0.016° 2θ.
(Bruker, Coventry, U.K.) with CuKα radiation. Spectra were obtained in the range 4 < 2θ < 20◦ at an
◦
angular step-size of 0.016◦ 2θ.

2.5.5. Mechanical Properties Testing Techniques
2.5.5.The
Mechanical
strengthProperties Testing
of the supplied Techniques
cement was validated according to BS EN 196-1 [21]. All samples
wereThetested at a ofloading
strength speed cement
the supplied of 0.5 was
MPa/s on a 100
validated kN servo
according to BShydraulic
EN 196-1 machine (Dartec,
[21]. All samples
Stourbridge, U.K.). Mean strength values of the specimens tested were calculated.
were tested at a loading speed of 0.5 MPa/s on a 100 kN servo hydraulic machine (Dartec, Stourbridge,
U.K.). Mean strength values of the specimens tested were calculated.
2.5.6. Carbon Dioxide (CO2) Footprint
2.5.6. Carbon Dioxide (CO2 ) Footprint
Preliminary estimation of the CO2 footprint of the initial pastes was derived from compressive
Preliminary
strength of cement estimation of theevaluated
pastes (MPa) CO2 footprint of embodied
against the initial pastes was 2derived
CO2. (ECO fromof
). The levels compressive
ECO2 have
strength of cement
been agreed in the pastes
UK and(MPa) evaluatedinagainst
are evaluated embodied
terms of kg CO2 perCOtonne
2 . (ECOof2 ). The
binding levels of
materialECO 2 have
[31].
been agreed in the UK and are evaluated in terms of kg CO2 per tonne of binding material [31].
• PC = 930 kg CO2/tonne
• PC =from
FA 930 coal burning power generation = 4 kg CO2/tonne
• kg CO 2 /tonne
•• FA LS from
= 32 kg CO
coal 2/tonne
burning power generation = 4 kg CO /tonne
2
• LS = 32be
It can CO2 /tonne
kgseen that in terms of CO2 footprint the use of FA as a supplementary cementitious
material is beneficial. This is the reason for which it was used in the paste design despite of its
It caninbe
shortage theseen
UK.that in terms of CO2 footprint the use of FA as a supplementary cementitious
Additionally:
material is beneficial. This is the reason for which it was used in the paste design despite of its shortage
• theμS
in = 14
UK. kg CO2/tonne [32]
Additionally:
• µS = 14 kg CO2 /tonne [32]
3. Results and Discussion
3. Results and Discussion
3.1. Characterization of Constituent Materials
3.1. Characterization of Constituent Materials
All commercially available materials listed in Section 2.1 were characterized with a selection of
All commercially
techniques available
(PSD, TGA/dTG, XRDmaterials listed in before
and SEM/EDX), Sectionimplemented
2.1 were characterized with a selection
in the cementitious of
matrices.
techniques (PSD, TGA/dTG, XRD and SEM/EDX), before implemented in the cementitious matrices.
3.1.1. PSD Results of CEM II/LS/FA/Condensed μS
3.1.1. PSD Results of CEM II/LS/FA/Condensed µS
The particle size distribution results of the four constituent materials reacted with water were
The particle
prepared size distribution
by colleagues in MANIT,results of the
India and arefour constituent
presented materials
below. reacted
Results are with
typical forwater were
this type of
prepared by colleagues in MANIT, India and are presented below. Results are typical
industrially available materials, as can be seen in Table 4 and in the following Figures 4–7. for this type of
industrially available materials, as can be seen in Table 4 and in the following Figures 4–7.
Table 4. PSD results of materials.
Table 4. PSD results of materials.
Mean Size Mode Size Median Size Diameter at 10% Diameter at 90%
Mean (μm)
Size (µm) Mode(μm)
Size (µm) Median Size (µm)
(μm) Diameter at 10% (µm)
(μm) Diameter at 90% (µm)
(μm)
CEMII
CEMII 11.38
11.38 2.74
2.74 3.25
3.25 1.40
1.40 22.16
22.16
LS
LS 12.14
12.14 2.44
2.44 3.21
3.21 1.36
1.36 31.89
31.89
FA 9.09 2.14 2.53 1.46 10.13
FA 9.09 2.14 2.53 1.46 10.13
µS 9.65 3.66 5.05 2.41 22.03
μS 9.65 3.66 5.05 2.41 22.03
Figure 4.
Figure 4. Normal
Normal distribution
distribution of
of CEMII.
CEMII.
Appl. Sci. 2020, 10, 2955 9 of 25
Appl.Sci.
Appl. Sci.2020,
2020,10,
10,xxFOR
FORPEER
PEERREVIEW
REVIEW 99 of
of 26
26
Figure
Figure5. Normal
Normaldistribution
distributionof
ofLS.
Figure 5.5. Normal distribution of LS.
LS.
Figure 5. Normal distribution of LS.
Figure
Figure6. Normal
Normaldistribution
distributionof
ofFA.
Figure 6.6. Normal distribution of FA.
FA.
Figure 6. Normal distribution of FA.
Figure
Figure7.
7.Normal
Normaldistribution
distributionof
ofμS.
μS.
Figure
Figure 7.
7. Normal
Normal distribution of
distribution of μS.
µS.
3.1.2.
3.1.2.TGA
TGAResultsResultsof ofCEM
CEMII/LS/FA/μS
II/LS/FA/μS Figure 7. Normal distribution of μS.
3.1.2. TGA Results of CEM II/LS/FA/µS
II/LS/FA/μS
The
The thermogravimetric
thermogravimetric analyses
analyses results
resultsof of the
ofthe four
thefour constituent
fourconstituent
constituent materials
materials are
are presented
presented in
in Figure
Figure
The thermogravimetric
thermogravimetric
3.1.2. TGA Results of CEM analyses
analyses results
II/LS/FA/μSresults of the four constituent materials
materials are
are presented
presented ininFigure
Figure 8.
8.8.ItItcan
can bebe seen that practically
seenthermogravimetric
thatpractically the
practicallyanalyses only
the only
only mass loss
massoflossloss upon
upon heating
heating is observed
isis
observed for, CEMII
for,for,
CEMII and
andandLS, the
LS, the
the
It can
8. It canbebe seen
seen
The that
that practically the mass
results loss upon
upon
the four heating
heating
constituent is observed
observed
materials for,
are presented CEMIICEMIIand
in Figure LS, LS,
differential
differential mass
mass loss
lossofofwhich
which was
wasmeasured
measured to be
be42.4%
toloss 42.4% and
and5.95%,
5.95%, respectively.
respectively. The
The initial
initial amount
amount
differential
the differentialmass
8. It can be loss
massseen of which
loss
that was
of which
practically measured
was
the measured
only massto be 42.4%
to
upon and
beheating
42.4% 5.95%,
isand respectively.
5.95%,
observed CEMII The
andinitial
for,respectively. theamount
LS,The initial
ofofCaCO
CaCO 3 was calculated via stoichiometry [25] and yielded 14% of CaCO3 present in CEMII and 97%
was
differentialcalculated via stoichiometry [25]toand
and yielded 14% ofrespectively.
CaCO present in CEMII and 97%
of CaCO
amount 33 was
of CaCO 3mass
was loss
calculated of which
via
calculated wasstoichiometry
stoichiometry
via measured[25] be 42.4%
yielded
[25] and14%
and 5.95%,
yieldedof CaCO
14% 3of The initial
3 present
CaCO 3in amount
CEMII
present and
in 97%
CEMII
in LS.
inLS.
LS. Therefore,
of CaCO
Therefore, the
3 was LS
theLS powder
calculated
LSpowder
powder viais
isconsidered
stoichiometry
considered to
[25] be
tobeandalmost
yielded
bealmost
almost pure
14%
pure CaCO
of CaCO
CaCO 3 3and the
present
and composition
in CEMII
thecomposition and of
97% CEMII
in
and Therefore,
97% the
in LS. Therefore, the LSis considered
powder to
is considered to be pure CaCO
almost pure33 and
CaCOthe 3composition ofCEMII
of
and the composition CEMII
isisconsidered
considered asas86%
in LS. Therefore,
86%PC theand
PC and 14%
LS powder
14% LS. The
Theminor
is considered
LS. minor mass
to be almost
mass loss of
pure
loss FA
ofCaCO
FA with
3 and
with aathe
peak atatabout
composition
peak about of850 °C
CEMII
850 °Ccancanbe
◦be
be
is considered
of CEMII as 86%
is considered PCasand
86%14%PC andLS. The
14% minor
LS. Themassminor loss of
mass FA
losswithof FA a peak
with at about
a peak at850
about°C can
850 C
attributed is considered
to the as 86%
volatile PC andin14%
matter the LS. The minor
unburnt coal mass[33].loss of FA with a peak at about 850 °C can be
attributed
attributed
can to the
to
be attributed
attributed
the tovolatile
volatile
tothe matter
matter
thevolatile
volatile in the
in
matter
matter
the unburnt
unburnt
in theinunburnt coal
coal
the unburnt [33].
coal [33].coal [33].
[33].
Figure
Figure 8. Differential
8. Differential massloss
mass lossof
of microsized
microsized constituent
constituentmaterials.
materials.
Figure
Figure8.
8.Differential
Differentialmass
massloss
lossof
ofmicrosized
microsizedconstituent
constituentmaterials.
materials.
Figure 8. Differential mass loss of microsized constituent materials.
Appl. Sci. 2020, 10, 2955 10 of 25
3.1.3. XRD and SEM/EDX results of FA

3.1.3. XRD and SEM/EDX results of FA
Moreover, the different minerals present in the FA powder were determined by XRD
Moreover, the different minerals present in the FA powder were determined by XRD
crystallographic analysis [34]. As shown in Figure 9, mullite, quartz, hematite, lime and calcium
crystallographic analysis [34]. As shown in Figure 9, mullite, quartz, hematite, lime and calcium
carbonate are present [9].
carbonate are present [9].
Figure9.9. XRD
Figure XRD diffraction
diffractionpattern
patternof
ofFA.
FA.
Lastly,
Lastly,20
20 spectra were acquired
spectra were acquired via
viathe
theSEM/EDX
SEM/EDXcarried
carriedout
outonon a FA
a FA sample,
sample, fivefive of which
of which are
are
indicatively shown in Table 5. The presence of sulphur which has been reported to increase the
indicatively shown in Table 5. The presence of sulphur which has been reported to increase the
ettringite
ettringiteformation
formationduring
duringcement
cementhydration
hydrationwas
wasconfirmed
confirmed[35].
[35].
Table 5. SEM/EDX counts summary (% atomic) of FA.

Table 5. SEM/EDX counts summary (% atomic) of FA.
FA—All
FA—AllResults
Resultsin
inAtomic
Atomic% %Normalized
Normalizedtoto100%
100%
Spectrum
Spectrum CC OO Na
Na Mg
Mg Al
Al Si
Si PP SS Cl
Cl KK Ca
Ca Ti
Ti Fe
Fe
(1,1)
(1,1) 16.73
16.73 55.58
55.58 0.49 0.74 8.84
0.49 0.74 8.84 13.62
13.62 0.00
0.00 0.14
0.14 0.04
0.04 0.82
0.82 1.06
1.06 0.28
0.28 1.66
1.66
(2,1)
(2,1) 18.86
18.86 52.35
52.35 0.06 0.72 12.23
0.06 0.72 12.23 13.31
13.31 0.01
0.01 0.10
0.10 0.02
0.02 0.33
0.33 1.23
1.23 0.02
0.02 0.80
0.80
(3,1)
(3,1) 15.07
15.07 55.63
55.63 0.36
0.36 0.7 11.54
0.7 11.54 12.52
12.52 0.07
0.07 0.19
0.19 0.02
0.02 0.52
0.52 1.26
1.26 0.69
0.69 1.48
1.48
(4,1)
(4,1) 5.41
5.41 60.94 0.67 0.96 10.96
60.94 0.67 0.96 10.96 16.5
16.5 0.17 0.19
0.17 0.19 0.060.06 1.07
1.07 1.15
1.15 0.33
0.33 1.70
1.70
(5,1)
(5,1) 8.57
8.57 59.8
59.8 0.35 0.52 12.34 15.08
0.35 0.52 12.34 15.08 0.1
0.1 0.09 0.05
0.09 0.05 0.60
0.60 1.45
1.45 0.21
0.21 0.94
0.94
Mean 16.97 55.1 0.52 0.77 8.13 12.62 0.09 0.21 0.01 0.62 1.35 0.20 3.42
Mean 16.97 55.1 0.52 0.77 8.13 12.62 0.09 0.21 0.01 0.62 1.35 0.20 3.42
Stdv 6.48 3.05 0.17 0.52 2.37 2.36 0.08 0.21 0.05 0.18 1.55 0.14 3.29
Stdv 6.48 3.05 0.17 0.52 2.37 2.36 0.08 0.21 0.05 0.18 1.55 0.14 3.29
3.2.
3.2. Step
Step 2:
2: Testing
Testing and
and Step
Step 3:
3: Selecting
Selecting best
best Performing
Performing Pastes
Pastes of
of the
the Binary
Binary and
and Ternary
TernaryCementitious
Cementitious
Matrices
Matrices
After Step 1 was presented in Section 2.3, in which the concept behind the designing of cementitious
After Step 1 was presented in Section 2.3, in which the concept behind the designing of
matrices was unfolded, in this section the results of sample testing and selecting best performing pastes
cementitious matrices was unfolded, in this section the results of sample testing and selecting best
is analyzed. Apart from the pure CEMII paste (B1), nine additional Portland limestone cement initial
performing pastes is analyzed. Apart from the pure CEMII paste (B1), nine additional Portland
formulations (B2-10) were designed, containing different proportions of CEMII and limestone or CEMII,
limestone cement initial formulations (B2-10) were designed, containing different proportions of
limestone and fly ash, as already discussed. Best performing pastes were judged according to the
CEMII and limestone or CEMII, limestone and fly ash, as already discussed. Best performing pastes
delivered compressive strength and embodied carbon dioxide content. As shown below, best relations
were judged according to the delivered compressive strength and embodied carbon dioxide content.
between strength and embodied CO2 were obtained for B7: PC60LS20FA20 and B8: PC45LS20FA35,
As shown below, best relations between strength and embodied CO2 were obtained for B7:
which delivering 80 MPa/t/t and 110 MPa/t/t, respectively. These two formulations were selected
PC60LS20FA20 and B8: PC45LS20FA35, which delivering 80 MPa/t/t and 110 MPa/t/t, respectively.
to be further optimized, later, forming the quaternary cementitious matrices. Thermal analyses
These two formulations were selected to be further optimized, later, forming the quaternary
cementitious matrices. Thermal analyses were also performed on all initial cementitious matrices (B1-
B10). All results are presented in the following sections.
Appl. Sci. 2020, 10, 2955 11 of 25
were also performed on all initial cementitious matrices (B1-B10). All results are presented in the
Appl. Sci. 2020,sections.
following 10, x FOR PEER REVIEW 11 of 26
3.2.1.
3.2.1.Compressive
CompressiveStrength
StrengthofofBinary
Binaryand
andTernary
TernaryCementitious
CementitiousMatrices
Matrices(B1-B10)
(B1-B10)
Binary
Binaryand
andternary
ternary cementitious
cementitious matrices (B1-B10)
(B1-B10) were
weretested
testedinincompression
compressionatatday
day7,7,
2828 and
and 56,
56,
as as shown
shown in in Figure
Figure 10.10.
70
B1-PC86LS14 B2-PC80LS20 B3-PC70LS30
B4-PC66LS14FA20 B5-PC51LS14FA35 B6-PC36LS14FA50
60 B7-PC60LS20FA20 B8-PC45LS20FA35 B9-PC30LS20FA50
Cylinder compressive strength (MPa)
B10-PC60LS40
50
40
30
20
10
0
7 28 56
Time (days)
Figure
Figure10.
10.Cylinder
Cylindercompressive
compressivestrength
strengthofofbinary
binaryand
andternary
ternarycementitious
cementitiousmatrices
matrices(B1-B10).
(B1-B10).
Thecompressive
The compressivestrength
strengthtests
testsallowed
allowedthe
therejection
rejectionofofB1,
B1,B2
B2and
andB3
B3on
onthe
thegrounds
groundsofofhigh
highPC
PC
contentand
content andperformance
performancethat
thatcan
canbebeachieved
achievedwith
withgreener
greenercombinations.
combinations.For
Forexample,
example,B5
B5showed
showed
betterlong
better longterm
termperformance
performancethan
thanB1.
B1.B9
B9was
wasalso
alsorejected
rejecteddue
duetotopoor
poorperformance.
performance.
3.2.2.Embodied
3.2.2. EmbodiedCO
CO
22ofofBinary
Binaryand
andTernary
TernaryCementitious
CementitiousMatrices
Matrices(B1-B10)
(B1-B10)
Then,the
Then, thesustainability
sustainabilitypotential
potentialofofall
allbinary
binaryand
andternary
ternarycementitious
cementitiousmatrices
matriceswas
wascalculated
calculated
with respect to the embodied CO
with respect to the embodied CO2 (E.CO 2 (E.CO2) 2
) of PC (930 kg CO
of PC (930 kg CO2/tonne),
2 /tonne), LS (32 kg CO /tonne)
LS (32 kg CO2/tonne)
2 andand FA
FA (4
(4 CO
kg kg 2CO 2 /tonne)
/tonne) [36,37].
[36,37]. TheThe results
results are presented
are presented in Table
in Table 6. 6.
EmbodiedCO
Table6.6.Embodied
Table CO2 2associated
associatedwith
withstrength
strengthofofbinary
binary&&ternary
ternarycementitious
cementitiousmatrices.
matrices.
PC
Sample
Formulation PC
E.CO2
LS E.CO2 FA E.CO2 Total E.CO2 Compression
Compression Strength Strength/E.CO2
Formulation
Composition LS E.CO2
(kg/tonne) FA E.CO2 (kg/tonne)
(kg/tonne) Total E.CO2 28 Days (MPa) Strength/E.CO2
(MPa/kg/tonne)
Sample E.CO2
(kg/tonne) Strength 28
Composition (kg/tonne) (kg/tonne) (kg/tonne) (MPa/kg/tonne)
B1 PC86LS14 (kg/tonne)
799.8 4.5 0.0 804.3 Days
48.4 (MPa) 0.06
B1 B2 PC86LS14
PC80LS20 744.0
799.8 6.4
4.5 0.00.0 750.4804.3 25.848.4 0.03 0.06
B3 PC70LS30 651.0 9.6 0.0 660.6 31.4 0.05
B2 B4
PC80LS20
PC66LS14FA20
744.0
613.8
6.4
4.5 0.8
0.0 619.1
750.4 45.6
25.8 0.07
0.03
B3 B5 PC70LS30
PC51LS14FA35 651.0
474.3 9.6
4.5 1.40.0 480.2660.6 31.231.4 0.06 0.05
B4 B6PC66LS14FA20
PC36LS14FA50 334.8
613.8 4.5
4.5 2.00.8 341.3619.1 24.845.6 0.07 0.07
B7 PC60LS20FA20 558.0 6.4 0.8 565.2 51.3 0.09
B5 B8PC51LS14FA35
PC45LS20FA35 474.3
418.5 4.5
6.4 1.41.4 426.3480.2 46.331.2 0.11 0.06
B6 B9PC36LS14FA50
PC30LS20FA50 334.8
279.0 4.5
6.4 2.02.0 287.4341.3 24.924.8 0.09 0.07
B7 B10PC60LS20FA20
PC60LS40 559.8
558.0 12.8
6.4 0.00.8 572.6565.2 41.051.3 0.09 0.09
B8 PC45LS20FA35 418.5 6.4 1.4 426.3 46.3 0.11
B9 PC30LS20FA50 279.0 6.4 2.0 287.4 24.9 0.09
B10 PC60LS40 559.8 12.8 0.0 572.6 41.0 0.09
By observing the results provided in Table 6, it is evident that B6 to B10 had the lowest total
E.CO2. Furthermore, B7, B8 and B10 had the lower environmental impact and exhibited the highest
Appl.
Appl. Sci.
Sci. 2020,
2020, 10, xx FOR PEER REVIEW 12
12 of
of 26
Appl. 10, FOR
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2955 REVIEW 12 of 25 26
mechanical
mechanical properties
properties in
in terms
terms ofof compressive
strength compared
compared amongst
amongst the
the initial
initial pastes.
pastes. As
As an
an
effect, B7, B8 By observing the results provided in Table 6, it is evident that B6 to B10 had the lowest total
effect, B7, B8 and B10 were the three selected bases for further optimization with the addition of
and B10 were the three selected bases for further optimization with the
E.CO2 . Furthermore, B7, B8 and B10 had the lower environmental impact and exhibited the highest
addition of
microsized elements.
microsized elements.
mechanical properties in terms of compressive strength compared amongst the initial pastes. As an
effect, B7, B8 and B10 were the three selected bases for further optimization with the addition of
3.2.3. Thermal
3.2.3. Thermal Analyses
Analyses
microsized of
of Binary
elements. Binary and
and Ternary
Ternary Cementitious
Cementitious Matrices
Matrices (B1-B10)
(B1-B10)
TG
TG analyses
analyses were
were
3.2.3. Thermal carried
carriedofout
Analyses out at
at 77and
Binary and
and 28
28 days,
days,
Ternary the
the results
results
Cementitious of
of which
Matriceswhich are
are shown
(B1-B10) shown in in Figures
Figures 1111 and
and
12. It should
12. It shouldTG be noted
beanalyses that
noted that initially the first nine bases were dry cured (B10 was only water cured),
were initially
carried outtheat 7first nine
and 28 days,bases wereof dry
the results whichcured (B10inwas
are shown only
Figures water
11 and 12. cured),
however none
howeverItnone had
shouldhad carbonated
carbonated
be noted since
since
that initially the CaCO
thenine
the first CaCO
bases3 content
content
3 were
is lower
is lower
dry cured than
than
(B10 was the
the
only initial
initial
water LS content
content in
LShowever
cured), in the
the
paste.
paste. none had carbonated since the CaCO 3 content is lower than the initial LS content in the paste.
Figure 11.
11. Ca(OH)
FigureFigure
Ca(OH) 2 content
2 content
11. Ca(OH) of binary
ofof
2 content binaryand
binary and ternary
ternary
and ternary cementitious
cementitious
cementitious matrices.
matrices.
matrices.
Figure 12.
12. CaCO
FigureFigure
CaCO 3 content
12. CaCO of
3 content
3 content
binary
of of binaryand
binary ternary
and ternary
and cementitious
ternarycementitious matrices.
matrices.
cementitious matrices.
In addition to the thermal analyses carried out at day 7 and day 28, the three selected cementitious
In
In addition
addition to
to the
the thermal
matrices (PC60LS40, thermal
PC60LS20FA20
analyses
analyses carried
carried out
and PC43LS20FA37),out at at
were
day
day 77 and
and day
reproduced, day 28,
water28,
cured
the
the three
three
after
selected
day 1selected
cementitious
cementitious
and TGmatrices
matrices (PC60LS40,
carried outPC60LS20FA20
(PC60LS40,
analyses were at day 1, 7, 28 and and
PC60LS20FA20 andForPC43LS20FA37),
56. PC43LS20FA37),
PC60LS40, TG analyses were
were reproduced,
were carried out water
reproduced, water
cured after
at day
day 1
90, and
as TG
well. Atanalyses
this point,
cured after day 1 and TG analyses were carried were
the carried
Ca(OH) out at day
consumption 1, 7,
will 28
be and 56.
discussed For PC60LS40,
(Table 7) in an
2 out at day 1, 7, 28 and 56. For PC60LS40, TG analyses TG
effort analyses
to
were shed more
carried out light
at dayinto theashydration
90, well. Atprocesses.
this To begin
point, the with, it can be noticed that until
willdaybe 28, that PC (Table
were carried out at day 90, as well. At this point, the Ca(OH)
Ca(OH) 2 consumption discussed
2 consumption will be discussed (Table
7) continues hydrating, the Ca(OH) content of PC60LS40 increased and from then after it remained
7) in
in an
an effort to shed
shed more light into the
the hydration processes. To Toinbegin with,
with, itit can be
be noticed that
2
effort
almost to
constant. more
It can belight into therefore,
claimed, hydration
that the processes.
presence of FA begin
PC60LS20FA20 can
increased noticed
the that
until day 28, that
until dayconsumption PC continues
28, that PCofcontinues hydrating, the Ca(OH) 2 content of PC60LS40 increased and from then
the Ca(OH)hydrating, the Ca(OH)2 content of PC60LS40 increased and from then
2 content significantly over all ages.
after
after it remained almost constant. It can be
it remained almost constant. It can be claimed,
claimed, therefore,
therefore, thatthat the
the presence
presence of of FA
FA inin
PC60LS20FA20 increased the consumption of the Ca(OH) 2 content significantly over all ages.
PC60LS20FA20 increased the consumption of the Ca(OH)2 content significantly over all ages.
Table
Table 7.
7. Comparison
Comparison of
of the
the Ca(OH)
Ca(OH)22 content
content of
of the
the selected
selected bases.
bases.
11 77 28
28 56
56
Appl. Sci. 2020, 10, 2955 13 of 25
Table 7. Comparison of the Ca(OH)2 content of the selected bases.
1 7 28 56
PC60LS40 7.5% 9.1% 10.3% 10.6%
PC60LS20FA20 7.2% 8.1% 8.2% 8.1%
PC43LS20FA37 4.0% 6.0% 5.9% 1.5%
As demonstrated in Table 7, PC60LS40 at day 1 contained 7.5% Ca(OH)2 and 9.1% at day 7. For the
first two pastes, PC60LS40 and PC60LS20FA20, which have the same PC content, the rate of hydration
of PC at day 1 and 7 is expected to be essentially unaltered. However, it can be observed that at early
ages, the Ca(OH)2 content of PC60LS20FA20 is significantly lower, particularly at day 7. This is a
strong indication that the pozzolanic activity of the FA present in this paste had already started by day
7, although it has been claimed that at high FA contents (PC45FA55) other researchers had noticed
Ca(OH)2 consumption by day 3 [38]. Nonetheless, FA content is one matter and PC content is another.
For this, the authors have adopted the PC/FA ratio, which is more representative in thermal analyses,
together with the full formulation dosages, since FA is feeding from the Ca(OH)2 produced during
cement hydration. The following observations were drawn:
• A paste containing 43%PC would be expected to generate 43/60 × 7.5% = 5.4% Ca(OH)2 based on
PC60LS40 Ca(OH)2 content at day 1.
• Also, a paste containing 43%PC would be expected to generate 43/60 × 7.2% = 5.2% Ca(OH)2
based on PC60LS20FA20 Ca(OH)2 content at day 1.
• As shown in Table 7, PC43LS20FA37 contained 4.0% Ca(OH)2 at day 1. This indicates that the
pozzolanic activity of a part of the FA present in the paste had already commenced.
• Inversely, a paste containing 43%PC would be expected to generate 43/60 × 9.1% = 6.5% Ca(OH)2
based on PC60LS40 Ca(OH)2 content at day 7.
• A paste containing 43%PC would be expected to generate 43/60 × 8.1% = 5.8% Ca(OH)2 based on
PC60LS20FA20 Ca(OH)2 content at day 7.
• As demonstrated in Table 7, PC43LS20FA37 contained 6.0% Ca(OH)2 at day 7. This indicates that
the pozzolanic activity of a part of the FA present in the paste had progressed by day 7, but the
reaction of the available FA particles could have been delayed.
• Continuing this train of thought, a paste containing 43%PC would be expected to generate 43/60
× 10.3% = 7.4% Ca(OH)2 based on PC60LS40 Ca(OH)2 content at day 28.
• Moreover, a paste containing 43%PC would be expected to generate 43/60 × 8.2% = 5.9% Ca(OH)2
• PC43LS20FA37 contained 5.9% Ca(OH)2 at day 28 (Table 7), implying that almost half of the FA
was unreacted by day 28 since the amount of Ca(OH)2 was equal to that of PC60LS20FA20.
• Also, a paste containing 43%PC would be expected to generate 43/60 × 10.6% = 7.6% Ca(OH)2
based on PC60LS40 Ca(OH)2 content at day 56.
• Lastly, a paste containing 43%PC would be expected to generate 43/60 × 8.1% = 5.8% Ca(OH)2
PC43LS20FA37 contained 1.5% Ca(OH)2 at day 56 (Table 7), implying that the remaining unreacted
FA was engaged in reactions by day 56. Although no carbonation was detected, even if that was the
case, the amount of Ca(OH)2 at day 56 is that low that any increase due to carbonation would still
be negligible.
3.2.4. Microstructural Characterization of Binary and Ternary Cementitious Matrices (B1, B7 and B10)
Backscattered (BSC) images were collected for PC86LS14 (B1), PC60LS20FA20 (B7) and PC60LS40
(B10) and are presented below. As illustrated in Figures 13–16, the microstructure of the PC86LS14,
PC60LS20FA20 and PC60LS40 exhibited typical characteristics of such pastes at day 28. A number of
Appl. Sci. 2020, 10, 2955 14 of 25

CaCO3 flakes, Ca(CO)2 (annotated as CH) crystals and nest-like C–S–H (annotated as CSH) are shown
in the PC/LSApaste. In Figure 13, flake-like C–S–H is B
mainly
B detected and some crystals of Ca(CO)2
A
covered by C–S–H are also noted. The presence of microcracks is visible as well.
Appl. Sci. 2020, 10, x FOR PEER REVIEW CSH 14 of 26
Microcracks
AA BB CSH
CSH CSH
CSH on CH
Microcracks
crystals
CSH
CSH
CSH on CH
crystals
CC
CC
Microcracks
Figure 13. BSC micrograph of B1-PC86LS14 28D at (A) 3000× magnification, (B) 1000× magnification
and (C) 100× magnification. Microcracks
In Figure 14A, hydration products surrounding reacted FA (annotated as rFA) particles can be
FigureFigure
identified. 13.
13.In BSC
Figure
BSC micrographofofB1-PC86LS14
14B a common
micrograph B1-PC86LS14 28D
hydrated28D at
FA at
rim(A)known
(A) 3000×
3000×magnification,
as (B)(B)
the “pull-out
magnification, 1000× magnification
feature”
1000× was captured.
magnification
and (C) 100× magnification.
It is reported as the “reminiscent” of the fully reacted FA particle [39].
and (C) 100× magnification.
In Figure 14A, hydration products surrounding reacted FA (annotated as rFA) particles can be
identified. AIn Figure 14B a common hydrated FA rimB B
known as the “pull-out feature” was captured.
It is reported as the “reminiscent” of theCSH
fully reacted FA particle [39].
rFA
CSH
rFA
A B
B
rFA CSH
rFA
CH CSH
CSH
rFA
CSH
rFA
CH CSH
CSH
C
rFA
C rFA
uFA rFA
rFA
uFA
Figure 14. BSC micrograph of B7-PC60LS20FA20 28D at (A) 3000× magnification, (B) 1000×
magnification [24] and (C) 100× magnification [24]. Reproduced with permission from [24], Copyright
ICE Publishing, 1987.
magnification [24] and (C) 100× magnification [24]. Reproduced with permission from [24], Copyright
ICE Publishing, 1987.
Unreacted fly ash particles are annotated as uFA. Furthermore, in Figure 14B, an entire plane of
Ca(CO)2 crystals can be distinguished above the flat plane of the rest of the surface, creating what
Appl.looks like10,
Sci. 2020, a crack,
2955 but in essence is the difference in levels between the two planes. In fact, in Figure
15 of 25
14C the entire surface is smooth and furthermore, a number of FA spherical particles can be observed.
A B
CH
CH
CSH
C D
CH
CH
CSH
CH
FigureFigure
15. 15.
BSC BSC micrograph
micrograph ofofB10-PC60LS40
B10-PC60LS40 1D
1D at (A)
(A) 1000×
magnification,(B)(B)
1000× magnification,
Appl. (C)
(C) 500× 500× magnification
magnification
Sci. 2020, and
and
10, x FOR PEER (D) 100× magnification.
(D) 100× magnification.
REVIEW 16 of 26
A B
CSH
CH CSH
C D
CH
CH
Figure
Figure 16. BSC
16. BSC micrograph
micrograph ofof B10-PC60LS4028D
B10-PC60LS40 28D at
at (A)
(A) 1000×
(C) 500× magnification and (D) 100× magnification.
(C) 500× magnification and (D) 100× magnification.
Formulation
In Figure PC60LS40 was
14A, hydration imaged
products at day 1 andreacted
surrounding day 28 due to the high interest
FA (annotated as rFA)itparticles
attracted.can
In be
Figure 15, different magnifications are offered, all showing a dense, cohesive microstructure
identified. In Figure 14B a common hydrated FA rim known as the “pull-out feature” was captured. lacking
It is microcracks,
reported as thewith a significant number of Ca(CO)2 crystals covered by C–S–H flakes. In Figure 16, a
“reminiscent” of the fully reacted FA particle [39].
dense microstructure again filled with hydration products can be observed at different
Unreacted fly ash particles are annotated as uFA. Furthermore, in Figure 14B, an entire plane of
magnifications. There are no signs of microcracks, while dense areas of flake-like C–S–H are covering
Ca(CO)2 crystals can be distinguished above the flat plane of the rest of the surface, creating what looks
most parts of the micrographs. Similar images have been collected after 90 days of hydration of this
specific composition [40].
3.3. Step 4: Optimizing Quaternary Cementitious Matrices

The first microstructural enhancement was completed with the addition of two different dosages
of μS (5% and 10% by mass) on PC60LS20FA20, creating quaternary cementitious matrices. The
results on compressive strength, Ca(OH)2 consumption and microstructure are shown in the
Appl. Sci. 2020, 10, 2955 16 of 25
like a crack, but in essence is the difference in levels between the two planes. In fact, in Figure 14C the
entire surface is smooth and furthermore, a number of FA spherical particles can be observed.
Formulation PC60LS40 was imaged at day 1 and day 28 due to the high interest it attracted.
In Figure 15, different magnifications are offered, all showing a dense, cohesive microstructure lacking
microcracks, with a significant number of Ca(CO)2 crystals covered by C–S–H flakes. In Figure 16,
a dense microstructure again filled with hydration products can be observed at different magnifications.
There are no signs of microcracks, while dense areas of flake-like C–S–H are covering most parts
of the micrographs. Similar images have been collected after 90 days of hydration of this specific
composition [40].
3.3. Step 4: Optimizing Quaternary Cementitious Matrices

The first microstructural enhancement was completed with the addition of two different dosages of
µS (5% and 10% by mass) on PC60LS20FA20, creating quaternary cementitious matrices. The results on
compressive strength, Ca(OH)2 consumption and microstructure are shown in the following sections.
Furthermore, although B8-PC45LS20FA35 showed optimum performance a slightly different paste
was adopted for further optimization; PC43LS20FA37. This was decided in an effort to reduce the PC
content even further. Hence, another microstructural enhancement was completed with the addition
of two different dosages of µS (3% and 6% by mass) on PC43LS20FA37, creating another series of
quaternary pastes. The results on compressive strength and Ca(OH)2 consumption are also shown in
the following sections.
3.3.1. Compressive Strength of Quaternary Cementitious Matrices

As depicted in Figure 17 the addition of µS in pastes containing at least 20% FA by mass of
binder is causing a retardation of the strength development, delivering lower compressive strengths.
More than that, 10% µS, delay the strength gain by 28 days. These results were expected since
according to CEN [41] the maximum allowable µS content in PC/µS cements is 10% by mass. In other
words, for every 1% µS by mass, at least 9% of PC content by mass, is required so that there will
be enough Ca(OH)2 produced by PC hydration for the µS to react with. Therefore, the 10% µS
addition was excessive and as an effect, unreacted µS particles were predicted to be distinguished by
Appl.
SEM Sci.investigations.
2020, 10, x FOR PEER REVIEW 17 of 26
60
Cylinder Compressive Strength |(MPa)
40
20
PC60LS20FA20
PC55LS20FA20+5%μS
PC50LS20FA20+10%μS
0
0 10 20 30 40 50 60
Time (Days)
Figure 17.
Figure Cylinder
17. Cylinder compressive
strength of modified
of μS µS modified cementitious
matrices basedbased
on
on PC60LS20FA20.
PC60LS20FA20.
As in the case of μS enhanced PC60LS20FA20, the μS enhanced low PC content PC43LS20FA37,

showed similar compressive strength gain characteristics, although the μS content was lower in both
combinations (Figure 18):
• At day 7 both series had similar starting points (about 21 MPa for PC60LS20FA20 and 25 MPa
Appl. Sci. 2020, 10, 2955 17 of 25
As in the case of µS enhanced PC60LS20FA20, the µS enhanced low PC content PC43LS20FA37,

showed similar compressive strength gain characteristics, although the µS content was lower in both
combinations (Figure 18):
• At day 7 both series had similar starting points (about 21 MPa for PC60LS20FA20 and 25 MPa for
PC43LS20FA37), indicating that pozzolanic reactions had already been initiated within the first
7 days.
• After day 28 the compressive strength of the reference paste is almost the same for both reference
pastes, but for the µS enhanced ones, an improvement was observed. Therefore, although high
LS contents are reported to be causing deterioration of the compressive strength at later ages the
presence of µS offered a limited (due to the additional presence of FA) enhancement.
A marginal improvement in strength was also observed at day 1, followed by deterioration at day
28 and 56 with respect to the reference paste. These results were in agreement with other findings,
suggesting that the increasing OPC replacement is liable for the decrease in both compressive and
flexural strengths [12]. The limited amount of PC and the high amount of FA present created some
antagonism with the µS particles. Moreover, since for 1% µS, at least 9% of PC content by mass,
is required so that the µS can react with the Ca(OH)2 produced by PC hydration for these series of
pastes, the µS content should have been limited to approximately 4.8% by mass. Furthermore, knowing
that for high replacements of PC with FA and LS the resulting strengths will be low, it was of particular
interest to investigate if the nanoparticles could alter the performance of the low PC content blended
cements, carried out in other research [42].
60
Cylinder Compressive strength (MPa)
40
20
PC43LS20FA37
PC43LS17FA37+3%μS
PC43LS14FA37+6%μS
0
0 10 20 30 40 50 60
Time (Days)
Figure 18. Cylinder compressive strength of µS modified cement pastes based on PC43LS20FA37.
Figure 18. Cylinder compressive strength of μS modified cement pastes based on PC43LS20FA37.
3.3.2. Embodied CO2 of Quaternary Cementitious Matrices
3.3.2. Embodied CO2 of Quaternary Cementitious Matrices
In addition to the E.CO2 values of PC, LS and FA pastes, the E.CO2 of µS modified pastes was
also In addition(taking
evaluated to the E.CO values=of14PC,
as µS2 E.CO 2 kgLS
COand FA pastes, the E.CO2 of μS modified pastes was
2 /tonne according to [43]. The results are presented
also evaluated (taking as μS E.CO 2 = 14 kg CO2/tonne according to [43]. The results are presented in
in Table 8, where the second quaternary series based on PC43LS20FA37 had the lowest total E.CO2 .
Table 8, wherePC43LS20FA37
Furthermore, the second quaternary
exhibitedseries based on
the highest PC43LS20FA37
mechanical had in
properties theterms
lowest
of total E.COof
the ratio 2.
Furthermore, PC43LS20FA37 exhibited the highest mechanical properties in terms of the

compressive strength/E.CO2 . Lastly, for such pastes the lower µS content seems to be delivering the ratio of
compressive
most optimalstrength/E.CO
results. 2. Lastly, for such pastes the lower μS content seems to be delivering the
most optimal results.
Table 8. Embodied CO2 (kg/tonne) associated with strength of quaternary cementitious matrices.
Compression
Formulation PC LS FA μS Total Strength/E.CO2
Strength 28
Composition E.CO2 E.CO2 E.CO2 E.CO2 E.CO2 (MPa/kg/tonne)
Appl. Sci. 2020, 10, 2955 18 of 25
Table 8. Embodied CO2 (kg/tonne) associated with strength of quaternary cementitious matrices.
Formulation PC LS FA µS Total Compression Strength Strength/E.CO2

Composition E.CO2 E.CO2 E.CO2 E.CO2 E.CO2 28 Days (MPa) (MPa/kg/tonne)
PC60LS20FA20 558.0 6.4 0.8 0.0 565.2 51.3 0.09
PC55LS20FA20+5%µS 511.5 6.4 0.8 0.7 519.4 42.7 0.08
PC50LS20FA20+10%µS 466.5 6.4 0.8 1.4 475.1 19.1 0.04
PC43LS20FA37 401.2 6.4 1.5 0.0 409.1 39.5 0.10
PC43LS17FA37+3%µS 401.2 5.4 1.5 0.4 408.5 30.0 0.07
PC43LS14FA37+6%µS 401.2 4.5 1.5 0.8 408.0 24.8 0.06
3.3.3. Thermal Analyses of Quaternary Cementitious Matrices

As shown in Figure 19, given that the reference paste contained at the various ages approximately
8% Ca(OH)2 , a paste containing 55%PC would be expected to generate 7.3% Ca(OH)2 and a paste
containing 50%PC would be expected to generate approximately 6.6% Ca(OH)2 Therefore, it can be
Appl. Sci. 2020, 10, that
argued x FORin PEER REVIEW
all cases the µS addition cause a further Ca(OH)2 consumption. Lastly, as shown in 19 of 26
Figure
Appl. Sci. 2020, 10,20 no carbonation
x FOR PEER REVIEW has taken place as the CaCO3 content is lower than the 20% LS content 19 of 26
present in the pastes in all combinations.
Figure 19. Ca(OH)2 content μS modified cementitious matrices based on PC60LS20FA20.

Figure Figure 19. Ca(OH)
19. Ca(OH) 2 content
2 content μSµS modified cementitious
modified cementitious matrices
matricesbased on PC60LS20FA20.
based on PC60LS20FA20.
Figure
Figure 20. 20. CaCO
CaCO 3 content
3 content
of µS
of μS modifiedcementitious
Figure 20. CaCO
The Ca(OH) 3 content of
2 consumption is μS modified
depicted cementitious
in Figure matricestobased
21. It is interesting on PC60LS20FA20.
note that after day 28 and by
ThedayCa(OH) consumption
56, the2Ca(OH) is depicted in Figure 21. It is interesting to note that after day 28 and
2 content in the reference paste reduced to 1.5% by mass. It has been reported that
by dayThe56,
for the
highCa(OH)
Ca(OH) 2 content
PC2 replacement
consumption in
by FA the
is (> reference
60%),
depicted depletion paste
in Figure reduced
of Ca(OH)
21. It 2ismay tobe1.5% bytomass.
observed
interesting after
noteoneIt year
that has been reported
[16,17].
after day 28 and
that
by day Therefore,
for 56,
highthePC given more
replacement
Ca(OH) time,
2 content
Ca(OH)
byinFA in this
the(>2reference ternary
60%), depletion system is expected
of Ca(OH)
paste reduced to
2 may
to 1.5% be depleted,
bybe if
observed
mass. the sample
It has after
been one year
reported
has not carbonated. However, the phenomena observed in composite cements can be more complex.
[16,17].
that forTherefore, given more by
high PC replacement time,FACa(OH)
(> 60%), 2 in this ternary
depletion system2 ismay
of Ca(OH) expected to be depleted,
be observed after oneifyear
the
sample
[16,17]. has not carbonated.
Therefore, given more However,
time, Ca(OH) the phenomena observed
2 in this ternary system in composite
is expectedcements can be more
to be depleted, if the
complex.
sample has Innot
fact, it has been
carbonated. reported
However, thethat combinations
phenomena observed containing
in composite65% cements
OPC andcan 35% of a
be more
formulation
complex. Inoffact, FA and LS produced
it has been reported similarthatamounts of Ca(OH)containing
combinations 2 after day 1. 65%However,
OPC and the minimum
35% of a
amount
formulationof Ca(OH)
of FA and 2 was reached for
LS produced the 30%
similar amounts FA and 5% LS2 after
of Ca(OH) formulation and not the
day 1. However, theminimum
35% FA
that for high PC replacement by FA (> 60%), depletion of Ca(OH)2 may be observed after one year
[16,17]. Therefore, given more time, Ca(OH)2 in this ternary system is expected to be depleted, if the
sample has not carbonated. However, the phenomena observed in composite cements can be more
complex. In fact, it has been reported that combinations containing 65% OPC and
Appl. Sci. 2020, 10, 2955
35% of a
19 of 25
formulation of FA and LS produced similar amounts of Ca(OH)2 after day 1. However, the minimum
amount of Ca(OH)2 was reached for the 30% FA and 5% LS formulation and not the 35% FA
In fact, it has been reported that combinations containing 65% OPC and 35% of a formulation of FA
formulation
and LS [12]. This was
produced attributed
similar amounts ofto the synergistic
Ca(OH) interaction of FA and LS. Although according
2 after day 1. However, the minimum amount of Ca(OH)2
to De Weerdt
was reachedet al.for[12]
the the
30%presence
FA and 5%of LSLS leads toand
formulation thenot
formation
the 35% FA offormulation
carboaluminate
[12]. Thishydrates,
was this
was not attributed
detectedto bythethe TG analyses
synergistic (Figure
interaction 22),
of FA andneither by theaccording
LS. Although XRD analyses shown
to De Weerdt in[12]
et al. detail
the in other
presence
publication [25]. of LS leads to the formation of carboaluminate hydrates, this was not detected by the TG
analyses (Figure 22), neither by the XRD analyses shown in detail in other publication [25].

Figure Figure 21. Ca(OH)
21. Ca(OH) 2 content
2 content μS µS modifiedcementitious
Figure Figure 22. CaCO

22. CaCO 3 content
3 content
of µS
of μS modifiedcementitious
3.3.4. Microstructural Characterization of Quaternary Cementitious Matrices
3.3.4. Microstructural Characterization of Quaternary Cementitious Matrices
Indicatively, four BSC micrographs of PC55LS20FA20+5%µS are shown in Figure 23. As discussed
earlier in Portland
Indicatively, four limestone cement pastes of
BSC micrographs withPC55LS20FA20+5%μS
high FA contents except for are
the needle-like
shown in hydration
Figure 23. As
products (Figure 23 C,D), CaCO3 flakes and Ca(OH)2 crystals a number of rims and reacted FA particles
discussed earlier in Portland limestone cement pastes with high FA contents except for the needle-
can be detected. It is interesting to note that the investigation of different areas did not yield indications
like hydration products
of unreacted (figure
FA particles. 23 correlating
Asfact C,D), CaCO flakes
well3 with theand Ca(OH)2 crystals
TG measurements showinga that
number
there wasof rims and
reacted FA
enoughparticles
Ca(OH)can be detected. It is interesting to note that the investigation of different areas
2 still present in the hydrated paste after day 28 and 56 should the FA have needed
did not yield indications
it to react with. Reactedof unreacted FA particles.
FA (rFA) particles A fact
are circled correlating
in Figure well withinthe
23B. Furthermore, TG 23B
Figure measurements
the
reaction of a FA particle leaving a characteristic mullite sphere [39] was
showing that there was enough Ca(OH)2 still present in the hydrated paste after day 28 and identified (enclosed in the
56 should
rectangle). It was suggested by Xu and Sarkar that the glass phase in FA has been reacted and the
the FA have needed it to react with. Reacted FA (rFA) particles are circled in Figure 23B. Furthermore,
crystalline phase is left almost intact. Adding to this, the typically acicular hydration product of FA in
in Figurethe23B the reaction of a FA particle leaving a characteristic mullite sphere [39] was identified
first 28 days can be seen in Figure 23B (enclosed in a rectangle). Lastly, the presence of microcracks
(enclosed in the rectangle).
is prominent, It was suggested
possibly signaling cracking dueby to Xu and heat
elevated Sarkar that the Therefore,
of hydration. glass phasethis in FA has been
specific
reacted and the crystalline
formulation phase isby
could be enhanced left almosttheintact.
reducing Adding
silica fume to this, the typically acicular hydration
content.
product of FA in the first 28 days can be seen in Figure 23B (enclosed in a rectangle). Lastly, the
presence of microcracks is prominent, possibly signaling cracking due to elevated heat of hydration.
Therefore, this specific formulation could be enhanced by reducing the silica fume content.
Comparing the reference paste PC60LS20FA20 (Figure 14) with the 5% μS (Figure 23) and the
10% μS (Figure 24) enhanced quaternary formulations and particularly the 200 times magnification
Appl. Sci. 2020, 10, 2955 20 of 25
Comparing the reference paste PC60LS20FA20 (Figure 14) with the 5% µS (Figure 23) and the 10%
µS (Figure 24) enhanced quaternary formulations and particularly the 200 times magnification there is
an indication that the µS enhanced pastes are less dense. This cannot be attributed to particle packing
that is expected to be enhanced, but credited to the high amount of FA present. The FA was already
feeding from the Ca(OH)2 , therefore the more reactive pozzolanic particles of µS may not be able to
access the Ca(OH)2 crystals encapsulated within the reacted FA particles. That is to say, although
Ca(OH)2 is not depleted in these quaternary formulations, the µS particles may be deactivated by the
inaccessibility of Ca(OH)2 created
Appl. Sci. 2020, 10, x FOR PEER REVIEW
by the hydration products around the much greater quantities of FA.
21 of 26
AA BB
Microcracks
rFA
CSH on CH CSH rFA

crystals CSH rFA
rFA
Microcracks
CSH
uFA
rFA
rFA
CSH CSH
CC DD
CH
Figure
Figure 23.23.BSC
BSCmicrograph
micrographofofPC55LS20FA20+5%µS
PC55LS20FA20+5%μS at at 28D
28D at
at (A)
(A) 200×
200×magnification,
magnification,(B)(B)1000×
1000×
magnification, (C) 3000× magnification and (D) 5000× magnification.
magnification, (C) 3000× magnification and (D) 5000× magnification.
AsAs depicted
depicted ininFigure
Figure24,24,aasimilar
similar microstructure
microstructure to tothe
thelower
lowerμS µScontent
content paste
pastecan bebe
can observed.
observed.
The only difference being the plethora of needle-like hydration products
The only difference being the plethora of needle-like hydration products detected at all magnifications detected at all
magnifications and the many unreacted μS particles (small, spherical bright elements).
and the many unreacted µS particles (small, spherical bright elements). The typically acicular hydration The typically
acicular
product hydration
of FA product
in the first 28 days ofcan
FAbe inseen
the in
first 28 days
Figure can be seen
24B (enclosed in ain Figure 24B
rectangle). (enclosed
Another in a
FA particle
rectangle). Another FA particle with hydration gel around it, is circled in Figure 23C. Reacted FA
with hydration gel around it, is circled in Figure 23C. Reacted FA particles are circled in Figure 24C.
particles are circled in Figure 24C. In agreement with Lothenbach et al. [16], the μS enhanced pastes
In agreement with Lothenbach et al. [16], the µS enhanced pastes showed a more refined pore structure,
showed a more refined pore structure, but are expected to deliver higher total porosities. That is to
but are expected to deliver higher total porosities. That is to say, capillary pores were expected to
say, capillary pores were expected to be reduced and finer pores slightly increased. This could partly
be reduced and finer pores slightly increased. This could partly explain the microcracks present in
explain the microcracks present in the images taken. The increased heat of hydration could be the
theother
images taken. The increased heat of hydration could be the other reason for the development of
reason for the development of microcracks as discussed for the +5%μS addition. Knowing that
microcracks
the presenceas discussed for the
of the cracks +5%µS to
is related addition. Knowing that
lower durability theformulations,
of the presence of the cracks
future is related
research on to
lower durability of the formulations, future research on quaternary pastes using this
quaternary pastes using this formulation should contain substantially lower μS contents. In fact, this formulation should
contain substantially
observations led to lower µS contents.
the reduction of theIn
μSfact, this observations
contents in the designled to the
of the reduction
quinary of the µS contents
combinations, based
in on
thePC43LS20FA37.
design of the quinary
As shown combinations,
in publishedbased
researchon four
PC43LS20FA37. As showncompeted
different formulations in published research
against the
reference paste PC43LS20FA37; (a) PC43LS17FA37 + 2.5%μS + 0.5%nS (where nS is the abbreviation +
four different formulations competed against the reference paste PC43LS20FA37; (a) PC43LS17FA37
2.5%µS + 0.5%nS (where
for nanoparticles of SiOnS
2),is(b)
thePC43LS17FA37
abbreviation for + nanoparticles
2.0%μS + 1.0%nS,of SiO(c)2 ),PC43LS14FA37
(b) PC43LS17FA37 + 2.0%µS
+ 5.5%μS +
+ 1.0%nS,
0.5%nS and(c) PC43LS14FA37
(d) PC43LS14FA37 + +5.5%µS
5.0%μS++ 1.0%nS
0.5%nS[42].andThe(d)lower additions of+nS5.0%µS
PC43LS14FA37 particles + performed
1.0%nS [42].
Thebetter,
lowerhowever,
additions theofpresence
nS particlesof high quantities
performed of pozzolanic
better, however, and highly pozzolanic
the presence materials, of
of high quantities
delayed hydration
pozzolanic and highlyreactions
pozzolanic andmaterials,
strength gain. In other
delayed words,reactions
hydration the nanoparticles
and strength were unable
gain. to
In other
leverage the already expected delayed reactions due to the presence of high volume fly ash and silica
fume content.
Appl. Sci. 2020, 10, 2955 21 of 25
words, the nanoparticles were unable to leverage the already expected delayed reactions due to the
presence of high volume fly ash and silica fume content.
AA B B ettringite
AA BB ettringite
Microcracks
Microcracks Microcracks
Microcracks
CSH
CSH CSH
CSH
rFA
rFA
CSH
CSH
CSH
CSH
rFA
rFA
CSH
CSH
ettringite
ettringite
CC D
D
D
ettringite
ettringite
CC
Figure
Figure 24.24.BSC
BSCmicrograph
micrographofofPC50LS20FA20+10%µS
PC50LS20FA20+10%μS at
PC50LS20FA20+10%μS at 28D
28Datat (A)
(A)200×
(A) 200×magnification,
1000×
(B) 1000×
1000×
magnification, (C) 3000×
magnification, (C) 3000× magnification and (D) 5000×
magnification and (D) 5000×
3000× magnification magnification.
5000×magnification.
magnification.
TheThe BSC micrographofofPC43LS20FA37

BSC PC43LS20FA37 at day day 28 is presented below (Figure 25). AA number of of
The BSC micrograph
micrograph of PC43LS20FA37 at at day 28
28 is
is presented
presented below
below (Figure
(Figure 25).
25). A number
number of
reacted
reacted and and unreacted particles,
unreacted particles, can be observed as expected according to the TG analyses which lead
reacted and unreacted particles, can
can be observed as
be observed expected according
as expected according to the TG
to the TG analyses
analyses which
which lead
lead
to to
thethe conclusionthat
conclusion thatatatthis
thisage
agealmost
almost half
half of
of the
the FA
FA particles
particles were
were still
stillunreacted),
unreacted), CaCO
CaCO3 flakes
flakes
to the conclusion that at this age almost half of the FA particles were still unreacted), CaCO33 flakes
andand Ca(OH)2crystals
Ca(OH) crystalswere
were also
also present
present and
and areas
areas of
of dense
densematter,
matter,believed
believedtoto tobebe
beC–S–H.
C–S–H.Similar
and Ca(OH)22 crystals were also present and areas of dense matter, believed C–S–H. Similar
Similar
description is valid for curing until day 1 and day 56 [42]. No cracks can be observed, rendering the
description
description is valid for curing
is valid forpromising until
curing until day 1 and
day 1 and day 56 [42]. No cracks can be observed, rendering
day 56 [42]. No cracks can be observed, rendering the the
specific formulation for further optimization.
specific formulation promising for further optimization.
specific formulation promising for further optimization.
A B
A uFA B
uFA
rFA
rFA CH
CH uFA
rFA rFA CSHuFA
CH CSH
rFA rFA
CH
Figure 25. BSC micrograph of PC43LS20FA37 at 28D at a) 1000× magnification and (B) 1000×
magnification.
Figure
Figure 25.
25. BSCBSCmicrograph of of
micrograph PC43LS20FA37 at 28D
PC43LS20FA37 at a)at 1000×
at 28D magnification
(A) 1000× and (B)
magnification 1000×
and (B)
magnification.
1000× magnification.
4. Conclusions
The present paper is the last part of an extensive research program carried out at the University
4. Conclusions
of Bath, aimed at investigating the effect of nanoparticles in sustainable blended cements. Although
The present
a significant paper of
number is the last have
papers part of an published
been extensive research program
on the effect carried
of various out at the University
nanoparticles on low
of carbon
Bath, aimed at investigating the effect of nanoparticles in sustainable blended
footprint composite cementitious formulations [5,8,10,25,27–30,40,42,44–47],cements. Although
the starting
a significant number of papers have been published on the effect of various nanoparticles on low
carbon footprint composite cementitious formulations [5,8,10,25,27–30,40,42,44–47], the starting
Appl. Sci. 2020, 10, 2955 22 of 25
4. Conclusions
The present paper is the last part of an extensive research program carried out at the University of
Bath, aimed at investigating the effect of nanoparticles in sustainable blended cements. Although a
significant number of papers have been published on the effect of various nanoparticles on low carbon
footprint composite cementitious formulations [5,8,10,25,27–30,40,42,44–47], the starting pastes and
the methodology of selecting formulation on performance based criteria, has never been discussed
before. The paper has introduced, analyzed, compared and discussed, a suite of binary (PC + LS) and
ternary (PC + FA + LS) cementitious matrices. Three ternary pastes were selected which were further
optimized with the addition of silica fume. Competing constituents and areas of improvements to
pave the way for the addition of the nanoparticles were identified. Moreover, the pozzolanic reactivity
in ternary and quaternary cement paste formulations was investigated, while the lowest possible
Portland cement content was employed. In addition to the above, a number of further conclusions
were made:
• Current research can expand on challenging formulations, which allow for significant reduction
in CO2 emissions, beyond allowable limits by current codes.
• It was demonstrated that optimizing blended or composite Portland cement pastes at high PC
replacement levels is an iterative process. This step by step methodology presented in the paper
can serve as a basis for other researchers in the field.
• In areas where pozzolanic materials are scarce, binary formulations can be developed as the
control mix, further enhanced by highly reactive materials, such as nanoparticles of SiO2 or
montmorillonite [10,29,44,47].
• In areas where fly ash is abundant and needs to be valorized, ternary blends can be developed
and again can be further enhanced with nanomaterials [22,25,42]. Similarly, quinary cementitious
matrices can be developed with both micro- and nanosized silica [42] for superior strength and
denser microstructure.
• It is essential that material characterization is thorough and extensive testing is necessary.
• The complicated interaction between the constituents was investigated with respect to strength
development, changes in the hydration reaction and microstructural enhancement.
Lastly, adding to the future research suggestions, apart from the addition of different types of
nanoparticles for strength and durability improvements, which has been previously mentioned, matrices
containing different types of supplementary cementitious materials can be generated. Some options
could include ground granulated blast furnace slag or geopolymers altering water demand, strength and
microstructural characteristics. This research has rendered the surpassing of the boundaries defined by
the current codes of practice, possible and therefore, further optimizations of blended pastes can be
expected in the near future.
Author Contributions: Conceptualization, S.P. and K.P.; methodology, S.P.; validation, S.P. and K.P.; formal
analysis, S.P. investigation, S.P.; data curation, S.P.; writing—original draft preparation, S.P.; writing—review and
editing, S.P. and K.P.; funding acquisition, K.P. Both authors have read and agreed to the published version of the
manuscript. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by European Commission funding, FIBCEM project, grant Number 262954.
Acknowledgments: The authors acknowledge the European Commission funding and all partners are thanked
for their input and for the supply of materials. The authors would also like to acknowledge the Department
of Chemical Engineering at the University of Bath for the use of the TG analyzer. The strength over embodied
CO2 calculations of pastes (shown in the respective columns in Tables 6 and 8) were carried out by Dr Juliana
Calabria-Holley and her help is greatly appreciated. The particle size distribution results of the four constituent
materials were prepared by colleagues in Maulana Azad National Institute of Technology (MANIT), Bhopal,
India with funding provided by the UK-India Education and Research Initiative (UKIERI) Program.
Conflicts of Interest: The authors declare no conflict of interest.
Appl. Sci. 2020, 10, 2955 23 of 25
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© 2020 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 (http://creativecommons.org/licenses/by/4.0/).

A Step by Step Methodology For Building Sustainabl

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Abstract: In an effort to produce cost-effective and environmentally friendly cementitious binders.

Appl. Sci. 2020, 10, 2955; doi:10.3390/app10082955 www.mdpi.com/journal/applsci

modifications with the addition of silica fume were identified

2. Materials and Methods

2.2. Preparation of Paste Combinations: Mixing, Casting, Demoulding, Curing

• Dry mixing of all powders with a spatula by hand.

2.3. Step 1: Design of Cementitous Matrices

Binary & Ternary Quaternary

Table 2. Quaternary µS enhanced cement paste formulations—Mix Proportions % by total mass

Sample PC (%) LS (%) FA (%) µS (%) w/b

Table 3. Quaternary µS enhanced cement paste formulations—low PC—Mix Proportions % by total

Sample PC (%) LS (%) FA (%) µS (%) w/b

2.4. Preparation of Pastes for Characterization

2.5. Experimental Techniques

2.5.1. Thermogravimetric Analyses and Differential Thermogravimetry (TGA/dTG)

A) Constituent materials B) Binary and ternary cementitious matrices

Thermogravimetric analyses and differential thermogravimetry (TGA/dTG) (all

C) Quaternary cementitious matrices

Embodied CO2 calculations for all optimized formulations

2.5.4. X-Ray Diffraction (XRD)

angular step-size of 0.016◦ 2θ.

Appl. Sci. 2020, 10, x FOR PEER REVIEW 9 of 26

Figure 5. Normal distribution of LS.

Figure 6. Normal distribution of FA.

3.1.3. XRD and SEM/EDX results of FA

Table 5. SEM/EDX counts summary (% atomic) of FA.

Table 7. Comparison of the Ca(OH)2 content of the selected bases.

Appl. Sci. 2020, 10, x FOR PEER REVIEW 14 of 26

3.3. Step 4: Optimizing Quaternary Cementitious Matrices

3.3. Step 4: Optimizing Quaternary Cementitious Matrices

3.3.1. Compressive Strength of Quaternary Cementitious Matrices

As in the case of μS enhanced PC60LS20FA20, the μS enhanced low PC content PC43LS20FA37,

As in the case of µS enhanced PC60LS20FA20, the µS enhanced low PC content PC43LS20FA37,

Furthermore, PC43LS20FA37 exhibited the highest mechanical properties in terms of the

most optimal results.

Formulation PC LS FA µS Total Compression Strength Strength/E.CO2

3.3.3. Thermal Analyses of Quaternary Cementitious Matrices

Figure 19. Ca(OH)2 content μS modified cementitious matrices based on PC60LS20FA20.

Appl. Sci. 2020, 10, x FOR PEER REVIEW 20 of 26

Figure Figure 22. CaCO

CSH on CH CSH rFA

TheThe BSC micrographofofPC43LS20FA37

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