Case Studies in Construction Materials 13 (2020) e00407

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Case Studies in Construction Materials

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Effect of sulfate activator on mechanical and durability

properties of concrete incorporating low calcium fly ash
Muhammad Asad Nawaza , Babar Alib,* , Liaqat Ali Qureshia ,
Hafiz Muhammad Usman Aslama , Iqrar Hussaina , Bilal Masooda ,
Syed Safdar Razac
a
Department of Civil Engineering, University of Engineering and Technology, Taxila, 47050, Pakistan
b
COMSATS University Islamabad-Sahiwal Campus, 57000, Pakistan
c
Department of Civil Engineering, Bahauddin Zakariya University, Multan, 66000, Pakistan

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

Article history: The use of fly ash as a cement replacement material brings economy and sustainability in
Received 10 May 2020 the concrete construction. Despite economic and environmental benefits, fly ash
Received in revised form 14 June 2020 incorporation in concrete reduces its early age performance. Therefore, the main objective
Accepted 14 July 2020
of this research is to increase the incorporation level of fly ash in the hybrid binder (cement
plus fly ash) utilizing the sulfate activation technique to overcome the issue of inferior
Keywords: performance at an early age. Replacement levels of fly ash with cement were kept as 20 %,
Fly ash
40 %, and 60 %. 2 % sodium sulfate (Na2SO4) by weight of binder was utilized as an activator.
Sulfate activation
Chemical activation
Compressive strength and flexural strength tests on standard samples were carried out at
Compressive strength the age of 3, 28 and 90 days. Durability tests namely apparent porosity, sorptivity
Sorptivity coefficient coefficient and chloride penetration tests were also conducted. Experimental results
Concrete durability showed sulfate activation increased the early age strength at all levels of fly ash. After
activation, concrete mix with 20 % and 40 % fly ash showed better strength performance
than that of the conventional concrete at all ages. Concrete with 20 % and 40 % fly ash upon
activation showed lower sorptivity and porosity than control mix at all ages. Similarly,
chloride penetrations of concrete with 20, 40 and 60 % activated fly ash was noticeably
lower than that of the control concrete. Chemical activation is also beneficial in reducing
the cost and carbon footprint per unit strength of the fly ash mixes.
© 2020 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC
BY license (http://creativecommons.org/licenses/by/4.0/).

1. Introduction

Fly ash is a finely pulverized fuel ash produced by combustion of older and harder anthracite in coal-fired boilers. Fly ash is
being produced in huge quantities in Pakistan, as coal power plants began to contribute significantly to satisfy electric power
demand. Its consumption in concrete can help in reducing the waste disposal problems; lowering the manufacturing cost
and impact of concrete on the natural environment.

* Corresponding author.
E-mail addresses: asadkhakhi143@gmail.com (M.A. Nawaz), babar.ali@cuisahiwal.edu.pk (B. Ali), liaqat.qureshi@uettaxila.edu.pk (L.A. Qureshi),
usmanaslam32954@gmail.com (H.M. Usman Aslam), iqrar.turi73@gmail.com (I. Hussain), bilal.masood@students.uettaxila.edu.pk (B. Masood),
safdarshah91@yahoo.com (S.S. Raza).

https://doi.org/10.1016/j.cscm.2020.e00407
2214-5095/© 2020 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/
4.0/).
2 M.A. Nawaz et al. / Case Studies in Construction Materials 13 (2020) e00407

Owing to the pozzolanic nature of fly ash, it can be used as the cement replacement material [1]. Although fly ash
improves the later age strength and durability [2–4], poor early strength associated with fly ash concrete restricts its
application in works where early strength is required to expedite construction. Enhancing the fly ash activity (mainly
due to its glass silica particles) to gain high early strength is a major focus among the researchers nowadays to increase
the goodwill of fly ash concrete in the constructionn industry. The activity of fly ash can be increased in three different
ways; (a) thermal activation (by calcining fly ash) (b) mechanical activation to increase the surface area of fineness of fly
ash particles by rigorous grinding (c) chemical activation by the dissolution of non-amorophouse content of fly ash
particles with the help of alkalies and sulfates. The processing of fly ash to finely ground particles increase its surface
area resulting in improved activity with portlandite (CH). But grinding technique may increase the cost of fly ash. The
calcination of fly ash, also called thermal activation, at elevated temperatures to burn its carbon contents increases
energy emissions or carbon footprint associated with fly ash. Therefore, chemical activation of fly ash by using the small
doses of chemical compounds during mixing of concrete (such as Na2SO4) can effectively reduce the cost to strength
ratio of concrete [5].
Currently the most commonly used percentages of fly ash are 20–30 % as the partial replacement of cement and
researchers [6–10] have investigated the high levels of fly ash with an aim to reduce the cement content of concrete.
Although, there are growing environmental pressures to increase consumption of fly ash in the concrete, other
parameters, such as, the rate of strength development and durability performance is jeopardized when fly ash levels
exceed 60–80 % [11]. Researchers have also investigated the possibility of 100 % replacement of Portland cement with fly
ash through the use of chemical activators [12–14]. Criado et al. [15] identified need to cure the concretes containing 50–
100 % fly ash at the elevated temperatures to reach the desired level of strength. As already explained, different
techniques can be used to chemically activate the fly ash namely thermal activation, mechanical grinding, and chemical
activation. So far, chemical activation has been proved to be the most effective in terms of cost to strength ratio compared
to the other techniques [5].
Various chemicals both alkaline and salts have been used to dissolute the glass particles of fly ash. Anhydrite of
calcium sulfate and gypsum were used to improve the strength of mortars containing 55 % fly ash under different
curing methods [16]. Poon et al. [16] reported that curing at 60
C for 6 h against normal curing improved the strength
of blended cement mortars by more than 70 % compared to that of the control concrete. Gypsum inclusion was
more beneficial than anhydrous CaSO4 at later ages. Activation of hybrid cement fly ash systems has been done using
Na2SO4 and a significant increase was noticed in the compressive strength at an early age [17]. Qian et al. [17] also
employed a mechano-chemical activation technique where fly ash was finely ground and its properties were
compared with that of the Na2SO4 activated fly ash. Their results showed that early age strength of Na2SO4 activated fly
ash was better than that of the mechanically grinded fly ash. Hefni et al. [18] reported that in 40 % fly ash concrete,
Na2SO4 (2.5 % by mass of binder) and sodium silicate (4 % by mass of binder) were the most effective activators
compared to the sodium hydroxide and lime-silicate in terms of increasing the early and later age strength properties.
Hefni et al. [18] also reported that Na2SO4 did not affected workability badly compared to other activators. Lynsdale
et al. [10] reported that 50 % fly ash concrete with 1 % Na2SO4 showed improvement in the durability over the extended
periods.
In past, studies focused on improving the compressive strength of fly ash concretes using different chemical activators
[9,15–18], but very few information [10] is available on durability performance of chemically activated fly ash concretes.
Permeability related durability properties of activated fly ash concretes have not been studied properly, so far.

2. Significance of research

A developing country like Pakistan largely depends on the coal power plants to meet its needs of electricity that generates
a huge waste in the form of bottom and fly ashes. According to an estimate of Ali and Qureshi [20], Pakistan produces about 5
million tons of fly ash annually which is about 10 % of the annual clinker production of the country. But a very few studies [21]
are present that investigate mechanical and durability performance of fly ash from local sources in concrete. To increase the
goodwill of fly ash concrete in Pakistan and globally, it is necessary to overcome its drawbacks of inferior early age properties
in concrete and the solutions needs to be efficient and economical simultaneously.
The main objective of this research is to advance the early strength of concrete with different levels of Class F fly ash
(obtained from Port Qasim Coal Power Plant, Karachi, Pakistan) using a low-cost chemical activator like Na2SO4. Previously
conducted studies [16–19,22] have focused on the strength evolution of concrete or mortar or binder pastes. The durability of
chemically activated fly ash systems is the main challenge and very few information is available in this area [22]. Besides that,
literature is very deficient on the investigation of Pakistani fly ashes with and without activator. For this purpose, the present
study evaluates the durability parameters i.e. apparent porosity, sorptivity coefficient, chloride penetrations of Na2SO4
activated fly ash concrete in addition to the important strength parameters namely compressive strength and flexural
strength. The effect of Na2SO4-activation is investigated on the concrete with three different low–medium–high percentages
of fly ash. The results of this study prove the usefulness of a small dosage of Na2SO4 (2 % by mass of binder) in advancing the
mechanical and durability performance of fly ash concrete.
 M.A. Nawaz et al. / Case Studies in Construction Materials 13 (2020) e00407 3

3. Experimental program

3.1. Materials

3.1.1. Portland cement and fly ash

General purpose 43 Grade cement was used as per ASTM-C150 [23]. Fly ash of Class-F type according to ASTM-C618 [24]
was obtained from Port Qasim power plant, Karachi. Port Qasim power plant uses a bituminous grade of coal imported from
Indonesia which produces Class F type of fly ash with very low calcium content. Physical and chemical properties of cement
and fly ash are provided in Table 1.

3.1.2. Aggregates
Quarry sand of Lawrance Pur was used as fine aggregate. Margalla crush was used as coarse aggregate. General properties
of aggregates are shown in Table 2. Gradation curves of both fine and coarse aggregates follows ASTM C33 [25].

3.1.3. Sodium sulfate

Laboratory grade Na2SO4 was used with 98.5 % purity having excellent solubility in water.

3.1.4. Water and chemical admixture

Tap water was used for the mixing of all concrete mixtures. Sikament 520 as a high range water reducing admixture was
used to achieve the desired level of workability.

3.2. Composition of concrete mixtures

A total of seven concrete mixtures were prepared. Details of each mix are shown in Table 3. A mix design ratio of 1:1.5:3 by
weight was used throughout all mixtures. Fly ash was used to replace cement at levels of 20 %, 40 %, and 60 %. The dosage of
Na2SO4 was kept constant as 2 % by weight of binder (cement plus fly ash). This dosage of Na2SO4 activator was selected
considering the permissible SO3 content of the binder. According to a Chinese Standard GB175-2007, the content of SO3 in
cement should be less than 3.5 %. Whereas, according to ASTM C150, this content should not exceed 3.5 % when C3A content
is greater than 8 %. The cement, fly ash, and Na2SO4 provide 3.01 %, 0.64 %, and 56.32 % of SO3, respectively. The calculation of
SO3 content is given in Table 4. In all mixes the dosage of SO3 is well below 3.5 %, except for mix with 20 % FA where SO3
slightly increases beyond 3.5 %.
A slump of about 120  5 mm was maintained to keep the level of workability same for all mixtures. To reach this level of
workability, plasticizer was used in all concrete mixtures. The dosage of plasticizer was kept equal for all mixes as at this
dosage all mixes reached the target slump in the range of 115125 mm. FA particles are smaller than those of the cement that
may decrease the workability of mixes but the filling effect of fly ash particles at the same time can decrease the demand of
water to attain the normal consistency. Therefore, no significant difference in the workability of mixes was observed with the
rising volume of fly ash in binder at the constant plasticizer dosage. The fresh density of all mixtures was about 2440 kg/m3.

3.3. Preparation and testing of specimens

All concrete mixes were prepared in a mechanical mixer of 0.15-m3 capacity. First of all, the solid ingredients were mixed
for about 3 min. Then water was added, and mixing continued for further 4-mins. In case of activated mixtures, Na2SO4 was
pre-dissolved in the water and subsequently used in the mixing of concrete.
For compression strength, 100-mm cubes were cast following BS:EN 12390-3 [26] and tested in compression testing
machine of 3000 kN capacity. For flexural strength/modulus of rupture, prisms of 100  100  500 mm were cast and tested
under center-point loading as per ASTM-C293 [27]. Concrete disks of 50 mm thickness and 100 mm diameter were used for
sorptivity coefficient following the ASTM-C1585 [28]. For apparent porosity concrete discs of 50 mm thickness and 100 mm
diameter were used and tested as per ASTM-C642 [29]. Chloride ion penetration in each concrete mixture was measured by
the method explained by Ali and Qureshi [30,31]. For each test, three replicate specimens of a mixture were tested, and their
average result is reported in this case study.

Table 1
Properties of binders.

Materials Physical Characteristics Chemical composition (%)

Sp. gravity Fineness (cm2/g) SiO2 Al2O3 Fe2O3 CaO MgO SO3 LOI
Cement 3.07 3765 19.7 4.03 3.21 61.97 2.44 3.01 1.93
Fly ash 2.18 4350 58.19 23.56 8.61 3.52 1.77 0.64 4.82
4 M.A. Nawaz et al. / Case Studies in Construction Materials 13 (2020) e00407

Table 2
Properties of aggregates.

Property Sand Coarse aggregates

Max. nominal size (mm) 4.75 19.50
Min. nominal size (mm) 0.075 4.75
Bulk density (kg/m3) 1650 1578
Saturated surface dry (SSD) water absorption (%) 1.40 1.51
10 % fine value (kN) – 157
Specific gravity 2.66 2.72

Table 3
Composition of concrete mixtures.

Mix Fly Activated/Un- Portland Fly ash (kg/ Sand Coarse Superplasticizer Water Na2SO4
ID ash activated cement m3) (kg/ aggregates (kg/m3) (kg/ (kg/m3)
(kg/m3) m3) (kg/m3) m3)
CON 0% – 430 0 645 1290 4.3 215 0
U-F20 20 % Un-activated 344 86 645 1290 4.3 215 0
A-F20 Activated 344 86 645 1290 4.3 215 8.6
U-F40 40 % Un-activated 258 172 645 1290 4.3 215 0
A-F40 Activated 258 172 645 1290 4.3 215 8.6
U-F60 60 % Un-activated 172 258 645 1290 4.3 215 0
A-F60 Activated 172 258 645 1290 4.3 215 8.6

ID = Identity; U: Un-activated fly ash; A: Activated fly ash.

Table 4
Calculation of SO3 content for different combinations of cement and fly ash.

Mix ID SO3 from cement (%) SO3 from fly ash (%) SO3 from Na2SO4 activator (%) Total SO3 in binder (%)
CON 3.03 0 0 3.03
U-F20 2.424 0.128 0 2.55
A-F20 2.424 0.128 1.12 3.54
U-F40 1.825 0.256 0 2.08
A-F40 1.825 0.256 1.12 3.20
U-F60 1.20 0.384 0 1.58
A-F60 1.20 0.384 1.12 2.70

Fig. 1. (a) Compressive strength of each mix (b) relative compressive strength of each mix w.r.t CON.
 M.A. Nawaz et al. / Case Studies in Construction Materials 13 (2020) e00407 5

4. Results and discussions

4.1. Compressive strength

Results of compression testing are shown in Fig. 1. Relative compressive strength of each mix with respect to control mix
is shown in Fig. 1(b). Overview of results show that compressive strength at 3 and 28-days decreases with the rising volume
of fly ash. Use of Na2SO4 activator significantly improves the early age compressive strength of fly ash concrete.
The reduction in strength due to fly ash can be explained by ascribed to glass surface layers of its particles that are chemically
stable and dense. These stable layers protect spongy and amorphous particles in the binder matrix; therefore, fly ash particles
react very slowly with calcium hydroxide/portlandite (CH). Hence, fly ash concrete mixtures develop lower early age strength
and take a longer duration to achieve full strength. At 3-days, compressive strength reduces by about 15 %, 35 % and 53 % at the 20
%, 40 %, and 60 % fly ash, respectively (see Fig.1(b)). At the age of 28 days, these reductions reduce to 3 %,11 %, and 34 %. It is worth
mentioning here that only 34 % reduction in compressive strength is noticed with the 60 % replacement of cement with fly ash.
With the advancement in pozzolanic reaction, concretes with 20 % and 40 % fly ash reach the potential of control concrete at 90-
days. Whereas, 60 % fly ash concrete shows 25 % lesser compressive strength than that of the control mix. Fly ash contributes to
strength development in two different ways: (1) pozzolanic reaction of fly ash particles with CH which is dominant in the
mixtures containing low volumes of fly ash i.e. 20 % (2) filling effect: fly ash particles fills up spaces between fine aggregates and
cement particles efficiently that also contributes to compressive stiffness of concrete and this effect contributes to strength in
the mixes containing high volumes of fly ash i.e. 40 % and 60 %. Furthermore, a significant reduction in CH content (due to
decrease in calcium oxide content of binder) reduces the pozzolanicity in the high-volume fly ash mixes; and the improvements
in compressive strength largely depends upon the filler effect [32].
To improve the early strength of fly ash concrete, Si, Al and low Ca chains must be disintegrated by gaining a high alkaline
environment that accelerates the speed of pozzolanic reaction [33]. Improved alkalinity led to increased CS hydrate gel and
ettringite formation in concrete which improves the early age strength. Due to chemical activation of fly ash with 2 % Na2SO4
early strength significantly improved (at the age of 3 days). Compressive strength of 20 % and 40 % fly ash concretes increased
by about 23 % and 8 % as compared to control concrete. Similarly, for the same levels of fly ash, compressive strength of
activated mixes was 34 % and 64 % higher than those of un-activated mixes. 60 % fly ash concrete also showed improvements
in the compressive strength at 3 days upon activation and showed 61 % more strength than its corresponding un-activated
mix. Increase in early age strength due to chemical activation can be ascribed to the achievement of high alkalinity levels and
ettringite formation that helps in effective consumption of CH [34]. This can be explained by Eq. (1). NaOH production
increases the alkalinity of solution that dissociates glassy particles of fly ash and speeds up the pozzolanic reaction [35].
Increase in the concentration of SO42 increases the formation of ettringite which is an essential component contributing a
huge deal to the early strength. It can be seen that for mixes without activator, the difference in strengths at the age of 28 and
90 days is higher, but for activated mixes this difference reduces. This indicates the early consumption of CH due to
activation. Although 60 % fly ash does not reach to the level of conventional concrete the strength of 28 MPa is sufficient to
qualify for the normal strength concrete, hence it is a cheap option to utilize a high volume of fly ash in concrete with
activator. It can also be observed that the mixes without activator achieve strength at higher rates between 28 and 90 days
than that of the mixes with activated fly ash.
Yields
CaðOHÞ2 þ Na2 SO4 þ 2H2 O ! CaSO4 :2H2 O þ NaOH ð1Þ

Fig. 2. (a) Flexural strength of each mix (b) relative flexural strength of each mix w.r.t CON.
6 M.A. Nawaz et al. / Case Studies in Construction Materials 13 (2020) e00407

4.2. Flexural strength

Results of flexural testing follow the same trend as those of the compression testing, see Fig. 2. Relative analysis of these
results is provided in Fig. 2(b). Influence of Na2SO4 activation was pronounced at 3-days. Both 20 % and 40 % activated levels
of fly ash performed better than control concrete by a significant margin at 3- days. The difference in flexural strength of un-
activated and activated mixes reduced at 90-days. Concretes with 20 % or 40 % fly ash and Na2SO4 activator performed better
than control mix. Flexural strength of 60 % fly ash concrete showed improvement upon activation and but not even closer to
the conventional concrete at all ages of testing. Fly ash mixes without Na2SO4 activator showed the highest rate of strength
development than that of the mixtures with activator. Upon activation, the rate of pozzolanic reaction is increased and large
amounts CH are consumed at the early ages. Therefore, un-activated fly ash mixes develop strength later than those of the
activated mixes. A strong correlation (R2 = 0.76) exists between the results of compressive and flexural strength, see Fig. 3.

4.3. Sorptivity coefficient

The results of sorptivity coefficient are shown in Fig. 4. The trend in the results indicates that fly ash inclusion beyond 20 %
is harmful to the sorptivity resistance of concrete. 20 % inclusion of fly ash results in the tremendous improvement in
sorptivity resistance of concrete as compared to control concrete. Upon activation, sorptivity coefficient of fly ash concretes
reduces further. Similar to results of strength testing, positive effect of fly ash was prominent at the age of 3-days. These
improvements are attributed to the production of ettringite at early ages that reduces the connectivity between capillary
pores. Concretes with both 20 % and 40 % fly ash levels show the sorptivity coefficient lesser than that of the control concrete.
In addition to activation and consumption of CH, filling effect of particles also contribute positive role in reducing the
connectivity between capillary pores. Concretes with 20 % and 40 % fly ash show less sorptivity than control concrete at 90-
days with and without Na2SO4 activator.
Although 60 % fly ash concrete showed the reduction in sorptivity with the increasing age, it did not outperform control
concrete. Value of sorptivity coefficient of 60 % fly ash concrete without activator is well below the upper limit of sorptivity
coefficient for structural concrete (max = 0.21 mm/min1/2) under report published by Australian Cement, Aggregate and
concrete community [36]. Therefore, concrete incorporating 60 % Pakistani fly ash can reach the standards of both
compressive strength and sorptivity resistance of normal strength structural concrete.

4.4. Apparent porosity

Results of apparent porosity are presented in Fig. 5. Apparent porosity represents water accessible porosity of concrete
and it has a strong influence on durability parameters of concrete. It represents the pore volume of concrete that connects the
outer surface of the concrete to the internal microstructure. The ingression of harmful chemicals and subsequent
deterioration of concretes largely depends on the porosity of concrete. Apparent porosity reduces slightly at 20 % fly ash, but
further incorporation of fly ash leads to an increase in porosity. Upon activation, concretes with 20 % and 40 % fly ash show
lower porosity than control mix at all ages. A drastic increase in porosity is observed at 60 % fly ash addition. This might be
due to availability of unreacted fly ash particles that only show efficiency in filling effect. Reduction in CH content occurs
when fly ash level rise in the binder. This reduces the pozzolanicity of fly ash particles. Furthermore, along with formation of
ettringite, increase in alkalinity (sodium hydroxide) released by the reaction indicated in Eq. (1) contributes to the growth of

Fig. 3. Correlation between compressive strength and flexural strength (y-intercept = 0).
 M.A. Nawaz et al. / Case Studies in Construction Materials 13 (2020) e00407 7

Fig. 4. Results of sorptivity coefficient.

Fig. 5. Results of apparent porosity.

sodium aluminum silicate hydrates (NASH), as explained by the Donatello et al. [37], see Eqs. (2)–(6).
Yields
Na2 SO4 þ H2 O ! 2Naþ þ SO2
4 ð2Þ

Yields
C 3 S þ H2 O ! CSH þ CH ð3Þ
(Accelerates in the presence of SO42)
Yields
2Naþ þ SO2
4 þ CH ! CS þ NaOH ð4Þ

Yields
CH þ NaOH þ FA ! ðC; NÞASH ð5Þ

Yields
CS þ C 3 A ! Ettringite ð6Þ
The results of porosity, sorptivity coefficient and compressive strength are related to each other as in Fig. 6. Regression
analysis shows good strength (R2 = 0.85) of the correlation that exists between these parameters. These results indicate that
8 M.A. Nawaz et al. / Case Studies in Construction Materials 13 (2020) e00407

the microstructural developments that results in improvement of mechanical properties are also responsible for the
reduction in permeable and capillary pore volume of concrete. Similar conclusions were also reported by Velandia et al. [10].

4.5. Chloride penetration

Chloride penetrations in cylinders cast for each of the mixture are presented in Fig. 7. Each cylinder in Fig. 7, corresponds
to one out of three specimens with penetration value closer to the median value. When 0.1N-AgNO3 solution was sprayed on
surface of split cylinders dipped in NaCl solution, penetrated chlorides convert into silver colored AgCl, which is easily
recorded with the visual observation.
As compared to control concrete, chloride penetrations, in un-activated fly ash mixtures, increased with the increasing fly
ash percentage. Activated fly ash mixes show improvements in durability, because of the lower penetrations than those
observed in mixes without activator and concrete mix. It can be concluded that activator plays useful role in upgrading the
durability of fly ash concretes. Average chloride penetration in each mix are shown in Fig. 8. Activated mixtures with 20 % and
40 % fly ash showed high chloride penetration resistance than control sample by sufficient margin. Activated mixtures with
60 % fly ash also performed better than the control concrete. Fly ash particles rich in alumina compared to cement particles
are very effective in chloride binding [11] and activation with Na2SO4 activator further reduces the connectivity between
capillary and permeable pores.

4.6. X-ray diffraction analysis

It is very well established that portlandite or calcium hydroxide (CH) is a crucial hydration product of Portland cement
and hybrid cements. The amount of free CH present in the binder paste reflects the degree of hydration of binder and it also
reflects the degree of completion of pozzolanic reaction of fly ash particles with CH. Less amount of CH in binder paste
reflects high degree of hydration or degree of completion of pozzolanic reaction. The difference in the amounts of CH in the
characteristics-peaks of XRD patterns between Na2SO4 activated and un-activated pastes (with 40 % fly ash and 60 % Portland
cement) is shown in Fig. 9. A clear difference in characteristic peaks of un-activated and activated pastes is observed. A large
amount of CH is detected in case of un-activated paste, whereas, activated paste shows lesser amount of CH and high amount
of ettringite. Large ettringite production also leads to consumption of CH, as shown in Eq. (1). Besides that, calcium silicate
(CS) formation also slightly increased with the activation. Consumption of quartz in the pozzolanic reaction is also an
indicator of production of more CS. It can be concluded that formation of ettringite and more CS products improves the
strength of Na2SO4 activated mixes, especially at early ages.

4.7. Comparison of cost and carbon footprint of mixes

Unit cost and equivalent carbon emissions of raw materials are given in Table 5. These values of raw materials were used
to calculate cost and carbon footprint of each mix per cubic meter without considering the impact of transportation, see
Fig. 10. Cost of concrete reduces significantly with the rising volume of fly ash. Na2SO4 activator addition increases the cost of

Fig. 6. Variation of porosity and sorptivity coefficient with compressive strength (a) surface plot and (b) regression surface (R2 = 0.85).
 M.A. Nawaz et al. / Case Studies in Construction Materials 13 (2020) e00407 9

Fig. 7. Visual observation of chloride penetration in each mix.

fly ash mixes, but still activated mixes show lower cost than that of the control mix. Similar trends are noticed in carbon
footprint of mixes with the variation in fly ash percentage. This is because fly ash has very low cost and carbon footprint as
compared to Portland cement.
It is not fair to judge the economy of mixes without considering the produced strength (benefit). Therefore, utilizing the
cost and carbon footprints of mixes given in Fig. 10, and compressive strengths of corresponding mixes at 3 and 28-days, cost
per unit strength and carbon footprint per unit strength of all mixes were calculated, see Fig. 11. These results show that with
and without chemical activator, fly ash mixes are economical than that of the control concrete. Considering economic
performance at 3-days, A-F20 and A-F40 are economical than that of the control mix. 60 % fly ash containing mixes are
uneconomical compared to control mix. Whereas, carbon footprint per unit strength of all fly ash mixes is noticeably lower
than that of the control mix with and without activator. At 28-days, lower cost per unit strength is associated with un-
activated fly ash mixes. This is because at later ages, the difference reduces between the compressive strength values of un-
activated and activated mixes. Therefore, the positive role of chemical activation in the economy is noticed at early ages. A
tremendous reduction in the carbon footprint of concrete is also noticed with the rising volume of fly ash at 28-days. At both
3 and 28-days, activation reduces the carbon footprint per unit production of compressive strength. This can be ascribed to a
small increase in carbon footprint with the addition of 2 % Na2SO4 and a significant improvement in compressive strength.
Therefore, positive effect of activation on compressive strength becomes more dominant over the negative effect of
activation on carbon footprint.
10 M.A. Nawaz et al. / Case Studies in Construction Materials 13 (2020) e00407

Fig. 8. Average chloride penetration in each mixture.

Fig. 9. XRD analysis of U-F40 and A-F40 pastes (excluding aggregates); step-length = 0.02, scan-rate = 8
/min and 2u variation = 7-70
.

Table 5
Unit cost and carbon footprint of raw materials (excluding transportation impact).

Raw material Unit costs of raw materials (PKR/kg) Carbon footprint (kg-CO2/kg)
Cement 14 [21] 0.898 [38]
Fly ash 5.5 [21] 0.004 [38]
Sand 0.92 [21] 0.002 [38]
Coarse Aggregate 0.72 [21] 0.053 [38]
Plasticizer 210 [21] 0.002 [38]
Water 0.15 [21] 0
Na2SO4 60* 0.47**

PKR: Pakistani Rupee.

*
Local price.
**
From Ref. [39].
 M.A. Nawaz et al. / Case Studies in Construction Materials 13 (2020) e00407 11

Fig. 10. Cost and carbon footprint of each mixture.

Fig. 11. Cost and carbon footprint of each mix per unit compressive strength.

5. Conclusions

Mechanical and durability properties of a Pakistani fly ash (with low calcium oxide content) was studied with and
without Na2SO4 activator. Following important conclusions are derived from the results:

 No significant drop in mechanical strength (compressive strength and flexural strength) is noticed up to 20 % incorporation
of fly ash w.r.t control concrete. Concretes with 20 % and 40 % fly ash levels perform better than control concrete at 90-days.
Whereas, 60 % fly ash concrete shows only 26 % lower compressive strength than that of the control concrete at 90-days.
Mechanical strength dropped significantly at 3-days and 28-days with the rising level of fly ash. With Na2SO4 activator, 20
% and 40 % fly ash concretes reach the potential of control mix at both 3 and 28-days. The difference between mechanical
strength values reduces between activated and un-activated fly ash mixes with the increasing age of mix. 60 % fly ash
concrete with Na2SO4 activation reached the 89 % potential of control concrete at 90-days.
 Permeability related durability properties (sorptivity coefficient, porosity and chloride penetration) of fly ash concretes
were not badly affected as mechanical properties. Concretes with 20 % and 40 % fly ash show permeability properties
comparable to those of the control concrete especially at 28 and 90-days. Na2SO4 activation further reduced the
12 M.A. Nawaz et al. / Case Studies in Construction Materials 13 (2020) e00407

permeability by blocking the connectivity between the pores owing to consumption of CH in pozzolanic reaction and
ettringite formation. With Na2SO4 activation, 60 % fly ash concrete showed chloride penetration resistance more than that
of the control concrete.
 Cost per unit strength analysis of mixes suggests that both activated and un-activated mixes are economical than control
mix at 28-days. Activated mixes are economical than un-activated mixes only at early age. Whereas, un-activated mixes
become more economical than activated mixes at later ages i.e. 28-days. This is because at later ages, the difference
between the strength values of un-activated and activated mixes reduces. Carbon footprint per unit strength reduces with
the addition of Na2SO4 activator at both early and later ages.

Declaration of Competing Interest

Authors have no conflict of interest to declare.

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