Construction and Building Materials 159 (2018) 567–577

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Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

An overview and experimental study on hybrid binders containing date

palm ash, fly ash, OPC and activator composites
Walid Al-Kutti a, Muhammad Nasir a,b,⇑, Megat Azmi Megat Johari b, A. B. M. Saiful Islam a,
Abdullah A. Manda c, Nawaf I. Blaisi d
a
Department of Civil and Construction Engineering, College of Engineering, Imam Abdulrahman Bin Faisal University, Dammam 31451, Saudi Arabia
b
School of Civil Engineering, Universiti Sains Malaysia, Nibong Tebal 14300, Pulau Penang, Malaysia
c
Department of Basic Sciences, College of Engineering, Imam Abdulrahman Bin Faisal University, Dammam 31451, Saudi Arabia
d
Department of Environmental Engineering, College of Engineering, Imam Abdulrahman Bin Faisal University, Dammam 31451, Saudi Arabia

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Overview on CO2 emission, alternate

cement approaches and date palm
waste is presented.
 Binary and ternary hybrid blend were
prepared by partially replacing OPC
with DPA, GDPA, FA and NaOH.
 Flow, compressive strength, XRD,
TGA, surface area and pore volume
were evaluated.
 Non-hybrid ternary blend performed
better and recommendations for
hybrid binders’ efficiency is made.

a r t i c l e i n f o a b s t r a c t

Article history: Global warming due to high greenhouse gasses emission coupled with excessive energy involved in con-
Received 21 September 2017 crete manufacturing process is indeed an alarming threat. To overcome the problem, numerous
Received in revised form 1 November 2017 researches have been carried out to partially replace ordinary Portland cement (OPC) with supplementary
Accepted 7 November 2017
cementitious materials (SCMs) that includes agricultural or industrial solid wastes, development of alter-
native binder known as geopolymer concrete made of one or more pure SCMs using alkaline activators
and elevated temperature curing or by development of hybrid cement system that incorporates alkaline
Keywords:
activation of OPC-based SCMs. This study aims to: (1) carry out an overview on: CO2 emission by con-
Date palm ash (DPA)
Fly ash (FA)
struction industry; alternate cement systems such as partial replacement, geopolymers and most impor-
Hybrid binder tantly hybrid binders; as well as identification of date palm ash (DPA) as a potential waste material and
Alkaline activation (2) develop novel hybrid alkali activated binders with a combination of agro-industrial waste to form bin-
Strength ary and ternary mortar binders cured under water up to 28-days. The utilized SCMs include fly ash (FA),
Microstructure ground date palm ash (GDPA) i.e. alkali activated or raw DPA i.e. non-activated. These hybrid and non-
hybrid binders were compared through physical properties such as strength and workability along with

⇑ Corresponding author at: School of Civil Engineering, Universiti Sains Malaysia,

Nibong Tebal 14300, Pulau Penang, Malaysia.
E-mail addresses: wasalem@iau.edu.sa (W. Al-Kutti), nasir@student.usm.my,
mnmuhammad@iau.edu.sa (M. Nasir), cemamj@usm.my (M.A. Megat Johari),
asislam@iau.edu.sa (A. B. M. Saiful Islam), aamanda@iau.edu.sa (A.A. Manda),
niblaisi@uod.edu.sa (N.I. Blaisi).

https://doi.org/10.1016/j.conbuildmat.2017.11.017
0950-0618/Ó 2017 Elsevier Ltd. All rights reserved.
568 W. Al-Kutti et al. / Construction and Building Materials 159 (2018) 567–577

microstructural properties by hydration products and pore volume. X-ray diffraction (XRD) technique
was employed to get the mineral composition; phase decomposition of unreacted water, C-S-H/C-A-S-
H gel and Ca(OH)2 had been studied by Thermogravimetric analysis (TGA) while nitrogen adsorption test
determined surface area of particles as well as pore volume of the paste. The results revealed potential
use of DPA as a strong and sustainable material in ternary blend with FA and OPC in conventional
non-hybrid binder that can efficiently maximize clinker replacement without energy utilization in alka-
line activation.
Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction solid stockpiles and landfill, recycling them in concrete results in

minimizing cost of construction as well as reduction in ecological
Strict environmental legislations are being imposed by the glo- imbalance. Technically, they are proven to produce more or less
bal authorities, that are also applicable to concrete industries hav- same concrete resulted thru neat OPC. Several researches have
ing major branches of cement manufacturing plants, ready-mix been done to find out optimum dosage of each SCMs to be partially
plants and pre-cast concrete plants, to cope with the alarming mixed with OPC, effects on mix design and exposure conditions.
threat of global warming, climatic changes and ozone layer deple- For instance, Shamshad et al. [13] proposed compliance criteria
tion due to high greenhouse gasses emission and excessive energy for 100% OPC, 7.5% SF and 20% FA concrete by varying cementitious
involved in its manufacturing process [1,2]. The boom of concrete material content and w/cm ratio. The results of compressive
construction is worldwide growing exponentially resulting in esti- strength and durability properties of SF cement concrete was found
mated concrete consumption per capita of about 1 m3 which uses a superior. ACI committee 305 specifies fresh concrete temperature
huge amount of cement, a primary construction material [3]. Glob- limit of 35 °C while Nasir et al. [14,15] recently studied the perfor-
ally, cement plants are responsible for about 3.5% [4] to 5% [5] of mance of plain and blended cement concretes cast at in-situ tem-
total anthropogenic carbon dioxide (CO2) discharge with an inten- perature of 25–45 °C. They found that compared to neat OPC,
sity of 222 kg/ton of cement production [6]. It is further reported partial replacement of SCMs including 10% SP, 30% FA, 70% GGBFS,
that cement industries are estimated to discharge up to 1.5 billion 7% SF and 20% NP results better at higher temperature. A review on
tons per year of CO2 into the atmosphere [7] and each year it will waste products used as SCMs to replace OPC concluded that some
remain increasing at the rate of almost 6% from 1988 to 2015 [8]. SCMs like FA, SF and GGBFS have already proven advantageous.
Moreover, it is estimated that production of every ton of traditional However, there is a growing demand for identifying underutilized
cement emits nearly same quantity of CO2 into the atmosphere waste product and to partially incorporate with or to replace OPC
among which amount of CO2 through combustion of fossil fuel in that may potentially serve for the benefits of built infrastructure
the kiln operation, production process and the transportation of and the environment [16].
cement accounts for 40%, 50% and 10%, respectively [9]. In fact, Incorporation of SCMs as an alternative alkaline activated bin-
chemical and fuel burning process in cement manufacturing emits der (AAB) also known as geopolymer has been continuously gain-
50% and 40% of CO2, respectively into the atmosphere [5]. It is ing popularity since last two decades as it is 100% OPC free. The
reported that addition of 30% FA as ordinary Portland cement term ‘‘geopolymer” was first introduced by Davidovits in 1999
(OPC) replacement can reduce 30% of CO2 emission [10]. According [17] and AAB have been developed by incorporating source mate-
to the US Portland Cement Association (PCA) [11], different cement rials which are chemically inorganic in nature and rich in silica (Si)
type manufacturing of each ton releases approximate CO2 as fol- and alumina (Al) [18]. However, the relevant research on this topic
lows: (a) Ordinary Portland cement – 1.02 tons/ton, (b) Fly ash- was started during late 1930s by Feret [19] and Purdon [20].
based cement – 0.014 ton/ton, (c) Geo-polymer cement by slag Recently, Hossain et al. [21] reviewed 92 papers of last decade
production – 0.31 tons/ton and (d) Geo-polymer cement thru by- focusing on the durability of concrete and mortar prepared with
product of slag = 0.21 ton/ton. alkali-activated pozzolanic binder. They concluded that fly ash
In this regard numerous researches have been carried out by (FA), blast furnace slag (BFS), metakaolin (MK), rice husk ash
concrete technologists and they started sustainable construction (RHA) and palm oil fuel ash (POFA) has been extensively studied
practice in these three common ways: (1) partially replacing OPC (both individually or blending with different activators and con-
with one or more supplementary cementitious materials (SCMs) centrations) to improve various properties of binder as compared
that includes agro-industrial solid wastes such as palm oil fuel to traditional cement specimens that enabled lowering disposal
ash (POFA), rice husk ash (RHA), date palm ash (DPA), fly ash (FA), problem associated with waste products, reduction in traditional
natural pozzolan (NP), silica fume (SF), ground granulated blast fur- cement consumption, minimizing overall construction cost and
nace slag (GGBFS), superpozz (SP) and metakaolin (MK); (2) devel- decreasing CO2 discharge. Pacheco-Torgal et al. [22] reviewed 70
oping alternative binder known as geopolymer concrete that may research papers concerning durability aspect of alkali-activated
made of one or more SCMs using alkaline activators and require ele- binders and discussed its advantages and disadvantages based on
vated temperature curing; (3) developing hybrid cement binder the test properties that includes: acid attack, alkali–silica reaction,
that requires partial replacement of SCMs to OPC along with alka- reinforcement corrosion, resistance to elevated temperature, fire
line activation. There are other techniques being also adopted for and freeze–thaw and efflorescence. Several researchers have inves-
minimizing the CO2 emission by concrete industries such as captur- tigated effect of alkaline activation of various 100% SCMs or their
ing CO2, use of alternate fuel source or modifying process of clinker blends, such as with FA [23], with NP [24], with GGBFS [25], with
manufacturing at cement plant, however, substitution of clinker by MK [26], with RHA [27] and with POFA [28]. Among these SCMs,
alternate SCMs is the most effective and economical solutions that FA is most widely used source material owing to its availability
can be easily applicable to the ready-mix plant [3,12]. in abundance, more economical and high potential for geopolymer
Utilizing the SCMs as partial replacement has been continu- development [29].
ously studied since last 3 decades due to its economical, ecological An advanced innovative approach being recently researched is
and technical benefits. As these are waste products that requires hybrid cement which can be developed by combining alkaline
 W. Al-Kutti et al. / Construction and Building Materials 159 (2018) 567–577 569

Fig. 1. Schematic diagram of manufacturing process and stages of ternary hybrid cement [Courtesy: Bo Qu et al.].

SCMs to OPC [30–32]. In hybrid system, more OPC is possible to between 20 and 60% replacement ratio) generated mainly (N,C)–
replace with SCMs such that concrete mixture with even less than A–S–H and less (N,C)–S–H gels even at 20% FA replacement
30% OPC or clinker can be formed [33–35]. Fig. 1 shows the stages whereas, municipal solid waste incinerator ash (MSWI) did not
of hybrid cement production consisting of ordinary Portland clin- produce (N,C)–A–S–H at any replacement level when activated
ker, GGBFS, FA and alkaline activators at an American plant [36]. thru 5% (by weight) mixture of Na2SO4 and CaSO4 [42].
Alkaline activator in hybrid system helps compensating the dilu- Among agricultural waste, RHA and POFA are mainly focused in
tion effect of OPC and these systems are possible to develop research. However, date palm tree is considered as one of the old-
through alkali activated (AA) OPC-Slag cement, AA OPC- est and highest number of trees on earth. It is estimated that
Phosphorus slag cement, AA FA cement and AA multiple-SCMs around 105 million trees of several types of date palm exists [43]
blended cements [32]. Hybrid cementitious materials are reported and typically each tree generates waste of 25 leaves per season
to achieve improved mechanical and durability characteristics [44].
even at early ages [37,38] while presence of hydration products In civil engineering application, the use of date palm is very lim-
differ with OPC-based materials and it entirely depend on source ited. For instance, Khellou et al. [45] initiated the utilization of date
material or aluminosilicate precursor utilized. Garcia-lodeiro palm ash (4–12%) blended with gypsum-calcareous materials
et al. [39] found several hydration products formed in hybrid bin- (crusting tuff) to investigate the mechanical characteristics in the
ders such as calcium silicate hydrate (C-S-H) due to hydration of pavement construction of Algeria. The authors recommended the
OPC with water, sodium aluminosilicate hydrate (N-A-S-H) which potential scope in extending their research from the findings that
is primary outcome of AA of alumina and silica as well as calcium 8% ash replacement results optimum mix that can significantly
aluminosilicate hydrate (C-A-S-H) and (N,C)-A-S-H gel which enhance the mechanical properties in terms of compressive
depend on the pH and ratio of content of silica/alumina and cal- strength and bearing index. Additionally, Al-Kutti et al. [46] incor-
cium/silica in these systems. Paloma et al. [37] compared hybrid porated the date palm ash (DPA) by partially replacing (10, 20 and
binder and non-AA binder prepared with FA, GGBFS and 20% 30%) Type I cement in concrete and mortar. They found that 10%
OPC. The results of hybrid binder showed 50% more compressive DPA dosage significantly enhance the mechanical and durability
strength at early age, less heat of hydration and lower setting time properties as compared to 100% OPC specimens. Recently, Gunar-
due to the presence of C-A-S-H, N-A-S-H and (N,C)-A-S-H gels. For- ani and Chakkravarthy [47] studied the suitability of date palm
mation of such gels were also noticed in another study that pro- seed ash (DPSA) by partially replacing conventional cement at an
duced hybrid binder blended with 70% FA and 30% OPC [39]. interval of 2% up to 10% and evaluated strength, water absorption,
Murillo et al. [40] developed hybrid binder based on alkali- sorptivity and alkalinity of mortar specimens in India. The results
activated (AA) ceramic tile waste (CTW) and OPC. They optimised indicated that 4% DPSA was optimum dosage of replacement to
the molar ratios of silica/alumina and sodium oxide/silica and OPC while 2% and 8% replacement level can be beneficially used
achieve 28-day compressive strength of 58.15 MPa due to densifi- for construction requiring higher acid resistance and bond
cation of binder because OPC was used as a calcium source that strength, respectively.
formed C-A-S-H gel and also because of AA of CTW. Angulo- In the light of above cited literature, it can be admitted that
Ramírez [41] studied the kinetic, mechanical and microstructural cement is an essential element for providing the basic shelter to
characteristics of 80% OPC + 20% GGBFS hybrid binders AA by luxurious life of human being. Since traditional cement is one of
NaOH and NaSiO2 + NaOH that resulted in, respectively 4.5 and the major cause for depleting natural resources, emitting CO2 into
10.8 times higher compressive strength at 1-day curing as com- the atmosphere and consuming large amount of energy during the
pared to 100% OPC. Their hybrid cement also showed reduction entire phase of its production, there is a vast scope and promising
in heat of hydration and denser microstructure producing C-S-H, future of locally available agro-industrial waste that may offer eco-
C-A-S-H and hydrated gehlenite. In summary, the maximum possi- nomical and sustainable construction along with improved dura-
ble replacement level of waste materials and nature of gels gener- bility as compared to traditional cement construction. The review
ated in hybrid system is highly dependent on nature and type of of the literature shows that there are several agro-industrial mate-
waste product incorporated as well as concentration and type of rials utilized by researchers as partial replacement and developing
activator used. For instance, FA-based hybrid cement (studied alkali activated binders that are historically proven fit for construc-
570 W. Al-Kutti et al. / Construction and Building Materials 159 (2018) 567–577

tion purposes. However, no study investigated the date palm ash as 2.1.2. Pre-treatment for hybrid binder
a binary and ternary blend and use of activated SCMs in the pres- To improve the properties of binder, DPA was first ground to increase the sur-
face area and hence pozzolanicity. Grinding was carried out in a laboratory grinder
ence of OPC to develop hybrid binder without oven curing. Hence, at medium speed for 15 min and at high speed for another 10 min, for a quantity of
most date palm waste are stockpiled as landfill or burnt as these 100 gm DPA in each cycle, such that ground DPA (GDPA) passed through # 200
trees are abundantly available in Arab countries that are already sieve (75 mm). Secondly, unburnt carbon was measured by putting the GDPA sam-
rich with fossil fuel resources and generate electricity from it, ple in Sterilization Binder oven (accuracy ± 1.5 °C) at 110 °C for 24 h to eliminate
the moisture and thereafter exposing the sample in Nabertherm Muffle furnace at
unlike Malaysia. However, at some places in Saudi Arabia the date
the rate of 5 °C/min and next programmed to expose at constant temperature of
palm waste is collected to form wood which is later burn at high 700 °C for 1 h period. Unburnt carbon was calculated from the differences in origi-
temperature in oven to form fire coal that generates DPA which nal weight and weight of sample after calcination process and expressed as percent-
is being considered as waste product. Therefore, utilizing the date age. This calcination process resulted in 2.5% un-burnt carbon in GDPA enabling it
palm ash in construction sector can offer improved binder proper- suitable for use in concrete production. Study [50] showed that removal of unburnt
carbon through calcination process partly transforms the amorphous structure of
ties along with creating sustainable built environment to a large geopolymer into crystalline phase. Thirdly, sodium hydroxide pellets were
extent. employed to prepare solution of 8 M NaOH solution in water and it was allowed
In this vein, this study aims to utilize 10% DPA or 25% FA as par- to cool down for 1 day because of exothermic reaction. Similar methodology have
tial replacement of OPC to form hybrid binary blend and combina- been adopted in previous study for its effectiveness on eliminating unburnt carbon
on POFA [51].
tion of DPA, FA and OPC to form a hybrid ternary blend in order to
maximize the reduction of OPC amount in mortar mixtures. Fur-
ther, mixtures with DPA were pre-treated with grinding and calci- 2.1.3. Mixture proportion and preparation of specimens
nation process, represented as GDPA, and these mixtures were In all mixtures desert sand was used as fine aggregate having specific gravity of
2.82 and water absorption of 0.7%. 10% DPA or GDPA [46] and/or 25% FA [52]
added with 8 M NaOH solutions as partial replacement of mix
cement dosage was used to partially replace OPC in binary and ternary mixtures.
water along with the presence of OPC to avoid oven curing and The ratio of cementitious materials to sand and w/cm ratio was maintained con-
to study the effect of alkali-activated solution on OPC-agro- stant as 1:2.75 and 0.485, respectively, as per ASTM C 109 [53]. 8 M NaOH solution
industrial-based cement. The effect of representative fresh and [54] was used in hybrid mixtures (M3 and M6) by an amount of 0.302 ml per gram
mechanical properties in terms of flow and compressive strength of GDPA. Table 2 shows the mix proportion of mortar and paste. A total of 6 mixes
were prepared. M1 is a control mix with 100% OPC. M3 and M6 are hybrid binder
was evaluated. In addition, characterization tests were conducted having addition of alkali-activated NaOH solution and rest of the mixes are non-
to study the microstructure of the paste. hybrid binders. M2 to M4 are binary binders and M5 and M6 are ternary binders.
4.73 L bowl capacity mortar mixer having planetary and revolving action type
paddle was employed for preparing mortar as follows, according to ASTM C 305
2. Materials and methods [55]. First, water and/or NaOH solution was filled into the mixing bowl then OPC
and/or SCMs were introduced then sand was added. The ingredients were mixed
2.1. Materials for 6–8 min. After mixing, flow was measured and mortar was filled in two layers
to 50 mm cubical moulds and vibrated each layer for 10 s. The top surface was lev-
2.1.1. OPC and SCMs elled with trowel, covered with plastic sheet and placed at laboratory temperature
Type I – ordinary Portland cement (OPC) confirming to ASTM C 150 [48] was (25 ± 2 °C) to set. The specimens were demoulded after 24 h, and immersed in
used in preparation of all mixtures. Class F Fly ash confirming to ASTM C 618 water for curing till the age of compressive strength and microstructural tests.
[49] was procured from Saudi Ready-mix Company. Date palm ash (DPA) was pro-
cured from recycling date palm factory in the Eastern part of Saudi Arabia where
date palm waste is collected from the surroundings. These palm waste is grinded 2.2. Test methods
and compressed to make wood which are later burnt in an oven at high tempera-
ture to prepare coal while the residue is again a waste product known as DPA. 2.2.1. Chemical composition analysis
Raw DPA was sieved to exclude the unwanted large particle size of coal waste As shown the chemical composition in Table 1, the highest silica content was
and material retained on # 100 (150 mm) and # 200 (75 mm) sieve size was utilized found in FA followed by DPA and OPC, respectively. CaO content is found most in
in DPA mixes. The specific gravity of OPC, FA and DPA was 3.15, 2.10 and 2.43, OPC while alumina content is highest in FA cement. Other oxides are present in
respectively. Table 1 shows the chemical composition of plain and precursor small quantities with marginal difference in all cements.
cementitious materials.

2.2.2. Surface area and pore volume

Table 1
The surface area, pore volume and pore radius of the paste were measured after
Chemical composition of OPC and SCMs.
28 days of curing. Pore structure was studied by QuantachromeÒ ASiQwinTM – Auto-
Parameter Weight (%) mated Gas Sorption Data Acquisition and Reduction instrument thru liquid
nitrogen.
OPC DPA FA
SiO2 20 35.93 46.5
Fe2O3 3 0.78 2.37 2.2.3. Flow
CaO 63 13.04 8.38 Mortar flow of each mix was measure as per ASTM C 1437 [56]. In this test, flow
Al2O3 6 0.65 35.3 mould was centred on the flow table. Immediately after mortar mixing, flow mould
MgO 1.5 6.36 1.86 was filled in two layers each being compacted by tamper for 20 times and cut off
K2O 0.5 7.4 0.57 the excess mortar by means of steel blade trowel. Thereafter, mould was gradually
Na2O 0.5 3.6 0.4 lifted in upward direction and flow table was dropped for 25 times. Finally, the
Na2O + 0.658K2O 0.83 8.47 0.78 resulting base diameter was recorded and increase in mould base diameter of the
LOI 0.73 8.41 3.5 mortar mass is expressed as the percentage of the initial base diameter (100
mm). According to European standard EN 1015-6:1999, the final diameter is an

Table 2
Mixture proportion.

Mix ID Mix Proportion OPC (kg/m3) DPA (kg/m3) GDPA (kg/m3) FA (kg/m3) Sand (kg/m3) NaOH solution (kg/m3) Free water (kg/m3)
M1 100% OPC 666.67 – – – 1833.33 – 323.33
M2 10% DPA + 90% OPC 600 66.67 – – 1833.33 – 323.33
M3 10% GDPA + 90% OPC 600 – 66.67 – 1833.33 20.13 303.20
M4 25% FA + 75% OPC 500 – – 166.67 1833.33 – 323.33
M5 10% DPA + 25% FA + 65% OPC 433 66.67 – 166.67 1833.33 – 323.33
M6 10% GDPA + 25% FA + 65% OPC 433 – 66.67 166.67 1833.33 20.13 303.20
 W. Al-Kutti et al. / Construction and Building Materials 159 (2018) 567–577 571

indicator of consistency as follows: (1) <140 mm – dry consistency, (2) 140 mm– 0.10
200 mm – plastic consistency and (3) >200 mm – fluid consistency. This diameter M1 M2 M3
is the representative of the mortar workability [57]. M4 M5 M6
0.08
2.2.4. Compressive strength

Pore volume (cc/g)

Compressive strength was determined on 50 mm cubic specimens, according to 0.06
ASTM C 109. Mortar specimens were taken out from water tank at 3, 7 and 28 days
of curing and compressive strength was measured at constant loading rate. At each
age, four specimens were tested from each batch and their average values were 0.04
reported.

0.02
2.2.5. X-ray diffraction (XRD) analysis
In this study, XRD technique was employed to get the mineral composition of
the pulverized paste sample at the age of 28 days using Rigaku’s Ultima IV X-ray
0.00
Diffractometer. Analysis was run through Cu Ka radiation source at an acceleration
9 90 900
voltage of 40 kV and 40 mA current whereby X-ray intensity readings were
Radius (Å) [log scale: base 10]
recorded at a scanning rate of 2.5°/min between the angle of incident X-ray ranging
from 10 to 100 degrees (2h) thus producing series of peaks.
Fig. 3. Pore volume variation with pore radius in all mixture.

2.2.6. Thermogravimetric analysis (TGA)

This technique was used to study phase decomposition of: unbound evapora- Table 3
tion of water, formation of C-S-H/C-A-S-H gel and consumption of Ca(OH)2. This test Summary of nitrogen adsorption test results.
was performed after 28 days on paste specimens by means of TGA-50 type detector.
TGA readings were measured at every second until the temperature of paste spec- Mix ID Pore radius (Å) Surface area (m2/g) Pore volume (cc/g)
imens reaches 599 °C.
M1 18.128 31.90 0.051
M2 18.181 10.98 0.046
M3 18.176 31.50 0.061
3. Results and discussion
M4 18.163 40.78 0.071
M5 18.177 30.60 0.062
3.1. Surface area & pore volume M6 19.135 46.20 0.075

Figs. 2 and 3 shows the variation in surface area and pore vol-
ume of the pastes with respect to pore radius, respectively. The all binders from M3 to M6 as 19.5, 39, 21.5 and 47%, respectively
summary of surface area, pore volume and pore radius of the while pore volume in M2 reduced about 9.5%. The increased poros-
pastes in all mixtures is presented in Table 3. From the data in ity with increase in surface area may be attributed to the non-
Table 3, it can be noticed that a linear correlation exists between uniform packing and inadequate dispersion of finer/variable size
surface area and pore volume among all mixture with a R-square particles in the binary and ternary paste matrix. A study [59] on
value of more than 0.8. The direct relationship between the surface fineness of FA also confirmed thru mercury intrusion porosimetry
area and pore volume for a constant w/cm ratio would be the con- test wherein the gel porosity marginally increases with increase
sequence of increased water demand in the hybrid binder that may in fineness of FA in blended cement paste mixes at all FA replace-
result in porous structure. Further, the results indicated that the ment level between 20 and 40% by weight to OPC. However, some
average pore radius of all the mixture was about 11.5 Å with slight contradictory research also exits in this vein. For instance, it is also
variation. However, the surface area of control mix was noted to be reported that the surface area tends to increase up to 44 m2/g but it
31.90 m2/g which was 65% reduced with the addition of coarser is due to the presence of high unburned carbon content of up to
DPA in M2 while the pre-treatment in M3 increased the fineness 19% [60]. Moreover, researchers [61] termed FA as ‘‘micro-
of paste and, hence, hybrid binary binder resulted in comparable aggregate” that can impart positive particle packing effect in the
surface area as in control mix. Likewise, the surface area of binary binder matrix resulting in pore structure refinement. Nonetheless,
mix M4 was noted to be 40.78 m2/g that indicates FA cement par- it is suggested that the surface area in the range of 16 and 136 m2/g
ticles were smaller than OPC while the addition of DPA and GDPA can be achieved with BET method in FA or other powdered SCMs
in M4 resulted in 25% reduction and 13% increment in surface area ensuring its reliability in the field of concrete technology [51,62].
of M5 and M6 paste, respectively [58]. The pore volume of the con-
trol mixture paste was recorded as 0.051 cc/g which increased in
3.2. Flow

60 Fig. 4 shows the percentage of mortar flow from the original

M1 M2 M3
M4 M5 M6 mortar filled in flow mould and cut-off limits for consistency based
50 on flow diameter. For the same w/cm ratio in both alkaline acti-
Surface area (m²/g)

vated and non-alkaline activated mixtures, the flow in M3 and

40 M5 was comparable to M1 (control – 100% OPC mix) being approx-
imately 44%. The highest flow was measured in M4 (51.2%) consist-
30 ing of 25% FA + 75% OPC while the flow of M2 was relatively stiff
(41.2%). Hybrid mixes (M3 and M6) prepared with alkaline activa-
20
tion resulted in more flow as compared to the same non-hybrid
mixtures (M2 and M5). The difference between M2 and M3 was
10
6% while it was 10% among M5 and M6. As compared to control
mix, the flow in DPA-based binders (M2 and M3) was 7.5 and
0
1.5% less while the flow in FA-based binders (M4, M5 and M6)
9 90 900
Radius (Å) [log scale: base 10] was about 15, 0 and 11.5% higher, respectively. The final mortar
flow diameter was measured between 150 and 205 in all mixture
Fig. 2. Surface area variation with pore radius in all mixture. such that M1 to M6 accounts for 180, 170, 178, 205, 180, 198
572 W. Al-Kutti et al. / Construction and Building Materials 159 (2018) 567–577

55 that rate of strength development in M1 and M3 was minimum

So > 200 mm flow dia. and it was generally highest in FA-based binders (M4–M6). For
50
instance, the difference in compressive strength at 3 and 28 day
45 Plasc was 8.8, 13.8, 6.3, 20.2, 15.8 and 19.2 MPa among M1 to M6,
Mortar flow (%)

40
respectively. It indicates that FA produces secondary hydration at
later ages. This is in agreement with a study [68] that explained
35 that the overall quality of final SCM product is governed by both
30 cementing efficiency which FA cement exhibit considerably low
Dry strength at early ages by reacting as a filler material and pozzolanic
25 reaction which is highly dependent on chemical composition spe-
20 cially the amount of Alumina and Silica in FA cement and become
M1 M2 M3 M4 M5 M6 active by Portlandite (CH) formed during the hydration reaction
Mix ID thus producing extra hydrated gel. This secondary hydration pro-
duct fills the capillary pores in cement-based materials and
Fig. 4. Mortar flow in all mixture.
enhance the strength. Studies [69,70] reported that low early age
strength and reactivity of FA cement can be significantly improved
by reducing the water to binder ratio, varying the dosage of FA and
curing temperature. The higher rate of strength development in
and 150 mm average diameter, respectively. This indicates that the
FA-based mixture is in agreement with similar study that
consistency of all mortar lies under the category of plastic state
addressed that the potential pozzolanic activity and quick hydra-
excluding M4 which was slightly higher than 200 mm falling under
tion reaction can be achieved because of relatively large specific
the range of fluid consistency [57]. The beneficial role of FA-based
surface area or finer FA particles [71]. Further, the lower strength
mixtures to increased fluidity is mainly attributed to the ball bear-
in hybrid binders is possibly due the insufficient molarity of NaOH
ing of FA particles owing to its spherical shape that facilitates
solution and absence of Na2SiO3 alkaline activators as reported by
movement of adjacent particles and provide plasticizing effect
several researchers. Salami et al. [28] revealed that 12 M NaOH(aq)
[63–65]. It is also in close agreement with the studies [63] that
results in better durability in engineered alkaline activated POFA
confirmed enhanced plasticizing effect in FA cement is due to its
mortar mix as compared to those prepared with 10 and 14 M
lesser specific gravity as compared to OPC that results in more
NaOH(aq). Similarly, Memon et al. [72] also studied the effect of
paste volume as well as because of slow rate of hydration reaction
NaOH concentration between 8 and 14 M and found positive effect
and gel formation at early age. Further, the reduction in flow
of NaOH concentration up to 12 M on strength. Because increase in
spread in M5 and M6 ternary mixtures is probably due to the addi-
NaOH concentration tends to increase the solubility of aluminosil-
tion of non-spherical and non-uniform DPA particles to the FA and
icate in cements [73] that results in high compressive strength of
OPC. Such findings were also reported in GGBFS-FA based geopoly-
geopolymer mortar and concrete [74,75]. However, highly alkaline
mer concrete wherein consistency decreased with inclusion of
solution may significantly influence the hydration process of OPC
GGBFS content by 30% in 400 kg/m3 binder content due to the
which retards the formation of gel products [76,77]. Further, com-
accelerated hydration reaction of Ca species and the angular parti-
bination of NaOH and Na2SiO3 found to be effective alkaline activa-
cles of GGBFS compared to the spherical shape of FA [66,67].
tors in enhancing the compressive strength and other concrete
properties by their dissolution feature of source material that
3.3. Compressive strength results in better bond between mix constituents and forms almost
pore less structure, as highlighted in researches [29,74,78].
Fig. 5 shows the development of compressive strength of mor-
tar specimens with period of curing. Compressive strength varied 3.4. X-ray diffraction (XRD) analysis
among each mix and with age. Control mix (M1) resulted in max-
imum compressive strength at all ages. At the early age of 3 days, Fig. 6 shows the X-ray diffractograms of M1 and M3 to M6
compressive strength in M1 was found to be 55.3 MPa which is 22, pastes. The XRD patterns represent high amorphous and partial
19, 25, 39 and 42% more than M2, M3, M4, M5 and M6, respec- crystalline structure between the 2-theta ranging from 15 to 68
tively. Similarly, compressive strength at the later age of 28 days degree while such high peaks were commonly noted in the range
was found to be 64.1 MPa which is 11, 20, 3, 23 and 20% more than of 20–40 degree in all mixtures [24,79,80]. The spectra peaks in
M2, M3, M4, M5 and M6, respectively. However, it can be noticed all mixture were matched and identified from the pattern diffrac-
tion files (PDFs) and literature based on the XRF results and
expected outcomes. The appeared phases include quartz (SiO2)
[PDF Card # 00-014-0654], cristobalite (Cr) [60], calcite (CaO)
70 [PDF Card # 01-072-1937] [24,81,82], anorthite (A) also known
3 day
as C(A)-S-H (CaAl2Si2O8) [54], mullite (2Al2O3.SiO2) [PDF Card #
Compressive Strength, MPa

7 day
60
28 day 00-015-0776] [83], hematite (Fe2O3) [PDF Card # 00-001-1053]
50 [83] and calcium silicate hydrate (C-S-H) [25,81,82,84].
The XRD patterns illustrates that the presence of C-S-H in the
40 matrix along with the polymeric gel formed as anorthite is due
to the addition of aluminosilicate-rich DPA and FA cementitious
30
material that tend to enhance the strength and microstructural
20 characteristics of the binary and ternary binder [29,85,86]. Further,
Higher Na and Ca in DPA with respect to FA cement prompted the
10 C-S-H formation which might have been replaced Ca (from C-S-H)
M1 M2 M3 M4 M5 M6
Mix ID with Na and also Al (from FA) by Ca to convert into N-A-S-H and C-
A-S-H gel, respectively that mainly contributes to the strength of
Fig. 5. Development of compressive strength in all mortar mixture. matrix in M5 [87].
 W. Al-Kutti et al. / Construction and Building Materials 159 (2018) 567–577 573

Fig. 6. X-ray diffractogram. [Q: quartz, Cr: cristobalite, C: calcite, A: anorthite, M: mullite, H: hematite, C-S-H: calcium silicate hydrate.]

High Ca source in SCMs (13 and 8.4% in DPA and FA, respectively et al. [89] observed that more C-S-H crystals are likely to form
in this study) has been reported to play positive role in strength when both NaOH and Na2SiO3 were used as alkaline activators in
development under alkaline environmental condition [88]. Moon contrast to mix prepared with only NaOH solution. The low
574 W. Al-Kutti et al. / Construction and Building Materials 159 (2018) 567–577

amount of cations in NaOH alkaline solution and absence of Na2- the main hydration product, a mix of cementitious gels C-(A)-S-
SiO3 lead to the insignificant improvement in strength in hybrid H + C-A-S-H. These gels take up a larger portion of aluminium
ternary binders along with insufficient extent of dispersion of and are intensely polymerised than traditional C-S-H gel in the
SiO2 in the form of quartz and cristobalite, as depicted in XRD spec- presence of good activator, which is in close agreement with the
tra of M6 compared to other mixes. XRF analysis also indicated that previous study [36].
SiO2 to Al2O3 ratio in FA was 1.32 which was compensated by addi-
tion of DPA having such ratio of approximately 55.30. TGA results
also confirmed that the hydrated gel was generated less in hybrid 3.5. Thermogravimetric analysis (TGA)
ternary binder as compared to M5. Davidovits have also empiri-
cally proven that the mechanical strength and polymerization pro- Fig. 7 shows the 28-day TGA curves of all paste mixtures with
cess to form extent of C-S-H is based on high concentration of respect to temperature. Fig. 8 and Table 4 summarizes the total
alkaline solution that enables dissolution of Si and Al ions in the weight loss from room temperature (25 °C) to up to 599 °C. The
FA-based binder, SiO2 to Na2O ratio in alkaline activator, amount maximum total weight loss was recorded in M1 = 10.87% followed
of Ca in source materials and SiO2 to Al2O3 ratio in source by M4, M5, M6, M3 and M2, respectively in decreasing order such
materials. Hybrid cement owes its good mechanical strength to that the trend resembles with that in compressive strength of mor-
tar. During phase I, evaporation of unbound mix water/NaOH solu-
tion taken place at weight loss interval between 25 and 105 °C. The
results indicate that the higher the unbound water, the lower
102 amount of water was required for achieving maximum degree of
M1 M2 M3 hydration reaction. In other words, highest amount of chemically
100 M4 M5 M6 bound water and hydration progress was noticed in mixes pre-
pared with any SCMs [90] but it is not necessary that degree of
98
hydration and amount of bound water have a direct relationship
TGA (%)

96 [91]. This is also well-documented that SCMs are sensitive to water

both as a mix water and at the time of curing due to the facts that
94
their particle size is small and surface area is higher as compared to
92 OPC that increases their water demand [92,93]. It is further noted
that hybrid mixtures M3 and M6 utilized less amount of free water
90 to complete hydration reaction because of the contribution of
NaOH solution in it as partial replacement of water that chemically
88
accelerates the hydration reaction fulfilling the water demand.
0 100 200 300 400 500 600 700
Temperature (°C) Quantitatively, the unbound water in M2 to M6 ranged between
7 and 42% lesser than control mix. During phase II, decomposition
Fig. 7. Weight loss curve in all mixture. of hydration products (C-S-H and C-A-H) taken place at weight loss
interval between 110 and 300 °C. The most C-S-H and C-A-H gel
was found in FA-based mixtures (M4 to M6) which may be the
consequence of secondary hydration reaction at later stages and
12.0 formation of extra gel [94]. It can be justified from the compressive
10.5
M1 M2 M3 M4 M5 M6 strength data wherein the rate of strength development from 3 day
to 28 day was recorded highest in FA-based mixtures. The TGA
9.0 weight loss in M2 and M3 was minimum that means less hydrated
Weight loss (%)

7.5 gel produced and less strength development. During phase III,
dehydroxylating of portlandite taken place at weight loss interval
6.0
between 450 and 550 °C. It can be noticed that consumption
4.5 amount of CaOH2 in SCMs is directly proportional to the formation
of C-S-H gel in phase II due to pozzolanic reaction, excluding the
3.0
opposite trend in control mix that does not proceed with sec-
1.5 ondary hydration. Phase III thus validates phase II in that port-
landite was most consumed in mixture M2 to M6 by pozzolanic
0.0
Total wt. loss Phase I Phase II Phase III reactivity and produced further C-S-H and C-A-H gel while OPC
mix did not utilize the CH formed after hydration reaction and
Fig. 8. Total weight loss and loss during each phase. resulted in low rate of strength development.

Table 4
Summary of total weight loss and loss during each phase.

Mix ID Total weight loss (%) Phase I Phase II Phase III

25–110 (°C) evaporation of 110–300 (°C) decomposition of 450–550 (°C) decomposition of
unbound mix water/NaOH C–S–H and C–A–H Ca(OH)2
WL% (WL/WL in OPC) WL% (WL/WL in OPC) WL% (WL/WL in OPC)
M1 10.87 4.80 1.00 3.67 1.00 1.56 1.00
M2 7.38 2.81 0.58 2.68 0.73 0.90 0.58
M3 9.42 4.44 0.93 2.87 0.78 1.37 0.88
M4 10.62 4.04 0.84 4.64 1.26 1.17 0.75
M5 10.24 3.94 0.82 4.74 1.29 0.91 0.59
M6 9.70 4.39 0.92 3.93 1.07 0.73 0.47
 W. Al-Kutti et al. / Construction and Building Materials 159 (2018) 567–577 575

4. Conclusions 2017-314-Eng. Support from School of Civil Engineering at Univer-

siti Sains Malaysia is also acknowledged.
Based on the thorough studies following conclusions can be
drawn:

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