Construction and Building Materials 159 (2018) 567–577

Contents lists available at ScienceDirect

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

Strict environmental legislations are being imposed by the glo-
bal authorities, that are also applicable to concrete industries hav-
ing major branches of cement manufacturing plants, ready-mix
plants and pre-cast concrete plants, to cope with the alarming
threat of global warming, climatic changes and ozone layer deple-
tion due to high greenhouse gasses emission and excessive energy
involved in its manufacturing process [1,2]. The boom of concrete
construction is worldwide growing exponentially resulting in esti-
mated concrete consumption per capita of about 1 m3 which uses a
huge amount of cement, a primary construction material [3]. Glob-
ally, cement plants are responsible for about 3.5% [4] to 5% [5] of
total anthropogenic carbon dioxide (CO2) discharge with an inten-
sity of 222 kg/ton of cement production [6]. It is further reported
that cement industries are estimated to discharge up to 1.5 billion
tons per year of CO2 into the atmosphere [7] and each year it will
remain increasing at the rate of almost 6% from 1988 to 2015 [8].
Moreover, it is estimated that production of every ton of traditional
cement emits nearly same quantity of CO2 into the atmosphere
among which amount of CO2 through combustion of fossil fuel in
the kiln operation, production process and the transportation of
cement accounts for 40%, 50% and 10%, respectively [9]. In fact,
chemical and fuel burning process in cement manufacturing emits
50% and 40% of CO2, respectively into the atmosphere [5]. It is
reported that addition of 30% FA as ordinary Portland cement
(OPC) replacement can reduce 30% of CO2 emission [10]. According
to the US Portland Cement Association (PCA) [11], different cement
type manufacturing of each ton releases approximate CO2 as fol-
lows: (a) Ordinary Portland cement – 1.02 tons/ton, (b) Fly ash-
based cement – 0.014 ton/ton, (c) Geo-polymer cement by slag
production – 0.31 tons/ton and (d) Geo-polymer cement thru by-
product of slag = 0.21 ton/ton.
In this regard numerous researches have been carried out by
concrete technologists and they started sustainable construction
practice in these three common ways: (1) partially replacing OPC
with one or more supplementary cementitious materials (SCMs)
that includes agro-industrial solid wastes such as palm oil fuel
ash (POFA), rice husk ash (RHA), date palm ash (DPA), fly ash (FA),
natural pozzolan (NP), silica fume (SF), ground granulated blast fur-
nace slag (GGBFS), superpozz (SP) and metakaolin (MK); (2) devel-
oping alternative binder known as geopolymer concrete that may
made of one or more SCMs using alkaline activators and require ele-
vated temperature curing; (3) developing hybrid cement binder
that requires partial replacement of SCMs to OPC along with alka-
line activation. There are other techniques being also adopted for
minimizing the CO2 emission by concrete industries such as captur-
ing CO2, use of alternate fuel source or modifying process of clinker
manufacturing at cement plant, however, substitution of clinker by
alternate SCMs is the most effective and economical solutions that
can be easily applicable to the ready-mix plant [3,12].
Utilizing the SCMs as partial replacement has been continu-
ously studied since last 3 decades due to its economical, ecological
and technical benefits. As these are waste products that requires
minimizing cost of construction as well as reduction in ecological
imbalance. Technically, they are proven to produce more or less
same concrete resulted thru neat OPC. Several researches have
been done to find out optimum dosage of each SCMs to be partially
mixed with OPC, effects on mix design and exposure conditions.
For instance, Shamshad et al. [13] proposed compliance criteria
for 100% OPC, 7.5% SF and 20% FA concrete by varying cementitious
material content and w/cm ratio. The results of compressive
strength and durability properties of SF cement concrete was found
superior. ACI committee 305 specifies fresh concrete temperature
limit of 35 °C while Nasir et al. [14,15] recently studied the perfor-
mance of plain and blended cement concretes cast at in-situ tem-
perature of 25–45 °C. They found that compared to neat OPC,
partial replacement of SCMs including 10% SP, 30% FA, 70% GGBFS,
7% SF and 20% NP results better at higher temperature. A review on
waste products used as SCMs to replace OPC concluded that some
SCMs like FA, SF and GGBFS have already proven advantageous.
However, there is a growing demand for identifying underutilized
waste product and to partially incorporate with or to replace OPC
that may potentially serve for the benefits of built infrastructure
and the environment [16].
Incorporation of SCMs as an alternative alkaline activated bin-
der (AAB) also known as geopolymer has been continuously gain-
ing popularity since last two decades as it is 100% OPC free. The
term ‘‘geopolymer” was first introduced by Davidovits in 1999
[17] and AAB have been developed by incorporating source mate-
rials which are chemically inorganic in nature and rich in silica (Si)
and alumina (Al) [18]. However, the relevant research on this topic
was started during late 1930s by Feret [19] and Purdon [20].
Recently, Hossain et al. [21] reviewed 92 papers of last decade
focusing on the durability of concrete and mortar prepared with
alkali-activated pozzolanic binder. They concluded that fly ash
(FA), blast furnace slag (BFS), metakaolin (MK), rice husk ash
(RHA) and palm oil fuel ash (POFA) has been extensively studied
(both individually or blending with different activators and con-
centrations) to improve various properties of binder as compared
to traditional cement specimens that enabled lowering disposal
problem associated with waste products, reduction in traditional
cement consumption, minimizing overall construction cost and
decreasing CO2 discharge. Pacheco-Torgal et al. [22] reviewed 70
research papers concerning durability aspect of alkali-activated
binders and discussed its advantages and disadvantages based on
the test properties that includes: acid attack, alkali–silica reaction,
reinforcement corrosion, resistance to elevated temperature, fire
and freeze–thaw and efflorescence. Several researchers have inves-
tigated effect of alkaline activation of various 100% SCMs or their
blends, such as with FA [23], with NP [24], with GGBFS [25], with
MK [26], with RHA [27] and with POFA [28]. Among these SCMs,
FA is most widely used source material owing to its availability
in abundance, more economical and high potential for geopolymer
development [29].
An advanced innovative approach being recently researched is
hybrid cement which can be developed by combining alkaline
 W. Al-Kutti et al. / Construction and Building Materials 159 (2018) 567–577
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
replace with SCMs such that concrete mixture with even less than
30% OPC or clinker can be formed [33–35]. Fig. 1 shows the stages
of hybrid cement production consisting of ordinary Portland clin-
ker, GGBFS, FA and alkaline activators at an American plant [36].
Alkaline activator in hybrid system helps compensating the dilu-
tion effect of OPC and these systems are possible to develop
through alkali activated (AA) OPC-Slag cement, AA OPC-
Phosphorus slag cement, AA FA cement and AA multiple-SCMs
blended cements [32]. Hybrid cementitious materials are reported
to achieve improved mechanical and durability characteristics
even at early ages [37,38] while presence of hydration products
differ with OPC-based materials and it entirely depend on source
material or aluminosilicate precursor utilized. Garcia-lodeiro
et al. [39] found several hydration products formed in hybrid bin-
ders such as calcium silicate hydrate (C-S-H) due to hydration of
OPC with water, sodium aluminosilicate hydrate (N-A-S-H) which
is primary outcome of AA of alumina and silica as well as calcium
aluminosilicate hydrate (C-A-S-H) and (N,C)-A-S-H gel which
depend on the pH and ratio of content of silica/alumina and cal-
cium/silica in these systems. Paloma et al. [37] compared hybrid
binder and non-AA binder prepared with FA, GGBFS and 20%
OPC. The results of hybrid binder showed 50% more compressive
strength at early age, less heat of hydration and lower setting time
due to the presence of C-A-S-H, N-A-S-H and (N,C)-A-S-H gels. For-
mation of such gels were also noticed in another study that pro-
duced hybrid binder blended with 70% FA and 30% OPC [39].
Murillo et al. [40] developed hybrid binder based on alkali-
activated (AA) ceramic tile waste (CTW) and OPC. They optimised
the molar ratios of silica/alumina and sodium oxide/silica and
achieve 28-day compressive strength of 58.15 MPa due to densifi-
cation of binder because OPC was used as a calcium source that
formed C-A-S-H gel and also because of AA of CTW. Angulo-
Ramírez [41] studied the kinetic, mechanical and microstructural
characteristics of 80% OPC + 20% GGBFS hybrid binders AA by
NaOH and NaSiO2 + NaOH that resulted in, respectively 4.5 and
10.8 times higher compressive strength at 1-day curing as com-
pared to 100% OPC. Their hybrid cement also showed reduction
in heat of hydration and denser microstructure producing C-S-H,
C-A-S-H and hydrated gehlenite. In summary, the maximum possi-
ble replacement level of waste materials and nature of gels gener-
ated in hybrid system is highly dependent on nature and type of
waste product incorporated as well as concentration and type of
activator used. For instance, FA-based hybrid cement (studied
569
between 20 and 60% replacement ratio) generated mainly (N,C)–
A–S–H and less (N,C)–S–H gels even at 20% FA replacement
whereas, municipal solid waste incinerator ash (MSWI) did not
produce (N,C)–A–S–H at any replacement level when activated
thru 5% (by weight) mixture of Na2SO4 and CaSO4 [42].
Among agricultural waste, RHA and POFA are mainly focused in
research. However, date palm tree is considered as one of the old-
est and highest number of trees on earth. It is estimated that
around 105 million trees of several types of date palm exists [43]
and typically each tree generates waste of 25 leaves per season
[44].
In civil engineering application, the use of date palm is very lim-
ited. For instance, Khellou et al. [45] initiated the utilization of date
palm ash (4–12%) blended with gypsum-calcareous materials
(crusting tuff) to investigate the mechanical characteristics in the
pavement construction of Algeria. The authors recommended the
potential scope in extending their research from the findings that
8% ash replacement results optimum mix that can significantly
enhance the mechanical properties in terms of compressive
strength and bearing index. Additionally, Al-Kutti et al. [46] incor-
porated the date palm ash (DPA) by partially replacing (10, 20 and
30%) Type I cement in concrete and mortar. They found that 10%
DPA dosage significantly enhance the mechanical and durability
properties as compared to 100% OPC specimens. Recently, Gunar-
ani and Chakkravarthy [47] studied the suitability of date palm
seed ash (DPSA) by partially replacing conventional cement at an
interval of 2% up to 10% and evaluated strength, water absorption,
sorptivity and alkalinity of mortar specimens in India. The results
indicated that 4% DPSA was optimum dosage of replacement to
OPC while 2% and 8% replacement level can be beneficially used
for construction requiring higher acid resistance and bond
strength, respectively.
In the light of above cited literature, it can be admitted that
cement is an essential element for providing the basic shelter to
luxurious life of human being. Since traditional cement is one of
the major cause for depleting natural resources, emitting CO2 into
the atmosphere and consuming large amount of energy during the
entire phase of its production, there is a vast scope and promising
future of locally available agro-industrial waste that may offer eco-
nomical and sustainable construction along with improved dura-
bility as compared to traditional cement construction. The review
of the literature shows that there are several agro-industrial mate-
rials utilized by researchers as partial replacement and developing
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
a binary and ternary blend and use of activated SCMs in the pres-
ence of OPC to develop hybrid binder without oven curing. Hence,
most date palm waste are stockpiled as landfill or burnt as these
trees are abundantly available in Arab countries that are already
rich with fossil fuel resources and generate electricity from it,
unlike Malaysia. However, at some places in Saudi Arabia the date
palm waste is collected to form wood which is later burn at high
temperature in oven to form fire coal that generates DPA which
is being considered as waste product. Therefore, utilizing the date
palm ash in construction sector can offer improved binder proper-
ties along with creating sustainable built environment to a large
extent.
In this vein, this study aims to utilize 10% DPA or 25% FA as par-
tial replacement of OPC to form hybrid binary blend and combina-
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-
nation process, represented as GDPA, and these mixtures were
added with 8 M NaOH solutions as partial replacement of mix
water along with the presence of OPC to avoid oven curing and
to study the effect of alkali-activated solution on OPC-agro-
industrial-based cement. The effect of representative fresh and
mechanical properties in terms of flow and compressive strength
was evaluated. In addition, characterization tests were conducted
to study the microstructure of the paste.
2. Materials and methods
2.1. Materials
2.1.1. OPC and SCMs
Type I – ordinary Portland cement (OPC) confirming to ASTM C 150 [48] was
used in preparation of all mixtures. Class F Fly ash confirming to ASTM C 618
[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
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.
Raw DPA was sieved to exclude the unwanted large particle size of coal waste
and material retained on # 100 (150 mm) and # 200 (75 mm) sieve size was utilized
in DPA mixes. The specific gravity of OPC, FA and DPA was 3.15, 2.10 and 2.43,
respectively. Table 1 shows the chemical composition of plain and precursor
cementitious materials.
2.1.2. Pre-treatment for hybrid binder
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
at medium speed for 15 min and at high speed for another 10 min, for a quantity of
100 gm DPA in each cycle, such that ground DPA (GDPA) passed through # 200
sieve (75 mm). Secondly, unburnt carbon was measured by putting the GDPA sam-
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
the rate of 5 °C/min and next programmed to expose at constant temperature of
700 °C for 1 h period. Unburnt carbon was calculated from the differences in origi-
nal weight and weight of sample after calcination process and expressed as percent-
age. This calcination process resulted in 2.5% un-burnt carbon in GDPA enabling it
suitable for use in concrete production. Study [50] showed that removal of unburnt
carbon through calcination process partly transforms the amorphous structure of
geopolymer into crystalline phase. Thirdly, sodium hydroxide pellets were
employed to prepare solution of 8 M NaOH solution in water and it was allowed
to cool down for 1 day because of exothermic reaction. Similar methodology have
been adopted in previous study for its effectiveness on eliminating unburnt carbon
on POFA [51].
2.1.3. Mixture proportion and preparation of specimens
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]
cement dosage was used to partially replace OPC in binary and ternary mixtures.
The ratio of cementitious materials to sand and w/cm ratio was maintained con-
stant as 1:2.75 and 0.485, respectively, as per ASTM C 109 [53]. 8 M NaOH solution
[54] was used in hybrid mixtures (M3 and M6) by an amount of 0.302 ml per gram
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
having addition of alkali-activated NaOH solution and rest of the mixes are non-
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
[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
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-
elled with trowel, covered with plastic sheet and placed at laboratory temperature
(25 ± 2 °C) to set. The specimens were demoulded after 24 h, and immersed in
water for curing till the age of compressive strength and microstructural tests.
2.2. Test methods
2.2.1. Chemical composition analysis
As shown the chemical composition in Table 1, the highest silica content was
found in FA followed by DPA and OPC, respectively. CaO content is found most in
OPC while alumina content is highest in FA cement. Other oxides are present in
small quantities with marginal difference in all cements.

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
summary of surface area, pore volume and pore radius of the
pastes in all mixtures is presented in Table 3. From the data in
Table 3, it can be noticed that a linear correlation exists between
surface area and pore volume among all mixture with a R-square
value of more than 0.8. The direct relationship between the surface
area and pore volume for a constant w/cm ratio would be the con-
sequence of increased water demand in the hybrid binder that may
result in porous structure. Further, the results indicated that the
average pore radius of all the mixture was about 11.5 Å with slight
variation. However, the surface area of control mix was noted to be
31.90 m2/g which was 65% reduced with the addition of coarser
DPA in M2 while the pre-treatment in M3 increased the fineness
of paste and, hence, hybrid binary binder resulted in comparable
surface area as in control mix. Likewise, the surface area of binary
mix M4 was noted to be 40.78 m2/g that indicates FA cement par-
ticles were smaller than OPC while the addition of DPA and GDPA
in M4 resulted in 25% reduction and 13% increment in surface area
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
all binders from M3 to M6 as 19.5, 39, 21.5 and 47%, respectively
while pore volume in M2 reduced about 9.5%. The increased poros-
ity with increase in surface area may be attributed to the non-
uniform packing and inadequate dispersion of finer/variable size
particles in the binary and ternary paste matrix. A study [59] on
fineness of FA also confirmed thru mercury intrusion porosimetry
test wherein the gel porosity marginally increases with increase
in fineness of FA in blended cement paste mixes at all FA replace-
ment level between 20 and 40% by weight to OPC. However, some
contradictory research also exits in this vein. For instance, it is also
reported that the surface area tends to increase up to 44 m2/g but it
is due to the presence of high unburned carbon content of up to
19% [60]. Moreover, researchers [61] termed FA as ‘‘micro-
aggregate” that can impart positive particle packing effect in the
binder matrix resulting in pore structure refinement. Nonetheless,
it is suggested that the surface area in the range of 16 and 136 m2/g
can be achieved with BET method in FA or other powdered SCMs
ensuring its reliability in the field of concrete technology [51,62].
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
55
So > 200 mm flow dia.
50
45 Plasc
Mortar flow (%)
40
35
30
Dry
25
20
M1 M2
Fig. 4. Mortar flow in all mixture.
and 150 mm average diameter, respectively. This indicates that the
consistency of all mortar lies under the category of plastic state
excluding M4 which was slightly higher than 200 mm falling under
the range of fluid consistency [57]. The beneficial role of FA-based
mixtures to increased fluidity is mainly attributed to the ball bear-
ing of FA particles owing to its spherical shape that facilitates
movement of adjacent particles and provide plasticizing effect
[63–65]. It is also in close agreement with the studies [63] that
confirmed enhanced plasticizing effect in FA cement is due to its
lesser specific gravity as compared to OPC that results in more
paste volume as well as because of slow rate of hydration reaction
and gel formation at early age. Further, the reduction in flow
spread in M5 and M6 ternary mixtures is probably due to the addi-
tion of non-spherical and non-uniform DPA particles to the FA and
OPC. Such findings were also reported in GGBFS-FA based geopoly-
mer concrete wherein consistency decreased with inclusion of
GGBFS content by 30% in 400 kg/m3 binder content due to the
accelerated hydration reaction of Ca species and the angular parti-
cles of GGBFS compared to the spherical shape of FA [66,67].
3.3. Compressive strength
Fig. 5 shows the development of compressive strength of mor-
tar specimens with period of curing. Compressive strength varied
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,
compressive strength in M1 was found to be 55.3 MPa which is 22,
19, 25, 39 and 42% more than M2, M3, M4, M5 and M6, respec-
tively. Similarly, compressive strength at the later age of 28 days
was found to be 64.1 MPa which is 11, 20, 3, 23 and 20% more than
M2, M3, M4, M5 and M6, respectively. However, it can be noticed
70
Compressive Strength, MPa
60
50
40
30
20
10
M1 M2
Fig. 5. Development of compressive strength in all mortar mixture.
W. Al-Kutti et al. / Construction and Building Materials 159 (2018) 567–577
that rate of strength development in M1 and M3 was minimum
and it was generally highest in FA-based binders (M4–M6). For
instance, the difference in compressive strength at 3 and 28 day
was 8.8, 13.8, 6.3, 20.2, 15.8 and 19.2 MPa among M1 to M6,
respectively. It indicates that FA produces secondary hydration at
later ages. This is in agreement with a study [68] that explained
that the overall quality of final SCM product is governed by both
cementing efficiency which FA cement exhibit considerably low
strength at early ages by reacting as a filler material and pozzolanic
reaction which is highly dependent on chemical composition spe-
cially the amount of Alumina and Silica in FA cement and become
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
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
FA-based mixture is in agreement with similar study that
addressed that the potential pozzolanic activity and quick hydra-
tion reaction can be achieved because of relatively large specific
surface area or finer FA particles [71]. Further, the lower strength
in hybrid binders is possibly due the insufficient molarity of NaOH
solution and absence of Na2SiO3 alkaline activators as reported by
several researchers. Salami et al. [28] revealed that 12 M NaOH(aq)
results in better durability in engineered alkaline activated POFA
mortar mix as compared to those prepared with 10 and 14 M
NaOH(aq). Similarly, Memon et al. [72] also studied the effect of
NaOH concentration between 8 and 14 M and found positive effect
of NaOH concentration up to 12 M on strength. Because increase in
NaOH concentration tends to increase the solubility of aluminosil-
icate in cements [73] that results in high compressive strength of
geopolymer mortar and concrete [74,75]. However, highly alkaline
solution may significantly influence the hydration process of OPC
which retards the formation of gel products [76,77]. Further, com-
bination of NaOH and Na2SiO3 found to be effective alkaline activa-
tors in enhancing the compressive strength and other concrete
properties by their dissolution feature of source material that
results in better bond between mix constituents and forms almost
pore less structure, as highlighted in researches [29,74,78].
3.4. X-ray diffraction (XRD) analysis
Fig. 6 shows the X-ray diffractograms of M1 and M3 to M6
pastes. The XRD patterns represent high amorphous and partial
crystalline structure between the 2-theta ranging from 15 to 68
degree while such high peaks were commonly noted in the range
of 20–40 degree in all mixtures [24,79,80]. The spectra peaks in
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)
[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 #
7 day
28 day 00-015-0776] [83], hematite (Fe2O3) [PDF Card # 00-001-1053]
[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
matrix along with the polymeric gel formed as anorthite is due
to the addition of aluminosilicate-rich DPA and FA cementitious
material that tend to enhance the strength and microstructural
characteristics of the binary and ternary binder [29,85,86]. Further,
Higher Na and Ca in DPA with respect to FA cement prompted the
C-S-H formation which might have been replaced Ca (from C-S-H)
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
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-
SiO3 lead to the insignificant improvement in strength in hybrid
ternary binders along with insufficient extent of dispersion of
SiO2 in the form of quartz and cristobalite, as depicted in XRD spec-
tra of M6 compared to other mixes. XRF analysis also indicated that
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
ternary binder as compared to M5. Davidovits have also empiri-
cally proven that the mechanical strength and polymerization pro-
cess to form extent of C-S-H is based on high concentration of
alkaline solution that enables dissolution of Si and Al ions in the
FA-based binder, SiO2 to Na2O ratio in alkaline activator, amount
of Ca in source materials and SiO2 to Al2O3 ratio in source
materials. Hybrid cement owes its good mechanical strength to
102
M1
100 M4
98
TGA (%)
the main hydration product, a mix of cementitious gels C-(A)-S-
H + C-A-S-H. These gels take up a larger portion of aluminium
and are intensely polymerised than traditional C-S-H gel in the
presence of good activator, which is in close agreement with the
previous study [36].
3.5. Thermogravimetric analysis (TGA)
Fig. 7 shows the 28-day TGA curves of all paste mixtures with
respect to temperature. Fig. 8 and Table 4 summarizes the total
weight loss from room temperature (25 °C) to up to 599 °C. The
maximum total weight loss was recorded in M1 = 10.87% followed
by M4, M5, M6, M3 and M2, respectively in decreasing order such
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
amount of water was required for achieving maximum degree of
M2 M3 hydration reaction. In other words, highest amount of chemically
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
hydration and amount of bound water have a direct relationship

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
4. Conclusions
Based on the thorough studies following conclusions can be
drawn:
1. DPA can be beneficially utilized along with FA as a ternary bin-
der with OPC to maximize replacement of clinker (up to 35%).
This M5 mixture yield a 28-day compressive strength of 49.5
MPa which is about 23 and 20% lower than traditional control
mixes M1 and M4, respectively but only 1.7 MPa lower than
the ternary hybrid binder. Therefore, with present methodol-
ogy, non-hybrid binder should be preferred on hybrid binders
to avoid excessive energy and cost involved in grinding, calcina-
tion and alkaline activation process.
2. Consistency of all mixture remained in plastic limit. Flow
spread in hybrid paste was slightly higher than non-hybrid
pastes due to the characteristics of NaOH. FA enhanced spread
due to the ball bearing effect provided by the smooth and
spherical particles while addition of DPA in mixture reduced
the flow because of its non-uniform and irregular texture.
3. XRD spectra demonstrated that the presence of C-S-H and anor-
thite formed is attributed to the addition of aluminosilicate-rich
FA, high Na and Ca content and SiO2 to Al2O3 ratio in DPA that
tend to enhance the strength and microstructural characteris-
tics of the binary and ternary binder. Insufficient extent of dis-
persion of SiO2 in the form of quartz and cristobalite in hybrid
paste is mainly due to poor alkaline activator synthesis.
4. The unbound water in TGA test for M2 to M6 ranged between 7
and 42% was lesser than control mix indicating DPA and FA based
binder require more water for hydration and pozzolanic reac-
tions. Therefore, aluminosilicate feature and pozzolanic reaction
caused most production of C-S-H and C-A-H gel in FA-based mix-
ture that accounts 7–29% higher than control mix. These gel for-
mation is validated by TGA% loss at higher temperature that
showed higher consumption of Ca(OH)2 in these mixes. M5 pro-
duced 29% more gel and consumed 40% Ca(OH)2 as compared to
control mix while about 20% more gel and Ca(OH)2 consumption
was found than that in hybrid ternary mix.
5. Potential use of DPA in cement-based materials will tend to
minimize the solid waste landfill issue. Moreover, utilizing date
palm waste in generating electricity in Arab countries will
produce DPA in bulk quantity that will further maximize its
practicability in construction industry as an environment
friendly and durable material as well as prolong the natural
oil reserves and its sustainability.
Following recommendations could be drawn from the study
and literature:
1. 25% FA replacement into OPC can reduce about 25% CO2 emis-
sion due to cement manufacturing plants while addition of
10% DPA in such mix can beneficially minimize further global
CO2 discharge.
2. The performance of hybrid binders in M3 and M6 can be
improved by increasing and optimising the molarity content
and concentration of NaOH as well as addition of Na2SiO3 alka-
line activators. Further, it may be possible to use high volume
FA and slag in conjunction with DPA and replace up to 70% clin-
ker in the presence of good activator.
Acknowledgement
The authors are indebted to the DSR at Imam Abdulrahman Bin
Faisal University for their support under the research grant No.
575
2017-314-Eng. Support from School of Civil Engineering at Univer-
siti Sains Malaysia is also acknowledged.
References
[1] K.H. Mo, U.J. Alengaram, M.Z. Jumaat, S.P. Yap, S.C. Lee, Green concrete partially
comprised of farming waste residues: a review, J. Clean. Prod. 117 (2016) 122–
138.
[2] T. Błaszczyński, M. Król, Usage of green concrete technology in civil
engineering, Proc. Eng. 122 (2015) 296–301.
[3] E. Gartner, Industrially interesting approaches to ‘low-CO2’ cements, Cem.
Concr. Res. 34 (9) (2004) 1489–1498.
[4] L.J. Hanle, CO2 Emissions Profile of The U.S. Cement Industry, 2004.
[5] H. Klee, E. Coles, The cement sustainability initiative – implementing change
across a global industry, Corp. Soc. Responsib. Environ. Manage. 11 (2) (Jun.
2004) 114–120.
[6] E. Worrell, L. Price, N. Martin, C. Hendriks, L.O. Meida, Carbon dioxide
emissions from the global cement industry, Annu. Rev. Energy Environ. 26
(1) (2001) 303–329.
[7] P.K. Mehta, Concrete in the marine environment, Modern Concrete Technology
Series, CRC Press, 1991.
[8] J. Davidovits, Global warming impact on the cement and aggregates industries,
World Resour. Rev. 6 (2) (1994) 263–278.
[9] M.S. Imbabi, C. Carrigan, S. McKenna, Trends and developments in green
cement and concrete technology, Int. J. Sustainable Built Environ. 1 (2) (2012)
194–216.
[10] R.K. Dhir, T.G. Jappy, Exploiting wastes in concrete, Proceedings of the
international seminar held at the University of Dundee, Scotland, UK on 7
September 1999, Thomas Telford, 1999.
[11] T. Błaszczyński, M. Król, Concrete and problem of carbon dioxide emission
reduction, Insulations 3 (2014) 28–30.
[12] K.-H. Yang, Y.-B. Jung, M.-S. Cho, S.-H. Tae, Effect of supplementary
cementitious materials on reduction of CO2 emissions from concrete, J.
Clean. Prod. 103 (2015) 774–783.
[13] S. Ahmad, W.A. Al-Kutti, O.S. Baghabra Al-Amoudi, M. Maslehuddin,
Compliance criteria for quality concrete, Constr. Build. Mater. 22 (6) (2008)
1029–1036.
[14] M. Nasir, O.S.B. Al-Amoudi, H.J. Al-Gahtani, M. Maslehuddin, Effect of casting
temperature on strength and density of plain and blended cement concretes
prepared and cured under hot weather conditions, Constr. Build. Mater. 112
(2016) 529–537.
[15] M. Nasir, O.S.B. Al-Amoudi, M. Maslehuddin, Effect of placement temperature
and curing method on plastic shrinkage of plain and pozzolanic cement
concretes under hot weather, Constr. Build. Mater. 152 (2017) 943–953.
[16] J.M. Paris, J.G. Roessler, C.C. Ferraro, H.D. DeFord, T.G. Townsend, A review of
waste products utilized as supplements to Portland cement in concrete, J.
Clean. Prod. 121 (2016) 1–18.
[17] J. Davidovits, Chemistry of geopolymeric systems, terminology, Geopolymer
99 (292) (1999) 9–39.
[18] A. Mehta, R. Siddique, An overview of geopolymers derived from industrial by-
products, Constr. Build. Mater. 127 (2016) 183–198.
[19] R. Feret, Slags for the manufacture of cement, Rev. Mater. Constr. Trav. 22
(1939).
[20] A.O. Purdon, The action of alkalis on blast-furnace slag, J. Soc. Chem. Ind. 59 (9)
(1940) 191–202.
[21] M.M. Hossain, M.R. Karim, M.K. Hossain, M.N. Islam, M.F.M. Zain, Durability of
mortar and concrete containing alkali-activated binder with pozzolans: a
review, Constr. Build. Mater. 93 (2015) 95–109.
[22] F. Pacheco-Torgal, Z. Abdollahnejad, A.F. Camões, M. Jamshidi, Y. Ding,
Durability of alkali-activated binders: a clear advantage over Portland
cement or an unproven issue?, Constr Build. Mater. 30 (2012) 400–405.
[23] E. Gomaa, S. Sargon, C. Kashosi, M. ElGawady, Fresh properties and
compressive strength of high calcium alkali activated fly ash mortar, J. King
Saud Univ. Eng. Sci. (2017) 356–364.
[24] M. Ibrahim, M.A. Megat Johari, M.K. Rahman, M. Maslehuddin, Effect of
alkaline activators and binder content on the properties of natural pozzolan-
based alkali activated concrete, Constr. Build. Mater. 147 (2017) 648–660.
[25] M.O. Yusuf, M.A. Megat Johari, Z.A. Ahmad, M. Maslehuddin, Strength and
microstructure of alkali-activated binary blended binder containing palm oil
fuel ash and ground blast-furnace slag, Constr. Build. Mater. 52 (2014) 504–
510.
[26] F. Pacheco-Torgal, D. Moura, Y. Ding, S. Jalali, Composition, strength and
workability of alkali-activated metakaolin based mortars, Constr. Build. Mater.
25 (9) (2011) 3732–3745.
[27] C. Suksiripattanapong, T.-A. Kua, A. Arulrajah, F. Maghool, S. Horpibulsuk,
Strength and microstructure properties of spent coffee grounds stabilized with
rice husk ash and slag geopolymers, Constr. Build. Mater. 146 (2017) 312–320.
[28] B.A. Salami, M.A. Megat Johari, Z.A. Ahmad, M. Maslehuddin, Durability
performance of palm oil fuel ash-based engineered alkaline-activated
cementitious composite (POFA-EACC) mortar in sulfate environment, Constr.
Build. Mater. 131 (2017) 229–244.
[29] H. Xu, J.S.J. Van Deventer, The geopolymerisation of alumino-silicate minerals,
Int. J. Miner. Process. 59 (3) (2000) 247–266.
576 W. Al-Kutti et al. / Construction and Building Materials 159 (2018) 567–577
[30] P. Nath, P.K. Sarker, Use of OPC to improve setting and early strength
properties of low calcium fly ash geopolymer concrete cured at room
temperature, Cem. Concr. Compos. 55 (2015) 205–214.
[31] A. Palomo, P. Krivenko, I. Garcia-Lodeiro, E. Kavalerova, O. Maltseva, A.
Fernández-Jiménez, A review on alkaline activation: new analytical
perspectives, Mater. Constr. 64 (315) (2014) 22.
[32] C. Shi, A.F. Jiménez, A. Palomo, New cements for the 21st century: the pursuit
of an alternative to Portland cement, Cem. Concr. Res. 41 (7) (2011) 750–763.
[33] K.-H. Yang, J.-K. Song, A.F. Ashour, E.-T. Lee, Properties of cementless mortars
activated by sodium silicate, Constr. Build. Mater. 22 (9) (2008) 1981–1989.
[34] I. García-Lodeiro, O. Maltseva, Á. Palomo, A. Fernández-Jiménez, Cimenturi
hibride alcaline. Partea i: fundamente/hybrid alkaline cements. Part i:
fundamentals, Rev. Rom. Mater. 42 (4) (2012) 330.
[35] A. Palomo, O. Maltseva, I. Garcia-Lodeiro, A. Fernández-Jiménez, Cimenturi
hibride alcaline. Partea a ii-a: factorul clincher*/hybrid alkaline cements. Part
ii: the clinker factor, Rev. Rom. Mater. 43 (1) (2013) 74.
[36] B. Qu, A. Martin, J.Y. Pastor, A. Palomo, A. Fernández-Jiménez, Characterisation
of pre-industrial hybrid cement and effect of pre-curing temperature, Cem.
Concr. Compos. 73 (Oct. 2016) 281–288.
[37] A. Palomo, O. Maltseva, I. García-Lodeiro, A. Fernández-Jiménez, Hybrid
alkaline cements. Part II: the clinker factor, Rev. Rom. Mater. Rom. J. Mater.
43 (1) (2013) 74–80.
[38] A. Fernández-Jiménez, E. Flores, O. Maltseva, I. García-Lodeiro, Á. Palomo,
Cimenturi hibride alcaline. Partea a iii-a-durabilitate si aplicatii industriale/
hybrid alkaline cements. Part iii. Durability and industrial applications, Rev.
Rom. Mater. 43 (2) (2013) 195.
[39] I. Garcia-Lodeiro, A. Fernandez-Jimenez, A. Palomo, Hydration kinetics in
hybrid binders: early reaction stages, Cem. Concr. Compos. 39 (2013) 82–92.
[40] L.M. Murillo, S. Delvasto, M. Gordillo, in: 11 – A Study of a Hybrid Binder Based
on Alkali-activated Ceramic Tile Wastes and Portland Cement BT – Sustainable
and Nonconventional Construction Materials Using Inorganic Bonded Fiber
Composites, Woodhead Publishing, 2017, pp. 291–311.
[41] D.E. Angulo-Ramírez, R. Mejía de Gutiérrez, F. Puertas, Alkali-activated
Portland blast-furnace slag cement: mechanical properties and hydration,
Constr. Build. Mater. 140 (2017) 119–128.
[42] I. Garcia-Lodeiro, V.C. Taboada, A. Fernández-Jiménez, Á. Palomo, Recycling
industrial by-products in hybrid cements: mechanical and microstructure
characterization, Waste Biomass Valorization 8 (5) (2017) 1433–1440.
[43] B. Agoudjil, A. Benchabane, A. Boudenne, L. Ibos, M. Fois, Renewable materials
to reduce building heat loss: characterization of date palm wood, Energy Build.
43 (2) (2011) 491–497.
[44] Z. Abdelouahhab, E.J. Arias-Jimenez, Date Palm Cultivation, No. 156, Food and
Agriculture Organization (FAO), 1999.
[45] A. Khellou, A. Kriker, A. Hafssi, K. Belbarka, K. Baali, Effect of the addition of by-
product ash of date palms on the mechanical characteristics of gypsum-
calcareous materials used in road construction, AIP Conf. Proc. 1758 (1) (2016)
30005.
[46] W. Al-Kutti, A.B.M.S. Islam, M. Nasir, Potential use of date palm ash in cement-
based materials, J. King Saud. Univ. Eng. Sci. (2017).
[47] G.I. Gunarani, S.P. Chakkravarthy, Experimental studies on effect of Date Seed
Ash (DSA) on strength properties of cement sand mortar, in: Earth and
Environmental Science Conference – ICCIEE, 2017, https://doi.org/10.1088/
1755-1315/80/1/012015.
[48] ASTM C150, Standard Specification for Portland Cement, 2012.
[49] ASTM C618, Standard Specification for Coal Fly Ash and Raw or Calcined
Natural Pozzolan for Use in Concrete, 2015.
[50] J. Temuujin, A. Van Riessen, Effect of fly ash preliminary calcination on the
properties of geopolymer, J. Hazard. Mater. 164 (2) (2009) 634–639.
[51] C. Chandara, E. Sakai, K.A.M. Azizli, Z.A. Ahmad, S.F.S. Hashim, The effect of
unburned carbon in palm oil fuel ash on fluidity of cement pastes containing
superplasticizer, Constr. Build. Mater. 24 (9) (2010) 1590–1593.
[52] S.C.K. Bendapudi, P. Saha, Contribution of fly ash to the properties of mortar
and concrete, Int. J. Earth Sci. Eng. 4 (6) (2011) 1017–1023.
[53] ASTM C109/C109M, Standard Test Method for Compressive Strength of
Hydraulic Cement Mortars (Using 2-in. or [50-mm] Cube Specimens), 2013.
[54] M.O. Yusuf, M.A.M. Johari, Z.A. Ahmad, M. Maslehuddin, Influence of curing
methods and concentration of NaOH on strength of the synthesized alkaline
activated ground slag-ultrafine palm oil fuel ash mortar/concrete, Constr.
Build. Mater. 66 (2014) 541–548.
[55] ASTM C305, Standard Practice for Mechanical Mixing of Hydraulic Cement
Pastes and Mortars of Plastic Consistency, 2014.
[56] ASTM C1437, Standard Test Method for Flow of Hydraulic Cement Mortar,
2007.
[57] BS EN 1015, Determination of Consistence of Fresh Mortar by Flow Table and
Bulk Density, 1999.
[58] P. Chindaprasirt, C. Jaturapitakkul, T. Sinsiri, Effect of fly ash fineness on
microstructure of blended cement paste, Constr. Build. Mater. 21 (7) (2007)
1534–1541.
[59] P. Chindaprasirt, C. Jaturapitakkul, T. Sinsiri, Effect of fly ash fineness on
compressive strength and pore size of blended cement paste, Cem. Concr.
Compos. 27 (4) (2005) 425–428.
[60] A.M. Zeyad, M.A. Megat Johari, B.A. Tayeh, M.O. Yusuf, Efficiency of treated and
untreated palm oil fuel ash as a supplementary binder on engineering and
fluid transport properties of high-strength concrete, Constr. Build. Mater. 125
(2016) 1066–1079.
[61] J.L. Provis, P. Duxson, J.S.J. van Deventer, The role of particle technology in
developing sustainable construction materials, Adv. Powder Technol. 21 (1)
(2010) 2–7.
[62] K. Pedersen, A. Jensen, M. Skjothrasmussen, K. Damjohansen, A review of the
interference of carbon containing fly ash with air entrainment in concrete,
Prog. Energy Combust. Sci. 34 (2) (Apr. 2008) 135–154.
[63] C.Y. Lee, H.K. Lee, K.M. Lee, Strength and microstructural characteristics of
chemically activated fly ash–cement systems, Cem. Concr. Res. 33 (3) (2003)
425–431.
[64] J.H. Kim, N. Noemi, S.P. Shah, Effect of powder materials on the rheology and
formwork pressure of self-consolidating concrete, Cem. Concr. Compos. 34 (6)
(2012) 746–753.
[65] D.P. Bentz, C.F. Ferraris, M.A. Galler, A.S. Hansen, J.M. Guynn, Influence of
particle size distributions on yield stress and viscosity of cement–fly ash
pastes, Cem. Concr. Res. 42 (2) (2012) 404–409.
[66] P.S. Deb, P. Nath, P.K. Sarker, The effects of ground granulated blast-furnace
slag blending with fly ash and activator content on the workability and
strength properties of geopolymer concrete cured at ambient temperature,
Mater. Des. 62 (2014) 32–39.
[67] P. Nath, P.K. Sarker, Effect of GGBFS on setting, workability and early strength
properties of fly ash geopolymer concrete cured in ambient condition, Constr.
Build. Mater. 66 (2014) 163–171.
[68] C. Cao, W. Sun, H. Qin, The analysis on strength and fly ash effect of roller-
compacted concrete with high volume fly ash, Cem. Concr. Res. 30 (1) (2000)
71–75.
[69] M. Kobayakawa, H. Ozu, S. Hanehara, K.R. Hwang, F. Tomosawa, The influence
of mix proportion and curing temperature on pozzolanic reaction ratio of fly
ash, Taiheiyo Cem. Kenkyu Hokoku (J. Taiheiyo Cem. Corp. Jpn. (Japan) 139
(2000) 14–27.
[70] D.P. Bentz, C.F. Ferraris, I. De la Varga, M.A. Peltz, J.A. Winpigler, Mixture
proportioning options for improving high volume fly ash concretes, Int. J.
Pavement Res. Technol. 3 (5) (2010) 234–240.
[71] F. Sanchez, K. Sobolev, Nanotechnology in concrete – a review, Constr. Build.
Mater. 24 (11) (2010) 2060–2071.
[72] F.A. Memon, M.F. Nuruddin, S. Khan, N. Shafiq, T. Ayub, Effect of sodium
hydroxide concentration on fresh properties and compressive strength of self-
compacting geopolymer concrete, J. Eng. Sci. Technol. 8 (1) (2013) 44–56.
[73] H.A. Gasteiger, W.J. Frederick, R.C. Streisel, Solubility of aluminosilicates in
alkaline solutions and a thermodynamic equilibrium model, Ind. Eng. Chem.
Res. 31 (4) (1992) 1183–1190.
[74] D. Hardjito, S.E. Wallah, D.M.J. Sumajouw, B.V. Rangan, On the development of
fly ash-based geopolymer concrete, Mater. J. 101 (6) (2004) 467–472.
[75] D. Hardjito, C.C. Cheak, C.H.L. Ing, Strength and setting times of low calcium fly
ash-based geopolymer mortar, Mod. Appl. Sci. 2 (4) (2008) 3.
[76] S. Martinez-Ramirez, A. Palomo, Microstructure studies on Portland cement
pastes obtained in highly alkaline environments, Cem. Concr. Res. 31 (11)
(2001) 1581–1585.
[77] S. Martinez-Ramirez, A. Palomo, OPC hydration with highly alkaline solutions,
Adv. Cem. Res. 13 (3) (2001) 123–129.
[78] A. Fernández-Jiménez, A. Palomo, M. Criado, Microstructure development of
alkali-activated fly ash cement: a descriptive model, Cem. Concr. Res. 35 (6)
(2005) 1204–1209.
[79] B.A. Salami, M.A.M. Johari, Z.A. Ahmad, M. Maslehuddin, Impact of added
water and superplasticizer on early compressive strength of selected mixtures
of palm oil fuel ash-based engineered geopolymer composites, Constr. Build.
Mater. 109 (2016) 198–206.
[80] H.M. Khater, B.A. El-Sabbagh, M. Fanny, M. Ezzat, M. Lottfy, Effect of nano-
silica on alkali activated water-cooled slag geopolymer, ARPN J. Sci. Technol. 2
(3) (2012) 170–176.
[81] A. Sharmin, U.J. Alengaram, M.Z. Jumaat, M.O. Yusuf, S.M.A. Kabir, I.I. Bashar,
Influence of source materials and the role of oxide composition on the
performance of ternary blended sustainable geopolymer mortar, Constr. Build.
Mater. 144 (2017) 608–623.
[82] G.M.N. Baston, A.P. Clacher, T.G. Heath, F.M.I. Hunter, V. Smith, S.W. Swanton,
Calcium silicate hydrate (CSH) gel dissolution and pH buffering in a
cementitious near field, Mineral. Mag. 76 (8) (2012) 3045–3053.
[83] J.M. Mejía, E. Rodríguez, R.M. de Gutiérrez, N. Gallego, Preparation and
characterization of a hybrid alkaline binder based on a fly ash with no
commercial value, J. Clean. Prod. 104 (2015) 346–352.
[84] W. Hunnicutt, Characterization of calcium-silicate-hydrate and calcium-
alumino-silicate-hydrate, 2013.
[85] J.E. Oh, P.J.M. Monteiro, S.S. Jun, S. Choi, S.M. Clark, The evolution of strength
and crystalline phases for alkali-activated ground blast furnace slag and fly
ash-based geopolymers, Cem. Concr. Res. 40 (2) (2010) 189–196.
[86] K. Somna, C. Jaturapitakkul, P. Kajitvichyanukul, P. Chindaprasirt, NaOH-
activated ground fly ash geopolymer cured at ambient temperature, Fuel 90
(6) (2011) 2118–2124.
[87] I. Ismail, S.A. Bernal, J.L. Provis, R. San Nicolas, S. Hamdan, J.S.J. van Deventer,
Modification of phase evolution in alkali-activated blast furnace slag by the
incorporation of fly ash, Cem. Concr. Compos. 45 (2014) 125–135.
[88] A. Palomo, A. Fernández-Jiménez, G. Kovalchuk, L.M. Ordoñez, M.C. Naranjo,
OPC-fly ash cementitious systems: study of gel binders produced during
alkaline hydration, J. Mater. Sci. 42 (9) (2007) 2958–2966.
[89] J. Moon et al., Characterization of natural pozzolan-based geopolymeric
binders, Cem. Concr. Compos. 53 (2014) 97–104.
 W. Al-Kutti et al. / Construction and Building Materials 159 (2018) 567–577 577

[90] I. Pane, W. Hansen, Investigation of blended cement hydration by isothermal
calorimetry and thermal analysis, Cem. Concr. Res. 35 (6) (2005) 1155–1164.
[91] M. Whittaker, M. Zajac, M. Ben Haha, F. Bullerjahn, L. Black, The role of the
alumina content of slag, plus the presence of additional sulfate on the
hydration and microstructure of Portland cement-slag blends, Cem. Concr. Res.
66 (2014) 91–101.
[92] X. Zhang, J. Han, The effect of ultra-fine admixture on the rheological property
of cement paste, Cem. Concr. Res. 30 (5) (2000) 827–830.
[93] C. Artelt, E. Garcia, Impact of superplasticizer concentration and of ultra-fine
particles on the rheological behaviour of dense mortar suspensions, Cem.
Concr. Res. 38 (5) (2008) 633–642.
[94] B. Wu, G. Ye, Development of porosity of cement paste blended with
supplementary cementitious materials after carbonation, Constr. Build.
Mater. 145 (2017) 52–61.