Construction and Building Materials 143 (2017) 522–536

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Construction and Building Materials

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

The long term engineering properties of cementless building block work

containing large volume of wood ash and coal fly ash
Chee Ban Cheah ⇑, Wei Ken Part, Mahyuddin Ramli
School of Housing, Building and Planning, Universiti Sains Malaysia, 11800 Penang, Malaysia

h i g h l i g h t s

Standard consistency and setting time performance of HCWA-PFA binder paste.

Long term mechanical performance of HCWA-PFA block work up to 365 days.

Thorough characterization on the aluminosilicate bond framework of HCWA-PFA geopolymer.

Large volume reuse of biomass and coal energy sector by products for building block work production.

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

Article history: The reuse of pulverised fuel ash (PFA) and high calcium wood ash (HCWA) offers a two folds solution
Received 23 November 2016 towards addressing the waste management problem and reduce the carbon footprint of concrete mate-
Received in revised form 3 March 2017 rial. In order to enable sizeable application of such recycling method to produce block work for the con-
Accepted 17 March 2017
struction industry, a comprehensive framework of knowledge on the mechanical strength performance of
Available online 27 March 2017
the concrete product containing large volume of PFA and HCWA needs to be established. Hence, it is the
primary aim of the study to report a comprehensive assessment on the mechanical strength performance
Keywords:
of concrete block work produced with the sole use of PFA and HCWA as the primary binder phase. The
Recycling
Mechanical properties
PFA and HCWA binder phase with small dosage of sodium silicate was characterized in terms of its stan-
Hybrid binder dard consistency and setting times. Besides, a thorough assessment on the mechanical strength of block
Geopolymer work produced with PFA-HCWA binder was conducted. Mechanical strength assessment covers the com-
Load bearing block work pressive strength, flexural strength and velocity of ultrasonic pulse propagation through the material.
Besides, the fourier transformed infrared (FTIR) assessment was also performed to characterize the alu-
minosilicate bonds of the primary binder phase. The increasing mass ratio of HCWA was found to raise
the water demand of the HCWA-PFA binder paste. Besides, the HCWA:PFA combination ratio of 50:50
and 40:60 has been found to exhibit the optimal flexural and compressive strength performance. It
has also been established that the block work produced using HCWA:PFA combination ratio between
30:70 up to 90:10 meets the California Concrete Masonry Technical Committee requirement as class N
concrete block work unit.
Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction
OPC concrete brick is defined as concrete masonry unit made
from Portland cement, water, and suitable aggregates, with or
without the inclusion of other materials as per ASTM C55 Standard
Specification for Concrete Brick. The most distinct advantage of
OPC concrete brick over fired clay brick is the ability to attain the
required strength and properties without the need of high temper-
ature kiln firing. However, the utilization of OPC as sustainable
⇑ Corresponding author.
E-mail address: cheahcheeban@usm.my (C.B. Cheah).
building material has come under heavy scrutiny in recent years
due to the environmental impact by the clinker production [1,2].
In fact, the production of Portland Cement (PC) clinker from the
cement production plants worldwide emit up to 1.5 billion tons
of CO2 annually, which accounts for around 5% of the total man-
made CO2 emission and if the undesirable trend continues, the fig-
ure will rise to 6% by year 2015 [3–5].
Demand for electricity in developing countries has increased by
leaps and bounds in recent years due to the growth in world pop-
ulation and economic. Recent study forecasted the world energy
consumption to be increased by 47% from 2007 to 2035 [6]. In
Malaysia, only 5.5% of total electricity was generated using

http://dx.doi.org/10.1016/j.conbuildmat.2017.03.162
0950-0618/Ó 2017 Elsevier Ltd. All rights reserved.
 C.B. Cheah et al. / Construction and Building Materials 143 (2017) 522–536
renewable energy sources and 94.5% of electricity was generated
using fossil fuels such as natural gas, coal and oil in the year
2009. The wood processing industry in Malaysia represents a great
potential to be used as renewable energy source to supplement the
power/electricity demand as it is considered as one of the largest
untapped biomass resource in Malaysia [7]. According to Vassilev
et al. [8], wood wastes are the more preferable fuel for biomass fur-
naces as the incineration of wood waste yields relatively less resid-
ual and fly ash in comparison to other biomasses such as
agricultural and herbaceous wastes. Though the aforementioned
practices provide a great solution to the solid waste management
of wood waste residues, the use of wood wastes such as sawdust,
woodchips and offcuts as fuel have resulted in a significant amount
of fine wood waste ash as a by-product material in which the
industry found limited practical applications for the recycling of
the fine particulate ash materials [9].
Pulverised fuel ash (PFA) or more commonly known as fly ash
(FA), an industrial by-products of coal burning power plant indus-
try, makes up of 75–80% of global annual ash production [10]. As
94.5% of total electricity generated in Malaysia is by the mean of
fossil fuels such as natural gas, coal and oil, an enormous amount
PFA is expected to be generated annually. The coal-fired power
generation industry in Malaysia consumed approximately 8 mil-
lion tons of coal annually. In 2010, the Malaysian government
implemented a policy that eventually increased the national coal
powered electricity by 40% due to the rapid economic growth
and this has further increased the amount of PFA generated and
this hazardous industrial by-product mandates a proper disposal
or recycling methods [11].
Blended geopolymers is a new category of geopolymeric binder
which is produced by the combination of two or more industrial
waste ashes followed by subsequent stabilization and solidification
using chemical activators. The dual advantages of waste utilization
and more importantly the alteration in Si/Al and Ca/Si in geopoly-
mer system prompted sudden rush in the amount of researches in
the field of blended geopolymer during recent years [12–17]. Ever
since it was known that C-S-H gel can be co-exist with geopoly-
meric gel in a single system and contributes to the overall strength
gain [18], various researchers has utilized high calcium waste
material such as GGBFS and ASTM class C fly ash to blend with
ASTM class F fly ash in order to achieve a higher early strength gain
and shorter setting time which is beneficial for the application in
pre-cast industry [19,20]. Canfield et al. [21] investigated the role
of calcium in fly ash based geopolymers by blending high and
low calcium fly ash. It was found that calcium played two major
roles during the geopolymerization of the blended fly ash geopoly-
mer specimen, (i) calcium was found to aids the dissolution of sil-
ica and alumina species from the FA particles, yielding higher
tetrahedral silicate and aluminate monomer concentration as
shown in FTIR, XRD and TGA/DSC results, (ii) calcium also func-
tions as a counter-balancing cation when incorporated into the
geopolymer pore structure. In a separate study, The workability
of fresh geopolymer concrete consisted of GGBFS and FA showed
a decreasing trend with the increase in slag content and decrease
of SS/SH ratio due to the enhancement in reactivity in the presence
of GGBFS in FA based geopolymer system [12]. Other waste mate-
rials rich in silica such as rice husk ash (RHA) and palm oil fuel ash
(POFA) have also found considerably interest amongst geopolymer
researchers in the field of blended geopolymer [22–25]. Tyni et al.
[26] had conducted a feasibility study to utilize fly ash and bottom
ash fraction collected from circulating fluidize bed boiler combust-
ing mixture of peat and wood as geopolymeric binder constituent.
Results obtained from the scanning electron microscopy and X-ray
diffraction assessments are indicative of the formation of amor-
phous geopolymer phases in the peat and wood blended fly ash
paste activated with 5 M NaOH solution. Besides, it has also been
523
found that the use of high concentration (10 M) NaOH activator
solution produced semi-geopolymeric phases which also com-
prised of crystalline zeolite.
Prior work done by the authors has established the potential for
large volume reuse of high calcium wood ash (HCWA) and PFA as
the primary binder phase in the fabrication of mortar block [27,28].
In the study [27], geopolymer mortar were fabricated with HCWA–
PFA hybridization ratio of 100:0, 70:30, 60:40 and 50:50 using two
different water/binder ratios of 0.30 and 0.35. The mechanical per-
formance and durability performance of the HCWA–PFA mortar
block was assessed. It has been established that the combination
of HCWA-PFA at mass ratio of 70:30, 60:40 and 50:50 is optimum
for self-induced hardening even without the presence of any alkali
activator. This is largely contributed by the arcanite mineral com-
pound which is inherently present in the HCWA material. It has
also been established that the curing of HCWA-PFA mortar block
under moist curing condition of relative humidity 80 ± 5% is favor-
able over water curing condition. This is evident as all the water
cured test specimens exhibited inferior mechanical strength per-
formance as compared to the moist cured equivalent test speci-
mens largely due to de-polycondensation caused by water
intrusion [28]. It has also been found that the mechanical strength
development of HCWA-PFA geopolymeric system was mainly con-
tributed by geopolymeric reaction which formed K-A-S-H geopoly-
meric framework at early age of hardening followed by the
formation of the secondary C-S-H framework through pozzolanic
reaction. Besides, the hydrothermal treatment regime of full
immersion in hot water bath at 70 °C was found to accelerate the
mechanical strength gain at early age of 7 days but impair the total
porosity and subsequently water absorption property of the mate-
rial. This is largely due to the induced formation of cracks at the
interfacial transition zone of the paste and aggregate phase due
to vast differences in thermal expansion coefficient of the two
phases [29].
In general, though a substantial body of knowledge has been
established on the properties of blended geopolymer, and specifi-
cally HCWA-PFA geopolymer, there are still areas which are scar-
cely explored namely the setting behaviour of the paste and long
term mechanical strength development over a prolonged duration
of curing.
The present work is an extended investigation on the HCWA-
PFA paste standard consistency and setting times performance.
Besides, new body of knowledge on the long term engineering per-
formance of the HCWA-PFA building block up to 365 days with
various HCWA-PFA combination ratio between 0:100 and 100:0
at 10% increments has also been established in the present study.
This is done to establish a thorough understanding on the long
term performance of the material for its intended application in
the building construction industry.
2. Materials and methods
2.1. Materials
2.1.1. High calcium wood ash (HCWA)
HCWA is a by-product acquired from an industrial scale fully automatic boiler
unit (commercially known as Bio-Turbomax boiler) used in the rubber wood timber
product manufacturing industry. The wood biomasses used as fuel in the boiler
were derived from local rubber wood species dominantly Hevea Brasiliensis. The
wood biomasses were incinerated under a self-sustained burning condition within
an atmosphere with a turbulent air flow supplied by an in-built air pump unit. The
temperature of incineration was maintained within the range of 800 ± 10 °C [30].
Raw wood ash extracted from the boiler unit was sieved through a laboratory sieve
with an opening size of 600 mm to remove large agglomerated ash particles and car-
bonaceous materials. Resultant materials had a specific surface area of 5671 cm2/g
and specific gravity of 2.43. The physical properties and chemical compositions of
HCWA had been established and described deliberately in prior study of the authors
[27] and are shown in Table 1.
524 C.B. Cheah et al. / Construction and Building Materials 143 (2017) 522–536

Table 1 ing water was incorporated in the mortar mix at a predetermined w/b ratio of 0.30.
Chemical composition and physical parameters of HCWA and PFA [27]. This was to achieve the degree of mix consistency which is suitable for compaction
using the hydraulic press while at the same time exhibit optimal mechanical
Chemical Composition and Physical Parameters % by total mass strength performance [27]. The mortar samples are referred based on the percent-
HCWA PFA age (%) of PFA replacement with HCWA and expressed as %HCWA. Meanwhile, the
paste samples were demarcated with the nomenclature system of WAxFAy where x
MgO 8.70 5.94 is the mass % of HCWA and y is the mass % of PFA.
Al2O3 1.30 17.61
SiO2 2.70 43.22
P2O5 2.70 0.23 2.2.2. Mixing, forming and curing
SO3 2.80 – Each batch of mortar was homogenized using an epicyclic type mechanical
Cl 0.10 – mixer complying with specifications in ASTM Standard C305 [33]. During the mix-
K2O 12.00 1.31 ing of mortar mixes containing HWCA and PFA were initially dry mixed at a low
CaO 61.00 11.28 mixing speed for 3 min prior to the addition of other constituent materials. Further
TiO2 0.11 0.88 mixing sequences and durations were performed in accordance to standard proce-
MnO 0.86 0.14 dures prescribed in ASTM Standard C305 [33]. Upon completion of the mixing, mor-
Fe2O3 1.30 13.73 tar blocks with edge dimensions of 290  140  100 mm were formed with
ZnO 0.10 – hydraulic press. The forming of the mortar block was performed using a constant
SrO 0.22 – volumetric compression ratio of 1.48. All the mortar blocks produced were then
PbO Trace – allowed to set in air for 24 h at ambient temperature of 28 ± 5 °C and relative
CuO 0.01 – humidity 80 ± 5%. Subsequently, the test specimens were further cured by wrap-
Rb2O 0.05 – ping the hardened HCWA-PFA geopolymer mortar blocks with a layer of HDPE film
C 6.70 1.80 to prevent moisture loss till the testing ages of 7, 28, 90, 180 and 365 days.
Na2O – 0.43
Median particle diameter, d50 (mm) 8.39 13.82 2.2.3. Assessment on the standard consistency, initial and final setting time of HCWA-
Loss on ignition (%) 18.00 1.80 PFA paste
Water demand properties namely standard consistency and paste setting prop-
erties including initial and final setting time of HCWA-PFA blended geopolymer
pastes with a fixed sodium silicate content were determined in accordance to test-
2.1.2. Pulverised fuel ash (PFA)
ing methods specified in BS EN 196-3 [34] using the Vicat apparatus. The weighted
Pulverised fuel ash (PFA) used in this study was collected from the precipitator
proportion of HCWA and PFA was first dry blended using the standard epicyclic
unit of local coal fuelled power plant. Results obtained from Blaine fineness analysis
indicated that PFA used in the study had a specific surface area of 3244 cm2/g. The mixer for 3 min in order to obtain homogeneity of the two blended materials. Next,
mixing water was added to the blended HCWA-PFA powder to a certain extent
specific gravity of PFA was determined to be 2.8. Similarly, the details on the phys-
whereby the resultant HCWA-PFA geopolymer paste exhibited a penetration depth
ical and chemical properties of the PFA has been characterized and deliberated
of 6 ± 2 mm between the plunger and base plate. The water content at that partic-
extensively in prior work of the authors [27] and are shown in Table 1.
ular extent was then recorded as the water content to achieve HCWA-PFA geopoly-
mer paste with standard consistence. HCWA-PFA geopolymer paste was then cured
2.1.3. Sodium silicate under moist condition for the subsequent initial and final setting time assessment.
Commercial grade C140 of sodium silicate (Na2SiO3) solution with a modulus Periodical examination was done on the penetration of HCWA-PFA geopolymer
ratio of 2.1 (SiO2/Na2O, SiO2 = 36.5%, Na2O = 18.0%), specific gravity of 1.67 at paste. The initial setting time was determined as the time required for the
20 °C and a total solid content of approximately 52.75% was used as the sole alka- HCWA-PFA geopolymer paste to obtain sufficient stiffness to provide resistance
line activator in sample preparation. towards the penetration of Vicat needle such that the distance between the needle
and the base plate is 6 ± 3 mm. For the determination of final setting time, the filled
2.1.4. Aggregates and mixing water Vicat mould was inverted and subsequent testing was conducted on the face in
Fine aggregates used were locally sourced quartzitic natural river sand in which the mould was inverted. HCWA-PFA geopolymer paste was deemed to have
uncrushed form with a specific gravity of 2.65 and a maximum aggregate size of achieved final set when the Vicat needle only penetrates the paste by only 0.5 mm
5 mm. Fine aggregates were dried to saturated surface dry conditions for use as a or when the time where Vicat needle failed to leave a ring mark attachment onto
constituent material in mortar mixes. Fine aggregates were graded in accordance the surface of HCWA-PFA geopolymer paste.
to BS812: Part 102 [31] and the grading of fine aggregates used were in compliance
with overall grading limits of BS 882 [32]. The fineness modulus of the fine aggre- 2.2.4. Flexural strength, compressive strength and ultrasonic pulse velocity assessment
gates was determined to be 3.26. Potable water from local water supply network HCWA-PFA geopolymer mortar prisms with edge dimensions of
was used as mixing water. The mix design for the geopolymer mortar block are 290  140  100 mm were tested as per procedures prescribed in ASTM Standard
shown in Table 2. C348 [35] for the determination of flexure strength. The reported flexural strengths
at given ages of mortar are the average of the three numbers of specimens tested.
2.2. Methods Subsequently, compressive strength test was performed using the test apparatus
and method prescribed in ASTM C 349 [36].
2.2.1. Mixture proportioning and mixing The density or the compactness of HCWA-PFA geopolymer mortar block can be
The binder: sand were maintained constant at 1:2.25 for all mortar mixes pro- estimated by measuring the propagation velocity of a transmitted ultrasonic pulse
duced. The PFA was partially replaced using HCWA at high substitution levels of 0% across the cross sectional area of HCWA-PFA geopolymer mortar block. This is made
to 100% by total binder weight at stepped increment of 10%. A corresponding set of possible by an ultrasonic pulse generator equipped with a transducer which com-
hydrated ash paste was produced using the aforementioned ash hybridization ratio plies with the standard specification prescribed in BS EN 12504-4 [37]. The test
for the standard consistency and setting time performance assessment. The various was conducted on three representative HCWA-PFA geopolymer mortar block sam-
mix proportions of HCWA-PFA geopolymer mortar are summarized in Table 3. Mix- ples measuring 290  140  100 mm dimension at various curing ages of 7, 28, 90,

Table 2
Mix proportion of HCWA-PFA geopolymer mortar block work.

Mix Designation PFA (kg/m3) HCWA (kg/m3) Sand (kg/m3) Na2SiO3 (kg/m3) Water (kg/m3) Water/binder ratio
WA0FA100 656 0 1476 33 197 0.3
WA10FA90 66 590 1476 33 197 0.3
WA20FA80 131 525 1476 33 197 0.3
WA30FA70 197 459 1476 33 197 0.3
WA40FA60 262 394 1476 33 197 0.3
WA50FA50 328 328 1476 33 197 0.3
WA60FA40 394 262 1476 33 197 0.3
WA70FA30 459 197 1476 33 197 0.3
WA80FA20 525 131 1476 33 197 0.3
WA90FA10 590 66 1476 33 197 0.3
WA100FA0 0 656 1476 33 197 0.3
 C.B. Cheah et al. / Construction and Building Materials 143 (2017) 522–536
Table 3
Standard consistency of HCWA-PFA geopolymer paste with various HCWA-PFA
hybridization ratios.
Mix Designation Standard Consistency
WA0FA100 0.25
WA10FA90 0.26
WA20FA80 0.27
WA30FA70 0.3
WA40FA60 0.35
WA50FA50 0.36
WA60FA40 0.38
WA70FA30 0.38
WA80FA20 0.41
WA90FA10 0.45
WA0FA100 0.49
180 and 365 days of moist curing. The measurement of the ultrasonic pulse velocity
was conducted on the constant path length of 290 mm through the cross section of
HCWA-PFA geopolymer mortar block samples. The ultrasonic pulse generator
record the time taken for the pulse to propagate through the aforementioned path
length by the means of 52 kHz transducer of 50 mm diameter. In order to ensure
high accuracy of measurement, petroleum gel was applied on the surface of the
transducer and the surface of the mortar block sample before each measurement
was taken. The result of UPV was taken as the average value of the three tested sam-
ples of HCWA-PFA geopolymer mortar block.
2.2.5. Fourier transformed infrared (FTIR) spectroscopy assessment
The changes in terms of functional group and the bonding characteristic of
HCWA-PFA geopolymer paste at various hybridization ratios and moist curing ages
was assessed by the utilization of fourier transform infrared spectroscopy (FTIR)
using the spectrometer Perkin Elmer system 2000 series model. The use of FTIR is
intended to monitor the evolution and development of the Si-O-T (T: Si or Al)
and Al-O bond within the geopolymer paste as the geopolymerization progress. This
is an essential assessment to verify the formation of polysialate, poly-sialate-siloxo
and poly-sialate-disiloxo phases within the binder system as the reaction pro-
gresses [38]. Similar application of FTIR method for such assessment had been prac-
ticed in a number of recent studies [39–41] related to characterization on the
development of the geopolymeric framework. The KBr pellet method was utilized
for sample preparation. KBr:HCWA-PFA powder ratio was made constant at 1:200
and was pelletized into 13 mm diameter disc using a hydraulic press at constant
pressure of 8 tons/m2. The pelletized sample was then scanned from wavenumbers
ranging from 400 to 4000 cm1 at 4 cm1 resolution.
3. Results and discussion
3.1. Stamdard consistency of HCWA-PFA blended geopolymer binder
Standard consistency of HCWA-PFA geopolymer cement paste
with various hybridization ratios is presented in Table 3. It is
observed that gradual addition of HCWA content brings about cor-
responding increase in water demand in order to achieve standard
consistency for HCWA-PFA geopolymer paste system. The afore-
mentioned phenomenon is due to the angular particle shape and
porous nature of HCWA if compared with PFA particle. The mixing
water is trapped in the interstitial spacing between HCWA parti-
cles due to the angular effect and also within the pores that pre-
sents on the surface of HCWA particles. This imparts a higher
degree of mixing water needed to wet the HCWA-PFA particles
due to the higher contact surface area so that desirable lubricating
effect which enable standard consistency to be achieved for
HCWA-PFA geopolymer paste system that contains higher propor-
tions of HCWA. On the other hand, the ball bearing effect due to the
spherical and smooth nature of PFA particle resulted in significant
lower water demand in order to achieve the desired standard con-
sistency of HCWA-PFA geopolymer paste which contains higher
proportion of PFA.
3.2. Initial and final setting time of blended geopolymer binder
The setting properties namely initial and final setting time of
HCWA-PFA geopolymer paste with 5% of Na2SiO3 addition is
525
shown in Table 4. The setting properties of HCWA-PFA geopolymer
paste system is a function of the degree of reactivity of the hybrid
geopolymeric system.
It can be observed that HCWA-PFA paste mixes WA30FA70-
WA50FA50 exhibited the lowest initial setting time if compared
to other HCWA-PFA paste mixes. On the other hand, HCWA-PFA
paste mixes WA0FA100-WA20FA80 and WA60FA40-WA0FA100
exhibited similar initial setting performance, whilst higher initial
setting time was observed if compared with WA30FA70-
WA50FA50 group of HCWA-PFA paste mixes. The aforementioned
phenomenon is due to the higher degree of reactivity in
WA30FA70-WA50FA50 paste mixes that resulted in rapid develop-
ment of geopolymeric products in the form of K-A-S-H, N-A-S-H
and C-A-S-H gels. This in turns culminated in rapid hardening of
the HCWA-PFA geopolymer paste and the subsequent observed
lower initial setting time. For HCWA-PFA geopolymer paste that
contains high PFA and HCWA content, namely WA0FA100-
WA10FA90 and WA90FA10-WA100FA0 mixes, it can be observed
that higher PFA content mixes exhibited delayed initial setting
properties if compared with mixes with high HCWA content. This
is most probably due to the lower reactivity of PFA during the ini-
tial stage of curing, caused by the low alkaline activator and ambi-
ent temperature curing. On the other hand, the hydraulic
properties in HCWA-PFA geopolymer paste with higher HCWA
content are prevalent and this contributed towards the faster hard-
ening rate and lower initial setting properties observed.
Similar final setting performance of WA30FA70-WA50FA50 can
be observed, where the aforementioned mixes exhibited lowest
final setting time properties, culminated by the continuous forma-
tion of geopolymeric products and the subsequent hardening of the
HCWA-PFA geopolymer paste. However, for HCWA-PFA geopoly-
mer paste with high PFA and HCWA content, a contrasting final
setting property is observed. WA90FA10 and WA100FA0 geopoly-
mer paste mixes exhibited delayed final setting time if compared
with WA0FA100 and WA10FA90 mixes. The aforementioned phe-
nomena could be due to the higher dissolution of aluminosilicate
species in PFA during the final setting period and resulted in a
higher degree of geopolymeric products formation and subsequent
lower final setting performance observed. It is also indicative of the
continuous dissolution process of aluminosilicate materials even
under mild alkaline activator and the ambient temperature curing
condition.
3.3. Compressive strength
The compressive strength development of HCWA-PFA geopoly-
mer mortar blocks over a curing period up to 365 days is presented
in Fig. 1. At 7 days of moist curing, compressive strength of HCWA-
PFA geopolymer mortar blocks increased with increasing HCWA
Table 4
Initial and final setting time of HCWA-PFA geopolymer paste with various HCWA-PFA
hybridization ratios.
Mix Designation Initial Setting Time (min) Final Setting Time (min)
WA0FA100 70 320
WA10FA90 70 300
WA20FA80 40 260
WA30FA70 30 240
WA40FA60 20 200
WA50FA50 30 280
WA60FA40 50 300
WA70FA30 50 310
WA80FA20 60 330
WA90FA10 40 353
WA100FA0 50 340
526 C.B. Cheah et al. / Construction and Building Materials 143 (2017) 522–536
content up to 50% which is WA50FA50 mortar mix which exhibited
compressive strength of 22.28 MPa.
It is notable that there is a significant increment in terms of
compressive strength between WA10FA90 and WA20FA80 mortar
mixes where the compressive strength rose from 5.15 MPa to
13.16 MPa between the aforementioned mortar mixes. Beyond
WA50FA50 mortar mix, compressive strength of HCWA-PFA
geopolymer mortar blocks exhibited a steady decrease until
WA100FA0 mortar mix. For mortar blocks with low HCWA content
such as WA0FA100 and WA10FA90, compressive strength develop-
ment is mostly governed by the formation of C-A-S-H geopoly-
meric gel resulted from the reaction of dissolved calcium, silicate,
aluminate ions from the PFA source material and the soluble sili-
cate from the chemical activator which is sodium silicate. Due to
the scarce amount of calcium ions present in PFA (approximately
10%) and the relatively low alkalinity of the geopolymeric system,
the compressive strength of HCWA-PFA geopolymer mortar block
with low HCWA content is rather low. For mortar blocks with high
HCWA content namely WA100FA0 and WA90FA10, compressive
strength development is mostly governed by the hydraulic nature
of HCWA and the formation of C-S-H mineral framework from the
reaction of portlandite and soluble silicates from sodium silicate. It
can be said that the optimum HCWA-PFA geopolymer mortar block
mixes lie between WA40FA60 to WA60FA40 after 7 days of moist
curing. The strength development in the aforementioned mixes is
governed by the formation of potassium polysialates (K-A-S-H)
geopolymer framework due to the higher dissolution rate of alumi-
nosilicate compound from PFA where the alkalinity of the geopoly-
mer system contributed by both potassium hydroxide (arcanite
mineral) and sodium hydroxide (sodium silicate) which resulted
in higher amount of soluble silicates and aluminates. Formation
of C-S-H framework is also anticipated but in a lesser amount
due to the higher reactivity of K+ ions compared with Ca2+ ions.
Upon 28 days of moist curing, it is observed that the optimum
compressive strength was exhibited by WA40FA60 mixes, a shift
towards higher PFA content mortar blocks from the previous opti-
mum mix at 7 days of moist curing for WA50FA50 mortar blocks
which exhibited compressive strength of 29.76 MPa. It is antici-
pated that upon 28 days of moist curing, the primary geopolymeric
45.00
40.00
35.00
Compressive Strength (MPa)
30.00
25.00
20.00
15.00
10.00
5.00
0.00
0 10
Fig. 1. Compressive strength development of HCWA-PFA geopolymer mortar block up to 365 days of moist curing.
framework will be that of C-A-S-H. This is due to the cation defi-
ciencies phenomena where there is lack of charge balancing ions
in the dissolved Si and Al species due to the relatively low amount
of K2O present in HCWA (approximately 12%). Therefore, at this
particular timeframe, Ca2+ ions will in turns act as charge balancing
ions and resulted in the formation of geopolymeric precursor in the
form of gehlenite framework (C-A-S-H).
Upon long term moist curing exposure at 90, 180 and 365 days
of moist curing, WA40FA60 remains the mortar block mix which
possessed the highest compressive strength where its 90, 180
and 365 days compressive strength is 36.50, 37.87 and
37.98 MPa, respectively. It is also observed that the rate of long
term compressive strength development is higher for HCWA-PFA
geopolymer mortar blocks with higher PFA content. During long
term curing, mortar mixes with higher PFA content contains higher
amount of dissolved silicate and aluminate species, which in turns
triggered the continuous formation of (Ca, K)-A-S-H geopolymeric
framework and culminated in higher rate of long term compressive
strength development of HCWA-PFA geopolymer mortar blocks
with higher PFA content namely WA50FA50 to WA30FA70 mortar
block mixes. Similar finding where (Ca, K)-A-S-H geopolymer gel
constitute the long term geopolymeric product formation in high
calcium geopolymer system was reported by Puligilla and Mondal
[42].
Based on the compressive strength results, HCWA-PFA geopoly-
mer mortar blocks mixes from WA20FA80 to WA80FA20 are qual-
ified to be classified as normal weight solid load bearing unit with
a minimum average 28 days compressive strength of 13.10 MPa
prescribed under the specification ASTM C 90.
3.4. Flexural strength
Flexural strength of cementitious composite is of importance
for estimation of minimum bending load that one cementitious
composite can sustain before the initiation of cracks. It is also a
measurement of diagonal tensile resistance which is an important
parameter of a masonry unit [43]. During service life of a masonry
wall unit or mortar block, the most common defect will be that of
sulphate attack where sulphate ions originated from underground
7D
28D
90D
180D
365D
20 30 40 50 60 70 80 90 100
HCWA Content (%)
 C.B. Cheah et al. / Construction and Building Materials 143 (2017) 522–536
soil propagate through the mortar block masonry wall unit by cap-
illary movement, forming expansive crystals such as ettringite
within the matrix structure and causes internal expansion which
leads to the formation of micro-cracks and subsequent failure of
the whole masonry structure. The rate at which the sulphate ions
penetrate through the matrix structure depends on various factors,
one of those is the presence of cracks of the masonry unit, where
the flexural strength of the masonry unit plays an important role
in controlling the cracks formation in the aforementioned masonry
unit.
Flexural strength behaviour of HCWA-PFA geopolymer mortar
blocks with various hybridization ratios over a prolonged curing
period is shown in Fig. 2. At 7 days of curing ages, HCWA-PFA
geopolymer mortar blocks with low HCWA and PFA content
namely. WA0FA100, WA10FA90, WA20FA80, WA80FA20,
WA90FA10 and WA100FA0 mortar mixes exhibited significantly
low flexural strength as compared to other mixes. This is probably
due to the weak bonding within the binder paste and also the
bonding between binder matrix and the aggregate particle. On
the other hand, WA30FA70, WA40FA60, WA50FA50, WA60FA40
and WA70FA30 geopolymer mortar block mixes exhibited
enhanced flexural strength in comparison to other mortar mixes.
The governing factor for the aforementioned phenomena is due
to the higher degree of geopolymerization where the formation
of K-A-S-H geopolymeric gel resulted in a denser geopolymer
matrix with stronger bonds between the binder paste matrix and
aggregate particle, thus enhanced the resistance of the aforemen-
tioned HCWA-PFA geopolymer mortar mixes towards tensile rup-
ture. HCWA-PFA geopolymer mortar mix WA60FA40 exhibited
the highest flexural strength of 1.48 MPa.
Upon 28 days of moist curing, it is observed that all the HCWA-
PFA geopolymer mortar blocks exhibited gradual increase in flexu-
ral strength. However, it is noted that upon 28 days of moist cur-
ing, WA40FA60 geopolymer mortar blocks exhibited highest
flexural strength amongst other mortar blocks, a shift toward
geopolymer mortar blocks with higher PFA content, indicating con-
tinuous and higher degree of geopolymeric reaction taking place in
HCWA-PFA geopolymer mortar blocks with higher PFA content
such as mixes with higher amount of silicate and aluminate. Due
to the cation deficiency phenomena as per discussed in the previ-
ous section, it is expected that the main geopolymer product upon
3.00
2.50
Flexural Strength (MPa)
2.00
1.50
1.00
0.50
0.00
0 10
Fig. 2. Flexural strength development of HCWA-PFA geopolymer block work up to 365 days of moist curing.
527
28 days of moist curing of HCWA-PFA geopolymer mortar blocks
will be that of (Ca,K)-A-S-H geopolymer gels. Upon 28 days of
moist curing, HCWA-PFA geopolymer mortar block mixes
WA30FA70-WA90FA10 meet the minimum flexural strength
requirement of 0.93 MPa prescribed by California Concrete
Masonry Technical Committee to be qualified as class N concrete
block work [43].
Upon prolonged moist curing up to. 90 and 180 days,
WA40FA60 geopolymer mortar blocks consistently outperformed
other mortar blocks mixes in terms of flexural strength perfor-
mance, consistent with the 28 days flexural strength results. It is
observed that during this particular timeframe, the flexural
strength development of HCWA-PFA geopolymer mortar blocks
with higher HCWA content namely WA70FA30, WA80FA20,
WA90FA10 and WA100FA0 geopolymer mortar blocks was stag-
nant with no significant increment in flexural strength. During pro-
longed moist curing, continuous geopolymeric reaction is expected
to take place mainly due to the ambient temperature curing
approach utilized throughout the whole research project, albeit
in a slower rate if compared to conventional geopolymer mixes
which utilized elevated temperature curing. Thus, the dissolution
process of silicate and aluminate species from PFA will continue
for a prolonged period of curing if the geopolymer mixes were sub-
jected to ambient temperature curing. The continuous formation of
(Ca,K)-A-S-H geopolymer gels in geopolymer mortar blocks with
higher readily soluble silicate and aluminate species in mortar
blocks with higher PFA content culminated in a higher flexural
strength development observed during moist curing period from
90 to 180 days.
Focusing on the flexural strength development of HCWA-PFA
geopolymer mortar blocks upon 365 days of moist curing, all the
fabricated geopolymer mortar blocks exhibited constant/enhanced
flexural strength if compared with corresponding test specimens
upon 180 days of moist curing. HCWA-PFA geopolymer mortar
blocks with higher HCWA content such as WA70FA30, WA80FA20,
WA90FA10 and WA100FA0 mortar blocks maintained their flexu-
ral strength upon moist curing for 365 days, indicating there is lit-
tle/no geopolymeric reaction taking place in the aforementioned
mortar block mixes upon prolonged curing period. For other
HCWA-PFA geopolymer mortar blocks, it is observed that there is
still gradual increase in terms of flexural strength even after
7D
28D
90D
180D
365D
20 30 40 50 60 70 80 90 100
HCWA Content (%)
528 C.B. Cheah et al. / Construction and Building Materials 143 (2017) 522–536
365 days of moist curing, indicating a continuous long term
geopolymeric reaction taking place in the aforementioned mortar
block mixes, most notably in mixes with high PFA content such
as WA30FA70 and WA40FA60 mortar blocks mixes where the
average increase in flexural strength from 180 days moist cured
samples is around 30%. The continuous increase in flexural
strength of HCWA-PFA geopolymer mortar block over prolonged
moist curing period up to 365 days is indicative of the enhance-
ment in the formation of geopolymeric product due to the addition
of mild alkaline activator of 5 wt.% of sodium silicate. This is
because for during initial trial mix of HCWA-PFA geopolymer mor-
tar block without the addition of alkaline activator, flexural
strength of the hardened mortar block decrease during prolonged
moist curing period up to 90 days, mainly due to the increase in
surface porosity of the hardened mortar block.
A review on the compressive strength and flexural strength
results are indicative that the optimum range of HCWA composi-
tion is 20–60% by total binder weight. When the HCWA content
is below 20% by mass, the hybrid binder system would be deficient
of the arcanite mineral which is inherently present in the chemical
composition of HCWA and essential to initiate the geopolymeriza-
tion reaction especially at early age of the test specimens. On the
other hand, when the HCWA content is in excess of 60%, the dis-
placement of the PFA glassy aluminosilicate phase from the binder
system could have resulted in deficiency of the glassy aluminosil-
icate mineral for continuous geopolymerization and secondary
hydration reaction to form additional binder framework. This
resulted in a significantly lowered rate of the formation of new
geopolymeric phases and hydration product which is reflected in
the low rate of mechanical strength development for test speci-
mens with HCWA content below 20% or in excess of 60%. The find-
ing is consistent with the observation in prior studies [27–29]
whereby a reversal in the uptrend of the mechanical strength
was observed when the HCWA content was increased beyond
60% by total mass of binder.
3.5. Ultrasonic pulse velocity of propagation across the HCWA-PFA
block work
Ultrasonic pulse velocity (UPV) test is one of the most estab-
lished non-destructive test methods for estimation of concrete
strength. Although there is no physical relationship between ultra-
sonic pulse velocity and the strength of concrete, due to its relation
with the density of concrete, ultrasonic pulse velocity test was
viewed as the most rationale and reliable non-destructive test
method for preliminary strength indication of hardened concrete.
Besides, UPV test is also useful for detecting cracks, voids, deterio-
ration and the uniformity of concrete [44].
The UPV of HCWA-PFA geopolymer mortar blocks subjected to
continuous moist curing up to 365 days of exposure is presented
in Fig. 3. At 7 days of moist curing, HCWA-PFA geopolymer mortar
blocks with higher PFA content, namely WA0FA100 and
WA10FA90 exhibited inferior UPV value in comparison to other
HCWA-PFA geopolymer mortar blocks. This indicates the highly
porous nature of the two aforementioned mortar blocks due to
the low degree of geopolymeric reaction which resulted in a low
density of the internal matrix during early age of curing. The opti-
mum HCWA-PFA geopolymer mortar blocks for UPV test lies
between WA40FA60, WA50FA50 and WA60FA40 mortar blocks,
consistent with the compressive strength results shown in the ear-
lier section.
Upon 28 days of moist curing, all the HCWA-PFA geopolymer
mortar blocks showed gradual increment in terms of UPV value,
with the exception of WA0FA100 and WA10FA90 geopolymer mor-
tar blocks, which exhibited an increase of 82% and 22% in compar-
ison with the UPV value after 7 days of moist curing, respectively.
In WA0FA100 and WA10FA90 mortar blocks, the strength develop-
ment is mostly governed by the formation of geopolymeric gel, in
this case N-A-S-H gels due to the scarcity of calcium ion (low
HCWA content). In addition, the slow strength development during
early ages is due to the utilization of ambient temperature curing
and also the relatively low alkalinity of the aforementioned mortar
block mixes due to the low HCWA content. Therefore, it can be said
that for HCWA-PFA geopolymer mortar blocks with low HCWA
content, significant geopolymeric reaction is only taken place after
7 days of moist curing condition. It is also notable that upon
28 days of moist curing, HCWA-PFA geopolymer mortar block
which showed the highest UPV value is WA40FA60 mortar block
mix, a shift from WA50FA50 if compared to 7 days UPV results,
consistent with the compressive strength result. The rigorous for-
mation of C-A-S-H geopolymeric gel filled the voids and interfacial
transition zone in mortar block mixes with higher PFA content dur-
ing 28 days of moist curing, thus resulted in a denser
microstructure.
During prolonged moist curing from 90 to 365 days, there is still
a gradual increase in UPV value for all the HCWA-PFA geopolymer
mortar blocks, with the exception of WA70FA30, WA80FA20,
WA90FA10 and WA100FA0 mortar block mixes, which showed lit-
tle or no increase in terms of UPV value for the prescribed moist
curing time frame. Generally, the optimum HCWA-PFA geopolymer
mortar blocks is WA40FA60 to WA60FA40 which exhibited a
steady increase in UPV value in the range of 2–5% for the moist cur-
ing period from 90 to 365 days. For HCWA-PFA geopolymer mortar
blocks containing higher PFA content especially WA0FA100 and
WA10FA90 mortar block mixes, a significant increase in UPV value
was observed as 87.6% and 29.6% increment, respectively. This
reaffirms the compressive strength result which showed similar
trend and finding. Even during prolonged curing period (90–
365 days of moist curing), (Ca,K)-A-S-H geopolymeric gel was con-
tinuously formed and filled up the capillary pore and interstitial
zones of HCWA-PFA paste matrix and HCWA-PFA paste-
aggregate interface which resulted in a denser microstructure,
especially for HCWA-PFA geopolymer mortar blocks with high
PFA content.
3.6. The empirical correlation between compressive strength and
flexural strength of HCWA-PFA block work
From the laboratory investigation, it was observed that an
empirical correlation exists between the compressive strength
(fcu) and flexural strength (fcf) of HCWA-PFA geopolymer mortar
blocks at moist curing ages up to 365 days. Regression analysis
was performed on the individual HCWA-PFA geopolymer mortar
block mixes utilizing the compressive strength and flexural
strength data acquired and the following correlations was
obtained:
WA0FA100 : f cf ¼ 0:0279f cu þ 0:0393; R2 ¼ 0:989 ð1Þ
WA10FA90 : f cf ¼ 0:0323f cu þ 0:1227; R2 ¼ 0:948 ð2Þ
WA20FA80 : f cf ¼ 0:0683f cu  0:0962; R2 ¼ 0:937 ð3Þ
WA30FA70 : f cf ¼ 0:0517f cu þ 0:265; R2 ¼ 0:960 ð4Þ
WA40FA60 : f cf ¼ 0:0484f cu þ 0:3455; R2 ¼ 0:958 ð5Þ
WA50FA50 : f cf ¼ 0:0822f cu  0:4684; R2 ¼ 0:876 ð6Þ
WA60FA40 : f cf ¼ 0:1012f cu  0:6488; R2 ¼ 0:951 ð7Þ
 C.B. Cheah et al. / Construction and Building Materials 143 (2017) 522–536 529

4000.00

3500.00

Ultrasonic Pulse Velocity (m/s)

3000.00

2500.00
7D

2000.00 28D

90D
1500.00
180D
1000.00 365D

500.00

0.00
0 10 20 30 40 50 60 70 80 90 100
HCWA Content (%)
Fig. 3. Ultrasonic pulse velocity development of HCWA-PFA geopolymer mortar block up to 365 days of moist curing.

WA70FA30 : f cf ¼ 0:0542f cu  0:4663; R2 ¼ 0:992 ð8Þ pressive strength and UPV of HCWA-PFA geopolymer mortar
blocks at any given moist curing ages. Thus, compressive strength
WA80FA20 : f cf ¼ 0:0978f cu  0:4558; R2 ¼ 0:839 ð9Þ of HCWA-PFA geopolymer mortar blocks at various moist curing
ages can be predicted with high degree of precision using the equa-
tions as stated below:
WA90FA10 : f cf ¼ 0:1709f cu  0:8707; R2 ¼ 0:853 ð10Þ
WA0FA100 : f cu ¼ 4  106 V 2  0:0077V þ 6:3602; R2 ¼ 0:977
2
WA100FA0 : f cf ¼ 0:1675f cu  0:4454; R ¼ 0:903 ð11Þ ð13Þ
The regression analysis indicated a strong linear relationship
between the compressive strength and flexural strength of
WA10FA90 : f cu ¼ 1  105 V 2  0:0393V þ 45:948; R2 ¼ 0:990
HCWA-PFA geopolymer mortar blocks cured at moist curing ages ð14Þ
up to 365 days. The high R2 value of the Eqs. (1)–(11) which ranged
between 0.839 and 0.992 indicated high degree of reliability to WA20FA80 : f cu ¼ 7  105 V 2  0:4589V þ 726:42; R2 ¼ 0:849
predict the compressive strength of HCWA-PFA geopolymer mor- ð15Þ
tar block with known flexural strength, or vice versa. The relation-
ship between compressive strength and flexural strength of
WA30FA70 : f cu ¼ 6  105 V 2  0:4053V þ 667:38; R2 ¼ 0:958
individual HCWA-PFA geopolymer mortar block mixes at various
moist curing ages up to 365 days is presented in Fig. 4. ð16Þ
In such an empirical correlation is derived for the prediction of
the flexural strength performance of the HCWA-PFA block work as WA40FA60 : f cu ¼ 0:0001V 2 þ 0:9612V  1783:4; R2 ¼ 0:919
given in a general form in Eq. (12). The empirical model is useful ð17Þ
for the purpose of crack development prediction of block work
structure under both static and seismic load [45]. WA50FA50 : f cu ¼ 0:0004V 2 þ 2:875V  5060:2; R2 ¼ 0:906
f cf ¼ xfcu  y ð12Þ ð18Þ

where x = multiplier coefficient and y = subtraction constant.

WA60FA40 : f cu ¼ 0:0002V 2 þ 1:5461V  2734; R2 ¼ 0:998
3.7. Relation between UPV and compressive strength of HCWA-PFA ð19Þ
geopolymer mortar blocks
WA70FA30 : f cu ¼ 3  105 V 2  0:1451V þ 171:97; R2 ¼ 0:867
The relationship between compressive strength (fcu) and ultra- ð20Þ
sonic pulse velocity (V) for HCWA-PFA geopolymer mortar blocks
is shown in Fig. 5. It can be observed that for any given UPV value, WA80FA20 : f cu ¼ 2  105 V 2  0:1003V þ 148:85; R2 ¼ 0:872
WA30FA70-WA60FA40 HCWA-PFA geopolymer mortar blocks
ð21Þ
exhibited higher compressive strength if compared with others
HCWA-PFA geopolymer mortar blocks namely WA0FA100-
WA20FA80 and WA70FA30-WA100FA0 mixes. WA90FA10 : f cu ¼ 2  105 V 2  0:1365V þ 205:22; R2 ¼ 0:925
Regression analysis was done on the individual HCWA-PFA ð22Þ
geopolymer mortar block mixes and is presented and the empirical
relationship is presented in Eqs. (13)–(23). The high R2 values for WA100FA0 : f cu ¼ 2  105 V 2  0:1334V þ 183:92; R2 ¼ 0:984
Eqs. (13)–(23) which ranged between 0.849 and 0.998 implied that ð23Þ
there is a strong quadratic relationship exists between the com-
530 C.B. Cheah et al. / Construction and Building Materials 143 (2017) 522–536

2.5
WA0FA100

WA10FA90
2
WA20FA80

WA30FA70
Flexural Strength (MPa)

1.5
WA40FA60

WA50FA50

1 WA60FA40

WA70FA30

0.5 WA80FA20

WA90FA10

WA100FA0
0
0 10 20 30 40 50
Compressive Strength (MPa)

Fig. 4. Relationship between compressive strength and flexural strength of individual HCWA-PFA geopolymer mortar block mixes at various moist curing ages up to
365 days.

45
WA0FA100
40
WA10FA90

35 WA20FA80
Compressive strength (MPa)

30 WA30FA70

WA40FA60
25
WA50FA50
20
WA60FA40
15
WA70FA30
10
WA80FA20

5 WA90FA10

0 WA100FA0
0 500 1000 1500 2000 2500 3000 3500 4000
Ultrasonic pulse velocity (m/s)

Fig. 5. Relationship between compressive strength and ultrasonic pulse velocity of individual HCWA-PFA geopolymer mortar block mixes at various moist curing ages up to
365 days.

3.8. Aluminosilicate bond analysis by fourier transformed infrared
spectroscopy
The FTIR spectra of HCWA-PFA geopolymer pastes cured at var-
ious ages were shown in Figs. 6–9. The major bands associated
with WA0FA100 paste are located at 478, 778, 1020, 1453, 1640
and 3438 cm1. For WA40FA60 geopolymer paste major bands
were detected at 458, 618, 712, 875, 996, 1117, 1429, 1636 and
3438 cm1. Finally, peaks corresponding to WA100FA0 geopoly-
mer paste were detected at 446, 618, 712, 871, 965, 1047, 1429,
1460, 1632 and 3461 cm1.
In WA0FA100 geopolymer paste, the visible band at 478 cm1 is
associated with the bending vibration of Si-O-Si and O-Si-O while
the band at approximately 778 cm1 is corresponding to the sym-
metric stretching vibration of Si-O-Si. The broad and distinct band
centered at 1020 cm1 is due to the assymetric stretching vibration
of Si-O-T (T = Al, Si) non-bridging bond, which indicate that the
reaction product is mainly consist of chain structure C-A-S-H gel.
Visible band centered at 1453 cm1 is associated with the assymet-
ric stretching vibration of O-C-O, which indicates the presence of
carbonates in WA0FA100 geopolymer paste. The carbonates were
believed to be that of sodium carbonate due to the atmospheric
carbonation of the mild sodium silicate (5% of binder weight) alka-
line activator media [14]. While distinct bands observed at 1640
and 3438 cm1 was associated with the bending vibration of H-
O-H and stretching vibration of O-H. The aforementioned bands
were due to the weakly bound water molecules which adhered
on the surface or trapped in cavities between the rings of the
polysialate-siloxo geopolymeric products [46,47].
As for WA100FA0, distinct difference in terms of peak intensity
was observed on the assymetric stretching vibration of O-C-O
where WA100FA0 has a significantly higher degree of intensity of
carbonate compound if compared with WA0FA100 geopolymer
paste. This is most probably due to the high amount of CaO present
 C.B. Cheah et al. / Construction and Building Materials 143 (2017) 522–536 531

Fig. 6. FTIR spectra of HCWA-PFA geopolymer paste upon 7 days of moist curing.

Fig. 7. FTIR spectra of HCWA-PFA geopolymer paste upon 28 days of moist curing.

in HCWA which exist as calcite mineral as per the XRD diffrac- WA100FA0 geopolymer paste system [48]. Besides, there is no
togram of HCWA raw material. The visible sharp band at around major band associated with the assymetric stretching vibration
871 cm1 is also indicative of the presence of carbonates in the of Si-O-T (T = Al, Si). Instead, WA100FA0 geopolymer paste showed
532 C.B. Cheah et al. / Construction and Building Materials 143 (2017) 522–536

Fig. 8. FTIR spectra of HCWA-PFA geopolymer paste upon 90 days of moist curing.

Fig. 9. FTIR spectra of HCWA-PFA geopolymer paste upon 365 days of moist curing.

two visible bands centered at 1047 and 965 cm1, which is most
probably due to the low amount of silicate and aluminate in
HCWA.
Upon hybridization between HCWA and PFA such as in
WA40FA60 geopolymer paste mix, it can be seen that the intensity
of bending vibration of H-O-H and stretching vibration of O-H
increased if compared with the IR spectra of WA0FA100 and
WA100FA0. The increase in the amount of weakly bounded water
molecules in WA40FA60 geopolymer paste is indicative of higher
reactivity and the formation of geopolymeric products. Further-
 C.B. Cheah et al. / Construction and Building Materials 143 (2017) 522–536
more, it was observed that the assymetric stretching vibration of
Si-O-T (T = Al, Si) band shifted to lower frequencies wavenumber,
indicating a more polymerized framework was formed, consistent
with the mechanical performance explained in the previous chap-
ter. It is also indicative that structural reorganization and forma-
tion of new geopolymeric products is taking place in the
WA40FA60 geopolymer paste during the alkali activation process
[49]. The intensity of carbonates peak centered at around
1429 cm1 and 875 cm1 was also found to reduce as a result of
the reduction of HCWA content in WA40FA60 geopolymer paste.
FTIR spectra of WA0FA100, WA100FA0 and WA40FA60
geopolymer paste at various moist curing ages is presented in
Figs. 10–12, respectively. For WA0FA100 geopolymer paste
(Fig. 10), gradual increase in the band intensity of the assymetric
stretching vibration of Si-O-T (T = Al, Si) can be observed from 7
to 365 days of moist curing. This can be attributed to the continu-
ous formation of geopolymeric product over prolonged moist cur-
ing duration. It is also notable that the band shifted toward lower
frequency number as the moist curing ages increased, which is an
indication of the formation of new reaction product and subse-
quent structural reorganization during the alkali activation pro-
cess. The other possibility of the aforementioned phenomenon
could be due to the increasing number of tetrahedral aluminium
atoms in WA0FA100 geopolymer paste system as the stretching
mode are sensitive towards the Si:Al composition of the geopoly-
meric framework [50]. The narrow band centered at around
470 cm1 which is associated with the bending vibration of Si-O-
Si and O-Si-O exhibited the same phenomenon, where the
increased in the band’s intensity is more pronounce upon 90 and
365 days of moist curing. The observed phenomenon could be
due to the increased formation of geopolymeric product namely
N-A-S-H gels during prolonged moist curing duration, consistent
with the mechanical performance of WA0FA100 geopolymer mor-
tar block, where there is a significant increase in terms of compres-
sive strength between 90 to 365 days of moist curing duration.
Fig. 10. FTIR spectra of WA0FA100 geopolymer paste at various moist curing ages.
533
As for WA100FA0 geopolymer paste (Fig. 11), the distinct differ-
ence in terms of IR spectra over 365 days of moist curing duration
is the increase in band’s intensity at 1436 cm1 which is associated
with the assymetric stretching vibration of O-C-O, which is indica-
tive of carbonate in the system. The increase in intensity is more
notable during the early age of curing of 7–28 days of moist curing.
This is most probably due to the formation of calcite as a result of
the carbonation reaction of Ca2+ ions. There is also increase in
intensity in visible peaks at around 1120 cm1 and 980 cm1
which is associated with the assymetric stretching vibration of
Si-O-T (T = Al, Si). The reaction between Ca(OH)2 and K2O liberated
as a result of HCWA hydration and the sodium silicate resulted in
the formation of K-A-S-H and C-A-S-H type geopolymer gel [51].
Over prolonged curing duration of 90–365 days, IR spectra of
WA100FA0 paste do not exhibit significant changes in terms of
both intensity and wavenumber. This implied that most of the
reaction product development in WA100FA0 paste system
occurred during the early age of moist curing of 7–28 days. The
finding is consistent with the mechanical strength performance
of WA100FA0 geopolymer mortar block where upon 90 days of
moist curing, the compressive strength development remains con-
stant until 365 days.
In WA40FA60 geopolymer paste system (Fig. 12), it can be seen
that the bands associated with the stretching vibration of O-H and
bending vibration of H-O-H which is 3639 cm1 and 1639 cm1,
respectively exhibited an increase in intensity over the duration
of moist curing up to 365 days. The increase in intensity signified
the increase in the amount of weakly bound water molecules
which is adsorbed or trapped in large cavities between the chains
of geopolymeric products which in turn implied the continuous
formation of geopolymeric products in WA40FA60 geopolymer
paste system over moist curing duration up to 365 days. In addi-
tion, the aforementioned bands exhibited a shift in wavenumber
to a higher frequency number of 3439 cm1 to 3474 cm1 for
stretching vibration of O-H and 1639 cm1 to 1650 cm1 from 7
534 C.B. Cheah et al. / Construction and Building Materials 143 (2017) 522–536

Fig. 11. FTIR spectra of WA100FA0 geopolymer paste at various moist curing ages.

Fig. 12. FTIR spectra of WA40FA60 geopolymer paste at various moist curing ages.

to 365 days of moist curing. This is an indication of the formation 4. Conclusions

of highly polymerized geopolymeric network [49] and is consistent
with the compressive strength results discussed in the previous Based on the results of the laboratory investigation, the follow-
chapter. ing conclusions of study can be derived.
 C.B. Cheah et al. / Construction and Building Materials 143 (2017) 522–536
1. In HCWA-PFA hybrid geopolymer paste system, as the HCWA
content increased, the amount of mixing water required to
achieve standard consistency increased proportionally due to
the angular particle shape and the porous nature of HCWA in
comparison with PFA.
2. HCWA-PFA geopolymer paste WA30FA70-WA50FA50 showed
higher rate of initial and final setting characteristic, if compared
with WA0FA100-WA20FA80 and WA60FA40-WA100FA0. The
faster rate of initial and final setting is due to the higher degree
of reactivity in WA30FA70-WA50FA50 geopolymer paste which
resulted in rapid development of geopolymeric products and
resulted in subsequent hardening of the aforementioned
geopolymer paste.
3. HCWA-PFA geopolymer mortar blocks WA50FA50 and
WA40FA60 showed highest compressive and flexural strength
performance during the early age of moist curing between 7
and 28 days. Over prolonged moist curing between 90 days
and 365 days, WA30FA70 consistently showed optimum com-
pressive and flexural strength performance amongst the
HCWA-PFA geopolymer mortar block mixes.
4. Based on the 28 days compressive strength results of HCWA-
PFA geopolymer mortar blocks, WA20FA80 to WA80FA20
geopolymer mortar block mixes can be qualified as normal
weigth solid load bearing unit with a minimum average 28 days
compressive strength of 13.10 MPa prescribed under the speci-
fication ASTM C 90. On the other hand, HCWA-PFA geopolymer
mortar block mixes WA30FA70-WA90FA10 meet the minimum
flexural strength requirement of 0.93 MPa prescribed by Cali-
fornia Concrete Masonry Technical Committee to be qualified
as class N concrete masonry unit.
5. HCWA-PFA geopolymer mortar block WA40FA60-WA60FA40
exhibited highest UPV value during both early and prolonged
moist curing duration up to 365 days. Highest long term devel-
opment rate of UPV was observed for HCWA-PFA geopolymer
mortar block with higher PFA content such as WA0FA100 and
WA10FA90 while mortar block mixes with high HCWA content
such as WA90FA10 and WA100FA0 showed negligible enhance-
ment in terms of UPV value over prolonged moist curing period.
The enhancement in UPV value for HCWA-PFA geopolymer mor-
tar block is due to the formation of various phases of geopoly-
meric products which resulted in a denser microstructure.
6. The hybridization between HCWA and PFA in WA40FA60 paste
brings about an increase in the intensity of IR spectra associated
with the bending vibration of H-O-H and stretching vibration of
O-H, which corresponded to the amount of weakly bound
water. This indicates the rigorous polycondensation process in
WA40FA60 where large amount of weakly bound water was
expelled. The high degree of geopolymerization taking place
in WA40FA60 paste can also be justified by the increase in
peaks associated with the assymetric stretching vibration of
Si-O-T (T = Al, Si) over prolonged moist curing condition.
7. The blockwork produced using the primary binder phase
derived from the combination of HCWA and PFA is viable for
use in building construction.
Acknowledgement
The author would like to acknowledge the Ministry of Science,
Technology and Innovation (MOSTI) – Malaysia, Malaysian Min-
istry of Higher Education and Universiti Sains Malaysia for funding
the study under the MOSTI Sciencefund (Project No.06-01-05-
SF0848). Fundamental Research Grant Scheme (FRGS) (203/
PPBGN/6711471) and Research University (RU) Grant (Grant no.
1001/PPBGN/814212 and 1001/PPBGN/814211).
535
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