Journal of Hazardous Materials 341 (2018) 257–267

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Journal of Hazardous Materials

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

Research Paper

High calcium fly ash geopolymer stabilized lateritic soil and

granulated blast furnace slag blends as a pavement base material
Itthikorn Phummiphan a , Suksun Horpibulsuk b,∗ , Runglawan Rachan c , Arul Arulrajah d ,
Shui-Long Shen e , Prinya Chindaprasirt f
a
Graduate Program in Construction and Infrastructure Management, Suranaree University of Technology, 111 University Avenue, Muang District, Nakhon
Ratchasima 30000, Thailand
b
School of Civil Engineering, Center of Excellence in Innovation for Sustainable Infrastructure Development, Suranaree University of Technology, Thailand
c
Department of Civil Engineering, Mahanakorn University of, Technology, Nong Chok District, Bangkok 10530, Thailand
d
Department of Civil and Construction Engineering, Swinburne University of Technology, Melbourne, Australia
e
Department of Civil Engineering, Shanghai Jiao Tong University and State Key Laboratory of Ocean Engineering, 800 Dong Chuan Road, Minhang District,
Shanghai 200240, China
f
Sustainable Infrastructure Research and Development Center, Department of Civil Engineering, Khon Kaen University, Khon Kaen, Thailand

h i g h l i g h t s

• Evaluation of Fly Ash (FA) based geopolymer stabilized lateritic soil/GBFS blend.
• Role of L, NaOH/Na2 SiO3 , GBFS content, and curing time were investigated.
• Microstructural development was examined via XRD and SEM analyses.
• UCS of FA geopolymer stabilized blends was compared with road authorities requirements.

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

Article history: Granulated Blast Furnace Slag (GBFS) was used as a replacement material in marginal lateritic soil (LS)
Received 25 January 2017 while class C Fly Ash (FA) was used as a precursor for the geopolymerization process to develop a low-
Received in revised form 26 July 2017 carbon pavement base material at ambient temperature. Unconfined Compression Strength (UCS) tests
Accepted 29 July 2017
were performed to investigate the strength development of geopolymer stabilized LS/GBFS blends. Scan-
Available online 31 July 2017
ning Electron Microscopy and X-ray Diffraction analysis were undertaken to examine the role of the
various influencing factors on UCS development. The influencing factors studied included GBFS content,
Keywords:
Na2 SiO3 :NaOH ratio (NS:NH) and curing time. The 7-day soaked UCS of FA geopolymer stabilized LS/GBFS
Geopolymer
Lateritic soil
blends at various NS:NH ratios tested was found to satisfy the specifications of the Thailand national road
Fly ash authorities. The GBFS replacement was found to be insignificant for the improvement of the UCS of FA
Granulated blast furnace slag geopolymer stabilized LS/GBFS blends at low NS:NH ratio of 50:50. Microstructural analysis indicated
Pavement base the coexistence of Calcium Silicate Hydrate (CSH) and Sodium Alumino Silicate Hydrate products in FA
geopolymer stabilized LS/GBFS blends. This research enables GBFS, which is traditionally considered as a
waste material, to be used as a replacement and partially reactive material in FA geopolymer pavement
applications.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction

Ordinary Portland Cement (OPC) is the most widely used

∗ Corresponding author at: School of Civil Engineering, Suranaree University of
Technology, 111 University Avenue, Muang District, Nakhon Ratchasima 30000,
Thailand.
E-mail addresses: suksun@g.sut.ac.th (S. Horpibulsuk), runglawa@mut.ac.th
(R. Rachan), aarulrajah@swin.edu.au (A. Arulrajah), slshen@sjtu.edu.cn (S.-L. Shen),
prinya@kku.ac.th (P. Chindaprasirt).
cementing agent in civil engineering infrastructure projects. The
production of OPC, however, emits a large amount of greenhouse
gases, notably CO2 into the atmosphere. Cement production world-
wide discharges up to 4.0 billion tons of CO2 annually [1–3]. The
production of just 1 ton of OPC releases about 1 ton of CO2 [4].
Pollution and global warming coupled with growing public
environmental awareness has been increasing rapidly in many

http://dx.doi.org/10.1016/j.jhazmat.2017.07.067
0304-3894/© 2017 Elsevier B.V. All rights reserved.
258 I. Phummiphan et al. / Journal of Hazardous Materials 341 (2018) 257–267
developed and developing countries. Environmentally friendly
alternative construction materials are increasingly being sought
[2]. Geopolymer, a novel green cementing agent manufactured
from various industrial waste by-products, is considered as an
alternative materials to OPC. Geopolymer is an inorganic alumi-
nosilicate material synthesized by mixing source materials rich in
silica (SiO2 ) and alumina (Al2 O3 ) such as Fly Ash (FA), metakaolin,
Granulated Blast Furnace Slag (GBFS) and Silica Fume (SF) with
alkali activators [5].
The engineering properties of geopolymers that are sought for
civil engineering applications include: high compressive strength
[6–8], rapid controllable setting and hardening [9], fire resistance
[10–12], acid and salt solution resistance [13], lack of deleterious
alkali–aggregate reactions and low shrinkage [14].
The commonly used activators for geopolymerization include
alkaline metal and alkaline earth metal compounds [15]. Generally,
the most effective activator providing the best performance for high
strength and other advantageous properties is a mixture combining
sodium hydroxide (NaOH) and sodium silicate (Na2 SiO3 ) [16]. The
use of large quantities of sodium silicate is not recommended for
the environment, as it imparts a high carbon footprint alkali. The
emission factors are 1.514 kg CO2 -e/ton [17] and 0.86 kg CO2 -e/ton
[18] for sodium silicate and cement production, respectively.
Both class F and class C Fly Ash (FA) as precursors have been
extensively used for the development of geopolymers [19–21]. The
class C FA contains high calcium oxide (CaO) and is designated as
a self-cementing FA. The Class C Fly ash has been used for mak-
ing concrete and soil stabilization without cement [22–24]. The
reaction between class C FA and the liquid alkaline activator there-
fore forms Calcium Silicate Hydrate (CSH) and Calcium Alumino
Hydrate (CAH), which co-exists with geopolymerization products.
Mechanical properties and microstructure of class F FA geopolymer
at ambient temperature were found to be improved by including
very fine GBFS as an additive [25,26]. This is as the FA-GBFS geopoly-
mer system will form aluminium-modified calcium silicate hydrate
(CASH) gel which coexists with sodium aluminosilicate hydrate
(NASH) gel [27,28]. The coexistence of CASH and NASH was also
evident for other FA and calcium-rich additive based geopolymers
[29,30].
Several researchers have used geopolymers in concrete applica-
tions. However, only in recent years research has been undertaken
on geopolymer improved demolition waste materials and soft soils
[31–38]. Phummiphan et al. [35] have first introduced the usage
of high calcium FA-based geopolymer to stabilized marginal lat-
eritic soil to develop a green pavement base in Thailand. The early
strength of the geopolymer stabilized marginal lateritic soil was
found to be enhanced by using a waste Calcium Carbide Residue
(CCR) as an additive [36]. The CCR was small-sized and was proven
to be a binder, which reacted with silica and alumina from soil
and FA, to form Calcium Silicate Hydrate (CSH) [39]. Phetchuay
et al. [40] first introduced a FA geopolymer to stabilize soft marine
clay in Australia and reported that the CCR not only improved
the strength of geopolymer stabilized clay but also provided low
carbon-emission when compared to cement stabilization.
Similarly, fine sized GBFS as an additive has been demonstrated
to enhance the engineering properties of class F FA geopolymer sta-
bilized recycled demolition aggregate [41,33] and FA geopolymer
stabilized spent coffee grounds [42] for pavement base/subbase
and subgrade applications, respectively. The very fine GBFS par-
ticles can react rapidly with a liquid alkaline activator and improve
the early strength of FA geopolymer stabilized materials. However,
crushing of GBFS to very fine particles is a costly and energy-
intensive process. A cost-effective and environmental-friendly
means is to reuse medium-sized GBFS as a replacement as well
as a partially reactive material for geopolymer stabilization.
Fig. 1. Particle size distribution of LS, FA and GBFS.
The study on the usage of medium-sized GBFS as a partial
replacement of lateritic soil in class C FA geopolymer stabiliza-
tion for sustainable pavement application is to date limited and
is the focus of this research. The usage of by-products (class
C FA and GBFS) and liquid alkaline activator without Portland
cement to stabilize marginal lateritic soil is novel and significant in
terms of engineering, economic and environmental perspectives.
Unconfined Compression Strength (UCS) was used to evaluate the
strength development of the FA geopolymers stabilized soil/GBFS
blends. Scanning Electron Microscopy (SEM) and X-ray Diffraction
(XRD) analysis were undertaken to investigate the effect of vari-
ous influencing factors on the strength development. The factors
studied included GBFS content, Na2 SiO3 :NaOH (NS:NH) ratio and
curing time. The outcome of this study will enable GBFS, an indus-
trial by-product, to be used as a replacement and partial reactive
material in FA geopolymer pavement applications.
2. Materials and properties
2.1. Soil sample
Lateritic Soil (LS) samples were obtained from a quarry in the
city of Rayong, Thailand. The Liquid Limit (LL), Plastic Limit (PL),
and Plasticity Index (PI) in accordance with ASTM D4318 [43] were
27.72%, 21.65%, and 6.07%, respectively while the specific gravity
(Gs ) was 2.58. The natural water content of LS was 10%. The grain
size distribution was determined by sieve analysis [44] as shown in
Fig. 1 and was compared to that specified for base/subbase mate-
rials by AASHTO and Department of Highways, Thailand [45,46].
The gradation of LS was within the specified limits. The LS was
a silty clayey sand (SC-SM) and A-2-4(0) according to the Uni-
fied Soil Classification System (USCS) [47] and the AASHTO [48],
respectively. The optimum moisture content (OMC) and maximum
dry unit weight (␥d,max ) of LS under modified Proctor energy [49]
were 8.0% and 20.85 kn/m3 , respectively. California Bearing Ratio
(CBR) value at 95% of ␥d,max was 14.7%. Los Angeles (LA) abrasion in
accordance with ASTM C131 [50] and ASTM C535 [51] was 52.9%.
When comparing the CBR and LA abrasion results to the spec-
ification of Department of Highways for subbase and engineering
fill materials (DOH 1989) (Table 1), LS did not meet the specified
subbase requirement but met the requirements of an engineering
fill material. In remote construction sites, located far away from
high quality quarry materials, chemical stabilized LS can poten-
tially be used as pavement construction materials. The chemical
stabilization of LS will lead to savings in haulage costs and will
furthermore minimize negative environmental impacts. Chemical
composition of LS obtained from X-ray Fluorescence (XRF) analy-
 I. Phummiphan et al. / Journal of Hazardous Materials 341 (2018) 257–267 259

Table 1
Engineering properties of LS compared with subbase and engineering fill material specifications (DRR 2013 and DOH 2000).

Engineering properties Soil sample Subbase Engineering fill material

Liquid limit (LL) (%) 27.72 <35 <40

Plastic index (PI) 6.07 <11 <20
California Bearing Ratio (CBR) at 95% of ␥d,max (%) 14.70 >25 >10
Los Angles abrasion (percent of wear) (%) 52.90 <60 <60

Fig. 2. SEM images of: (a) LS, (b) FA, and (c) GBFS.

Table 2 analysis. The iron oxides in lateritic soil was 10.9%, which is within
Chemical compositions of LS, FA, and GBFS.
the typical value (5.6% and 23.5% with most values less than 12%)
Chemical composition (%) LS FA GBFS (Chanthaburi, Rayong and Chonbuuri) previously reported by Tan-
SiO2 77.81 36.00 26.78 tiwanit and Changsuwan [52]. The SEM image (Fig. 2 (a)) showed
Al2 O3 4.42 16.80 6.96 that LS was irregular shape. The main mineral components of LS
Fe2 O3 10.93 17.64 18.65 were quartz, muscovite, illite and montmorillonite as shown in
CaO 1.13 26.73 30.38 Fig. 3(a). Peak intensity of crystalline elements composed of cal-
MgO N.D. N.D. 9.70
cite, calcium silicate, gehlenite and calcium aluminium oxide in LS
SO3 1.36 N.D. 1.74
K2 O 2.33 1.83 N.D. occurred between 25◦ 2␪ and 43◦ 2␪.
TiO2 1.33 0.48 0.89
MnO2 0.55 0.15 3.56 2.2. Fly ash
Br2 O 0.38 N.D. N.D.
Cr2 O3 N.D. N.D. 0.85
ZnO N.D. N.D. 0.48 Fly Ash (FA) was collected from the Mae Moh power plant in
Thailand. The chemical composition obtained from XRF of FA is
N.D. = not detected.
shown in Table 2. The main components of the FA (SiO2 , Fe2 O3 ,
Al2 O3 ) were 70.44% while CaO content was 26.73%. The FA was
sis using Horiba XGT-5200 X-ray Analytical Microscope is shown therefore classified as a high calcium class C. Particle size distri-
in Table 2. The samples were ground to essentially similar particle bution and microstructure of FA are illustrated in Figs. 1 and 2 b,
sizes and were then compressed by a pressed pellet with 200 kn respectively. The FA particles were fine-grained and spherical in
force for 30 s to have a 40 mm diameter specimen prior to XRF shape. The XRD pattern of FA showed that FA consisted mainly of
260 I. Phummiphan et al. / Journal of Hazardous Materials 341 (2018) 257–267

Q= Quartz (SiO2)
Q M= Muscovite (KAl 2(Si3Al) O 10(OH,F)2)
I= Illite (KAl 2Si3AlO 10(OH) 2)
K= Montmorillonite (Na 0.3Al 4Si6O15(OH) 64H2O)

LS
M M
Q M
K I Q
MI M Q Q M Q Q Q
Q
10 20 30 40 50 60
2 theta (degree)
(a)
Q= Quartz (SiO2) C
C= Calcite (CaCO 3)
A= Anhydrite (CaSO 4)
F= Maghemite (Fe2O3) C
S= Calcium Silicate (Ca 2SiO 4)
G= Gehlenite (Ca 2Al 2SiO 7) S
L= Calcium Aluminium Oxide S
(CaO.Al 2O3) L
SG S
G C
GBFS G C C
S G S CS G S SG S SG
L
A Q
C F
FA
Q
FA A F
F F

10 20 30 40 50 60 70
2 theta (degree)

Fig. 3. XRD pattern of (a) LS and (b) GBFS and FA.

glassy phase materials (amorphous humps between 7◦ 2␪ and 25◦
2␪) with some crystalline additions of anhydrite, quartz, calcite and
maghemite between 20◦ 2␪ and 37◦ 2␪ (Fig. 3b).
2.3. Granulated blast furnace slag
Granulated Blast Furnace Slag (GBFS) samples were obtained
from Siam Steel Mill Services Co., Ltd., Chonburi Thailand. The GBFS
was passed through a 2 mm (No.10) sieve, and air-dried at room
temperature. GBFS was non-plastic with a specific gravity of 3.54.
The main chemical compositions were 30.38% CaO, 26.78% SiO2 ,
18.65% Fe2 O3 , 9.70% MgO and 6.96% Al2 O3 as shown in Table 2.
The particle size distribution is shown in Fig. 1. The particle size
was similar to that of LS and much larger than that of FA. The SEM
image (Fig. 2c) indicated that the particles were generally irregular
in shape. The XRD pattern showed that GFBS contained traces of
calcite, calcium silicate, gehlenite and calcium aluminium oxide
(Fig. 3b). The amorphous humps of GBFS were in the region of 8◦
2␪ to 20◦ 2␪. Even though the chemical compositions of the GBFS
and FA were similar, however the FA was considered more reactive
than GBFS due to its higher reactive surface area.
2.4. Liquid alkali activator
The liquid alkaline activator (L) used was a mixture of sodium
silicate (Na2 SiO3 , NS) solution and sodium hydroxide (NaOH, NH)
solution with a concentration of 5 molars. The suitable concentra-
tion for L was generally between 4.5 and 18 molars [53–56,30].
A low NH concentration of 5 molars was considered in this study
to avoid health harm of workers and to have cost-effectiveness.
Na2 SiO3 solution consisted of Na2 O, SiO2 and H2 O which are 15.50%,
32.75%, and 51.75% by weight, respectively. Distilled water was
used throughout the experiments to produce the NH solution.
3. Sample preparation of fa geopolymer stabilized soil
In this study, the LS was oven-dried at 40 ◦ C for 3 days before
mixing with FA and GBFS. The FA content was fixed at 30% of the
total mix as suggested by Phummiphan et al. [35,36] while the GBFS
contents were varied to replace LS from 10% to 30%. The LS:FA:GBFS
ratios were thus 60:30:10, 50:30:20, and 40:30:30. Phummiphan
et al. [36] reported that the optimal NS:NH ratio providing the high-
est strength of FA geopolymer stabilized LS was between 100:0 and
50:50. The NS:NH ratios studied were 100:0, 90:10, 80:20, 50:50
and 40:60. Due to the large GBFS particles, even with similar chem-
ical composition to FA, the main geopolymerization reaction in the
stabilized LS can be attributed to the presence of FA.
The LS, FA and GBFS were firstly mixed together to ensure homo-
geneity by a soil mixer and then the L was sprayed on the LS, FA
and GBFS mixture during mixing for an additional 5 min. The mix-
tures were next compacted in a standard 101.6 mm diameter and
 I. Phummiphan et al. / Journal of Hazardous Materials 341 (2018) 257–267
Fig. 4. Compaction curves of FA-GBFS geopolymer stabilized LS.
116.4 mm height mold under modified Proctor energy according to
ASTM [49]. The compacted samples were demolded and immedi-
ately wrapped with plastic sheets and cured at room temperature
between 27–30 ◦ C. It was noted from the laboratory observation
that the setting time of class C FS geopolymer stabilized lateritic soil
was about 30 min. In this study, the sample preparation and com-
paction were completed within 15 min. This stabilization method
can be applied in pavement base and subbase applications in prac-
tice, where compaction for each section must be finished within
the setting time.
According to the Department of Highways (DOH) and Depart-
ment of Rural Roads, Thailand as well as road authorities in
Australia and other countries, the UCS is the critical design param-
eter and as such was used for comparison purposes in this study.
However, cyclic tests such as resilient modulus and permanent
strain are also important to understand the material performance
and are used for a mechanistic design and are recommended for
future study for a separate publication.
The soaked UCS value of the samples just after mixing was 0.
The UCS of soaked geopolymer samples was thus measured after
curing periods of 7, 28, and 60 days. The UCS samples were tested
using the Universal Testing Machine (UTM) with a compression
rate of 1 mm/min in accordance with ASTM [57], the specification
of Department of Highways [58] and Department of Rural Roads
[59], Thailand. The stress-strain and soil modulus were not pre-
sented in this paper as they must be determined from sample with
a 1: 2 diameter: height ratio, while the UCS samples were 1: 1.15
diameter: height ratio, which is specified by various national local
road authorities in Thailand and some other countries.
The growth of the geopolymerization products was demon-
strated using SEM and XRD analysis [60]. The small samples were
frozen at −195 ◦ C by immersion in liquid nitrogen and coated with
gold before SEM analysis [37]. The sample surface was scanned with
a focused beam of electrons using JEOL JSM-6010LV device. The
samples were also ground to fine powder for XRD tests to obtain
microstructural information of amorphous and crystalline phases.
The XRD scans were performed at 0–90◦ 2␪ by Bruker D8 ADVANCE
device. The XRD analysis using Cu X-ray tube was done on pow-
dered samples and patterns were obtained by scanning at 0.1◦ (2␪)
per min and at steps of 0.05◦ (2␪). The voltage and current of the
XRD analysis were set at 45 kV and 40 mA, respectively.
261
4. Results and discussion
4.1. Compaction characteristics of FA geopolymer stabilized
LS/GBFS blends
Fig. 4 illustrates the relationships between ␥d and liquid alkaline
activator, L content of the FA geopolymer stabilized LS/GBFS blends
for various LS:FA:GBFS ratios and NS:NH ratios. The ␥d,max values
of FA geopolymer stabilized blends for all GBFS contents tested
were higher than the ␥d,max value of the lateritic soil (without sta-
bilization) possibly because GBFS has a higher specific gravity than
lateritic soil. The compaction curves of FA geopolymer stabilized
LS/GBFS blends were dependent on the GBFS content and NS:NH
ratio. For a particular NS:NH ratio and GBFS content, ␥d of the FA
geopolymer stabilized LS/GBFS blends increased with increasing
LA content until ␥d,max reached an Optimum Liquid Content (OLC).
Beyond the OLC, ␥d decreased with the increased L content. For all
the NS:NH ratios, ␥d,max increased with increasing GBFS content,
due to the high specific gravity of GBFS. For 20% and 30% GBFS,
␥d,max tended to increase with decreasing the NS content while
the ␥d,max for the 10% GBFS sample showed the opposite trend.
However, the change in ␥d,max for all GBFS contents were insignifi-
cant when compared to the change in OLC. The OLC significantly
decreased with decreasing NS (increasing NH) because NH had
lower viscosity than NS (the viscosity of NH and NS was about 1.002
and 400 mPa.s at 20 ◦ C, respectively). In other words, NH lubricated
the soil particles and hence improved the compactibility. The rela-
tionships between OLC and NS contents for various GBFS contents
could be represented as linear functions as shown in Fig. 5.
4.2. Unconfined compressive strength of FA geopolymer stabilized
LS/GBFS blends
The relationships between UCS and GBFS content of the FA
geopolymer stabilized LS/GBFS blends at different curing times
and NS:NH ratios are shown in Fig. 6. The 7-day UCS of all stabi-
lized materials at various LS:FA:GBFS ratios compacted at OLC were
higher than the UCS specified by the Department of Rural Roads and
Department of Highways of Thailand (>1.724 MPa for light traffic
[59] and >2.413 MPa for heavy traffic [58]) and by the Australia
road authority (>3.5 MPa [61]). As shown in Fig. 6a–d, the 7-day
262 I. Phummiphan et al. / Journal of Hazardous Materials 341 (2018) 257–267
Fig. 5. OLC versus NS relationships for various GBFS contents.
UCS development of the stabilized LS/GBFS blends was dependent
upon NS:NH ratio. For NS:NH ratios of 100:0, 90:10 and 80:20,
the 7-day UCS values increased with increasing GBFS content until
the maximum values at optimal GBFS content were attained and
subsequently decreased. The optimal GBFS content decreased with
decreasing NS:NH ratios. The highest 7-day UCS was found at 20%
GBFS (optimal) and NS:NH = 100:0, which was equal to 10.46 MPa.
Fig. 6. The UCS of FA-GBFS geopolymer stabilized LS at various GBFS contents, cured at 7–60 days for different NS:NH ratios (a) 100:0, (b) 90:10, (c) 80:20 and (d) 50:50.
The same was however not observed for NS:NH = 50:50; i.e., GBFS
content did not affect the UCS development.
For the long-term curing (28–60 days), two strength character-
istics were noted for high NS:NH ratios (NS:NH = 100:0, 90:10 and
80:20) and low NS:NH ratio (NS:NH = 50:50). Referring to Fig. 6a–c
for the high NS:NH ratios, the LS:FA:GBFS = 60:30:10 was regarded
as optimal. The 60-day UCS values at LS:FA:GBFS = 60:30:10 were
18.02 MPa, 20.21 MPa and 18.74 MPa for NS:NH = 100:0, 90:10 and
80:20, respectively. In other words, the highest long-term UCS was
found at LS:FA:GBFS = 60:30:10 and NS:NH = 90:10. For the low
NS:NH of 50:50 (Fig. 6d), GBFS did not affect the UCS development;
i.e., GBFS was not required for the NS:NH = 50:50. Even though the
7-day UCS was lowest compared to that at higher NS:NH ratios,
the 28-day and 60-day UCS values for LS:FA:GBFS = 70:30:0 (no
GBFS) were the highest. NH had a significant effect on long term
UCS development because the reaction between NH and FA is
time-dependent; hence, the CSH develops at a long curing time of
90 days [36].
The highest 7-day UCS was found at NS:NH = 100:0
and LS:FA:GBFS = 50:30:20 while the highest 28-day and
60-day UCS values were found at NS:NH = 90:10 and
LS:FA:GBFS = 60:30:10. However, the 7-day UCS at NS:NH = 90:10
and LS:FA:GBFS = 60:30:10 was just slightly lower than that at
NS:NH = 100:0 and LS:FA:GBFS = 50:30:20. As such, NS:NH = 90:10
and LS:FA:GBFS = 60:30:10 are recommended in practice. The very
high 30% GBFS content (LS:FA:GBFS = 40:30:30) must however be
avoided, as it retarded the UCS development especially high NS:NH;
i.e. the UCS development was insignificant after 28 days of curing.
 I. Phummiphan et al. / Journal of Hazardous Materials 341 (2018) 257–267
Fig. 7. SEM images of stabilized samples with 90:10 NS:NH and 10% GBFS after 7, 28 and 60 days of curing.
4.3. SEM analysis
Investigation of microstructural development of FA geopoly-
mer stabilized LS/GBFS blends via SEM analysis is advantageous
for observing the chemical reaction and the growth of cementa-
tion matrix over the curing period. As the 60:30:10 LS:FA:GBFS
and 90:10 NS:NH are recommended in practice, the microstruc-
tural development with time (7, 28 and 60 days) of the sample with
this ingredient was examined and is presented in Fig. 7. For early
curing time of 7 days, the chemical reaction occured on the FA sur-
face (Fig. 7a). The etched holes and cementitious products on FA
particles, which indicated the chemical reaction between L and FA,
were observed after 28 days of curing (Fig. 7b). More etched holes
and cementitious products on the shell of FA particles were clearly
detected after 60 days of curing (Fig. 7c). This indicated the leaching
of silica and alumina oxides from FA by alkaline dissolution with
time. Hence, the UCS continued to develop even after 60 days of
curing.
Fig. 8 presents SEM images of the FA geopolymer stabilized
LS/GBFS blend at high 30% GBFS (LS:FA:GBFS = 40:30:10) for both
high and low NS:NH ratios = 90:10 and 50:50 and cured for 7, 14, 28
and 60 days in order to examine the negative impact of very high
GBFS contents. For high NS:NH ratio of 90:10, the microstructures
changed insignificantly with increasing curing times (Fig. 8c, e and
g), which was notably different with those at 60:30:10 LS:FA:GBFS
(Fig. 7). This indicated that GBFS retarded the geopolymerization
process over time. On the contrary, the microstructural change with
time was noted for low NS:NH ratios of 50:50 (Fig. 8d, f and h), indi-
263
cating that high NH caused time-dependent reaction with FA. This
also confirmed that GBFS did not affect the UCS development with
time even at very high content of 30% as shown in Fig. 6d.
4.4. XRD analysis
The XRD patterns of FA geopolymer stabilized LS/GBFS blend at
50:30:20 LS:FA:GBFS and at high and low NS:NH ratios of 90:10
and 50:50 are presented in Fig. 9 for 7 and 60 days of curing to
investigate the role of NS:NH ratios on the UCS development at a
particular GBFS content. The main traces consisted of Quartz, Mus-
covite, Microcline and Albite. The Quartz phases were mainly from
the LS. This indicated that LS was inert and insignificant reacted
with liquid alkaline activator. The presence of sodium alumino-
silicate in the form of Albite and the potassium alumino-silicate
in form of Muscovite and Microcline indicated the formation of
geopolymer products.
For the sample with high NS:NH ratio = 90:10 at early stage
(7 days − line A), the main traces were Calcium Silicate Hydrate
(CSH); Anorthite; Goethite while at a longer time (60 days) the main
traces were Anorthite, Goethite, Calcite with little CSH. This indi-
cated variation of cementitious products present at various curing
times. The CSH traces in the 7 days cured sample were consider-
ably higher than those in 60 days cured sample. This confirmed
that the significant CSH products occurred in the early stages of the
geopolymer process mainly due to the chemical reaction between
high calcium FA and NS.
264 I. Phummiphan et al. / Journal of Hazardous Materials 341 (2018) 257–267

Fig. 8. SEM images of stabilized samples at 30% GBFS NS:NH ratios of 90:10 and 50:50.

On the other hand, for the sample with low NS:NH ratio of 50:50,
the main traces were geopolymer products in the form of Anorthite,
Goethite and Calcite, with no appearance of CSH in early 7 days (see
line C in Fig. 9) whereas the 60-day traces were Anorthite, CSH,
Goethite and Calcite. It was noted that CSH traces were detected
in 60 days of curing but not in 7 days of curing while Anorthite,
Goethite and Calcite in 60 days of curing were slightly more than
those in 7 days of curing. This implied that the CSH products in
geopolymeric system were time-dependent for high calcium FA
geopolymer with low NS:NH ratio.
Notably, the chemical products for the stabilized samples at each
curing time depended on the NS:NH ratio. The high CaO (mainly
from FA) in the system, contributed to the development of CSH in
the early stage for high NS:NH ratio. Hence, the UCS results of the
samples resulted from the coexistence of CSH, calcite and the NASH
geopolymer gel. However, the excessive CaO will react with CO2 to
 I. Phummiphan et al. / Journal of Hazardous Materials 341 (2018) 257–267
Fig. 9. XRD results of stabilized samples at 20% GBFS and NS:NH ratios of 90:10 and 50:50 for different curing times.
form Calcite [62,63]. A high contents of 30% GBFS was thus found to
provide a negative effect on the UCS development. Without GBFS,
the 7-day UCS was found at NS:NH = 90:10 while the long-term UCS
was found at NS:NH = 50:50. The high short-term UCS was mainly
due to the rapid reaction between NS and CaO in FA, hence CSH
development while the high long-term UCS was mainly due to the
time-dependent reaction between NH and SiO2 and Al2 SiO3 in FA,
hence NASH development [36]. The GBFS replacement increased
CaO, SiO2 and Al2 SiO3, hence the very high short term and long
term UCS were found at NS:NH = 90:10.
5. Conclusions
This paper studied the viability of using two types of wastes
(class C FA and GBFS) with a liquid alkaline activator to stabilize
marginal lateritic soil to form a sustainable pavement base mate-
rial. The effect of GBFS, NS:NH ratio and curing time on the strength
development and microstructure of FA based geopolymer stabi-
lized LS/GBFS blends was investigated. The 7-day UCS of the FA
geopolymer stabilized LS/GBFS blends at various NS:NH ratios and
GBFS contents was comparable to the national road authority spec-
ifications of Thailand and Australia for cement stabilized pavement
material. The following conclusions can be drawn from this study:
1. The soaked 7-day UCS of FA geopolymer stabilized LS/GBFS
blends at various NS:NH ratios met the strength requirements
for both low and high volume roads specified by Department of
Highways and Department of Rural Roads, Thailand.
2. GBFS replacement improved the early 7-day UCS of FA geopoly-
mer stabilized LS at the high NS:NH ratios tested (especially at
NS:NH ≥ 80:20). The optimal GBFS content providing the highest
7-day UCS tends to decrease with decreasing NS:NH ratio. The
GBFS had little effect on early and long-term UCS of FA geopoly-
mer stabilized LS at low NS:NH = 50:50. The highest long term
265
28-day and 60-day UCS was found at 60:30:10 LS:FA:GBFS and
90:10 NS:NH, which are the recommended optimum ingredients
in practice.
3. For high NS:NH ratios (> 80:20), the SEM and XRD results indi-
cated that the cementitious products increased in volume when
the curing time increased at optimal GBFS; i.e., NS:NH = 90:10
and GBFS = 10%.
4. The coexistence of CSH and NASH for various NS:NH ratios was
explained by the XRD results. The significant CSH was detected
at an early stage of curing for high NS:NH while the significant
CSH was detected after a long curing time for low NS:NH. The
excessive CaO would react with CO2 and form Calcite for both
high and low NS:NH ratios; i.e., 30% GBFS provided a negative
effect on the UCS development.
5. The outcome of this research will enable GBFS to be used as
a replacement material with FA geopolymer to stabilize LS in
the development of a low carbon stabilized pavement base. 10%
content of GBFS is recommended at high NS:NH ratios (> 80:20).
Acknowledgements
This work was supported by the Thailand Research Fund under
the TRF Senior Research Scholar program Grant No. RTA5980005
and Suranaree University of Technology. The first author also
acknowledges a financial support from Department of Rural Roads,
Thailand for his Ph.D. studies.
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