Author's Accepted Manuscript

Behavior of low-calcium fly and bottom ash-based

geopolymer concrete cured at ambient temperature
Tianyu Xie, Togay Ozbakkaloglu

www.elsevier.com/locate/ceramint

PII: S0272-8842(15)00070-X
DOI: http://dx.doi.org/10.1016/j.ceramint.2015.01.031
Reference: CERI9795

To appear in: Ceramics International

Received date: 31 December 2014

Accepted date: 7 January 2015

Cite this article as: Tianyu Xie, Togay Ozbakkaloglu, Behavior of low-calcium fly and
bottom ash-based geopolymer concrete cured at ambient temperature, Ceramics
International, http://dx.doi.org/10.1016/j.ceramint.2015.01.031

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 Behavior of Low-Calcium Fly and Bottom Ash-Based Geopolymer Concrete Cured at

Ambient Temperature

Tianyu Xie1 and Togay Ozbakkaloglu2

ABSTRACT

This paper presents the results of an experimental study on the behavior of fly ash-, bottom ash- and

blended fly and bottom ash-based geopolymer concrete (GPC) cured at ambient temperature. A

total of 10 bathes of GPC and a single batch of ordinary Portland cement concrete (OPC) were

manufactured. The tests of compressive strength, elastic modulus, flexural strength, workability,

drying shrinkage and absorption capacity were carried out to determine the properties of fresh

concrete and mechanical and durability-related properties of hardened concrete. Test parameters

included the mass ratio of fly ash-to-bottom ash, liquid alkaline-to-coal ash binder ratio, coal ash

content and concrete type. The results indicate that the selected parameters significantly affect the

microstructure and the behavior of GPCs. It is seen that bottom ash-based GPCs exhibited

significantly lower geopolymerization than that of the fly ash-based GPCs, resulting in the inferior

behavior of the former compared to the latter.

Keywords: Geopolymer concrete (GPC); Bottom ash; Fly ash; Alkali-activated cement;

Compressive strength; Ambient temperature.

1. INTRODUCTION

It is well-understood that the manufacture of ordinary Portland cement (OPC)-based concretes

requires large quantities of fuel and raw materials, which are obtained through resource exhausting,

energy intensive processes that generate emission of large amounts of greenhouse gases

(essentially CO2 and NOX) into atmosphere. For every ton of OPC produced, nearly one ton of CO2

1
MPhil Candidate, School of Civil, Environmental and Mining Engineering, University of Adelaide, Australia.
2
(Corresponding author) Senior Lecturer, School of Civil, Environmental and Mining Engineering, University of Adelaide,
Australia. Tel : +618 8313 6477; Fax : +618 8313 4359; Email: togay.ozbakkaloglu@adelaide.edu.au
is generated and around 2.5 tons of materials, including fuel and other raw materials, are consumed

[1-8]. It is estimated that the emission of CO2 resulting from the production of OPC adds to about

1.35 billion tons per annum, or about 7% of the total greenhouse gas emissions to the earth’s

atmosphere [9, 10]. It is also predicted that global demand of the OPC will have increased by

almost 200% by 2050 from 2010 levels [8], and hence the impact of the OPC industry on the

environment is believed to become a real issue. With the aim of reducing the handicap of the

production of OPCs, a new type of green and environment-friendly concrete, namely, geopolymer

concrete (GPC) has recently received some research attention. The term ‘geopolymer’ was first

introduced by Davidovits in 1970s to represent the mineral polymers resulting from geochemistry,

as alternative building materials [11, 12]. The production of geopolymers takes place through the

geopolymerization process and it requires source materials that are rich in silica (Si4+) and alumina

(Al3+) content, such as coal ash, kaolin or metakaolin.

Current global production of coal ashes is estimated to be over 600 Mt per annum, of which the fly

ash, which is recognized as one of the world’s top 5 raw material sources [13], represents 75-80%.

A by-product of coal-fired power stations, fly ash is widely used as the source material to

manufacture geopolymer products, owing to its aluminosilicate composition, fine size, significant

amount of glassy content and availability across the world. However, it is estimated that 70-80% of

the produced fly ash is still being disposed of as waste, which causes the coal-fired power industry

significant concern in relation to environmental issues, while also demonstrating the surplus

availability of the material [14].

In the geopolymerization process of the fly ash based GPC, the reaction of aluminosilicate source

(i.e. fly ash) and alkali polysiliates results in the formation of a hardened material with three

dimensional polymeric chain and ring structure consisting of Si-O-Al-O bond structure [15-21]. A

review of the existing literature indicates that most of the existing studies on the behavior of coal
ash based geopolymer concrete have focused on the use fly ash as the aluminosilicate source (i.e.

[15-36]). These studies found that such geopolymer concretes have better durability-related (i.e. [21,

22, 24, 34]) and mechanical properties (i.e. [26, 27, 29]) compared to those of OPCs. Another type

of coal ash material, namely the bottom ash, which is produced during the combustion of coal and

has similar chemical composition to fly ash, in contrast, has received less research attention in the

area of geopolymers. As reported in the literature, bottom ash contains relatively large and

irregularly shaped particles with pores and cavities, which results in lower reactivity when used in

GPC [37-42]. As a result, at the moment, most of the bottom ash products are being buried in

landfills due to lack of development in recycling technologies [43]. Given the similar chemical

composition of the material to that of the fly ash and its higher worldwide availability, the

utilization of bottom ash in production of geopolymer concrete might form an attractive recycling

option. However, only a limited number of studies have been reported in literature to date on the

development of bottom ash based geopolymers, with the majority of these studies focusing on the

behavior of geopolymer pastes (i.e. [34, 39, 44-47]) and mortars (i.e. [37, 38, 40-43, 48-50]) and

only a single study reporting on the behavior of bottom-ash based geopolymer concretes (i.e. [51]).

The majority of the studies reported to date on fly- and bottom-ash based geoploymers have been

concerned with geopolymer products cured under higher temperatures (i.e. curing temperatures over

40 C), with only a few studies investigating the behavior of fly ash- (i.e. [30,52-56]) and bottom

ash- (i.e. [34, 43, 47] based geopolymers cured at ambient temperature. Furthermore, the studies on

bottom ash-based geopolymers all focused on the behavior of geopolymer pastes or mortars and no

study reported to date on bottom ash-based geopolymer concrete cured at ambient temperature. The

ambient environment is the typical curing condition of concrete in the majority of the standard

construction sites, and hence understanding the behavior of GPCs cured under ambient conditions is

of significant interest. Furthermore, it is well known that the stress-related mechanical properties

and other long- and short-term behavior of concrete not only depends the behavior of each
constituent materials but the interactions among them. A few studies have been reported to date on

the behavior of blended coal ash-based geopolymers (i.e. [38, 39, 40, 42, 48, 51]), with the majority

of these studies concerned with the behavior of geopolymer mortars and pastes and not concrete. It

is revealed by the careful review of the existing literature that no study has been reported to date on

the behavior of blended fly and bottom ash-based geopolymer concrete cured at ambient

temperature, and the only existing study on the behavior of blended coal ash based geopolymer

concrete adopted curing temperatures of over 60 C [51].

As the first experimental study reported to date on the behavior of bottom ash- and blended fly and

bottom ash- based geopolymer concrete cured under ambient temperature, the study presented in

this paper was aimed at examining the microstructure and mechanical and durability-related

properties of fly ash, bottom ash and blended fly and bottom ash based GPC. To establish relative

performance of GPCs with respect to OPCs, a companion OPC mix was also designed and

manufactured. The paper initially provides a summary of the experimental program, including

material properties, specimen properties and testing procedures. Following this, the results of the

experimental program are presented. Finally, a detailed discussion on the results of the experimental

study is provided, where the influences of mass ratio of fly ash-to-bottom ash, liquid alkaline-to-

coal ash binder ratio, coal ash content and concrete type are presented along with other key

experimental observations.

2. TEST PROGRAM

2.1 Test specimens

A total of 11 batches of concrete, including a single batch of OPC and 10 batches of GPCs, were

manufactured in the presented study. A series of tests were undertaken on each batch to establish

the properties of the fresh and hardened concrete, including workability, compressive strength,

elastic modulus, flexural strength, drying shrinkage, and absorption capacity. In addition,

microstructures of the hardened concretes were examined using scanning electron microscopy
(SEM). Two types of specimens were used in specimen testing, namely, cylinders and beams. The

cylinder specimens were 100 mm in diameter and 200 mm in height, whereas the beam specimens

were 100 mm in width, 100 mm in depth and 500 mm in length. To study the behavior of blended

coal ash and bottom ash based GPCs, some of the specimens were designed to have partial or

complete replacement of fly ash with bottom ash. All of the specimens were cured under ambient

conditions. The test parameters included: mass ratio of fly ash-to-bottom ash (MFA:BA), liquid

alkaline-to-binder ratio (l/b), coal ash content (MA) and concrete type (i.e. OPC or GPC). Three

nominally identical specimens were tested for each unique specimen configuration in every type of

test.

2.2 Materials

2.2.1 Coal ash

Two types of coal ashes, including fly ash and bottom ash, were blended in different mass ratios

and utilized in the present study. The fly ash and the bottom ash were obtained from Port Augusta

Power Station, South Australia. These coal ashes were added at different fly ash- to-bottom ash

mass ratios (MFA:BA) of 100:0, 50:50, 25:75 and 0:100 for the GPC mixes. Both the fly ash and the

bottom ash were pre-oven dried for 24 hours and cooled at room temperature for more than 3 hours

before the casting to reduce their moisture content.

2.2.2 Alkaline activator solution

The multi-compound alkaline activators applied in the present study were premixed by a local

supplier and they consisted of distilled water, sodium hydroxide (NaOH) solution and sodium

silicate (Na2SiO3) solution. The proportions of the three components of the alkaline activator

solution were 65.3% water, 24.8% Na2SiO3 and 9.9% NaOH by weight. The sodium hydroxide

(NaOH) solution at 14 M concentration was used in all GPC mixes. The sodium silicate solution

used in the alkaline solution had a silicon dioxide to sodium oxide ratio (SiO2/Na2O) of 3.22 in
weight (3.33 in molar) and had 62% water by the total weight. The alkaline activator solution was

premixed and left to rest for 24 hours at ambient temperature prior to casting.

2.2.3 Ordinary Portland cement (OPC)

The ordinary Portland cement (OPC) used in this research was classified as general purpose blended

cement and was obtained from a local supplier. The mix proportions of OPC concrete is given in

Table 1, and the chemical composition of the OPC is supplied in Table 2.

2.2.4 Aggregates

The coarse and fine aggregates of the present study consisted of crushed bluestone gravel with 7

mm and graded sand with 0.4 mm maximum nominal particle sizes, which were respectively

sourced from the McLaren Vale Quarry (Fleurieu Peninsula) and Price Pit (Yorke Peninsula). The

same aggregates were used in all concrete mixes and their amounts are supplied in Table 1.

2.3 Mix designs and specimen preparation

As shown in Table 1, seven of the 11 concrete mixes prepared in the present study were designed to

contain a single type of coal ash (i.e. either fly ash or bottom ash). These mixes had different

alkaline liquid-to-binder (l/b) ratios and the coal ash contents (MA). The remaining three GPC mixes

were manufactured as blended fly ash and bottom ash based GPCs. Two fly ash-to-bottom ash mass

ratios (i.e. MFA:BA= 50:50 or 75:25) were considered. As can be seen in Table 1, MFA:BA= 50:50

series GPCs contained sister mixes with different l/b ratios of 0.5 and 0.3 (i.e. B50F50-0.5 and

B50F50-0.3). The F100-0.5A and F100-0.5B series adopted an exact same mix design and they

were considered as repeat specimens to verify the results were reproducible. The single OPC mix

was designed with a water to cement (w/c) ratio of 0.5 as a companion to GPC mixes with a liquid-

to-binder (l/b) ratio of 0.5.

In the preparation of the OPC and GPC mixes, all the dry materials including the fine and coarse

aggregates and binder (i.e. coal ash or Portland cement) were initially mixed in an 80L capacity

rotating pan mixer with fixed blades for approximately three minutes. Subsequently, the liquid

components (i.e. premixed alkaline activator solution for the GPCs or water for the OPC) were

gradually added to the mixes and wet mixing continued for approximately five minutes to form the

concrete. Gentle external vibration was used throughout the pouring processes of all OPC and GPC

mixes to ensure proper placement of concrete. All mixing and pouring processes were conducted

under the ambient temperature for both OPC and GPC mixes.

Hardened GPC and OPC specimens were demolded after 24 hours after casting. Any GPC

specimens those were not fully hardened after these 24 hour periods were allowed extra time to cure

in their molds. The demolded specimens were then covered with plastic bags at the top and they

were left to cure at ambient temperatures until testing. The strength gain of the OPC and GPCs with

age was monitored by compression test at the ages of 3, 7, 28, 56 and 70 days. The temperature of

the specimens and ambient environment were monitored during the early stages of curing.

2.4 Specimen designation

The concrete series in Tables 1, 3-6 were labelled as follows: the letters B (for bottom ash) and F

(for fly ash) were used to represent the coal ash types used in the GPCs. Each letter was followed by

a number that was used to represent the particular mass ratio of fly ash-to-bottom ash used in the

mix in percentage. The letter combination OPC was used to indicate the ordinary Portland cement

concrete mix. Finally, the last number in the specimen designation was used to make a distinction

among the mixes with same amount of coal ash proportion but different l/b ratios. For the F100-0.5

series specimens, additional letters A and B were used at the end of the specimen designation to

distinguish between the two repeat batches. For instance, B50F50-0.5 is a GPC mix that contained a

blend of 50% bottom ash and 50% fly ash with an l/b ratio of 0.5.
2.5 Instrumentation and testing

The mechanical properties, including: compressive strength, flexural strength and elastic modulus

of concrete were tested using the universal testing machine in the Materials Laboratory of the

University of Adelaide. Prior to the compression tests, all cylinder specimens were first ground and

then capped at both ends to ensure uniform distribution of the applied pressure. The drying

shrinkage of the concrete was monitored up to 70 days of concrete age through measurement of

shrinkage strains and related weight losses of the specimens.

3. TEST RESULTS AND EXPERIMENTAL OBSERVATIONS

3.1 X-ray fluorescence (XRF) analysis of the coal ashes

The chemical compositions and the loss on ignition (LOI) of the fly ash and the bottom ash were

determined by using XRF (X-ray fluorescence). As can be seen from the results of the XRF analysis

given in Table 2, both the fly ash and bottom ash had no more than 5% calcium oxide (CaO) and

the most abundant oxides in these coal ashes were those of Si4+ and Al3+, which represented

approximately 80% of the content by weight. Based on these results the fly ash used in the present

study can be classified as type ‘F’ low-calcium fly ash according to ASTM standard C618-12a [57].

Due to the low CaO and significant SiO2 and Al2O3 contents of the coal ashes, the GPCs of the

present study contained mainly sodium aluminosilicate hydrates (N-A-S-H) with only an

insignificant amount of calcium silicate hydrates (C-S-H). The chemical composition of the bottom

ash reported in Table 2 indicates that the bottom ash had a higher content of SiO2 and a lower

content of Al2O3 compared to those of the fly ash from the same source, which resulted in a

significantly higher SiO2/Al2O3 ratio of the bottom ash compared to that of the fly ash (i.e. 2.16 vs

1.58 in weight).

3.2 Grading of FA and BA

The Particle Size Distribution (PSD) of the fly and bottom ashes were obtained through the sieving

test using a Malvern particle size analyzer. Figure.1 illustrates the PSD results for both ashes. It is

evident from the figure that compared to the fly ash the bottom ash contained coarser particles. The

median particle size of the fly ash was 12 µm, whereas that of the bottom ash was 54 µm.

3.3 Morphological characterization of the coal ashes by scanning electron microscopy (SEM)

The scanning electron microscopy (SEM) micrographs were evaluated to investigate the

microstructure of the coal ashes, as present in Figs. 2 (a) and (b). It can be seen from the Fig. 2 (a)

that the particles of the fly ash appear to be spherical and with varying sizes. As reported previously

[41], these tiny spheres are known as the cenospheres, which have perfectly rounded and intact

shapes. In addition, the micrograph of the fly ash also shows that there are no evidently visible

pores in the microstructure of the fly ash particles. Figure.2 (b) demonstrates the SEM micrograph

of the bottom ash. When compared with the SEM micrograph of the fly ash with the same

magnification (i.e. 2000X), the micrograph of the bottom ash illustrates that the particles of the

bottom ash were significantly larger and angular, with plenty of irregular fragments and only a

small amount of semi-spheres. The figure also shows some visible pores in the microstructure of the

bottom ash. These observations are in agreement with those reported previously on the

microstructure of the bottom ash [37, 41]. In addition, some foreign objects were observed in the

microstructure of the bottom ash samples, for instance, the rectangular shaped foreign object shown

in Fig. 2 (b). A composition test undertaken indicated the object primarily as Radium – a

radioactive earth-metal found in uranium ores. On the other hand, no foreign objects or impurities

were observed under SEM for the fly ash samples. These observations clearly indicate that the

bottom ash contains more impurities compared to the fly ash, and this can be explained by the fact

that the bottom ash is extracted from the base of the furnace, where larger and foreign objects can

fall and accumulate.

3.4. Observations of GPC during the curing process

3.4.1 Workability

The workability of each batch of concrete was obtained through slump tests performed in

accordance with ASTM standard C 143/C143 M [58]. As can been seen from the slump test results

summarized in Table 1, the workability of the GPC was found to increase with an increase in the l/b

ratio. This observation is in general agreement with those previously reported on the coal ash based

geopolymer [38, 48], and the increased workability can be explained by the fact that, with an

increase in fluid content, the interaction among the coal ash particles decreases due to an increase in

the interparticle distance, which in turn results in a lower interference among particles. In addition,

for the specimen series B100-0.5, B50F50-0.5, B25F75-0.5, F100-0.5A and F100-0.5B with

identical liquid-to-binder ratio (i.e. l/b =0.5), it was observed that the slump value increases with an

increase in the mass ratio of fly ash-to-bottom ash (MFA:BA). This observation indicates that the

spherical particle shape and smooth surface of the fly ash provide significant ball-bearing effects, as

was also noted previously [1, 30], which in turns result in an increase in workability compared to

that of the GPCs manufactured with bottom ash. The results also show that the OPC with a w/c ratio

that was equal to the l/b ratio of companion GPC mixes exhibited a significantly lower slump

compared to those of the GPCs.

3.4.2 Density

The hardened densities of the OPC and GPCs are reported in Table 1. The densities were

established from concrete cylinders at 28 days of age. It is evident from the results given Table 1

that the density of the GPCs increased with an increase in the mass ratio of fly ash-to -bottom ash

(MFA:BA). The results show that, with an otherwise identical mix design, the 100% bottom ash based

GPCs exhibited significantly lower densities compared to those of the 100% fly ash based GPCs.

This can be attributed to the more porous structure and larger and more irregularly shaped particles

of the bottom ash, which results in a GPC with a less dense and homogeneous microstructure. This

finding is in agreement with those reported in previous studies on GPCs [37, 41] and it can be

attributed to that the bottom ash-based concrete contains significant amount of residual liquid (i.e.
water and alkaline solution) that remains in its structure after casting. This free liquid subsequently

evaporates during the curing process, which results in significantly lower densities of the hardened

concrete. The observations presented in this section are also useful in explaining the drying

shrinkage and weight loss of GPCs during the shrinkage process, which are discussed later in the

paper.

3.4.3 Exothermic reaction

It is well established in the previous studies on OPC that the cement hydration reaction of OPC is

exothermic [59-61]. For GPCs, some of the existing studies on coal ash based geopolymer reported

that the mechanism of geopolymerization consists of three phases, including dissolution,

transportation/orientation and polycondensation, and it takes place through an exothermic process

[9, 62-64]. In addition, the exothermic reactions of the GPC were also experimentally observed in

some of the previous studies on coal ash based GPCs those are cured at higher temperatures (i.e. [37,

65, 66]). Therefore, to examine the exothermic reaction of GPCs cured under ambient conditions,

the surface temperature (Tc) of each GPC series and the ambient temperature (Ta) were monitored at

early stages of curing. It can be seen from the Tc and Ta values reported in Table 3 that no

significant difference was observed between Tc and Ta. This can be attributed to lower degree of

geopolymerization experienced by GPCs at ambient temperature, which resulted in an insignificant

exothermic reaction of the GPCs. The above observation is in support of a previous experimental

study done by Hardjito and Rangan [2], which found that fly ash based GPC did not experience a

significant exothermic reaction at around 60ºC curing condition. However, this finding is not in

general agreement with the theory of geopolymer concrete that geopolymers are formed through an

exothermic reaction. This seemingly unexpected observation can be explained by the slow chemical

reactions experienced in GPCs at lower ambient temperatures [47, 54], which resulted in a less

severe heat release process.

3.4.4 Efflorescence

It is well known that, in OPCs, the efflorescence is caused by the formation of carbonate deposits

through the reaction of soluble calcium with the water and CO2 near the surface of concrete [67, 68].

The efflorescence is generally not harmful for the OPCs except for the surface discoloration and it

is often seen as a ‘skin problem rather than a deep-seated disease’ [69]. However, previous research

established that the efflorescence is detrimental to the durability and mechanical properties of

geopolymer materials [31, 70-72]. It is well known that, the efflorescence formation in GPC is

mainly caused by the reaction of the atmospheric CO2 with the residual soluble alkalis at the surface

of resultant products of geopolymer binders, when the concrete products are exposed to humid air

or they get in contact with water [52, 73-75]. The mechanism of the efflorescence formation in GPC

can be described through the expressions given in Eqs. (1) and (2).

CO2 ( g ) + 2OH − ( aq ) → CO32 − ( aq ) + H 2O (1)

2 Na + (aq ) + CO32 − ( aq ) + 7 H 2O → Na2 CO3
7 H 2O ( s ) (2)

In the present study, the GPC specimens were cast and cured at ambient temperature and they were

exposed to the air. As Figs. 3 (a) and (b) show, visible efflorescence formations were observed in

some of the GPC specimens. With the aim of reducing the efflorescence, some of the subsequent

GPC specimens were cured under sealed conditions. As illustrated in Fig. 3 (b), appearance of

efflorescence was not observed in the sealed F100-0.5A series specimens, whereas efflorescence

was visible in the companion unsealed specimens manufactured using the same concrete mix design.

Figure 4 illustrates the influence of the efflorescence on the 7-day compressive strength (f’c) of the

F100-0.5A and F100-0.25 series. The comparisons indicate that the unsealed specimens exhibited

higher 7-day compressive strengths than those of the companion sealed specimens. This observation

can be attributed to that the sealed curing prevented the evaporation of water from the GPC, and the

presence of excess water in turn resulted in a lower compressive strength. In addition, as shown in

Fig. 5, for F100-0.25, F100-0.3 and F100-0.35 series, which contained around 20% additional fly

ash content compared to that of F100-0.5A and B series, no significant efflorescence was observed
even under the unsealed curing condition. This observation can be explained by the presence of

higher amount of the coal ashes in these mixes, which resulted in full utilization of the alkaline

solution during the geopolymerization process.

3.5 Scanning electron Microscope (SEM) analysis of the coal ash based concrete

The SEM micrographs of the hardened GPCs with different fly ash and bottom ash contents are

shown in Figs. 6 (a) to (e) and Figs. 7 (a) to (e) in 200X and 3500X magnifications, respectively.

These SEM micrographs present the microstructures of the B100-0.5, B50F50-0.5, F100-0.5A and

FA100-0.25 series of GPCs. Continuous mass of aluminosilicate can be observed from the SEM

micrographs shown in Figs. 6 (a) to (e) with 200X magnifications. The comparisons of the SEM

micrographs of the different GPC mixes in the same figure indicate that the denseness and

homogeneity of the GPC microstructure, as the indication of the degree of geopolymerization of

GPCs, increase with an increase in the mass ratio of fly ash-to-bottom ash (MFA:BA). This finding is

in support of those reported in previous studies that compared fly and bottom ash based GPCs,

where it was found that the smaller and more regular particle shape of the fly ash resulted in a

higher degree of geopolymerization [37, 41]. Another important observation that can be made based

on the SEM micrographs at 3500X magnification presented in Figs. 7 (a) to (e) is that in all GPC

mixes a certain amount of coal ash did not fully react during the geopolymerization process and

remained in the structure of the hardened concrete. This phenomenon can be explained by the

previously noted observation that the reaction of coal ash was relatively slow at ambient

temperature.

4. INFLUENCE OF TEST PARAMETERS ON OBSERVED BEHAVIOR

4.1 Mechanical properties of hardened concrete

4.1.1 Axial compressive strength

The compressive strengths (f’c) of the OPC and GPCs of the present study were obtained through

axial compression tests that were performed in accordance with ASTM standard C39/C39M-05 [76].

Table 4 presents the compressive strength (f’c) of each concrete mix, where the results were

averaged from compression tests on three 100 x 200 mm cylinders. Influences of liquid-to-coal ash

binder ratio (l/b), mass ratio of fly ash-to-bottom ash (MFA:BA), and coal ash content (MA) on the

compressive strength (f’c) of GPCs are discussed in the following sections.

4.1.1.1 Effect of alkaline liquid-to-coal ash binder ratio

The influence of alkaline liquid-to-coal ash binder (l/b) ratio on the compressive strength (f’c) of

GPCs is investigated through the comparison of the GPCs with different l/b ratios. As can be seen

from the results presented in Table 4 and Fig.8, in general, B100-0.3, F100-0.25 and F100-0.3

series GPCs with lower l/b ratios developed higher compressive strengths (f’c) compared to those of

the companion mixes with higher l/b ratios at a given age. This can be explained by the fact that the

increase in the l/b ratio leads to an increase in the water content of the reaction medium, thereby

reducing the friction between the particles, which in turn results in a decrease in the compressive

strength (f’c) [48, 77]. The above observation is in agreement with those reported previously on coal

ash based GPCs, which noted that the compressive strength (f’c) of GPCs increases with a decrease

in the l/b ratio [21, 22, 48, 53, 77]. It should be noted that the F100-0.25 series with lower l/b ratio,

in contrast, developed a slightly lower compressive strength (f’c) compared to that of the F100-0.3

series with higher l/b ratio. This seemingly unexpected observation can be explained by the fact that

F100-0.25 series had relatively lower workability compared to that of the F100-0.3 series, which

caused problems during the placement of concrete that affected the compressive strength negatively.

It can be seen from the results shown in Table 4 and Fig.8 that the compressive strengths of the

companion fly ash-based specimens, F100-0.5A and F100-0.5B, were similar to each other, and

they were significantly higher than that of their bottom-ash based counterpart, B100-0.5, which had
the same mix proportions. As mentioned in Section 3.1, the bottom ash used in the present study

had a higher SiO2/Al2O3 ratio compared to that of the companion fly ash. It was noted in previous

studies on GPCs that the coal ash based geopolymers manufactured using an ash with a higher

SiO2/Al2O3 ratio tend to develop higher compressive strengths (f’c) [21, 32]. However, the results of

the present study indicate that the influence of the lower degree of geopolymerization of the bottom

ash had a much more pronounced influence on the compressive strength compared to that of the

higher SiO2/Al2O3 ratio of the bottom ash.

The compressive strengths (f’c) given in Table 4 and Fig.8 also indicate that the compressive

strength (f’c) of OPC was significantly higher than those of the companion GPCs. As mentioned in

the previous section, the OPC used in the presented study was designed to have the same liquid-to-

binder ratio (l/b) and similar mix proportions with that of the B100-0.5, F100-0.5A and F100-0.5B

series GPCs. This pronounced difference between the compressive strengths of OPC and GPC can

be attributed to the differences in chemical reactions experienced by the two types of concretes,

namely hydration in OPC and geopolymerization in GPC. This observation indicates that GPCs

cured ambient temperature tends to develop lower compressive strengths than those of OPCs.

4.1.1.2 Effect of mass ratio of fly ash-to-bottom ash

To investigate the influence of mass ratio of fly ash-to-bottom ash on the compressive strength of

GPCs, comparisons were conducted among B100-0.5, B50F50-0.5, B25F75-0.5, F100-0.5A and

F100-0.5B series GPCs, which had an identical liquid-to-binder ratio (l/b) but different fly ash-to-

bottom ash mass ratios (MFA:BA) . The results shown in Table 4 and Fig.8 indicate that the

compressive strength (f’c) increased with an increase in the mass ratio of fly ash-to-bottom ash

(MFA:BA) used in GPCs. As the properties and quantities of the coarse and fine aggregates used in

the companion mixes remained nearly the same among these mixes, this observation indicates that

GPC mixes with a higher MFA:BA developed stronger geopolymer mortars. This observation is in
agreement with those reported in previous studies on blended fly and bottom ash based geopolymer

mortars [38-40, 42, 49], and it can be explained by the fact that the degree of polymerization of the

bottom ash-based geopolymer is lower than that of the fly ash-based geopolymer [38-40, 42, 49].

This results in a large amount of unreacted bottom ash particles in the structure of the hardened

GPCs, which adversely affect the compressive strength of the bottom ash based GPCs [37-42]. In

addition, as illustrated in the SEM micrographs shown in Figs.2 (a) and (b), the structure of bottom

ash-based GPCs contained micro-cracks and they were less uniform compared to that of the fly ash-

based GPCs, which also contributed to their lower compressive strengths.

4.1.1.3 Effect of coal ash content

The influence of coal ash content (MA) on the compressive strength of GPCs can be studied through

the comparison of the F100-0.5A, F100-0.5B, F100-0.25, F100-0.3 and F100-0.35 series of GPCs.

As noted previously, F100-0.25, F100-0.3 and F100-0.35 series contained around 20% more fly ash

compared to those of F100-0.5 series. It is evident from the results shown in Table 4 and Fig.8 that

the GPCs with higher coal ash content (MA) developed higher compressive strengths (f’c) than their

companions. As mentioned previously, the efflorescence formations were observed in F100-0.5A

and F100-0.5B series, but no visible efflorescence appeared on the F100-0.25, F100-0.3 and F100-

0.35 series of GPC specimens, which indicates that the alkalis were completely consumed in the

later mixes. These observations suggest that the degree of geopolymerization was relatively higher

in F100-0.25, 0.3, 0.35 series compared to that in F100-0.5A, B series, which contributed to the

higher compressive strength (f’c) of the former group.

4.1.2 Elastic modulus of GPC

The elastic moduli (Ec) of the selected series of GPC specimens were obtained through the

compression tests performed in accordance with ASTM standard C469 / C469M - 14 [78]. Figure 9

illustrates the comparison of elastic moduli of B50F50-0.5, B25F75-0.5 and F100-0.5A, which had

identical l/b ratio and coal ash content (MA). It can be seen from the Fig.8 that the elastic modulus of
GPCs increased with an increase in the fly ash-to-bottom ash, mass ratio (MFA:BA). The results also

indicate that there is a strong correlation between the elastic modulus (Ec) and the compressive

strength (f’c) of GPCs, with the elastic modulus of the concrete increasing with an increase in the

compressive strength. This observation was expected and it is in accord with the well-established

relationship between elastic modulus (Ec) and compressive strength (f’c) in OPCs.

4.1.3 Flexural strength of GPC

The flexural strengths (f’r,exp) of OPC and B100-0.5, B50F50-0.5, B25F75-0.5 and F100-0.5A series
GPC mixes of the present study were obtained through three-point bending tests performed in
accordance with ASTM standard C293/C293M-10 [79]. Three 100 mm × 100 mm × 500 mm
beams were tested for each mix at three different concrete ages (i.e. 7-day, 28-day and 70-day). It is
evident from the results summarized in Table 5 that, at a given concrete age, flexural strengths
(f’r,exp) of GPCs increased with an increase in the fly ash-to-bottom ash mass ratio (MFA:BA). The
results also indicate that the relationship between the compressive (f’c) and flexural strengths (f’r,exp)
of GPCs are similar to that in OPC, with an increase in the compressive strength (f’c) resulting in an
increase in the flexural strength (f’r,exp). The theoretical 28-day flexural strengths (f’r,theo) of the OPC
and GPCs, calculated from Eq. (3) as per ACI-318-08 [80], are also reported in Table 5.

f r',theo = 0.623 f c' (3)

where both f’r,theo and f’c are in MPa.

The comparisons the experimental and theoretical flexural strengths (f’r,exp and f’r,theo) at the

concrete age of 28 days show that the ACI-318-08 expression provides accurate estimates of the

flexural strengths of the OPC and GPCs with a higher fly ash mass ratio (i.e. MFA > 75%).

Conversely, in GPCs that contained higher amounts of bottom ash (i.e. B100-0.5 and B50F50-0.5),

the differences between the theoretical and experimental values of flexural strengths were

pronounced, with the ACI-318 expression underestimating the flexural strengths of the GPCs with

higher bottom ash mass ratios (MBA).

4.2 Durability-related properties of concrete

4.2.1 Drying shrinkage

Figures 10 and 11 respectively illustrate the shrinkage and related weight loss during the drying

progress of the OPC mix and B50F50-0.5, B25F75-0.5 and F100-0.5A series GPC mixes, which

were cured under constant moisture and ambient temperature up to the age of 70 days. It is evident

from Figs. 10 and 11 that the shrinkage strains and associated weight losses of the GPCs were

higher than that of the OPC. This is due to the lower degree of geopolymerization experienced by

GPCs at ambient temperature, which resulted in structures containing unreacted porous coal ashes.

These unreacted coal ashes were filled with water, which was subsequently released during the

chemical reaction process of geopolymers. In ambient curing conditions, this water evaporated over

a period of time resulting in higher drying shrinkage of GPCs. It was also observed that GPCs with

a lower fly ash-to-bottom ash mass ratio (MFA:BA) exhibited significantly higher drying shrinkage

compared to that of GPCs with a higher fly ash to bottom ash mass ratio (MFA:BA). As explained in

Section 3.4.4, the bottom ash contained particles that are larger, more porous and more irregularly

shaped compared to the particles of fly ash, resulting in a higher ‘water holding’ effect of bottom

ash-based GPCs.

4.2.2 Absorption capacity

Absorption tests were carried out on B100-0.5, B50F50-0.5, B25F75-0.5, F100-0.5A and F100-0.25

series GPCs in accordance with ASTM standard C642-13 [81]. 48 hours after casting in ambient

temperature, the hardened GPC specimens were initially dried in the oven at a temperature of 105

C over 24 hours, and then they were subsequently cooled at the room temperature to determine their

oven-dried masses (MO). Following this, the specimens were immersed in water for 48 hours to

establish their saturated surface-dry masses (MS). The absorption capacity (Ai) of GPCs was

determined from Eq. (4), as per ASTM C642-13 [81], and the calculated values are shown in Fig.

12.

Ai = ( M S − M O ) / M O ×100 (4)
It can be seen from the results given in Fig.12 that the absorption capacities of GPCs increase with a

decrease in the mass ratio of fly ash-to-bottom ash (MFA:BA). As was discussed in previous sections,

this can be explained by the lower degree of geopolymerization observed in bottom based GPC,

which in turns leads to a more porous structure and higher absorption capacity.

5. CONCLUSIONS

This paper has presented the results of an experimental study on the behavior fly ash, bottom ash

and blended fly and bottom ash based geopolymer concrete cured at ambient temperature. Based on

the results and discussions presented in this study, the following conclusions can be drawn ：
1. The workability of the coal ash based GPCs is directly related to the mass ratio of fly ash-to-

bottom ash (MFA:BA) and the liquid-to-binder ratio (l/b), and mixes with a higher fly ash content

and l/b ratio exhibit a better workability.

2. No significant exothermic reactions were observed during the curing of the GPCs at the ambient

temperature. This indicates that GPCs cured at ambient temperature do not undergo exothermic

processes to the extent that are experienced by conventional OPCs.

3. Efflorescence of GPCs can be reduced by using sealed curing method. However, these curing

conditions also tend to decrease the early-age compressive strength of GPCs. It is also found that

increasing the coal ash content (MA) with respect to the activator solution can also eliminate

efflorescence.

4. SEM micrographs show that the density and homogeneity of the GPC increase with an increase

in the mass ratio of fly ash-to-bottom ash (MFA:BA). This indicates that fly ash undergoes a higher

degree of geopolymerization compared to that seen in bottom ash. SEM micrographs also show

that a large amount of coal ash remains in the hardened GPC structures, which suggests that at

the ambient temperature coal ash based GPCs undergo a lower degree of geopolymerization.

5. Compressive strength (f’c) of coal ash-based GPCs increases with a decrease in the liquid-to-

binder ratio (l/b) or an increase in the mass ratio of the fly ash-to-bottom ash (MFA:BA).
 6. OPC exhibits a higher compressive strength (f’c) than that of a companion GPC that is

manufactured with the same liquid-to-binder ratio (l/b) and cured under ambient conditions.

7. Both the elastic modulus (Ec) and flexural strength (f’r) of GPCs have strong correlations to their

compressive strength (f’c), and they both increase with an increase in fly ash-to-bottom mass

ratio (MFA:BA). ACI-380 model, which is given to predict the flexural strength of OPCs, also

provides reasonable estimates of flexural strengths of GPCs manufactured with fly ash mass

ratios (MFA) higher than 75%.

8. The ambient temperature cured coal ash-based GPCs exhibit a higher drying shrinkage compared

to that of OPCs due to the large amount of unreacted coal ash particles in the hardened GPC

structure that results from a lower degree of geopolymerization when coal ash based GPC is

cured at ambient temperature.

9. GPCs with a lower fly ash-to-bottom ash mass ratio (MFA:BA) develop higher drying shrinkage

due to the lower degree of geopolymerization they experience, and the presence of large, porous

and irregularly shaped unreacted bottom ash particles they contain. Likewise, GPCs with a lower

MFA:BA exhibits a higher absorption capacity.

6. ACKNOWLEDGEMENTS

The authors would like to extend their gratitude to Ms. Poon, and Messrs. Chong, James and

Warren, who performed the experimental procedures presented in this paper. The authors would

also like to thank Adelaide Brighton Pty Ltd for their generous donation of the test materials used in

the study reported in this paper.

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LIST OF TABLE CAPTIONS

Table 1. Mix proportions of concrete

Table 2. Chemical compositions of cement, fly ash and bottom ash (XRF analysis)

Table 3. Temperature of GPCs and ambient temperature during early curing ages

Table 4. Axial compressive strength of concrete at different curing ages

Table 5. Flexural strength of concrete at different curing ages

 Table 1. Mix proportions of concrete

OPC Bottom ash-based GPC Blended coal ash-based GPC Fly ash-based GPC
Label OPC B100-1.1 B100-0.5 B50F50-0.5 B50F50-0.3 B25F75-0.5 F100-0.5A F100-0.5B F100-0.25 F100-0.3 F100-0.35
3
FA (kg/m ) 0 0 0 200 200 300 400 400 475 475 475
3
BA (kg/m ) 0 220 400 200 200 100 0 0 0 0 0
3
Cement (kg/m ) 400 0 0 0 0 0 0 0 0 0 0
3
Aggregate (kg/m ) 1265 1325 1269 1269 1329 1280 1280 1280 1253 1248 1235
3
Sand (kg/m ) 542 567 543 550 550 547 547 547 539 535 529
3
NaOH+Na2SiO3 (kg/m ) 0 240 200 200 123 200 200 200 119 140 166
3
Water (kg/m ) 200 0 0 0 0 0 0 0 0 0 0
Liquid/Binder ratio (l/b) 0.5 1.1 0.5 0.5 0.3 0.5 0.5 0.5 0.25 0.3 0.35
Slump (mm) 35 160 150 220 185 165 250 260 60 140 235
3 1
Hardened density (kg/m ) 2389 2088 2035 2282 2286 2345 2377 2393 2378 2372 2382
1. At concrete age of 28 days.
Table 2. Chemical compositions of the cement fly ash and the bottom ash (XRF analysis)

Compositions Cement Fly ash Bottom ash

SiO2 21% 49% 54%
Al2O3 6% 31% 25%
Fe2O3 3% 3% 4%
CaO 64% 5% 5%
MgO 2% 3% 2%
Na2O 0% 4% 3%
K2O 1% 1% 1%
SO3 1% 0% 0%
TiO2 - 2% 2%
P2O5 - 1% 1%
SrO - <0.1% <0.1%
Mn2O3 - 0% 0%
LOI* - 0% 2%
1. Loss on Ignition
Table 3. Temperatures of GPCs and ambient temperature during early curing ages

Tc (˚C)1/Ta (˚C)2 after mixing

Concrete series
1-hour 2-hour 3-hour 4-hour
B100-0.5 17.6/17.4 17.7/17.6 17.4/17.5 17.5/17.3

B50F50-0.5 17.5/17.5 17.4/17.4 17.4/17.4 18.2/18.5

B25F75-0.5 16.4/16.2 16.3/16.1 16.3/16.3 16.4/16.1

F100-0.5A 17.4/17.5 17.3/17.5 17.2/17.7 17.4/17.5

F100-0.25 17.5/17.1 17.5/17.7 17.4/17.0 16.7/17.7

1. Surface temperature of the concrete

2. Ambient temperature.
Table 4. Axial compressive strength of concrete at different curing ages

f'c (7-day) f'c (28-day) f'c (56-day) f'c (70-day)

Concrete series
(MPa) (Mpa) (Mpa) (Mpa)

OPC 28.4 38.3 38.9 39.1

B100-1.11 - 0.3 0.6 1.1
B100-0.5 0.2 0.6 - -
B50F50-0.5 0.8 1.1 1.5 1.8
B50F50-0.3 1.4 3.5 5.4 6.2
B25F75-0.5 3.6 8.4 10.2 12.7
F100-0.5A 7.3 18.8 29.3 32.1
F100-0.5B 7.1 19.5 29.7 33.2
F100-0.25 11.0 30.4 44.4 48.2
F100-0.3 12.6 34.3 - -
F100-0.35 9.4 27.2 - -
1. The B100-0.5 series of GPC was too soft for testing at the age of 7 days
 Table 5. Flexural strength of concrete at different curing ages

Concrete f'r,exp (7-day) f'r,exp (28-day) f'r,exp (70-day) f'r,theo1

series (MPa) (Mpa) (MPa) (MPa)
B100-0.5 0.30 0.58 - 0.48
B50F50-0.5 0.67 0.83 1.42 0.65
B25F75-0.5 1.01 1.69 2.69 1.80
F100-0.5A 1.52 2.56 3.58 2.70
OPC - 3.67 - 3.85
1. The theoretical values of flexural strength were calculated by the expression given in ACI-380-08.

LIST OF FIGURES

Figure 1. Sieving test results of fly ash and bottom ash: Particle Size Distribution (PSD)
32
Figure 2. SEM images of the coal ashes (2000X magnification): a) fly ash; b) bottom ash

Figure 3. Efflorescence in geopolymer concrete: a) Efflorescence at the edge of the beam specimen;

b) Comparison between a cylinder with efflorescence present (on the left) and a sealed cylinder that

exhibits no efflorescence (on the right)

Figure 4. 7-day compressive strength of sealed and unsealed F100-0.5 and F100-0.25 sereis of

GPCs

Figure 5. Appearances of F100-0.25, F100-0.3, F100-0.35series: no visible efflorescence

Figure 6. SEM micrographs (200X magnificantion) : a) B100-0.5 series; b) B50F50-0.5 series; c)

B25F75-0.5 series; FA100-0.5A series;F100-0.25 series

Figure 7. SEM micrographs (3500X magnificantion) : a) B100-0.5 series; b) B50F50-0.5 series; c)

B25F75-0.5 series; F100-0.5A series;FA100-0.25 series

Figure 8. Compressive strength of concrete at 28 days

Figure 9. Elastic modulus of GPCs at the age of 28 days

Figure 10. Drying shrinkage of geopolymer concrete (shrinkage strain)

Figure 11. Weight loss of geopolymer concrete during the shrinkage process

Figure 12. Absorption capacity of GPCs

33
 100
90

Pass percentage (%)

80
70
60
50
40
30
20
Fly ash
10
Bottom ash
0
1.0 10.0 100.0
Sieve size (µm)

Figure 1. Sieving test results of fly ash and bottom ash: Particle Size Distribution (PSD)

34
 (a)

(b)

Figure 2. SEM images of the coal ashes (2000X magnificantion): a) fly ash; b) bottom ash

35
 (a)

(b)

Figure 3. Efflorescence in geopolymer concrete: a) Efflorescence at the edge of the beam specimen;
b) Comparison between a cylinder with efflorescence present (on the left) and a sealed cylinder that
exhibits no efflorescence (on the right)

36
 15
Sealed Unsealed

Compressive strength, f'c (Mpa)

12

0
F100-0.5A FA100-0.25

Figure 4. 7-day compressive strength of sealed and unsealed FA100-1 and FA120-1 series of GPCs

37
Figure 5. Appearances of F100-0.25, F100-0.3 and F100-0.35 series: no visible efflorescence

(a) (b)

38
 (c) (d)

(e)

Figure 6. SEM micrographs (200X magnificantion): a) B100-0.5 series; b) B50F50-0.5 series; c)

B25F75-0.5 series; FA100-0.5A series;F100-0.25 series

(a) (b)

39
 (c) (d)

(e)

Figure 7. SEM micrographs (3500X magnificantion): a) B100-0.5 series; b) B50F50-0.5 series; c)

B25F75-0.5 series; F100-0.5A series;FA100-0.25 series

40
 B100-1.1
B100-0.5
B50F50-0.5
B50F50-0.3
B25F75-0.5
F100-0.5A 1
F100-0.5B
F100-0.25
F100-0.3
F100-0.35
OPC

0 8 16 24 32 40
Compressive strength, f'c (MPa)

Figue 8. Compressive strength of concrete at 28 days

41
 12

Elastic modulus, Ec (GPa)

9

0
B50F50-0.5 B25F75-0.5 F100-0.5A

Figure 9. Elastic modulus of GPCs at 28 days

42
 0 7 14 21 28 35 42 49 56 63 70
0

Shrinkage strain(microstrain)
-500

OPC
-1000

-1500
FA100-0.5A
B25F75-0.5
-2000

B50F50-0.5
-2500

Curing age (day)

Figure 10. Drying shrinkage of geopolymer concrete (shrinkage strain)

43
 0 7 14 21 28 35 42 49 56 63 70 77
0

OPC
-1

Weight loss (%) -2

FA100-0.5A

-3 B25F75-0.5

-4 B50F50-0.5

-5

Curing age (day)

Figure 11. Weight loss of geopolymer concrete during the shrinkage process

44
 6

Absorption capacity (%)

4

0
B100-0.5 B50F50-0.5 B25F75-0.5 F100-0.5A F100-0.25

Figure 12. Absorption capacity of GPCs

45