Silicon

https://doi.org/10.1007/s12633-020-00799-2

ORIGINAL PAPER

Effects of Compositional and Physico – Chemical Mix Design

Parameters on Properties of Fly Ash Geopolymer Mortars
A. Naghizadeh 1 & S. O. Ekolu 2

Received: 4 August 2020 / Accepted: 20 October 2020

# Springer Nature B.V. 2020

Abstract
The present experimental study investigated the effects of mix design parameters on workability and compressive strength of fly
ash geopolymer (FA – GPC) mortars. Observed effects of the compositional parameters comprising SiO2/FA, Na2O/FA and
H2O/FA mass ratios, were inter – linked with those of the physico – chemical mix parameters namely:– the concentration of
sodium hydroxide solution, ratio of sodium silicate to sodium hydroxide, and the alkali activator to raw material ratio. In the
preparation of mortars, low calcium (Class F) FA was activated using a combined solution of sodium hydroxide and sodium
silicate, and mixed with fine aggregate at the aggregate to FA ratio of 2.25. Altogether, seventy – two (72) mortar mixtures were
prepared by varying the values of compositional parameters. It was found that the SiO2/FA ratio of 0.08 to 0.11, Na2O/FA ratio of
0.05 to 0.08, and H2O/FA ratio of 0.32 to 0.37, are the optimum ranges that gave the best workability values and compressive
strength results, depending on the H2O/FA ratio. In mix design, the various values of compositional parameters are obtained by
appropriately combining the aforementioned physico – chemical parameters.

Keywords Fly ash . Geopolymer . Composition . Mortar . Compressive strength . Workability

1 Introduction processing conditions employed [6]. Several studies have re-

Various aluminosilicate materials including fly ash (FA),
ground granulated blast – furnace slag (GGBS), metakaolin
(MK), palm oil fuel ash (POFA), volcanic ash (VA), rice husk
ash (RHA), etc. can be suitably used as raw materials for
geopolymer cement (GPC) formulation [1–5]. Some of the
aluminosilicate materials are industrial wastes or by – prod-
ucts that are available in large quantities worldwide. Reuse of
such wastes and by – products as starting materials for pro-
ducing GPC binders, promotes waste management and sus-
tainability. Moreover, the production cost of GPC binders is
much lower than that of ordinary Portland cement (OPC).
Besides the mentioned environmental benefits, GPC binders
also exhibit superior or similar performance characteristics as
OPC, depending on the starting material used and the
* A. Naghizadeh
anaghizadeh@uj.ac.za
1
Department of Engineering Sciences, University of the Free State,
Bloemfontein, South Africa
2
Department of Civil Engineering Science, University of
Johannesburg, Johannesburg, South Africa
ported the remarkable durability performance properties of
GPC binders, including their high resistance to sulphate attack
[7, 8], superior acid resistance [9, 10], low expansion due to
alkali – silica reaction [11–14], and their resistance to high
temperature [15–17].
A crucially important environmental benefit that has
attracted high research interest, is the potential contribution
of GPC binders towards lower carbon emissions, as opposed
to the OPC system that significantly adds to the ongoing glob-
al CO2 emissions worldwide [18–20]. Although GPC binders
have been a subject of several investigations in the literatures,
there are still a number of aspects that need extensive scientific
researches, before this emerging binder system can be widely
employed in the engineering construction industry.
The present study aimed at comprehensively investigating
the influences of different mix design factors on properties of
fly ash geopolymer (FA – GPC) mortars, focussing on com-
positional parameters. Previously, Naghizadeh and Ekolu [21]
proposed a comprehensive mix design method for FA – GPC
mortars prepared using a combined solution of sodium hy-
droxide and sodium silicate, as the alkali activator. In the
study, two (2) categories of mixture factors were identified,
(i) the physico – chemical parameters namely: – the

concentration of sodium hydroxide, sodium silicate to sodium
hydroxide ratio, the activator to FA ratio; and (ii) composi-
tional parameters namely:– the SiO2/FA, Na2O/FA and H2O/
FA. An investigation on physico – chemical parameters is
already reported in Naghizadeh and Ekolu [22]. An attempt
is made in the present study, to inter – relate the effects of
physico – chemical mix parameters with those of the compo-
sitional factors herein investigated.
2 Literature Review
There are a number of factors that influence the properties of
GPC binders. They include the mixing and curing conditions,
quality and types of raw materials, mixture parameters, etc.
Among these factors, mixture parameters comprising the liq-
uid to solid (L/S) ratio and composition of the alkali activator
used, play a crucial role in the geopolymerization process.
Studies [14, 23, 24] have shown that these mixture parameters
majorly influence the mechanical and durability properties of
GPC binders.
Ryu et al. [23] studied the effects of sodium silicate
to sodium hydroxide ratio and of sodium hydroxide
concentration, on compressive strength and workability
of FA – GPC mortars. In their study, Class F, FA was
activated using a combined solution comprising sodium
hydroxide and sodium silicate of 3.0 silicate modulus
with 40% solids content. The concentration of sodium
hydroxide solution was varied from 6 M to 12 M, while
the sodium silicate to sodium hydroxide ratio was var-
ied from 0.33 to 3.00. Control samples were also pre-
pared using the sodium hydroxide solution solely or
sodium silicate solution solely, as the alkali activators.
Mortar cubes of 50 mm size were cast for compressive
strength testing and cured at 60 °C for 24 h, followed
by storage at room temperature. Results showed that an
increase in the concentration of sodium hydroxide solu-
tion from 6 M to 12 M, while the ratio of sodium
silicate to sodium hydroxide was kept constant at 1.0,
led to rise in the 28 – day compressive strength from
25.9 to 44.8 MPa, respectively. At 9.0 M concentration
of sodium hydroxide, there was gain in the 28 – day
compressive strength from 22.8 to 43.1 MPa as the ratio
of sodium silicate to sodium hydroxide increased from
0.33 to 1.0. However, further increase in the ratio of
sodium silicate to sodium hydroxide to 3.0, resulted in
reduction of compressive strength to 32.3 MPa. Mortars
that were made using sodium hydroxide solely or sodi-
um silicate solely as the alkali activators, exhibited rel-
atively much lower compressive strengths of 13.8 MPa
and 13.1 MPa, respectively.
The total amount of activator used in a mixture also has a
significant effect on properties of FA – GPC binders. A
Silicon
previous study by the authors [22] showed that L/S ratio has
a pessimum effect on the compressive strength of FA – GPC
mortars, regardless of the sodium silicate to sodium hydroxide
ratio. Increase in L/S from 0.3 to 0.5 improved the compres-
sive strength of mortars, while further increase of L/S to 0.6
adversely affected strength. The observed improvement in
strength as L/S was increased up to 0.5, is attributed to rise
in concentration of OH− ions in the mixture. A higher amount
of OH− arising from the activator, promotes the dissolution of
FA particles at early stages, releasing more SiO4 and AlO4 to
participate in geopolymerization. However, an increase in L/S
ratio also increases the total amount of water present in the
mixture. As expected, an excessive amount of water in the
mixture, adversely affects the properties of the final GPC
product [25]. In the study by Naghizadeh and Ekolu [22],
the observed reduction in compressive strength when the
L/S ratio was increased beyond 0.5, is attributed to the
resulting excessive amount of water in the mixture.
The SiO2/Na2O ratio of an alkali activator, has been con-
sidered in several studies as an important parameter affecting
the geopolymerization reaction and properties of GPC binders
[2, 23, 24, 26–33]. Cho et al. [34] reported that the compres-
sive strength of FA – GPC pastes was significantly influenced
by the SiO2/Na2O ratio of an alkali activator. In their study,
FA – GPC paste mixtures were prepared using a combined
solution of sodium silicate and sodium hydroxide, as the alkali
activator. Paste prisms of 40 × 40 × 160 mm size were pre-
pared and cured at 70 °C for 24 h, then stored at room tem-
perature for 27 days. Results showed that compressive
strength of the pastes increased from 38 to 48 MPa with in-
crease in the SiO2/Na2O ratio of the alkali activator from 0.8 to
1.4. However, there was decrease in the 28 – day compressive
strength to 31 MPa, when the SiO2/Na2O ratio was increased
further up to 2.0.
Bignozzi et al. [35] also investigated the effect of SiO2/
Na2O ratio on mechanical properties of FA – GPC mortars.
In the study, two types of Class F, FA were activated using a
combined solution of sodium hydroxide and sodium silicate.
The mortars were prepared at a constant L/S ratio of 0.45,
while the SiO2/Na2O ratio of the activator was varied from
0.21 to 1.5. Results showed that compressive strength in-
creased from 30.2 to 66.1 MPa while flexural strength rose
from 6.2 to 9.3 MPa, when the SiO2/Na2O ratio was raised
from 0.21 to 1.5. Their findings are consistent with those
reported in other studies [29, 36, 37].
Analytical studies by Criado et al. [37] indicated that
lowering the SiO2/Na2O ratio of the activator, led to an
increase in the geopolymerization rate. In a similar study,
Khedmati et al. [38] reported that a decrease in the SiO2/
Na2O ratio of the alkali activator comprising a combined
sodium hydroxide and sodium silicate solution, led to
greater formation of aluminosilicate gel and reduced pore
volume within the GPC product.
Silicon

Some studies [25, 39, 40] have reported that a high water
content in GPC mixtures, may increase the amount of crystal-
line phases formed along with the amorphous gel product of
the geopolymerization reaction. Consequently, high water
content of the mixtures adversely affects strength develop-
ment, as further discussed in Section 4.2.2.
From the foregone literatures, it is evident that the amounts
of SiO2, Na2O and H2O present in the alkali activator, along
with the L/S ratio of the mixture, are key parameters that
majorly influence the properties of FA – GPC binders pre-
pared using an alkali activator comprising a combined solu-
tion of sodium hydroxide and sodium silicate. Since L =
SiO2 + Na2O + H2O by mass, it is sufficient to consider only
the three mass ratios of SiO2/FA, Na2O/FA and H2O/FA as
the key compositional mix parameters. The present study in-
vestigated the effects of these compositional parameters on
workability and compressive strength of FA – GPC mortars.
3 Experimental Study
3.1 Materials
Silica sand was supplied by Rolfes (pty) Ltd. in three (3)
size ranges, designated as fine (F) for ≤0.6 mm size, medium
(M) for 0.4–0.85 mm sizes and coarse (C) for 0.8–1.8 mm
particles. The fine aggregate used in the experiment was pre-
pared by mixing the F, M and C sand sizes in proportions of
37.5%, 12.5%, and 50%, respectively [41]. All the mortar
mixtures were made at the aggregate to FA ratio of 2.25.
3.2 Mixtures
3.2.1 Compositional Parameters
As already mentioned in Section 1.0, the present study
focussed at evaluating the effects of compositional param-
eters comprising SiO 2 /FA, Na 2 O/FA and H 2 O/FA, on
properties of FA – GPC mortars. Values of the mass ratios
SiO2/FA, Na2O/FA and H2O/FA in the mixtures, were de-
termined from the:- (i) mass of SiO2 in sodium silicate, (ii)
mass of Na2O in sodium hydroxide and sodium silicate
solution, and (iii) mass of H2O in sodium silicate solution,
sodium hydroxide solution and added water. Eqs. (1)–(8)
give the expressions that were used to calculate the re-
quired quantities, as follows:

Geopolymer mortar mixtures were prepared using Class F, FA

Na2 OðSHÞ þ Na2 OðSSÞ
as the aluminosilicate raw material, with a combined solution Na2 O=FA ¼ ð1Þ
of sodium hydroxide and sodium silicate, as the alkali activa- FA
tor. Standard silica sand was used as the fine aggregate. The SiO2 ðSSÞ
SiO2 =FA ¼ ð2Þ
FA used was obtained from Lethabo power plant of Eskom FA
SOC Ltd., South Africa. The particle sizes of FA ranged from H2 OðSHÞ þ H2 OðSSÞ þ H2 OðaddÞ
0.1 to 2000 μm with median diameters of d10 = 6 μm, d50 = H2 O=FA ¼ ð3Þ
FA
27.48 μm and d90 = 174.92 μm. The FA had a specific grav- Na2 OðSHÞ ¼ mass of solid NaOH in the mixture ð4Þ
ity of 2.24, while its specific surface area was 207.3 m2/kg. Na2 O molar mass
Table 1 gives the chemical composition of the FA used. 
2  NaOH molar mass
The alkali activator employed in the study was prepared by
Na2 OðSSÞ ¼ mass of sodium silicate solution ð5Þ
combining sodium hydroxide and sodium silicate solutions at
various proportions. The sodium hydroxide used had 99%  percentage of Na2 O in sodium silicate solution
purity and was supplied by Merck (pty) Ltd. Pellets of sodium SiO2ðSSÞ ¼ mass of sodium silicate solution ð6Þ
hydroxide were dissolved in distilled water to prepare varied
concentrations of 10 M to 20 M. The sodium silicate solution  percentage of SiO2 in sodium silicate solution
used was also obtained from Merck (pty) Ltd.; it had a com- H2 OðSSÞ ¼ mass of sodium silicate solution ð7Þ
position of 64% H2O, 8.3% Na2O and 27.7% SiO2 by mass.
 percentage of H2 O in sodium silicate solution
Solutions of sodium silicate and sodium hydroxide were
mixed at different ratios to prepare the alkali activator of var- H2 OðSHÞ ¼ mass of sodium hydroxide solution−Na2 OðSHÞ
ied compositional parameters (Eqs. 1–8 of Section 3.2.1). ð8Þ

Table 1 Chemical composition of the fly ash used [22]

Oxides Al2O3 CaO Fe2O3 MgO P2O5 K2O SiO2 Na2O TiO2 LOI*

(%) 30.27 4.59 3.58 1.06 0.38 0.77 56.45 0.14 1.57 0.42

*LOI – Loss on ignition

 Silicon

where, Na2O(SH) = mass of Na2O in sodium hydroxide solu-
tion, Na2O(SS) = mass of Na2O in sodium silicate solution,
SiO 2(SS) = mass of SiO 2 in sodium silicate solution,
H 2 O (SS) = mass of water in sodium silicate solution,
H2O(SH) = mass of water in sodium hydroxide solution,
H2O(add) = mass of added water in the mixture.
3.2.2 Mixing, Casting and Curing
Altogether, seventy – two (72) FA – GPC mortar mixtures
were prepared. The mixture proportions employed in the ex-
periment were compositional parameters comprising a varied
Na2O/FA ratio of 0.032 to 0.18, varied SiO2/FA ratio of 0 to
0.12, and H2O/FA ratio of 0.32, 0.35 or 0.37. The different
proportions of compositional parameters in the mixtures, were
obtained by varying the physico – chemical mix parameters
consisting of:– the concentration of sodium hydroxide solu-
tion, the amount of alkali activator comprising a combined
solution of sodium hydroxide and sodium silicate, the sodium
silicate to sodium hydroxide ratio, and the amount of added
water. Tables 2, 3 and 4 give the various mixture proportions
used to prepare the FA – GPC mortars.
The mortars were prepared by mixing fine aggregate with
FA for one minute, using a laboratory mortar mixer. The alkali
activator solution was then added while the mixer was run-
ning, and mixing continued for another two minutes. The
fresh mortar was then subjected to a flow test to measure
workability, as per ASTM C 1437 [42].
Cubes of 50 mm size were cast in moulds as per ASTM C
109 [43] and covered using a plastic cling film, then cured at
80 °C for 24 h. Afterwards, the cube samples were removed
from the oven and demoulded, then wrapped with a plastic
cling film, and placed back in the 80 °C oven for 27 days.
Following the completion of heat – curing, the cubes were
removed from the oven and left to cool down at ambient
temperature, then subjected to compressive strength testing.
4 Results and Discussion
It was determined in Naghizadeh and Ekolu [21], that the
main factors employed in mix design of FA – GPC mixtures
are of two (2) categories namely:– (i) the physico – chemical
parameters comprising the concentration of sodium hydroxide
solution, sodium silicate to sodium hydroxide ratio, and the
L/S ratio; and (ii) compositional parameters of mix ingredi-
ents, which comprise the Na2O/FA, SiO2/FA and H2O/FA
mass ratios. The two (2) categories of mix parameters are inter
- related since values of the compositional factors arise from
mix design combinations of the physico – chemical parame-
ters. The effects of physico – chemical parameters on proper-
ties of FA – GPC mortars are already given in Naghizadeh and

Table 2 Mixture proportions used to prepare FA – GPC mortars at a H2O/FA of 0.32

Mix No. Alkali activator Fine aggregate (g) Fly ash (g) Compositional parameters (ratio)

Concentration of Sodium Sodium Added Na2O/FA SiO2/FA H2O/FA

NaOH (M) silicate (g) hydroxide (g) water (g)

1 14 92 30 2 554 246 0.071 0.104 0.32

2 16 0 129 7 554 246 0.185 0.000 0.32
3 20 107 21 0 554 246 0.072 0.120 0.32
4 12 0 123 0 554 246 0.144 0.000 0.32
5 16 33 41 35 554 246 0.071 0.037 0.32
6 12 61 61 1 554 246 0.093 0.069 0.32
7 20 92 0 20 554 246 0.032 0.104 0.32
8 16 107 10 5 554 246 0.051 0.120 0.32
9 13 71 46 5 554 246 0.082 0.080 0.32
10 16 25 50 35 554 246 0.080 0.028 0.32
11 16 61 14 32 554 246 0.042 0.069 0.32
12 16 74 23 19 554 246 0.058 0.083 0.32
13 16 33 34 39 554 246 0.061 0.037 0.32
14 20 92 40 1 554 246 0.098 0.104 0.32
15 16 0 70 40 554 246 0.101 0.000 0.32
16 12 89 9 16 554 246 0.042 0.100 0.32
17 12 71 14 25 554 246 0.042 0.080 0.32
18 12 89 21 9 554 246 0.055 0.100 0.32
19 12 53 32 25 554 246 0.055 0.060 0.32
20 12 71 40 9 554 246 0.071 0.080 0.32
21 18 98 27 2 554 246 0.076 0.110 0.32
22 18 89 33 5 554 246 0.082 0.100 0.32
23 18 80 40 7 554 246 0.090 0.090 0.32
24 18 98 32 0 554 246 0.084 0.110 0.32
Silicon

Table 3 Mixture proportions used to prepare FA – GPC mortars at a H2O/FA of 0.35

Mix No. Alkali activator Fine aggregate (g) Fly ash (g) Compositional parameters (ratio)

Concentration of Sodium Sodium Added Na2O/FA SiO2/FA H2O/FA

NaOH (M) silicate (g) hydroxide (g) water (g)

25 14 74 25 24 554 246 0.058 0.083 0.35

26 20 107 20 8 554 246 0.071 0.120 0.35
27 16 33 41 42 554 246 0.071 0.037 0.35
28 20 92 0 27 554 246 0.032 0.104 0.35
29 16 33 34 46 554 246 0.061 0.037 0.35
30 16 25 50 42 554 246 0.080 0.028 0.35
31 14 107 11 11 554 246 0.051 0.120 0.35
32 10 61 20 33 554 246 0.042 0.069 0.35
33 20 92 40 8 554 246 0.098 0.104 0.35
34 16 0 70 47 554 246 0.101 0.000 0.35
35 10 71 59 0 554 246 0.084 0.080 0.35
36 12 99 0 23 554 246 0.035 0.111 0.35
37 12 89 9 24 554 246 0.042 0.100 0.35
38 12 71 14 32 554 246 0.042 0.080 0.35
39 12 89 21 16 554 246 0.055 0.100 0.35
40 12 53 34 32 554 246 0.058 0.060 0.35
41 12 92 33 6 554 246 0.071 0.104 0.35
42 12 71 39 17 554 246 0.071 0.080 0.35
43 18 107 30 0 554 246 0.084 0.120 0.35
44 18 89 34 12 554 246 0.084 0.100 0.35
45 18 80 40 14 554 246 0.090 0.090 0.35
46 18 105 37 0 554 246 0.094 0.118 0.35
47 16 25 50 42 554 246 0.080 0.028 0.35

Ekolu [22]. However, some key findings of the earlier study
[22] have been highlighted in the present paper, for purposes
of evaluating the inter – relationships between the two sets of
mix design parameters.
4.1 Effects of Physico – Chemical Mix Parameters on
Strength
Figure 1 gives the strength effects of physico – chemical mix
parameters comprising the concentration of sodium hydrox-
ide, sodium silicate to sodium hydroxide ratio, and the L/S
ratio [22]. It can be seen that each of the three (3) mix param-
eters shows a pessimum influence on compressive strength.
The optimum range values that gave the best compressive
strength results were the sodium hydroxide concentration of
12 M to 14 M (Fig. 1a), the sodium silicate to sodium hydrox-
ide ratio of 1.5 to 2.0 (Fig. 1b), and the L/S ratio of 0.4 to 0.6
(Fig. 1c).
4.2 Effects of the Compositional Parameters of Mix
Ingredients on Strength and Workability
4.2.1 Influence of SiO2/FA
Figure 2a–c gives the effects of SiO2/FA on the compressive
strength and workability properties of FA – GPC mortars
prepared at the Na2O/FA ratios of 0.054, 0.07 or 0.08 respec-
tively, while H2O/FA was maintained at 0.32, 0.35 and 0.35.
It can be seen that an increase of SiO2/FA from 0.06 to 0.10
led to strength gain from 52 to 63 MPa, for the Na2O/FA and
H2O/FA ratios of 0.054 and 0.32, respectively (Fig. 2a1).
However, there was about 27% strength loss with further in-
crease of the SiO2/FA ratio from 0.10 to 0.12. All the other
mortar mixtures prepared at the different Na2O/FA ratios of
0.07 and 0.08 (Fig. 2b1, c1), also exhibited a similar
pessimum effect of SiO2/FA on strength. The observed im-
provement in strength of FA – GPC mortars due to increase of
SiO2/FA from 0.06 to 0.10, is attributed to rise in the reactive
Si content of the mixture. The reduction in compressive
strength at higher values of the SiO2/FA ratio above 0.10, is
explained by precipitation of excessive Si out of the activator
solution at early stages of geopolymerization, thereby hinder-
ing further reaction [44]. It can be seen that the optimum SiO2/
FA values of 0.08 to 0.11, generally gave the highest com-
pressive strength levels for the different Na2O/FA and H2O/
FA ratios.
Figure 2a2–c2 shows that an increase in the SiO2/FA
ratio from 0.06 to 0.12, generally resulted in decrease of
workability. The observed reduction in workability may
be explained by the effect of SiO2 solids content on
viscosity of the alkali – activator. A higher SiO2 solids
content gives higher viscosity, which in turn reduces the
 Silicon

Table 4 Mixture proportions used to prepare FA – GPC mortars at a H2O/FA of 0.37

Mix No. Alkali activator Fine aggregate (g) Fly ash (g) Compositional parameters (ratio)

Concentration of Sodium Sodium Added Na2O/FA SiO2/FA H2O/FA

NaOH (M) silicate (g) hydroxide (g) water (g)

48 16 74 23 32 554 246 0.058 0.083 0.37

49 20 107 20 14 554 246 0.071 0.120 0.37
50 16 33 34 52 554 246 0.061 0.037 0.37
51 20 92 0 33 554 246 0.032 0.104 0.37
52 16 55 60 24 554 246 0.105 0.062 0.37
53 12 25 61 37 554 246 0.080 0.028 0.37
54 13 107 11 17 554 246 0.051 0.120 0.37
55 10 61 20 39 554 246 0.042 0.069 0.37
56 20 92 40 14 554 246 0.098 0.104 0.37
57 16 0 70 53 554 246 0.101 0.000 0.37
58 13 74 25 29 554 246 0.057 0.083 0.37
59 10 71 59 6 554 246 0.084 0.080 0.37
60 12 49 50 29 554 246 0.075 0.055 0.37
61 12 89 9 29 554 246 0.042 0.100 0.37
62 12 71 14 37 554 246 0.042 0.080 0.37
63 12 89 21 21 554 246 0.055 0.100 0.37
64 12 53 32 37 554 246 0.055 0.060 0.37
65 12 92 34 11 554 246 0.072 0.104 0.37
66 12 71 39 22 554 246 0.071 0.080 0.37
67 18 107 30 5 554 246 0.084 0.120 0.37
68 18 89 34 17 554 246 0.084 0.100 0.37
69 18 80 40 19 554 246 0.090 0.090 0.37
70 18 105 37 5 554 246 0.094 0.118 0.37
71 12 53 43 30 554 246 0.069 0.060 0.37
72 16 74 23 32 554 246 0.058 0.083 0.37

workability of fresh mortar mixtures. The workability
effect of SiO2/FA is also influenced by the Na2O/FA
ratio of the mixture. As SiO2/FA increased from 0.08
to 0.12, the mortar mixture that had a lower Na2O/FA
ratio of 0.054, exhibited rapid curvilinear reductions in
workability levels (Fig. 2a1). In contrast, those mixtures
with the higher Na 2 O/FA ratios of 0.07 and 0.08,
showed relatively lower workability levels that also re-
duced linearly as SiO2/FA increased from 0.08 to 0.12.
4.2.2 Influence of H2O/FA
All mixtures exhibited corresponding reductions in com-
pressive strength with increase in the H2O/FA ratio from
0.32 to 0.37, regardless of Na2O/FA and SiO2/FA ratios,
as seen in Fig. 3a1–c1. For example, mixtures with the
respective SiO2/FA and Na2O/FA ratios of 0.08 and 0.054
(Fig. 3a1) exhibited strength reduction from 59 to
38.2 MPa, due to increase in the H 2O/FA ratio from
0.32 to 0.37, respectively. The other graphs in Fig. 3b1
and c1, also exhibit a similar effect of the H2O/FA ratio
on compressive strength. Strength reduction due to increase
in water content of mixtures at higher H2O/FA ratios, is attrib-
uted to the resulting higher porosity levels of the mortars.
Some of the water used in mixtures, remains free or non –
reacted, after the geopolymerization reaction [45]. The pres-
ence of free water within the binder matrix results in a coarse
pore microstructure, which adversely affects strength. Also,
an increase in the amount of free water present in a mixture
may lead to the formation of crystalline phases along with the
amorphous gel. Since the amorphous phase is mostly respon-
sible for strength development in GPC binders, an increase in
Silicon

Compressive strength (MPa) 70

(a) workability. For example, mortar mixtures with the
60 Na2O/FA ratio of 0.054 and SiO 2/FA ratio of 0.06,
50 showed an increase in workability from 209 to
40 251 mm, upon rise in the H2O/FA ratio from 0.32 to
30
0.37 (Fig. 3a2). The observed increase in workability at
higher values of H2O/FA, is attributed to the role of
20 L/S= 0.4 water molecules as lubricants in the fresh mixture, prior
10 L/S= 0.5 to onset of the hardening phase.
0
10 M 12 M 14 M
Concentration of NaOH 4.2.3 Influence of Na2O/FA
70
Compressive strength (MPa)

(b) Figure 4a–c shows the effects of Na2O/FA on compres-

60
sive strength and on workability of the FA – GPC mortar
50 mixtures, prepared at the various SiO2/FA ratios of 0.08,
40 0.10 and 0.12, respectively. It can be seen that Na2O/FA
30
ratio exhibited a strongly significant strength effect on FA
– GPC mortars. In all the mortars, an increase in Na2O/FA
20
12M NaOH
ratio directly led to a corresponding rapid gain in strength,
10 14M NaOH regardless of the SiO2/FA and H2O/FA ratios, as seen in
0 Fig. 4a1–c1.
1 1.5 2 2.5 3 The influence of Na 2 O/FA ratio on compressive
Sodium silicate to sodium hydroxide ratio strength (Fig. 4a1–c1) was much stronger, compared to
the corresponding effects of the two other parameters,
70 SiO2/FA (Fig. 2a1–c1) and H2O/FA (Fig. 3a1–c1). For
(c)
Compressive strength (MPa)

60 example, mixtures prepared at the SiO2/FA and H2O/FA

50
ratios of 0.10 and 0.32 respectively (Fig. 4b1), showed
rapid increase in compressive strength results from the
40 moderate 30 MPa to a high 92 MPa, with rise in Na2O/
30 FA from 0.030 to 0.096 respectively. The observed rapid
strength gains associated with higher Na2O/FA ratio, are
20
Sodium silicate/sodium hydroxide=1.5 attributed to the resulting higher rate of
10 Sodium silicate/sodium hydroxide=2.0 geopolymerization, in turn leading to the formation of a
0 denser aluminosilicate gel [40]. An increase in Na2O/FA
0.3 0.4 0.5 0.6 ratio, increases the concentration of OH− ions in the mix-
L/S - Alkali activator to fly ash ratio ture, which in turn improves the dissolution of FA parti-
Fig. 1 Effects of physico – chemical mix parameters on compressive cles and the associated liberation of Si and Al, at the
strength of FA – GPC mortars a concentration of sodium hydroxide, b initial stages of geopolymerization [38, 46]. Higher con-
sodium silicate to sodium hydroxide ratio, c alkali activator to fly ash centrations of the liberated SiO4 and AlO4 species in FA –
(L/S) ratio [22]
GPC mixtures, lead to the formation of greater amounts of
amorphous aluminosilicate gel, a phase that is responsible
for strength development.
ratio of the crystalline to amorphous phase, leads to higher The FA – GPC mortars prepared at the SiO2/FA,
strength loss [25]. Furthermore, increase in water content re- Na2O/FA, and H2O/FA ratios of 0.10, 0.094 and 0.32
duces the concentration of OH− ions in FA – GPC mixtures, in respectively, gave the highest 28 – day compressive
turn leading to less dissolution of FA particles, which also strength of 93.5 MPa (Fig. 4b1). For mixtures prepared
adversely affects geopolymerization. at the low H2O/FA ratio of 0.32, it was observed that
There is a direct relationship between water content further increase of Na2O/FA beyond 0.094, resulted in a
and the workability of FA – GPC mortar mixtures. It flash set during mixing. Flash setting is an undesirable
can be seen in Fig. 3a2–c2 that a rise in H2O/FA ratio effect that is attributed to the rapid precipitation of alu-
from 0.32 to 0.37, correspondingly increased minosilicate gel at early stages of geopolymerization.
 Silicon

Fig. 2 Effects of SiO2/FA ratio on compressive strength and workability of FA – GPC mortars: a Na2O/FA = 0.054, b Na2O/FA = 0.07, c Na2O/FA =
0.08

Generally, the Na2O/FA ratio showed a pessimum
effect on workability of fresh FA – GPC mortars, as
evident in Fig. 4a2–c2. For instance, the mortar mixture
prepared at a SiO2/FA ratio of 0.10 and H2O/FA ratio
of 0.35, exhibited an increase of workability from 210
to 229 mm upon rise in Na2O/FA from 0.040 to 0.055
(Fig. 4b2). However, further increase in Na2O/FA up to
0.095, led to a corresponding rapid curvilinear reduction
in workability to 192 mm. This observed pessimum in-
fluence of Na2O/FA ratio on workability, was exhibited
by all the mixtures prepared at the different SiO2/FA
and H2O/FA ratios. Generally, the Na2O/FA values of
Silicon
Fig. 3 Effects of H2O/FA ratio on compressive strength and workability of FA – GPC mortars: a Na2O/FA = 0.054, b Na2O/FA = 0.07, c Na2O/FA = 0.08
0.05 to 0.07 optimally gave the best workability results
for the various FA – GPC mortar mixtures, as seen in
Fig. 4a2–c2.
5 Conclusions
This paper has presented an experimental study that was
conducted to investigate the effects of different mix design
factors on compressive strength and on workability of fly
ash geopolymer (FA – GPC) mortars. The present investi-
gation focused on the three (3) compositional parameters
comprising the SiO 2/FA, Na2O/FA and H2O/FA ratios,
while also considering the physico – chemical mix param-
eters namely: - the concentration of sodium hydroxide,
sodium silicate to sodium hydroxide ratio, the liquid to
solids ratio. Based on the experimental results obtained,
the following findings are drawn:

Fig. 4 Effects of Na2O/FA on compressive strength and workability of FA – GPC mortars: a SiO2/FA = 0.08, b SiO2/FA = 0.10, c SiO2/FA = 0.11
& Increase in the SiO2/FA ratio from 0.06 to 0.12, ex-
hibited a pessimum effect on compressive strength of
FA – GPC mortars, while workability corresponding-
ly decreased.
& Increase in the H2O/FA ratio from 0.32 to 0.37, directly
led to higher workability and to correspondingly lower
compressive strengths of the mortars.
& Increase in the Na2O/FA ratio from 0.05 to 0.08, led
to a rapid rise in compressive strength, while
exhibiting a pessimum effect on workability of the
FA – GPC mortars.
Silicon
& In summary, the optimum range values for the best work-
ability and compressive strength results of FA – GPC mor-
tars, were found to be the SiO2/FA ratio of 0.08 to 0.11,
Na2O/FA ratio of 0.05 to 0.08, and H2O/FA ratio of 0.32
to 0.37.
& Appropriate combination of the various physico – chem-
ical mix parameters comprising 12 M to 14 M concentra-
tion of sodium hydroxide, 1.5 to 2.5 ratio of sodium sili-
cate to sodium hydroxide, and 0.4 to 0.6 liquid to solids
ratio can be employed to obtain values that fall within the
aforementioned optimum ranges of compositional factors.
Silicon
Compliance with Ethical Standards
Conflict of Interest On behalf of all authors, the corresponding author
states that there is no conflict of interest.
References
1. Davidovits J (1994) Properties of geopolymer cements, First
International Conference on Alkaline Cements and Concretes,
11–14 October, Kiev, Ukraine, pp. 131–149
2. Pacheco-Torgal F, Castro-Gomez J, Jalali S (2008a) Alkali activat-
ed binders: a review. Part 1: historical background, terminology,
reaction mechanisms and hydratation products. Constr Build Mater
22:1305–1314
3. Khale D, Chaudhary R (2007) Mechanism of geopolymerization
and factors influencing its development: A review. J Mater Sci
42(3):729–746
4. Naghizadeh A, Ekolu SO (2017a) Pozzolanic materials and waste
products for formulation of geopolymer cements in developing
countries: a review. J Concr Soc South Afr 151:22–31
5. Ekolu SO, Thomas MDA, Hooton RD (2006) Studies on Ugandan
volcanic ash and tuff, Proceedings of 1st International Conference
on Advances in Engineering and Technology, 16–19 July, Entebbe,
Uganda, 75–83
6. Hardjito D, Wallah SE, Sumajouw DMJ, Rangan BV (2004) Brief
review of development of geopolymer concrete, George Hoff
Symposium, American Concrete Institute, Los Vegas, USA, pp.
1–10
7. Skvara F, Jilek T, Kopecky L (2005) Geopolymer materials based
on fly ash. Ceramics-Silikáty 49(3):195–204
8. Bakharev T (2005a) Durability of geopolymer materials in sodium
and magnesium sulfate solutions. Cem Concr Res 35:1233–1246
9. Bakharev T (2005b) Resistance of geopolymer materials to acid
attack. Cem Concr Res 35:658–670
10. Lakhssassi MZ, Alehyen S, El Alouani M, Taibi M (2019) The
effect of aggressive environments on the properties of a low calci-
um fly ash based geopolymer and the ordinary Portland cement
pastes. Mater Today Proc 13(3):1169–1177
11. Fernandez-Jimenez A, Puertas F (2002) The alkali – silica reaction
in alkali – activated granulated slag mortars with reactive aggregate.
Cem Concr Res 32:1019–1024
12. Fernandez-Jimenez A, Garcia-Lodeiro I, Palomo A (2007)
Durability of alkali – activated fly ash cementitious materials. J
Mater Sci 42:3055–3065
13. Slaty F, Khoury H, Rahier H, Wastiels J (2015) Durability of alkali
activated cement produced from kaolinitic clay. Appl Clay Sci 104:
229–237
14. Naghizadeh A, Ekolu SO (2017b) Investigation of mixture factors
influencing alkali – silica reaction in fly ash – based geopolymer
mortars. In: 71st RILEM Annu. Week ICACMS 2017, 3–8
September, Chennai, India, pp. 395–400
15. Cheng TW, Chiu JP (2003) Fire – resistant geopolymer produced
by granulated blast furnace slag. Miner Eng 16:205–210
16. Kong DLY, Sanjayan JG (2008) Damage behavior of geopolymer
composites exposed to elevated temperatures. Cem Concr Compos
30(10):986–991
17. Duxson P, Fernandez-Jimenez A, Provis JL, Lukey GC, Palomo A,
van Deventer JSJ (2007) Geopolymer technology: the current state
of the art. J Mater Sci 42(9):2917–2933
18. Huntzinger DN, Eatmon TD (2009) A life – cycle assessment of
Portland cement manufacturing: comparing the traditional process
with alternative technologies. J Clean Prod 17:668–675
19. Maddalena R, Roberts JJ, Hamilton A (2018) Can Portland cement
be replaced by low – carbon alternative materials? A study on the
thermal properties and carbon emissions of innovative cements. J
Clean Prod 186:933–942
20. Turner LK, Collins FG (2013) Carbon dioxide equivalent (CO2)
emissions: A comparison between geopolymer and OPC cement
concrete. Constr Build Mater 43:125–130
21. Naghizadeh A, Ekolu SO (2019a) A comprehensive mix design
method of fly ash geopolymer mortars. Constr Build Mater 202:
704–717
22. Naghizadeh A, Ekolu SO (2018) Effect of mix parameters on
strength of geopolymer mortars – experimental study,
Proceedings of the 6th International Conference on Durability of
Concrete Structures, 18–20 July, Leeds, United Kingdom, pp. 315–
319
23. Ryu GS, Lee YB, Koh KT, Chung YS (2013) The mechanical
properties of fly ash based geopolymer concrete with alkaline acti-
vators. Constr Build Mater 47:409–418
24. Gao K, Lin KL, Wang DY, Hwang CL, Shiu HS, Chang YM,
Cheng TW (2014) Effects SiO2/Na2O molar ratio on mechanical
properties and the microstructure on nano – SiO2 metakaolin –
based geopolymers. Constr Build Mater 53:503–510
25. Hajimohammadi A, van Deventer JSJ (2016) Solid reactant – based
geopolymers from rice hull ash and sodium aluminate. Waste
Biomass Valorization 8(6):2131–2140
26. Sukmak P, Horpibulsuk S, Shen SL (2013) Strength development
in clay – fly ash geopolymer. Constr Build Mater 40:566–574
27. Zhang Z, Provis JL, Wang H, Bullen F, Reid A (2013) Quantitative
kinetic and structural analysis of geopolymers. Part 2.
Thermodynamics of sodium silicate activation of metakaolin.
Thermochim Acta 565:163–171
28. Tchakoute HK, Elimbi A, Yanne E, Djangang CN (2013)
Utilization of volcanic ashes for the production of geopolymers
cured at ambient temperature. Cem Concr Compos 38:75–81
29. Silva de Vargas A, Dal Molin DCC, Vilela ACF, da Silva FJ, Pavão
B, Veit H (2011) The effects of Na2O/SiO2 molar ratio, curing
temperature and age on compressive strength, morphology and mi-
crostructure of alkali – activated fly ash – based geopolymers. Cem
Concr Compos 33(6):653–560
30. Pacheco-Torgal F, Castro-Gomez J, Jalali S (2008b) Alkali activat-
ed binders: a review. Part 2. About materials and binders manufac-
ture. Constr Build Mater 22:1315–1322
31. Xu H, van Deventer JSJ (2000) The geopolymerization of alumino
– silicate minerals. Int J Miner Process 59:247–266
32. Xu H, van Deventer JSJ (2002) Geopolymerisation of multiple
minerals. Miner Eng 15:1131–1139
33. Krishna Rao A, Kumar DR (2020) Effect of various alkaline binder
ratio on geopolymer concrete under ambient curing condition.
Mater Today Proc 27(2):1768–1773
34. Cho YK, Yoo SW, Jung SH, Lee KM, Kwon SJ (2017) Effect of
Na2O content, SiO2/Na2O molar ratio, and curing conditions on the
compressive strength of FA – based geopolymer. Constr Build
Mater 145:253–260
35. Bignozzi MC, Manzi S, Natali ME, Rickard WDA, van Riessen A
(2014) Room temperature alkali activation of fly ash: the effect of
Na2O/SiO2 ratio. Constr Build Mater 69:262–270
36. Lee WKW, van Deventer JSJ (2002) Structural reorganisation of
class F fly ash in alkaline silicate solutions. Colloids Surf A
Physicochem Eng Asp 211:49–66
37. Criado M, Fernandez-Jimenez A, de la Torre AG, Aranda MAG,
Palomo A (2007) An XRD study of the effect of the Na2O/SiO2
ratio on the alkali activation of fly ash. Cem Concr Res 37:671–679
38. Khedmati M, Alanazi H, Kim Y, Nsengiyumva G, Moussavi S
(2018) Effects of Na2O/SiO2 molar ratio on properties of aggregate
– paste interphase in fly ash – based geopolymer mixtures through
multiscale measurements. Constr Build Mater 191:564–574

39. Skvara F (2007) Alkali – activated materials or geopolymers?
Ceramics-Silikáty 51(3):173–177
40. Yusuf MO, Johari MAM, Ahmad AA, Maslehuddin M (2014)
Effects of H2O/Na2O molar ratio on the strength of alkaline acti-
vated ground blast furnace slag – ultrafine palm oil fuel ash based
concrete. Constr Build Mater 69:262–270
41. Ekolu SO (2014) Potential South African standard sand for cement
mortar testing and research, Proceedings of International
Conference in Construction Materials and Structures, 24–26
November, Johannesburg, South Africa, pp. 253–260
42. ASTM C1437 (2016) Standard test method for flow of hydraulic
cement mortar, Annual book of ASTM Standards, ASTM
International, West Conshohocken, PA. http://www.astm.org
43. ASTM C109/C109M (2016) Standard test method for compressive
strength of hydraulic cement mortars (Using 2 – in . or [ 50 – mm ]
Silicon
cube specimens), Annual book of ASTM Standards, ASTM
International, West Conshohocken, PA. http://www.astm.org
44. El-Dieb AS, Shehab EE (2014) Cementless concrete using ceramic
waste powder, Proceedings of International Conference in
Construction Materials and Structures, 24–26 November,
Johannesburg, South Africa, pp. 487–494
45. Duxson P, Provis JL (2008) Designing precursors for geopolymer
cements. J Am Ceram Soc 91(12):3864–3869
46. Naghizadeh A, Ekolu SO (2019b) Behaviour of fly ash geopolymer
binders under exposure to alkaline media. Asian J Civ Eng 20(6):
785–798
Publisher’s Note Springer Nature remains neutral with regard to jurisdic-
tional claims in published maps and institutional affiliations.