Ceramics International 43 (2017) 324–335

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Modeling and optimization of compressive strength and bulk density of

metakaolin-based geopolymer using central composite design: A numerical
crossmark
and experimental study
⁎ ⁎
M. Ghanbaria, A.M. Hadiana, , A.A. Nourbakhshb, , K.J.D. MacKenziec
a
School of Metallurgy and Materials Engineering, University of Tehran, Tehran, Iran
b
Department of Ceramic, Shahreza Branch, Islamic Azad University, Isfahan, Iran
c
MacDiarmid Institute for Advanced Materials and Nanotechnology, Victoria University of Wellington, Wellington, New Zealand

A R T I C L E I N F O A BS T RAC T

Keywords: Geopolymers have received considerable attention due to their properties and applications as environmentally
Metakaolin-based geopolymer friendly alternatives to ordinary Portland cement. This paper reports the use of a central composite design
Central composite design technique to model four synthesis parameters (curing temperature, SiO2/Al2O3, Na2O/SiO2, and H2O/Na2O
Optimization ratio) to optimize the compressive strength and bulk density of metakaolin-based geopolymer bodies. Thirty-
Compressive strength
one geopolymer paste compositions, derived by applying central composite design software, were prepared and
Bulk density
their compressive strengths and bulk densities were measured. The experimental data were then modeled by the
method of analysis of variance and the effect of the interactions between the four chosen variables parameters
on the compressive strength and bulk density was studied by surface plots. The optimum values of the four
variables, determined in this way, were a curing temperature of 67 °C, SiO2/Al2O3=2.90, Na2O/SiO2=0.20,
H2O/Na2O=13.75. The measured strength and density of this sample was 62.4 MPa and 1.59 g/cm3
respectively, and the amorphous character of this sample was demonstrated by XRD.

1. Introduction
In recent years, construction materials, including cement and
cementitious composites, have become increasingly interested in
environmentally-friendly materials, since industries producing conven-
tional cements emit approximately 7% of the total world's CO2 [1,2]. In
1972, Davidovits reported a new class of materials which he termed
“geopolymers” [3]. Since the CO2 emission from the production of
these geopolymers was 80% less than that from the production of
traditional Portland cement, these materials have attracted consider-
able attention since their discovery [3].
Geopolymers are X-ray amorphous three-dimensional aluminosili-
cates material consisting of a random network of tetrahedral AlO4 units
linked through oxygen atoms to SiO4 units, with charge balance
provided by alkali metal ions [4]. These materials can be synthesized
by activating a solid aluminosilicate source (clay [4] or waste materials
such as red mud [5], fly ash [6–9], volcanic ash [10] or slag [11]) with
strong alkali solution. The geopolymerisation mechanism involves
dissolution of the alumina and silica followed by gel formation yielding
a hard inorganic polymer structure [7].
Synthesis parameters such as the solvent type, raw materials, mix
composition and curing conditions play a key role in the properties of
hardened geopolymers [8,12]. Of these, the most important composi-
tion parameters are the SiO2/Al2O3 ratio, the R2O/Al2O3 ratio, the
SiO2/R2O ratio (R=Na+ or K+) and the liquid/solid ratio [13–15]. In
particular, the mechanical strength of geopolymers is strongly depen-
dent on the silica content; an increase in the SiO2/Al2O3 ratio results in
the formation of an increase in the number of Si–O–Si bonds which,
being stronger than Si–O–Al and Al–O–Al bonds, increase the strength
of the geopolymer [16]. Increasing the Si/Al or Na/Al ratios increases
the strength of geopolymers, provided these ratios do not exceed an
optimum value, above which the strength will decrease [17–21].
The effect of the curing conditions on the properties of geopolymers
has been extensively studied [22–27]. Heah et al. [24] concluded that
ambient-temperature curing of metakaolin-based geopolymers was not
viable, but increasing the temperature at 40–100 °C resulted in a
strength increase at 1–3 days. Curing at higher temperatures for longer
times resulted in a loss of strength due to the thermolysis of Si–O–Al–
O bonds [24].
The presence of water provides a medium for the dissolution of the
aluminosilicates, hydrolysis of Al3+ and Si4+ and polycondensation of
the resulting hydroxyl species, significantly affecting the formation

⁎
Corresponding authors.
E-mail addresses: Hadian@ut.ac.ir (A.M. Hadian), anourbakhs@yahoo.com (A.A. Nourbakhsh).

http://dx.doi.org/10.1016/j.ceramint.2016.09.159
Received 3 July 2016; Received in revised form 21 August 2016; Accepted 22 September 2016
Available online 23 September 2016
0272-8842/ © 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
M. Ghanbari et al. Ceramics International 43 (2017) 324–335

structure and properties of the geopolymer [27]. However, excessive determined by X-ray fluorescence (Philips PW 1480) is presented in
amount of water decrease the strength of geopolymers due to the Table 2. Sodium hydroxide (NaOH, 98% purity), and sodium silicate
increased size and volume of the pores [28–31]. solution (Na2O=8.2%, SiO2=27% and water=64.8% by mass) were the
Thus, increased oxide molar ratios do not necessarily result in alkaline activators. Deionized water was used throughout the experi-
higher compressive strengths, but it would be helpful to utilize a ments.
method of experiment design to enable the combined effect of these
parameters to be investigated simultaneously. Modeling and optimiza-
2.2. Sample preparation and testing
tion of effective parameters and properties of geopolymers were
investigated using different methods such as design of experiments
The experiment design and analysis was carried out using statistical
[32–36]. Response surface methodology is just such a method for
software developed by Stat-Ease Co on a Design expert 7. The 31
modeling and optimization of different processes in a cost-effective and
required experiments were designed using a CCD procedure with the
efficient manner. The technique of Central Composite Design (CCD)
range of parameters listed in Table 3 [3,27] and are presented in
was initially developed by Box and Wilson [37] and subsequently
Table 4, which summarizes the compositions of the 24 model points
improved by Box and Hunter [38]. The advantages of CCD are (i) the
and 7 additional random center points. These 31 compositions were
amount of information it provides is comparable to the three-level
prepared using a calculated amount of metakaolin, sodium silicate,
factorial method, (ii) it requires fewer experiments than full factorial
sodium hydroxide and deionized water. The mixtures were cast in
design, (iii) it is an efficient method for describing the majority of
cylindrical polyethylene molds with a ratio of height to diameter ratio
steady-state process responses [39]. CCD requires the standard 2k
of 2, vibrated for 20 min to remove entrapped air, sealed and cured for
factorial tests with its origin at the center, where k is the number of
24 h. at the temperatures specified in Table 4.
variables. In order to generate the quadratic terms and replicate tests at
Compressive strength tests were performed in triplicate on cured
the center, the 2k points are fixed axially at a distance α from the
samples according to ASTM C39. A universal testing machine (Santam,
center. The axial points, which are equidistant from the design center,
STM-50) was used for the measurements. The loading was displace-
allow rotatability, a property which ensures that the variance of the
ment-controlled at a constant rate of 0.5 mm/min for all tests. The bulk
model will be constant for all points. Replicates of the test at the center
densities of the samples were measured according to Archimedes'
are very important since they provide an independent estimate of the
principle (ASTM C20), and the average of five determinations of each
experimental error [38].
sample is reported.
After defining the desired range of values of the variables, these are
Modeling was carried out using the data collected from the CCD-
coded as ± 1 for the factorial points, 0 for the center points and ± α for
designed experiments for the two responses (compressive strength and
the axial points. The calculated codes as a function of the range of
bulk density). The suitability of the model was determined by the
interest of each factor is shown in Table 1 [40].
method of Analysis Of Variance (ANOVA) for each of the responses.
In the present study, the curing temperature (A), the molar ratios
The effect of the chosen parameters and their interactions on the
SiO2/Al2O3 (B), Na2O/SiO2 (C), and H2O/Na2O (D) are the parameters
responses was also analyzed by constructing main effect plots and
used to investigate their effect on the compressive strength and bulk
surface plots, the compressive strength and bulk density was optimized
density of metakaolin-based geopolymer bodies (MGBs) by the CCD
and the validity of the optimum values were tested. The crystalline
method. The resultant models giving the optimized parameters for
phases or amorphous character of the raw material and the optimized
mechanical properties are presented.
sample were determined by X-ray diffraction using Cu Kα radiation
(Philips-PW3170 diffractometer).
2. Experimental
3. Results and discussion
2.1. Materials
3.1. The statistical models and analysis of responses
Metakaolin (d50=4.96 ϻm) was prepared by calcining kaolinite at
750 °C for 24 h. The chemical composition of the resulting metakaolin, The results of ANOVA are given in Tables 5 and 6 for the
compressive strength and bulk density respectively. The term ‘p-value’

Table 1
Relationship between coded and actual values of a variable [40]. Table 3
The range for each factor used in the central composite experiment design.
Code Actual value of variable
Factor Symbol Coded variable level
-α Xmin
−1 [(Xmax+Xmin)/2]−[(Xmax−Xmin)/2β] (-α) −1 0 1 (+α)
0 (Xmax+Xmin)/2
+1 [(Xmax+Xmin)/2]+[(Xmax−Xmin)/2β] Temperature (°C) A 40 55 70 85 100
+α Xmax SiO2/Al2O3 B 2.15 2.90 3.65 4.40 5.15
Na2O/SiO2 C 0.15 0.20 0.25 0.30 0.35
Xmax and Xmin are the maximum and minimum values of X respectively, β=2k/4, k is the H2O/Na2O D 10 13.75 17.5 21.25 25
number of variables.

Table 2
Chemical composition of metakaolin (wt%).

SiO2 Al2O3 Fe2O3 CaO Na2O K2O MgO TiO2 MnO P2O5 S L.O.I

53.68 42.68 0.34 0.12 0.02 0.12 0.08 1.395 0.009 0.020 0.011 1.32

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Table 4
Sample compositions determined by central composite design and the corresponding experimental values of the sample responses.

Run no. (batch number) T (°C) SiO2/Al2O3 Na2O/SiO2 H2O/Na2O Compressive strength (MPa) Bulk density (g/cm3)

1 85 2.90 0.30 13.75 15.2 ± 0.7 1.24 ± 0.01

2 40 3.65 0.25 17.50 22.2 ± 1.6 1.20 ± 0.01
3 85 4.40 0.20 13.75 4.5 ± 1.7 1.49 ± 0.09
4 55 4.40 0.30 21.25 0.7 0.89 ± 0.02
5 100 3.65 0.25 17.50 9.1 ± 2.3 1.11 ± 0.02
6 70 3.65 0.25 17.50 10.7 ± 1.1 1.15 ± 0.01
7 55 2.90 0.20 21.25 9.5 ± 0.3 1.17
8 55 2.90 0.30 21.25 0.9 ± 0.1 0.93
9 70 3.65 0.25 10.00 52.3 ± 2.5 1.57
10 55 2.90 0.20 13.75 53.2 ± 3.2 1.50 ± 0.01
11 70 3.65 0.25 25.00 0.6 ± 0.1 0.87
12 55 4.40 0.30 13.75 24. 9 ± 6.4 1.22 ± 0.01
13 85 4.40 0.20 21.25 0 0.71 ± 0.03
14 85 2.90 0.30 21.25 1.4 ± 0.1 0.91
15 55 4.40 0.20 13.75 33.4 ± 0.6 1.47 ± 0.04
16 70 3.65 0.25 17.50 9.9 ± 1.5 1.13 ± 0.01
17 70 3.65 0.25 17.50 10.4 ± 1.1 1.14 ± 0.01
18 85 2.90 0.20 21.25 9.6 ± 3.6 1.13 ± 0.01
19 85 4.40 0.30 13.75 20.3 ± 5.8 1.18 ± 0.01
20 55 4.40 0.20 21.25 0 0.73 ± 0.02
21 70 3.65 0.25 17.50 9.7 ± 1.1 1.11 ± 0.01
22 85 4.40 0.30 21.25 0.4 0.88 ± 0.01
23 70 3.65 0.35 17.50 4.7 ± 0.5 0.96
24 70 5.15 0.25 17.50 0 0.81 ± 0.04
25 70 3.65 0.25 17.50 9.9 ± 0.9 1.14 ± 0.01
26 70 3.65 0.25 17.50 9.7 ± 2.0 1.14 ± 0.01
27 85 2.90 0.20 13.75 53.4 ± 2.1 1.52 ± 0.01
28 70 2.15 0.25 17.50 4. 7 ± 1.0 1.18 ± 0.01
29 70 3.65 0.15 17.50 22.1 ± 3.8 1.34 ± 0.05
30 55 2.90 0.30 13.75 22.5 ± 1.4 1.22 ± 0.01
31 70 3.65 0.25 17.50 10.3 ± 1.4 1.11 ± 0.01

Table 5 Table 6
ANOVA for compressive strength. ANOVA for bulk density.

Source Sum of df Mean F value p-value Note Source Sum of df Mean F value p-value
squares square prob > F squares square prob > F

Model 10.76 14 0.77 36.91 < 0.0001 Significant Model 1.50 14 0.11 28.88 < 0.0001 Significant
A-T 0.14 1 0.14 6.57 0.0208 Significant A-T 2.604E−3 1 2.604E−3 0.70 0.4141
B-SiO2/ 1.49 1 1.49 71.58 < 0.0001 Significant B-SiO2/ 0.13 1 0.13 36.05 < 0.0001 Significant
Al2O3 Al2O3
C-Na2O/ 0.29 1 0.29 13.78 0.0019 Significant C-Na2O/ 0.17 1 0.17 45.45 < 0.0001 Significant
SiO2 SiO2
D-H2O/ 6.35 1 6.35 305.12 < 0.0001 Significant D-H2O/ 1.00 1 1.00 2269.00 < 0.0001 Significant
Na2O Na2O
AB 0.063 1 0.063 3.04 0.1003 AB 5.625E−5 1 5.625E−5 0.015 0.9035
AC 0.021 1 0.021 1.01 0.3302 AC 5.625E−5 1 5.625E−5 0.015 0.935
AD 0.075 1 0.075 3.58 0.0766 AD 7.563E−4 1 7.563E−4 0.20 0.6574
BC 0.79 1 0.79 38.16 < 0.0001 Significant BC 0.039 1 0.039 10.53 0.0051 Significant
BD 0.22 1 0.22 10.49 0.0051 Significant BD 0.041 1 0.041 11.07 0.0043 Significant
CD 0.019 1 0.019 0.90 0.3579 CD 0.061 1 0.061 16.54 0.0009 Significant
A2 0.030 1 0.030 1.45 0.2463 A2 1.417E−3 1 1.417E−3 0.38 0.5450
B2 1.19 1 1.19 57.32 < 0.0001 Significant B2 0.031 1 0.031 8.39 0.0105 Significant
C2 5.688E−7 1 5.688E−7 2.732E−5 0.9959 C2 9.582E−4 1 9.582E−4 0.26 0.6179
D2 0.041 1 0.041 1.97 0.1793 D2 0.016 1 0.016 4.19 0.0575
Residual 0.33 16 0.021 Residual 0.059 16 3.704E−3

shows the degree of effectiveness of each term. Each factor with a p-
value less than 0.05 is considered to be effective parameter and those
with p-values larger than 0.05 are regarded as ineffective.
Table 5 shows that all four factors have a significant influence on
the compressive strength, and the interaction between the SiO2/Al2O3
and Na2O/SiO2 or SiO2/Al2O3 and H2O/Na2O molar ratio is signifi-
cant. Other interactions do not have a significant effect on the
compressive strength.
The results of ANOVA for the bulk density (Table 6) show that
curing temperature in this range has no significant effect, but the
influence of other factors is significant. Interactions between BC, BD
and CD have a significant effect on the bulk density.
The models, which were fitted to the results for the compressive
strength and bulk density, are given in Eqs. (1) and (2). Insignificant
terms were removed from these models, and modified quadratic
models were selected as suggested by the software. The models are
written in code and conversion of the actual values of the factors to
their coded values was carried out by the relationship [41]:

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Fig. 1. The model-predicted values vs. the observed results for compressive strength.
Fig. 2. The model-predicted values vs. observed results for bulk density.
Xc=(Xr −a )/ b
where Xc is the coded value of factor X, Xr is the actual value of the
factor, a is the average of the upper and lower actual values of any
factor and b is the average of difference of these two values.
log10 (Compressive strength + 0.53)
(MPa) = 1.02 − 0.075A − 0.25B − 0.11C − 0.51D + 0.22BC − 0.12BD
− 0.20 B2
Bulk density (g/cm3) = 1.16 − 0.075B − 0.084C − 0.20D + 0.049BC
− 0.051BD + 0.062CD − 0.036B2
2
The R-squared (R ) value was 0.947 and 0.949 for compressive
strength and bulk density respectively. The high R2 values indicate that
the models are statistically adequate and can be used to predict the
responses.
Figs. 1 and 2 compare the observed and model-predicted values of
the responses. The ideal line (y=x) passes through the points. R2 was
found to be 0.851 for the compressive strength response, and 0.918 for
the bulk density response. Since R2 should be at least 0.80 for a good fit
[42], this indicates a good correlation between observed and model
Ceramics International 43 (2017) 324–335
predicted values for both the compressive strength and bulk density.
3.2. Effect of the various parameters on the responses
In the study of the influence of the four processing parameters
(curing temperature, molar ratios of SiO2/Al2O3, Na2O/SiO2 and H2O/
Na2O) on the compressive strength and bulk density of MGBs, single-
parameter and two-parameter interaction response surface plots were
constructed by using the quadratic models suggested by the software to
describe the effect of the input variables on the compressive strength
and bulk density. The effect of these interactions on the responses
(compressive strength and bulk density) can be conveniently repre-
sented as response plots by retaining two variables at their central level
values and varying the other two parameters. The slope of these plots
indicates the sensitivity of the response to a particular factor. For
instance, a curvature or a steep slope in the response shows that the
response is sensitive to that factor while a relatively flat line indicates
that the response is insensitive to that specific factor [43].
3.2.1. Effect of individual parameters on the responses
The effects of the four process parameters on the compressive
strength are plotted in Fig. 3a–d. The Fig. 3b shows that at first the
compressive strength increases slightly with increasing SiO2/Al2O3
ratio, then decreases due to the formation of strong Si–O–Si bonds
[16], whereas an excessive increase of this ratio hinders geopolymer-
isation. Fig. 3d shows that the molar ratio H2O/Na2O exerts a
significant effect on the compressive strength; and increase in this
ratio causes a dramatic decrease in the compressive strength due to the
high porosity introduced by the evaporation of water. The other factors
(curing temperature and the molar ratio Na2O/SiO2) exert a less
negative effect on the compressive strength.
Fig. 4 shows the single effect of the various factors on the bulk
density. As shown in Table 6, the influence of the curing temperature
on the bulk density is insignificant, possibly because of the small
temperature range selected on the basis of temperatures known to be
appropriate for geopolymerisation. The other factors have approxi-
mately the same effect on the bulk density as their effect on the
compressive strength (see Fig. 4b–d).
3.2.2. Effect of interactions between parameters on the responses
The best approach for understanding the relationship between the
variables and responses and the effect of their interactions on the
responses is to utilize three dimensional (3D) plots. Since each model
includes four factors, the 3D plots were produced by varying two
parameters and holding the other two parameters at the central value.
Fig. 5 shows the interactions between the parameters and their
effect on the compressive strength, from which the following points can
be concluded:
(1) 1) Changing the temperature in this range has only a slight effect on
the compressive strength (Fig. 5a). There is a slight increase in the
compressive strength with increasing SiO2/Al2O3 molar ratio, but
(2) this is accompanied by a reduction in compressive strength for a
given temperature. A linear relationship exists between curing
temperature and compressive strength, with the effect of tempera-
ture on the compressive strength being approximately invariable
(Fig. 5a–c).
2) An increase in the Na2O/SiO2 molar ratio and temperature causes a
reduction in the compressive strength (Fig. 5b).
3) The compressive strength rapidly decreases with an increase in
curing temperature and H2O/Na2O ratio (Fig. 5c). At lower H2O/
Na2O ratios an increase in temperature causes the compressive
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Fig. 3. Effect of (a) curing temperature, (b) SiO2/Al2O3 molar ratio, (c) Na2O/SiO2 molar ratio, and (d) H2O/Na2O molar ratio on compressive strength.
strength to decrease but at higher values of this ratio the effect of
temperature is effectively insignificant.
4) Fig. 5d shows that the interaction between the SiO2/Al2O3 and
Na2O/SiO2 molar ratios on the compressive strength is difficult to
describe, although an excessive increase in SiO2/Al2O3 or Na2O/
SiO2 causes a decrease in the compressive strength. Intermediate
values of these molar ratios cause the compressive strength to
increase.
5) Fig. 5e and f show the effect of H2O/Na2O, SiO2/Al2O3, H2O/Na2O
and Na2O/SiO2 on the compressive strength. At constant SiO2/
Al2O3 or Na2O/SiO2 values the compressive strength rapidly
decreases with increasing H2O/Na2O ratio. The compressive
strength increases, then decreases with an increase in the SiO2/
Al2O3 ratio at lower H2O/Na2O values, and also decreases with
increasing Na2O/SiO2. At higher H2O/Na2O ratios, the molar ratio
of SiO2/Al2O3 or Na2O/SiO2 has no significant effect on the
compressive strength. Thus, the H2O/Na2O ratio has the greatest
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Ceramics International 43 (2017) 324–335
effect on the compressive strength by comparison with the other
parameters.
These observations can be understood in terms of the facilitation of
silica and alumina dissolution with increasing temperature. However,
increasing temperature causes evaporation of the water from samples,
generating cracks which decrease the compressive strength. An ex-
cessive increase in the H2O/Na2O ratio also interferes with the
geopolymerisation process. The effect of Na2O/SiO2 and SiO2/Al2O3
on the compressive strength can be explained by an increase in the Na+
ion concentration, allowing improved dissolution of the starting
material and the formation of strong oligomers with increased com-
pressive strength. However, when the molar ratio of Na2O/SiO2
exceeds a certain level, the system will become saturated with Na+
ions, preventing the formation of oligomers and decreasing the
compressive strength [44]. Increasing the SiO2/Al2O3 ratio also
increases the Si content, leading to the formation of an increased
M. Ghanbari et al.
Fig. 4. Effect of (a) curing temperature, (b) SiO2/Al2O3 molar ratio, (c) Na2O/SiO2 molar ratio, and (d) H2O/Na2O molar ratio on bulk density.
number of strong Si–O–Si bonds, and increasing the compressive
strength. However, if an excessive increase in the SiO2/Al2O3 molar
ratio is required, this may have to be satisfied by an increase in the
starting aluminosilicate; this may contain unreactive alkali-insoluble
components which act as defects and reduce the homogeneity of the
structure, causing the compressive strength to decrease [45]. Also, low
quantities of SiO2/Al2O3 molar ratio causes the formation of brittle
crystalline components, and decreases the compressive strength of
geopolymer bodies [46]. Thus, optimization of the properties of
geopolymer bodies requires a tradeoff between these two factors.
Fig. 6 shows the surface plots illustrating the effect of the
parameters on the bulk density. Fig. 6a–c show that the bulk density
is insensitive to the curing temperature in the selected range for given
values of SiO2/Al2O3, Na2O/SiO2 or H2O/Na2O. The bulk density
decreases with increasing SiO2/Al2O3 ratio as shown by the slight
curvature in Fig. 3a. The bulk density also decreases linearly with an
increase in Na2O/SiO2 or H2O/Na2O (see Fig. 3b and c). Other surface
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Ceramics International 43 (2017) 324–335
plots of the bulk density show similar behavior to that of the
compressive strength, reflecting the fact that bulk density and com-
pressive strength are closely correlated.
3.3. Optimization
The surface plots generated in this study were used by the software
to determine the conditions required to optimize the compressive
strength and the bulk density of the geopolymer product and determine
the maximum values of compressive strength and bulk density. Fig. 7
shows the optimum molar ratios of SiO2/Al2O3, Na2O/SiO2 and H2O/
Na2O are 2.90, 0.20 and 13.75 respectively.
Figs. 8 and 9 show contour plots for the compressive strength and
bulk density. Since the molar ratio H2O/Na2O has the greatest impact
on the responses, only the contour plots which contain the H2O/Na2O
ratio are presented and used to determine the optimum locations. The
first points shown by the software to have the highest value (0.987)
M. Ghanbari et al. Ceramics International 43 (2017) 324–335

Fig. 5. The effect of interactions between (a) temperature and SiO2/Al2O3, (b) temperature and Na2O/SiO2, (c) temperature and H2O/Na2O, (d) SiO2/Al2O3 and Na2O/SiO2, (e) SiO2/
Al2O3 and H2O/Na2O, and (f) Na2O/SiO2 and H2O/Na2O, on compressive strength.

were taken as the optimum parameters for compressive strength and
bulk density and were selected for testing. The predicted and observed
values of the responses and parameters for the selected optimum point
are shown in Table 7. The measured errors of < 5% indicate the validity
of the models. The XRD patterns of kaolinite, metakaolin and the
optimum sample (Fig. 10) The XRD pattern of kaolinite shows a minor
quartz impurity which survives both dehydroxylation and geopolymer-
ization. The broad base line hump in the XRD pattern of the optimum
geopolymer sample confirms the formation of a satisfactory product.
4. Conclusion
Response surface methodology and central composite design were
used to investigate the effect of four parameters (curing temperature,

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Fig. 6. The effect of interactions between (a) temperature and SiO2/Al2O3, (b) temperature and Na2O/SiO2, (c) temperature and H2O/Na2O, (d) SiO2/Al2O3 and Na2O/SiO2, (e) SiO2/
Al2O3 and H2O/Na2O, and (f) Na2O/SiO2 and H2O/Na2O, on bulk density.
Na2O/SiO2, SiO2/Al2O3, and H2O/Na2O molar ratios) and their inter-
actions on compressive strength and bulk density of metakaolin-based
geopolymer bodies. The responses were then modeled by means of
ANOVA statistical tables and surface plots, allowing the optimum
conditions for geopolymer formation to be obtained, as follows:
1) The optimum points predicted by the software as having the highest
desirability for the curing temperature, SiO2/Al2O3, Na2O/Si2O and
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H2O/Na2O molar ratios were 67 °C, 2.90, 0.20, and 13.75, respec-
tively. The predicted optimum compressive strength and bulk
density for this optimum point was 64.1 MPa and 1.55 g/cm3,
respectively. Preparing and testing of a geopolymer body formed
under the predicted optimum conditions gave experimental results
in satisfactory agreement with the predicted values (62.4 MPa and
1.59 g/cm3 for the compressive strength and bulk density respec-
tively)
M. Ghanbari et al.
Fig. 7. Effect of parameters on desirability of optimum locations: (a) temperature and SiO2/Al2O3, (b) temperature and Na2O/SiO2, (c) temperature and H2O/Na2O, (d) SiO2/Al2O3 and
Na2O/SiO2, (e) SiO2/Al2O3 and H2O/Na2O, and (f) Na2O/SiO2 and H2O/Na2O.
2) The curing temperature did not exert a significant effect on the bulk
density, but an increase in the curing temperature decreased the
compressive strength.
3) An increase in the SiO2/Al2O3 ratio increased the compressive
strength and bulk density up to a point but further increases in this
ratio caused a decrease in these properties. Importantly, the
332
Ceramics International 43 (2017) 324–335
interaction between the SiO2/Al2O3 and Na2O/SiO2 molar ratios
was found to influence the compressive strength and bulk density;
to optimize the properties of the geopolymer body these two ratios
should therefore be considered together as an excessive decrease or
increase of either can have negative effect on the compressive
strength and bulk density.
M. Ghanbari et al. Ceramics International 43 (2017) 324–335

Fig. 8. Contour plots showing effect of parameters on the compressive strength for
finding optimum conditions: (a) temperature and H2O/Na2O, (b) SiO2/Al2O3 and H2O/ Fig. 9. Contour plots showing effect of parameters on the bulk density for finding
Na2O, and (c) Na2O/SiO2 and H2O/Na2O. optimum conditions: (a) temperature and H2O/Na2O, (b) SiO2/Al2O3 and H2O/Na2O,
and (c) Na2O/SiO2 and H2O/Na2O.

4) Compared with the other parameters, the H2O/Na2O molar ratio

had the greatest impact on both the compressive strength and bulk 5) This study focused on numerical and experimental results to better
density, such that an increase in this ratio can significantly decrease understand the effect of the processing parameters and their
the compressive strength and bulk density. interactions. To gain an even better understanding of the numerical
results, microstructural investigations and other analyses are

333
M. Ghanbari et al.
Table 7
Corroborative test results for optimized values.
Conditions of predicted optimum point
Curing temperature (°C) SiO2/Al2O3 Na2O/SiO2 H2O/Na2O
67 2.90 0.20 13.75
Fig. 10. XRD patterns of kaolinite, metakaolin, and the optimum geopolymer sample.
required; these are beyond the scope of this article but are ongoing
and will be reported in the near future.
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