Construction and Building Materials 182 (2018) 360–370

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Construction and Building Materials

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What is the role of water in the geopolymerization of metakaolin?

Sungwoo Park, Mohammad Pour-Ghaz ⇑
Department of Civil, Construction, and Environmental Engineering, North Carolina State University, Raleigh, NC, United States

h i g h l i g h t s

 The role of water depends on NaOH/Metakaolin (N/M) ratio.

 Water mainly provides a medium to facilitate the geopolymerization reaction.
 At high N/M ratio, additional water is produced during geopolymerization.
 At low N/M ratio, water is physically and chemically bound within the structure.
 Pore size distribution depends on both water-to-solid ratio and N/M ratio.

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

Article history: Despite the significant advances in understanding the structure of geopolymers in the last decades, the
Received 28 March 2018 role of water in the geopolymerization of aluminosilicates and within the structure of geopolymers
Received in revised form 7 June 2018 remains elusive. The present paper investigates the role of water in the geopolymerization of metakaolin,
Accepted 8 June 2018
a low calcium aluminosilicate. We differentiate between different states of water in these materials and
discuss the nature and the origin of non-evaporable (chemically bound) water, and evaporable water. We
propose a conceptual model for the microstructure of metakaolin based geopolymers that accounts for
Keywords:
different states of water within their structure and discuss the implications of their composition on pore
Evaporable water
Geopolymer
size distribution.
Metakaolin Ó 2018 Elsevier Ltd. All rights reserved.
Non-evaporable water
Pore size distribution
NASH
NAS

1. Introduction in the title, investigates the role of water in the geopolymerization

It is well known that the production of portland cement results
in significant environmental emissions and implications; and
therefore, there has been a growing interest in developing alterna-
tive cementitious materials. A class of these alternative cementi-
tious materials is geopolymers produced using an aluminosilicate
source (e.g., slag, fly ash, or metakaolin) and alkaline solutions.
During the last few decades there has been a significant amount
of research on geopolymers. These research efforts have consider-
ably advanced our understanding of the geopolymerization and the
contribution of different factors to it. Despite these advances, the
role of water in geopolymerization and within the structure of
geopolymers are not well understood. The present paper, as stated
⇑ Corresponding author at: North Carolina State University, Department of Civil,
Construction, and Environmental Engineering, Campus Box 7908, 431C Mann Hall,
Raleigh, NC 27695-7908, United States.
E-mail address: mpourghaz@ncsu.edu (M. Pour-Ghaz).
of metakaolin.
Perhaps the first insights on the role of water in the geopoly-
merization comes from the earlier studies [1–8], that provided a
conceptual model for geopolymerization process involving three
steps: (1) dissolution and reorganization of aluminosilicate, (2)
condensation of oligomers into gels, and (3) continued linkage of
gel clusters to create polymer’s skeleton. While this conceptual
model has contributed to a holistic understanding of the geopoly-
merization process, the exact role of water in this model is unclear.
For example, while in [5] it has been suggested that water only
provides a medium for dissolution and restructuring of aluminosil-
icate source into geopolymer, others [7,9] have suggested that
polymerized gel is hydrated and water is a part of the hydrated
structure, although the amount of water that participates in the
formation of the structure is low, especially in case of low calcium
geopolymers [1,10].
The first hypothesis of the present paper is that if water
only provides a medium for the dissolution and restructuring of

https://doi.org/10.1016/j.conbuildmat.2018.06.073
0950-0618/Ó 2018 Elsevier Ltd. All rights reserved.
 S. Park, M. Pour-Ghaz / Construction and Building Materials 182 (2018) 360–370
aluminosilicate, the entire initial mixing water should be recover-
able after the completion of the reaction; any amount of water in
excess of the initial mixing water will signify production of water
during geopolymerization, and any amount of water deficient of
the initial mixing water will signify chemically bound water. To
evaluate this hypothesis we perform mass loss measurements of
geopolymer samples and compare the mass of the evaporable
water with mass of the initial mixing water. We explain the results
of these measurements in terms of mechanisms involved in the
geopolymerization and we also elucidate on the nature of evap-
orable and chemically bound water. The second hypothesis of this
work is that evaporable water within the structure has different
states, and each state requires different amount of energy for evap-
oration. Therefore, by utilizing different methods of drying, differ-
ent states of water can be identified. To evaluate this hypothesis,
we use nitrogen drying, oven drying, thermogravimetric analysis
(TGA), and cyclic desorption-absorption measurements.
We further discuss the consequences of our findings in address-
ing the above hypotheses and we propose a conceptual model for
the microstructure of metakaolin based geopolymer and discuss
the implications of the chemical composition of the geopolymer
on its microstructure and pore size distribution.
Before proceeding further we would like to mention that cal-
cium may play a significant role in geopolymerization. For exam-
ple, studies in [1,11–23] have discussed the role of calcium in
geopolymerization. In the present article, we investigate geopoly-
mers made with metakaolin, and therefore, the role of calcium
and its effect on the formation of different phases is out of the
scope of the present article.
2. Materials and methods
2.1. Materials
Commercially available metakaolin with chemical composition
and X-ray powder diffraction pattern shown in Table 1 and Fig. 1,
respectively, was used. The XRD measurements were performed
using Cu-Ka radiation (12 kV, 30 mA) with a scanning rate of 1°/
min from 5° to 80° (2h). The XRD indicates the presence of quartz
which is commonly found in commercial metakaolin [24–28].The
large labeled peak in Fig. 1 corresponds to quartz and other small
peaks indicate the presence of trace amount of other impurities.
2.2. Sample preparation
The mixture proportions for all specimens used in the present
study are summarized in Table 2. The samples are identified by
their NaOH/Metakaolin (N/M) and water-to-solid (w/s) ratios.
The samples are divided into two groups. Group 1, (No.1–4), was
prepared with 12-Mol sodium hydroxide solution. The w/s ratios
of the samples were 0.6, 0.7, 0.8, and 1.0, respectively. Since, in
Group 1, the alkali solution concentration is constant, the N/M
Table 1
Chemical composition of the metakaolin used
in the present work.
Constituent Content (%)
SiO2 52.94
Al2O3 43.36
Fe2O3 1.35
CaO 0.04
MgO 0.03
Na2O 0.02
K2O 0.17
SO3 0.06
Moisture content 0.75
Loss on ignition 0.45
361
Fig. 1. X-ray diffractograms of metakaolin used in the present study.
ratio increases with the increase of w/s ratio. Group 2 (No.5–8)
was designed to have the same N/M as that of Group 1 for speci-
men No.1 and 2, while having different w/s ratio. For example,
samples No.5 and 6 have the same N/M ratio as that of sample
No.1 and have different w/s ratios. As a result, the samples in
Group 2 use different concentrations of NaOH solution (9.6–15
Mol).
The sodium hydroxide solution was prepared one day prior to
producing the mixture. Geopolymers were synthesized by mixing
metakaolin and sodium hydroxide solution and mixed for 5 min.
Samples were cast in 20 mL high-density polyethylene cylindrical
vials with the diameter of 2.8 cm and the height of 5.7 cm, vibrated
for 3 min, and sealed with air-tight caps. Samples were cured in
room temperature for 1 day and then in an oven at 40 °C for 10
days. The mass of the vials were measured before and after the cur-
ing period to ensure no moisture loss had occurred during the cur-
ing period. The measurements indicated no mass change within
the measurement tolerance of ±0.1 mg.
2.3. Measurement of evaporable water
The amount of evaporable water was measured using oven dry-
ing at 100 ± 3 °C for 3 days. Given the fluctuations of the oven tem-
perature, 100 °C was chosen to ensure that the samples are not
exposed to temperatures above 105 °C. It should be noted that
the measurement of the amount of evaporable water is a function
of the choice of temperature and the findings of the present paper
are based on the choice of temperature herein. Three replicates
were used in all measurements. After completion of oven drying,
to check whether the water fully evaporated, TGA was performed
on the dried samples (for TGA procedure see Section 2.4). The max-
imum observed weight loss of the oven dried samples when mea-
sured with TGA was 0.8% with the majority of the population
having a weight loss of close to 0%, indicating that approximately
the entire evaporable water was removed during oven drying.
We used TGA measurements to corroborate our oven-drying
method since TGA is purged with nitrogen during the operation,
and therefore, provides a more severe and more accurately con-
trolled drying condition as compared to oven. The mass loss of
the vials were corrected for; vials showed 4 mg mass loss when
dried in oven at 100 ± 3 °C for 24 h, which is 3 orders of magnitude
smaller than the mass loss of the samples.
2.4. Thermogravimetric analysis
TGA tests were performed with the rate of 1°C/min starting
from room temperature (25 ± 2 °C) up to 1000 °C; the temperature
362 S. Park, M. Pour-Ghaz / Construction and Building Materials 182 (2018) 360–370

Table 2
Composition of the materials and naming convention used in the present work.

NO. Name MKa NaOH Water NaOH/MK w/sb Mol

1 N/M 0.40 – w/s 0.60 0.45 0.18 0.38 0.40 0.60 12.0
2 N/M 0.51 – w/s 0.70 0.39 0.20 0.41 0.51 0.70 12.0
3 N/M 0.62 – w/s 0.80 0.34 0.21 0.44 0.62 0.80 12.0
4 N/M 0.92 – w/s 1.00 0.26 0.24 0.50 0.92 1.00 12.0
5 N/M 0.40 – w/s 0.70 0.42 0.17 0.41 0.40 0.70 10.3
6 N/M 0.40 – w/s 0.75 0.41 0.17 0.43 0.40 0.75 9.6
7 N/M 0.51 – w/s 0.56 0.43 0.22 0.36 0.51 0.56 15.0
8 N/M 0.51 – w/s 0.60 0.42 0.21 0.38 0.51 0.60 14.0

Sample name indicates NaOH/Metakaolin (N/M) ratio and water-to-solid (w/s) ratio.
For example, N/M 0.40 – w/s 0.60 means NaOH/Metakaolin = 0.40 and w/s = 0.60.
a
Metakaolin.
b
Solid in w/s ratio includes metakaolin and sodium hydroxide.

increase rate was determined based on trial measurements. In all

TGA measurements, the initial weight of the samples was 10–15
mg.

2.5. Scanning electron microscopy and energy dispersive X-ray

spectrometry

To perform Scanning electron microscopy (SEM) and Energy

Dispersive X-ray Spectrometry (EDS) tests, 1.50  1.0  1.0 cm
geopolymer specimens were cast and cured using the material
preparation methodology described before. After curing, speci-
mens were dried under vacuum drying for 7 days and then pol-
ished using silicon carbide polishing paper of 800 and 1200 grits
to obtained a smooth surface. Trial SEM measurements were per-
formed to ensure that samples were satisfactorily polished in a
short time to minimize surface alternation due to exposure to
air. Measurements were performed on a 1.50  1.0 cm face of the
specimens.

2.6. Cyclic desorption and absorption isotherm

(a)
Cyclic desorption and absorption isotherm (CDA) tests were
performed on flat disk specimens of 0.7–1.05 mm thickness with
approximate weights of 8–10 mg. All the measurements were per-
formed using a commercially available dynamic vapor sorption
equipment (TA Instruments Q5000). The samples were submerged
in distilled water for 24 h before the start of the test. The test
started from saturated state (desorption) with stepwise reduction
in relative humidity (RH) from 97.5% to 7.5% at 10% decrements
and from 7.5% to 0% at 7.5% decrement. The equilibrium condition
at each RH step was defined as a weight change of less than 0.001%
for 15 min [29–31]. For the adsorption the exact procedure was
performed in reverse order.

2.7. Nitrogen drying

Granulated geopolymer samples were placed in dynamic vapor

sorption equipment at a constant condition of 0% RH (pure nitro-
gen) and 23 °C to measure the total mass loss corresponding to
the total amount of pore water. It is noted that, unlike CDA mea-
surements, the samples were not submerged in water before nitro-
gen drying. The equilibrium condition was defined similar to the
CDA test. (b)

Fig. 2. Evaporable water ratio for geopolymers with (a) different NaOH/Metakaolin
3. Results and discussion ratios and (b) different w/s ratios. Evaporable water ratio is the ratio of evaporable
water measured at 100 ± 3 °C to the initial mixing water.
3.1. Evaporable water
water to the initial mixing water. We refer to this ratio as evap-
Fig. 2a illustrates the results of evaporable water measurements orable water ratio. The error bars indicate the standard deviations
where the results are expressed as the mass ratio of evaporable of the measurements. Evaporable water ratio of less than 1.00
 S. Park, M. Pour-Ghaz / Construction and Building Materials 182 (2018) 360–370 363

suggests that less than the initial mixing water evaporated in oven
drying, and values larger than 1.00 indicates that more than the
initial mixing water evaporated.
The evaporable water ratios vary from 0.95 to 1.04 depending
on the N/M ratio. Geopolymer samples with higher NaOH/Meta-
kaolin ratio resulted in a higher evaporable water ratio. The highest
evaporable water ratio was 1.04 indicating production of 4% addi-
tional water during geopolymerization. Samples with lower N/M
ratio show an evaporable water ratio of less than 1.00, indicating
the presence of chemically bond water within the structure of
geopolymer. The data presented in Fig. 2a, is plotted as a function
of w/s ratio in Fig. 2b. Fig. 2b indicates that the evaporable water
ratio is not a function of w/s ratio since no trend is observed.
3.1.1. The origin of the additional water produced during
geopolymerization
The geopolymerization process is explained in three phases:
dissolution and reorganization, condensation, and polymerization.
The dissolution and reorganization of aluminosilicate create sev-
eral types of oligomers; oligomers connect and form large poly-
mers (or gel). When oligomers connect, the OH groups at their
end meet and release water by sharing an oxygen atom. The pri-
mely source of OH group is NaOH. Therefore, the additional water
produced in Fig. 2 during geopolymerization is a consequence of
the condensation process shown in Fig. 3b [3,8,32,33]. We would
like to mention that Fig. 3 only provides a schematic illustration
of the three steps of geopolymerization and other models and rep-
resentations can be found in [34–37].
The results in Fig. 2a show that as the N/M ratio increases, more
water is produced (evaporable water ratio increases). This is
because, the higher amount of NaOH in the system dissolves more
aluminosilicate [22,38], which in turn results in more condensa-
tion of oligomers, and consequently, production of more water.
3.1.2. The nature of chemically bound water
The results in Fig. 2a show that at low N/M ratios, some of the
initial mixing water remains within the materials after drying at
100 ± 3 °C, suggesting that a portion of the initial mixing water is
chemically bound within the structure. The geopolymerization
process shown in Fig. 3, however, does not account for any chem-
ically bound (non-evaporable) water. Therefore, we ask what is the
nature of the chemically bound water?
Duxson et al. [39] suggested that the non-evaporable water is
tightly held in small pores or hydroxyl groups on the surface of
the geopolymer gel; El-Naggar et al. [40] suggested that the pres-
ence of hydroxyl groups of Si or Al may be the source of non-
evporable water; and Dimas et al. [41] suggested that the non-
evaporable water is in the form of silanol groups. White et al.
[42] suggested that less than 5% of the initial mixing water is

Fig. 3. Schematic illustration of geopolymerization process: (a) reorganization of aluminosilicate, (b) gel formation from oligomers’ condensation, and (c) polymerization
(reconstructed from [32]).

Fig. 4. (a) Scanning electron microscope image of sample N/M 0.40 – w/s 0.60; (b) Energy-dispersive X-ray spectroscopy (EDS) analysis of S5 location.
364 S. Park, M. Pour-Ghaz / Construction and Building Materials 182 (2018) 360–370

physically bound in small pores or chemically bound as hydroxyl
groups attached to the Si-Al structure.
Our close examination of the microstructure of metakaolin
geopolymers with low N/M ratio under Scanning Electron Micro-
scope (SEM) shows the presence of particles mainly consisting of
silicon and oxygen. For example, Fig. 4(a typical measurement
selected from a large set of measurements) shows a SEM image
of N/M 0.40 – w/s 0.60 along with Energy-dispersive X-ray spec-
troscopy (EDS) of section S5 (a bright particle). This bright particle
mainly consists of silicon and oxygen. This indicates that these
bright particles mainly consist of silica. A characteristic of silica
is that its surface is hydroxylated [43–46] which of course requires
OH groups, and therefore, retain some of the initial mixing water.
The origin of the silica particles can be traced back either most

Fig. 5. EDS mapping images (left column) and DTA (right column) results: EDS mapping on (a) N/M 0.40 – w/s 0.60, (c) N/M 0.51 – w/s 0.70, (e) N/M 0.62 – w/s 0.80; DTA
results of (b) N/M 0.40 – w/s 0.60, (d) N/M 0.51 – w/s 0.70, and (f) N/M 0.62 – w/s 0.80. The green EDS mapping is Si, blue indicates Al, and red is Na. (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of this article.)
 S. Park, M. Pour-Ghaz / Construction and Building Materials 182 (2018) 360–370
likely to the quartz impurities in metakaolin (see Fig. 1) or possible
condensation of silica during geopolymerization. The condensation
of silica is a consequence of preferential condensation following
the preferred dissolution of alumina [38,47]. Preferential dissolu-
tion of alumina has been shown by Granizo et al. (2014) [38]
who conducted leaching tests on metakaolin geopolymers (pro-
duced with sodium hydroxide) and showed the presence of silica
at late stages of reaction in significantly larger amounts than that
of alumina. Therefore, in metakaolin geopolymers with low N/M
ratio, condensation of silica occurs and their hydroxylated surface
retains water in the form of chemically bound water.
The above discussion suggests, therefore, that at high N/M
ratios (i) the amount of chemically bound water should decrease
which is consistent with Fig. 2a; (ii) the amount of silica (number
of particles) should decrease since they will be dissolved by the
excess amount of NaOH [22,13]; we also note that at high concen-
trations of NaOH quartz will also dissolve [48,49]; to illustrate
this point we performed EDS mapping of three geopolymers of
increasing N/M ratios. The left column in Fig. 5 illustrates the
results where bright green particles indicate pure silica. Clearly
the amount of silica decreases with the increase of N/M ratio;
and (iii) since there is a smaller amount of silica at higher N/M
ratios, there should be a smaller amount of hydroxylated silica
surface.
Hydroxylated silica contains very small pores [46]. These pores
have been referred to as ‘‘ultramicro pores” because their diameter
is in the order of 1 nm [46]. Pores at the surface of hydroxylated sil-
ica saturate in the presence of water, and due to their very small
size, water is tightly held (physically bound) inside these ultrami-
cro pores. This physically bound water results in a distinct mass
loss in TGA, or equivalently a distinct peak in Differential Thermal
Analysis (DTA), at temperatures between 75 °C to 100 °C [46,45].
Duxson et al. (2007) [39] also observed this distinct peak in DTA
with increase of Si/Al ratio where condensation of silica is more
likely. The right column in Fig. 5 shows the DTA results corre-
sponding to the SEM images in the left column. Clearly with the
increase of N/M ratio, the peak in DTA results vanishes, indicating
the presence of less amount of physically bound water (or less
amount of hydroxylated silica surface). Note the correspondence
between disappearing bright particles in the left column and
vanishing pick in the right column.
3.2. States of water within the geopolymer structure
The foregoing discussion naturally suggests that water is held in
the forms of non-evaporable (chemically bound) and evaporable
Fig. 6. Schematical illustration of different states of water within the geopolymer structure along with experimental methods used for their quantification.
365
water within the structure of metakaolin geopolymer, and their
proportion depends on the availability of NaOH. The non-
evaporable water which evaporates at temperates above 100 °C
is the result of hydroxylated surface of silica and reduces with
increased concentration of NaOH (also reduces with decease of
Si/Al ratio). The evaporable water which evaporates at tempera-
tures below 100 °C consists of: (i) ‘‘pore water” within the larger
pore structure of the geopolymer, and (ii) ‘‘physically bound water”
which is within the ultramicro pores and evaporate at temperature
between 75–100 °C; the amount of physically bound water
decreases with increased concentration of NaOH. The pore water
can be further divided into ‘‘free pore water” and ‘‘high concentra-
tion pore solution” where the latter is produced during drying due
to the increase of concentration of salts (leftover NaOH in our case)
as pore solution evaporates. The high concentration pore solution
in fact does not evaporate under normal drying conditions even
when subjected to nitrogen drying at 0% RH and requires thermal
energy (heating up to 100 ± 3 °C) to evaporate. The proportions of
different forms of water can be identified using different experi-
mental methods.
Fig. 6 schematically illustrates proportions of different forms of
water within the geopolymer structure along with experimental
methods used to quantify them. Desorption isotherms are used
to quantify the free pore water held within different pore sizes;
oven drying of samples that are dried in nitrogen is used to mea-
sure the amount of high concentration pore solution; oven drying
of seal-cured samples are used to measure the total amount of
evaporable water; TGA method is used to quantify the amount of
physically bound water (temperatures between 75–100 °C) and
non-evaporable water (temperatures above 100 °C). We would like
to add that some error may always exist in quantifying and sepa-
rating physically bound water from non-evaporable water due to
the overlap in evaporation of physically bound water and the
decomposition of hydroxylated surface of silica at temperatures
close to 100 °C [46].
The results of our measurements in quantifying the amount of
water in different states in the metakaolin geopolymer structure
are summarized in Fig. 7 and Table 3. Fig. 7 suggests that the
majority of the water remains within the structure of geopolymer
as evaporable water and only a very small portion of the initial
mixing water transforms into non-evaporable water. This of course
has significant implications on the durability of geopolymers
specially against frost attack.
Fig. 7 also suggests that the pore size distribution of geopoly-
mers not only depends on the initial amount of water (w/s ratio)
but also is dependent on the chemical composition of the geopolymer
366 S. Park, M. Pour-Ghaz / Construction and Building Materials 182 (2018) 360–370

Fig. 7. Proportions of water with different states within the structure of metakaolin geopolymer. (a): N/M 0.40 – w/s 0.60, (b): N/M 0.40 – w/s 0.70, (c): N/M 0.51 – w/s 0.60,
(d): N/M 0.51 – w/s 0.70, and (e): N/M 0.62 – w/s 0.80.

Table 3
Proprtions of different status of water within the geopolymer structure.

Components Samples
N/M 0.40 – w/s 0.60 N/M 0.40 – w/s 0.70 N/M 0.51 – w/s 0.60 N/M 0.51 – w/s 0.70 N/M 0.62 – w/s 0.80
Pore water 0.424 0.509 0.491 0.568 0.675
Water with high concentration 0.091 0.110 0.071 0.089 0.101
Ultramicropore water 0.052 0.057 0.024 0.029 0.022
Water for hydroxylation 0.033 0.024 0.014 0.014 0.002

Values are normalized by the mass of the initial solid.

 S. Park, M. Pour-Ghaz / Construction and Building Materials 182 (2018) 360–370 367

(i.e., N/M ratio in this study). For example, comparing Fig. 7a (N/M N/M ratios affect the pore size distribution? and (2) how stable is
0.40 – w/s 0.60) and 7c (N/M 0.51 – w/s 0.60) shows that while the pore size distribution of geopolymers when subjected to cyclic
both materials have the same w/s ratio, their pore size distribution absorption and desorption?
and proportions of water in different states within their
microstructure is substantially different. The same applies to
Fig. 7b and 7d. In fact N/M ratio has a significant impact on the
pore size distribution and formation of large and small pores as
will be discussed in the next section.
Based on the results presented in Fig. 7, we have developed a
conceptual model of the microstructure of geopolymer that is
shown in Fig. 8. In this model the geoplymer gel forms the main
skeleton of the material with inclusions of silica residing within
this skeleton. The hydroxylated surface of silica accounts for the
non-evaporable water and physically bound water is held within
the ultramicro pores. The free pore water sits within the pores of
the main skeleton and when subjected to drying, high concentra-
tion pore solution is created.

3.3. Pore size distribution in geopolymers

In the preceding discussion of the results of Fig. 7, we briefly

highlighted the effect of geopolymer composition on the pore size
distribution. Two questions naturally arise: (1) how do w/s and Fig. 10. Pore size distribution from desorption isotherm test.

Fig. 8. Conceptual model of the structure of metakaolin geopolymer and different states of water within this structure.

Fig. 9. The macro and micro pore water contents. (a): macro pore arranged by w/s ratio and (b): micro pore arranged by NaOH/Metakaolin ratio.
368 S. Park, M. Pour-Ghaz / Construction and Building Materials 182 (2018) 360–370

To explain the effects of w/s and N/M ratios, we arbitrarily con-
sider the Kelvin pore radius equivalent to 97.5% relative humidity
as the limit separating macro and micro pores; in other words, we
identify pores with equivalent Kevin radius larger than 97.5% RH as
macro pores and those with smaller equivalent radius as micro
pores. Using these definitions, the results of the desorption
isotherms shown in Fig. 7 can be represented as those in Fig. 9.
Fig. 9a shows the amount of water in the macro pores (saturation
to 97.5% RH) and Fig. 9b shows the amount of water in micro pores
(below 97.5% RH) for the materials studied in this work. The results
in Fig. 9a suggests that the volume of large pores (macro pores) is
mainly a function of w/s ratio. In other words, addition of large
amount of water to the mixture (high w/s ratio) results in the for-
mation of large pores. The results of Fig. 9b suggests that the
amount of micro pores is mainly a function of N/M ratio and
decreases with the decrease of N/M ratio. In fact as the N/M ratio

Fig. 11. Multi-cyclic desorption and absorption isotherms. (a): N/M 0.40 – w/s 0.60, (b): N/M 0.40 – w/s 0.70, (c): N/M 0.51 – w/s 0.60, (d): N/M 0.51 – w/s 0.70, and (e): N/M
0.62 – w/s 0.80
 S. Park, M. Pour-Ghaz / Construction and Building Materials 182 (2018) 360–370
increases more water is produced from geopolymerization and this
produced water contributes to micro pores formation.
The relative size distribution of micro pores is shown in Fig. 10.
Curves in Fig. 10 are obtained by normalizing the desorption iso-
therms of materials to the total micro pore volume and then differ-
entiated by pore size in log scale. The pore size distribution shown
in Fig. 10 corresponds very closely to the measurements reported
by Takeda et al. [50] who used nitorgen desorption for the mea-
surements; also the distribution of the large pores corresponds to
the reported results by Kriven et al. [51], Papa et al. [52], and Are-
des et al. [53] who used Mercury Intrusion Porosimetry method for
obtaining pore size distribution. In Fig. 10, the relative volume frac-
tion of the pores with radius smaller than 0.002 lm increases with
the decrease of N/M ratio. In cases when the N/M ratio is the same
between two materials, for example, in case of N/M 0.40 - w/s 0.60
and N/M 0.40 -w/s 0.70, they show a similar pore size distribution.
We believe pores smaller than 0.002 lm are related to the interfa-
cial transition zones between the silica particles and geopolymer
skeletonthe due to ultramicropores on the silica surface.
Fig. 11, shows the results of CDA performed on the materials
tested in the present paper where three consecutive cyclic desorp-
tion absorption in evaluated. The DCA curves in Fig. 11 indicate
that while a small hysteresis is observed, overall the structure of
metakaolin based geopolymers is stable under cyclic desorption-
adsorption. Consequently, the conceptual model proposed in this
paper is also applicable to low calcium metakaolin based geopoly-
mers after being subjected to wetting and drying.
4. Summary and concluding remarks
In the present paper, the role of water in the geopolymerization
of low calcium metakaolin based geopolymers was investigated
and different states of water within their structure were identified.
In summary, the role of water depends on the chemical composi-
tion of these materials; specifically, for the materials discussed
herein, the role of water depends on NaOH/Metakaolin (N/M) ratio.
Water mainly provides a medium facilitating the geopolymer-
ization reaction. At high N/M ratios, additional water is produced
during geopolymerization which, along with the initial mixing
water, takes the form of evaporable water and resides within small
(micro) pores. At low N/M ratio, silica particles remain, or precipi-
tate after the reaction and a portion of water remains as non-
evaporable (chemically bound) water within the structure as a
results of the hydroxylated surface of precipitated or preexisting
silica. The hydroxylated silica surface itself contains very small
pores (ultramicro pores) and retains evaporable (physically bound)
water which requires higher amount of energy for evaporation.
The pore size distribution of metakaolin based geopolymers is
stable and depends on both water-to-solid (w/s) ratio and N/M
ratio; w/s ratio mainly contributed to the formation of large
(macro) pores while N/M ratio controls the formation of small
(micro) pores.
Based on the experimental findings, we proposed a conceptual
model for the microstructure of metakaolin based geopolymers.
In this model the geoplymer gel forms the main skeleton of the
material with inclusions of silica residing within it. The hydroxy-
lated surface of silica accounts for the non-evaporable water and
physically bound water is held within the ultramicro pores on
the surface of silica. The free pore water sits within the micro
and macro pores of the main aluminosilicate skeleton. When sub-
jected to drying, high concentration pore solution is created.
As far as the formation of the geopolymer gel is concerned,
water only provides a reaction medium. Therefore, geopolymers
do not hydrate. It is our opinion that the use of the term ‘‘hydrate”
in sodium aluminosilicate hydrate (NASH) which implies hydra-
369
tion is superfluous and the term sodium aluminosilicate (NAS) is
a more accurate representation of geopolymerization product.
The findings of the present study are based on experiments per-
formed on geopolymers produced using low calcium metakaolin
and pure sodium hydroxide. The applicability of these findings to
silicate containing activating solutions and other aluminosilicate
sources requires further examination and will be verified in the
future works.
Conflict of interest
None.
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