Int J Applied Ceramic Tech - 2023 - Bagci

Sustainable activation of pumice with partially variable substitutions of metakaolin and/or fumed
silica
Cengiz. Bagci,a,* Dogan Kafkas,a Devon M. Samuelb and Waltraud M. Krivenb,*

a
Department of Metallurgical and Materials Engineering, Faculty of Engineering, Hitit
University, Corum, 19030, TURKEY

b
Department of Material Science and Engineering, University of Illinois at Urbana-
Champaign, Urbana, IL, 61801, USA
* Correspondence: kriven@illinois.edu, cengizbagci@gmail.com
Abstract
Sustainable alkali activation of pumice from Turkish origin was studied by a partial
replacement of metakaolin and/or fumed silica additives. Following the characterization of
as-received pumice by XRF, XRD and NMR analyses, a series of powder mixtures were
prepared by introducing metakaolin and/or fumed silica (8, 14 and 20 M) into 1M of the
pumice. The mixtures were then dissolved in 11 M NaOH or sodium silicate solutions. The
slurries were poured into polyacetal molds to obtain geopolymer samples for mechanical tests
and cured in a constant 50 °C temperature/humidity oven for 48 h and then left for one week
to undergo additional curing at ambient temperature. The microstructural, mechanical and
thermal properties of the final geopolymer samples were determined by XRD, SEM, Weibull
analysis of 3-point flexural and compressive tests and thermal conductivity measurements.
Results showed that all the Weibull values were best for 14M of metakaolin and/or fumed
silica. The metakaolin-added pumice yielded higher compressive strengths of (53.78 ± 33.30
MPa) than fumed silica (10.87 ± 4.04 MPa) and fumed silica plus metakaolin (41.22 ± 5.16
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MPa). Thermal conductivities (0.19-0.46 Wm–1K–1) were also comparable to the thermal
conductivity of metakaolin-based geopolymers.
Key words: Pumice, alkali activation, geopolymer
1. Introduction
The negative effects of human beings on the environment have been ongoing due to
population growth, urbanization and unconscious use of existing resources.1 Undoubtedly,
increasing carbon footprint and climate change are leading in affecting socio-economic life
directly, and efforts to minimize this have gained accelerate in recent years.2 Therefore, while
developing materials for a sustainable life styles, as it should be in all areas, alternative
sources are being sought taking into consideration that production from cheap sources with
low energy and the current resources may be coming to an end in the foreseeable future.3
Geopolymers (GPs), known as alkali-activated aluminosilicates made at room
temperature, are themselves XRD amorphous, inorganic, polymeric, ceramic-like materials.4-

9
Their production involves the dissolution and rearrangement of any powdered natural or
industrial solid source (e.g. metakaolin, fly ash or ground granulated blast furnace slag
(GGBS))10-12 that is rich in alumina and silica, into a caustic alkaline liquid (e.g. NaOH,
Na2SiO3 KOH, K2SiO3 solutions).13-17 Being produced at room temperature from natural raw
materials makes the GPs an alternative binder to cement in terms of less energy consumption
and less carbon released into the atmosphere.18, 19 Metakaolin derived from kaolin is
generally utilized as a substantial solid source as it contains reactive aluminum silicate in
sufficient quantities and a suitable Si/Al ratio for a GP formulation.20-25 In recent years, for
the sustainability of this eco-friend material, it has been considered that any solid source
containing silica,26 aluminosilicate (e.g. volcanic tuff or rock), which is abundant in the

earth's crust, can be considered for the production of GP by increasing its reactivity for
geopolymerization.27, 28
Pumice is a volcanic rock that contains a high amount of alumina and silica formed
during the rapid cooling of the eruptive material. During volcanic activities, molten magma
under high temperatures and pressure violently erupts from the earth into the upper layers of
the atmosphere. Hot melts in the liquid form suddenly encounter a cold environment in the
upper layers of the atmosphere. As a result of this cooling, the water vapor and fumaroles in
the pyroclastic rock are subsequently removed from the body and form a very spongy rock
that does not have the opportunity to crystallize.29, 30 Since pumice can easily be processed
because of its lightweight, porous, amorphous nature,31, 32 it is directly used as a thermal
insulation material, as an aggregate33 or as powder additives in cement and concrete for the
construction industry. 34, 35 A significant amount of the world’s volcanic tuff reserves are
located in the USA, Italy and Turkey (15.8 %). A major amount of this is located in the
Cappadocian region where many volcanic activities took place. Reuse of pumice is also
considered as a solid source in GP formulation from economic and ecological points of view,
which is a waste-reducing approach.36 However its reactivity or dissolution capacity in an
alkali medium is lower than that of metakaolin, fly ash or ground granulated blast furnace
slag (GGBS).37 Efforts by some researchers have been spent to enhance the alkali activation
of pumice from different districts together with solid reactive additions, such as metakaolin
,38 cement,39 alumina,27 nano and micro silica,40 grinding fineness, 41,42 alkaline and/or heat
calcination.43, 44 Among these, the use of additives would be advantageous over other
methods in terms of both energy saving and easy modification of the chemical ingredients of
the pumice, which differs locally, to the suitable Si/Al ratio. The Si/Al ratio, defined from the
chemistry of the starting source, has a critical influence on geopolymerization and therefore
on the properties of resultant materials.45 The choice of alkaline solution is another key issue

in terms of the aluminosilicate dissolution, especially in the first stage of geopolymerization.
NaOH not only has a higher dissolving capacity, but it is also cheaper and more
environmentally friendly than KOH .46 As for alkali solution molarity, if its concentration is
low, sufficient strength cannot be achieved, and if it is high, the strength decreases again.47-49
Curing temperature and time are other important parameters that affect the resulting GP
structure.50-51 These studies for the sustainable use of locally cost-effective pumice in GP
production are still limited and need further research given the inferences mentioned above.
This study was focused on improving alkali activation of pumice of Turkish origin, by
blending a small amount of solid reactive additions of metakaolin and/or fumed silica with
NaOH solution. In particular, the solid portion of GP was prepared in molar variations of
reactive metakaolin and/or fumed silica with pumice and homogenized by dry mechanical
mixing. These solid mixes were then high-shear mixed with a moderate concentration of
NaOH solution and a series of GPs were fabricated by following the typical
geopolymerization process. The materials produced were characterized in terms of
geopolymerization, microstructure and Weibull statistical analyses of mechanical and thermal
properties. The results of this study should give an insight into low-cost activation of the new
green pumice binder pumice so that it could be more effectively reused in GP fabrication by
using reduced amounts of additive and eco-friendly alkaline activation, as well as optimum
drying conditions.
2. Experimental Procedures
2.1. Materials
Pumice was obtained from the Nevsehir area, which is located in the Central Anatolia
region of Turkey. As-received pumice was first crushed, finely ground to powder and then

passed through a 63 µm sieve. Some of the sieved powders were put onto an aluminum foil
and then calcined at 400 °C for 5 h in an open-air furnace. Metakaolin (Al2O3•2SiO2) to be
used as one of the additives was obtained by 6 h calcination of kaolin obtained from Eti
Maden, Turkey, at 900 °C, as well. The other additive was amorphous fumed silica, having
an average particle size of 0.007 µm (S5130, Sigma-Aldrich, CAS No: 112945-52-5). NaOH
pellets (S06203, Sigma-Aldrich, CAS No: 1310-73-2) were used to prepare sodium silicate
solution as an activation reagent.
2.2. Sample preparation
For sample preparation, an experimental design was made regarding the molar ratio of MK
(metakaolin), FS (fumed silica) and their mixture (FS+MK) with pumice as summarized in
Table 1. Three different molar amounts (8, 14 and 20 M) of each solid additive were
homogenized by mechanical mixing separately with one mole of pumice for 5 min. The Si/Al
ratio and the total amount of the additives were also addressed in Table 1. As for the liquid,
11 M NaOH solution was prepared by dissolving NaOH pellets in deionized (DI water).
Sodium silicate solutions (water glass) were separately made with subsequent additions of
calculated amounts of the fumed silica into the NaOH solution. All the liquid solutions were
left overnight under magnetic stirring and subsequently kept in a refrigerator at 4 ºC to reach
equilibrium for one week. Each of the solid mixes was then separately mixed with 11 M
NaOH or sodium silicate solutions to obtain final pumice based geopolymer samples as
denoted in Table 1. The mixing process was carried out in a mechanical mixer (Heidolph
RZR 2021) at 500 rpm for 3 minutes and at 1000 rpm for 3 minutes. The homogenized slurry
was poured into polyacetal Delrin® molds and prepared for Ø 5x10 mm compression testing
according to the ASTM C1424-1052 standard and 10x10x50 mm three-point bending
specimens according to the ASTM C78/C78M-1853 standard for mechanical testing. The

slurry-filled molds were then subjected to a degassing process to ensure sufficient reduction
of entrapped air bubbles and voids by keeping a hand on the mechanical vibrator. The slurry
was thermally matured by storing the mold wrapped in a plastic film in an oven at 50 ºC for
48 hours. Mold dimensions were 15x25 cm for flexural and 5x10 cm for compression
samples. The samples were kept in ambient conditions for 7 days after removed from the
mold were then subjected to mechanical tests.
2.3. Sample characterization
The composition of the as-received powder was determined by X-ray fluorescence
spectroscopy (XRF) using a Shimadzu EDX-7000 (rhodium source) spectrometer. The
powder was loaded into an ultralene cup and covered with ultralene film, and the sample
chamber was filled with He gas before analysis. The qualitative oxide composition was found
using a qualitative scan covering the elements from sodium through uranium. The major
oxide quantities were then measured more accurately with a quantitative scan that employed
filters (for potassium and subsequent elements) to reduce background noise. The “heated”
sample was not tested because the heat treatment would not affect the composition.
Crystallinity was examined by X-ray diffraction (Bruker D8 Advance) using Cu Kα
radiation (1.5418 Å wavelength). The instrument was equipped with panoramic Soller slits
and 0.2-mm incident slits. Scans ran from 10° to 80° in 2θ at 0.01° step sizes and at 0.1
s/step. The sample holder (a PMMA disc) produced a broad amorphous background with a
maximum at about 12° 2θ, after which it steadily decreased as the angle increased.
Aluminum coordination was determined by 27Al NMR on a Unity Inova 300
spectrometer (7.05 T field, 78.2019 MHz 27Al resonance frequency) with the samples packed

into zirconia rotors and employing magic-angle spinning at 10 kHz. Direct polarization
experiments were performed using an acquisition time of 5.12 ms, a recycle delay of 1 s, and
a pulse width of 0.8 µs, and 4000 total scans were collected. Spectra were referenced to a 1 M
Al(NO3)3 aqueous solution. The spectra were processed with MestReNova software.
Scanning electron microscopy (SEM) of the fracture surface of the geopolymer
samples was performed in a JEOL JSM 6060LV SEM (JEOL USA, Inc., Peabody, MA).
Some of the samples were coated with ~5 nm Au/Pd alloy to improve imaging quality.
Samples were imaged at different magnifications using secondary electron imaging at an
accelerating voltage of 20 kV in high vacuum mode.
For mechanical assessments, the compressive strength was calculated according to equation
(1).
F
𝜎= A Eq. 1
In Equation (1), F is the breaking load (N), and a is the cross-sectional area of the
sample (mm2). Three-point flexure (30 mm distance between supports) and compressive tests
were performed on a Shimadzu mechanical testing machine using a 100 kN load cell at 0.5
mm/min. Flexural and compressive strengths of the samples are according to the load
bending strength equation (2);

3𝐹𝐿
σ= Eq. 2
2𝑤𝑡 2
In equation (1), F= fracture load (N), L= distance between supports (mm), w=sample
width (mm), t= sample thickness (mm).
To confirm the data from compressive and flexural tests, a two-parameter Weibull
distribution function was utilized as represented in equation (3).54

𝜎 𝑚
[−𝑣( ) ]
𝐹(𝜎) = 1 − 𝑒 𝜎0 Eq. 3

where F(σ) is the cumulative probability distribution of the failure compressive or
flexural stresses of the sample, v is the non-dimensional volume, σ is the breaking stress, σo is
the scale parameter, and m is the shape parameter or Weibull modulus. In general, the higher
the Weibull modulus, the lower were the dispersion of failure stresses. The thermal properties
of the samples were measured with Lasercomb Fox 50 heat flow meter. In this device, in
which the thermal conductivity of polymers and ceramics can be measured according to
ASTM C518 standard55, samples with a diameter of 60 mm and a thickness of 3 mm were
prepared for the measurements.
3. Results and Discussion
The characterization of the starting material, in particular the particle size, has
important effects on the mechanical and microstructure properties of the final material.41-42 In
this context, first of all, a detailed characterization of the pumice collected from the field was
carried out to determine its suitability for geopolymerization.
A qualitative XRF scan identified primarily Si, Al, K, Fe, Ca, and Na, so these were
the only elements included in the quantitative scan. Various other transition metals were also
detected at levels insignificant to affect the geopolymerization reaction (0.1 wt. % or lower of
the respective oxides). The quantitative scan results are given below in Table 2. Compared to
metakaolin (Al2O3 • 2SiO2), the pumice was much richer in SiO2 and poorer in Al2O3. This
probably will reduce the reactivity of the material, as AlOn groups are the main reactive
species during geopolymerization. The Na2O and K2O may supplement any NaOH or KOH
solution mixed with the pumice while the CaO and Fe2O3 should not have a meaningful
effect due to their low concentration.

As-received pumice was heat-threated at 750 ºC for 2h X-ray diffractions for both
samples are seen below in Fig. 1. The samples produced a broad hump centered at about 22°
2θ and a very small peak at about 45° 2θ, indicating that they are almost entirely amorphous.
There is a slight increase in intensity relative to the background for the heat-treated sample,
but otherwise, its diffraction pattern was identical to the as-received sample.
The 27Al NMR spectra for both samples are shown below in Fig. 2. The spectra were
nearly identical, presumably because the heat-treatment temperature was quite low (750 °C).
The aluminum was almost entirely in four-fold coordination, although there was a very small
amount of six-coordinated Al based on the low-intensity peak at about 0 ppm occurring in
both spectra. These samples probably would not react very quickly because there was no
evident five-coordinated Al, which is the most reactive aluminum coordination for
geopolymerization. However, the lack of six-coordinated Al also implies that some reactions
may have occured, although slowly.56 Based on the composition (very high silica content) and
low amount of five-coordinated Al, this pumice would not be a good substitute for
metakaolin.57
XRD patterns of the reacted samples are given in Fig. 3. The XRD patterns indicated
that the addition of metakaolin enhanced the geopolymeric reaction in pumice. A broad hump
centered at about 22° 2θ in XRD of the pumice shifted to a 2 hump at 28º indicating the
well-known amorphous geopolymer formation. Furthermore, it was found that the two GP
samples (FS_14m and FS+MK_14M) showed similar trends in subsequent XRD patterns. It
was determined that the partially crystallized peaks on the amorphous hump of pumice
belong to anorthite (Ca(Al2Si2O8)58, quartz (SiO2) and illite (SiO2) in the case of MK and
FS+MK and only quartz in the case of FS.59

Photographs of some samples and micrographs of the pumice sample without additives are
seen in Fig. 4. From the macro images Fig. 4(a), it was seen that the structural integrity,
rigidity and smoothness of the surface in the silica fume-added samples were better than the
metakaolin-added samples. This determination is further confirmed by the flexural standard
deviations of these samples being approximately 3 or 4 times less in Table 4.In the fracture
surface SEM images of the pumice sample without additives, it was seen that a homogenized
reaction did not occur due to the presence of unreacted regions Fig. 4(b).60
Fig. 5 shows the probability plots of compressive strengths of the resultant 14M
samples. When the compressive strength of the resulting samples was evaluated
independently of the molar ratio, the compressive strength exhibited a wide distribution and
the standard deviation increased in the sample containing metakaolin (Fig. 5(a)) compared to
the samples containing silica fume (Fig. 5(b)) and metakaolin + fumed silica (Fig. 5(c)). This
was due to the poor structural integrity of the metakaolin samples in the photograph in Fig.
4(a). The metakaolin samples were prepared according to the Si/Al ratio in Table 1 and
therefore the amount of additives in the pumice were the closest to the typical geopolymer
formulation in the literature.14, 15 When the metakaolin samples are evaluated on a molar basis
(Table 2), it could be seen that the decreased Si/Al ratio resulted in a wider confidence
interval and consequently a decrease in the Weibull modulus. In a previous study,38 the
amount of metakaolin between 20-30 % by weight was used. Agglomeration of metakaolin as
the amount of metakaolin increased, which would give rise to inhomogeneous reaction
regions, could also be given as the reason for this wide distribution. Despite this constraint,
from the above XRD patterns in Fig. 3, high geopolymerization occurred in the samples

containing metakaolin. This was reflected in the compressive strength and which was
measured and found to be higher than in the case of FS or MK+FS.
Fig. 5(b) are probability plots of the compressive strength of the sample containing
fumed silica. In this sample, the Si/Al ratio was over the typical geopolymer content
(Na2O•Al2O3 •4SiO2 •11H2O) and was mostly used for high-temperature composites.45 Even
so, in this study, fumed silica was used because it was a typical component of geopolymer
materials and had a nano-size that could increase the reaction of pumice. At the same time,
this composition contains a relatively high molarity of NaOH, which favored the dissolution
of Si4+ and Al3+ ions the pumice, which is itself low reactive increased and the formation of
sodium aluminosilicate was enhanced leading to an increase in flexural and compressive
strength.61, 62 As can be seen from Table 1, the total amount of additives in this sample was
quite low as compared to other samples (Fig. 5(a) and Fig. 5(c)) due to the already high silica
content of pumice. In addition, due to the high Si/Al ratio, perfect structural integrity and near
net-shaped samples were obtained. Less weight loss was observed in these samples at the end
of seven days due to the high surface area of the silica fume and its subsequent water
retention. When the probability plot was correlated in Fig. 5(b) with Table 3, the compressive
strength showed a narrower distribution than the metakaolin sample due to the much
smoother surface from its macrograph in Fig. 4. Although there was no significant change in
the Weibull modulus, it is seen that the compressive strength was quite low. Ma et al.63
reported that high silica content reduces the overall porosity of the samples, which may
support a more uniform sample yield in samples with high silica compared to other samples.
However, the filling effect of silica in the structure was not reflected in the compressive
strength of the sample, because the sample could require an aging period of more than seven
days due to slow curing. These compressive strength results were also in agreement with the

very weak geopolymerization in the samples containing fumed silica as seen from its XRD
patterns in Fig. 3.
Fig. 5(c) presents the probability plots of the compressive strengths of the samples
containing fumed silica + metakaolin. Since the Si/Al ratio is in the middle of the other two
samples, the Weibull modulus and compressive strength of these samples were also seen to
lie between the two samples. In the XRD analyses in Fig. 3, the FS+MK_14M sample
exhibited a geopolymeric hump between the other two samples with the same molar ratios. In
this sample, the positive effect of metakaolin on compressive strength is seen. It has a
narrower confidence interval than the other two samples. It is seen from Fig. 5(a-c) that the
FS+MK 14M sample exhibited the narrowest strength distribution, the highest Weibull
modulus and compressive strength compared to the other samples due to both its metakaolin
content and its good structural integrity.
Weibull analysis results for the 8M, 14M, and 20M compositions of the MK, FS, and
FS+MK samples are given in Table 3. By the assessment of the Weibull parameters such as
modulus, mean together and the Weibull plots as chosen 14 M above, it could be concluded
that all the Weibull values were suitable for 14M samples in all three compositions. When the
compressive strength results were evaluated, since the best value was obtained from the
samples containing metakaolin and especially with 14M of MK, FS, MK+FS, these samples
were representative of the determined parameter space, and further mechanical and
microstructural analyzes of these samples were performed. From Table 2, Si/Al ratios of MK,
FS and MK+FS samples were 2.52, 3.71 and 5.75, respectively. The increase in the Si/Al
ratio resulted in increased elastic behavior in the samples.64 In Fig. 6, the load versus strain
curves of the 14M samples taken from Table 3 are given. It is seen that the resulting samples

exhibited different character load-strain curves depending on the type of addition. This meant
that the starting mixture could be designed according to the desired mechanical property of
the final material.
SEM micrographs of the fractured surface and polished surface of samples are shown
in Fig.7. Only the metakaolin-added sample Fig. 7(a) was mostly observed in well
homogenized and reacted regions as well as in partially reacted regions. The finer size (0.007
μm) of silica fume than pumice and metakaolin added exhibited a more uniform fracture
surface due to its high surface area in Fig. 7(b). Fig.7(c). The microstructures showed
macropores and cracks in the FS+MK_14M sample, along with homogeneous parts being
well-reacted due to the effect of metakaolin additions.16 Although the Si/Al ratio was
moderate in this sample, the small size of the silica fume promoted a finer and more uniform
structure, since the added amounts were approximately two times higher than in the others. It
was possible to encounter drying cracks, which are inevitable in single-phase geopolymer and
adversely affected their mechanical properties.17,18,19
As for polished surfaces (Figs 7 (d-f)), in addition to the drying cracked nature of
geopolymers, polished surfaces having voids resulted from unreacted solid alumina silicates
of varying size and shapes.20-25,57 The voids formed by the separation of the hardened solid
particles of pumice and metakaolin from the matrix structure during polishing and the tears
formed by these solid particles in the matrix structure are also seen in the examples. Until
now, no method has been developed that can accurately determine the amount of unreacted
starting material.15 However, the white deposits especially on the surface in Fig. 7(e) can be
attributed to carbonate-type compounds formed by the reaction of Na cations with
atmospheric CO2.65 In agreement with the macro images of the samples, the metakaolin

sample having a relatively little structural integrity is shown in Fig. 7(d) and the smooth
surfaces of the silica-containing samples are seen in (Figs 7(e) and (f).
The flexural strength Weibull distribution parameters of the 14M samples using
metakaolin and/or fumed silica are given in Table 4. Similar to the compression samples, the
3-pt bend strength of the samples containing metakaolin was 2-4 times higher than of the
other samples. The Weibull modulus was high in the FS+MK_14M sample because high
structural integrity resulted in high modulus due to both the contribution of metakaolin to
geopolymerization as well as the surface smoothness of silicon. In the case of MK_14M,
strength was the highest due to the reason explained above. It is seen that the mean flexural
strengths follow the same trend as the mean compressive strengths. Furthermore, the
metakaolin-containing samples exhibited higher flexural strengths similar to metakaolin-
based geopolymers. As the Si/Al ratio in the mixture increases, the flexural strength of the
geopolymer will increase thanks to the good bonding between the geopolymer mortar and the
aggregate, and the strong Si–O–Si interaction. However, although the Si/Al ratio is relatively
high in FS_14M and FS+MK_14M samples compared to MK_14M sample, the molecular
equilibrium of geopolymerization in FS+MK_14M is partially achieved and in FS_14M is
low due to the low Al2O3 amount. In addition, no aggregate from the starting material or
directly added was used in this study. These two situations caused a decrease in the
compressive strength of the samples.6, 15, 66
Table 5 presents the thermal resistance, thermal conductivity and bulk densities of
metakaolin-containing samples. The measured sample densities were compatible with each
other when the initial additives are taken into consideration and were generally comparable to
the densities of the metakaolin-based samples. Due to polycondensation during the

geopolymerization process, the porosity rate (70-80 %) in the amorphous pumice matrix
decreased significantly, increasing the density of pumice density (1 g/cm3)67 in the final
material.
Due to the higher density of alumina compared to silica, the density of the MK sample
also increased with the decrease in the Si/Al ratio. With this increase in density, an increase
in thermal conductivity values and a decrease in thermal resistance values were observed.
Furthermore, in the FS+MK sample, it was seen that the low thermal conductivity of fumed
silica reduced the conductivity value of this sample.68 A density of 1.798 g/cm3 was realized
in the sample with a Si/Al ratio of 2.15. Thermal conductivities were also measured to be ~2
times lower than the thermal conductivity of metakaolin-based geopolymers (0.53-0.8 Wm–
1
K–1).69
4. Conclusions
The alkali activation of pumice of Turkish origin could be achieved by using only a
partial addition of reactive metakaolin and/or fumed silica in a geopolymer formulation. After
it was determined that the pumice was XRD amorphous, NMR analyses showed that although
it did not contain five coordinated Al, but contained instead a very small amount of six
coordinated Al, pumice could be alkali activated. After seven days of aging, XRD patterns
indicated that the metakaolin addition produced more geopolymerization than did fumed
silica in the pumice. From the Weibull plots, it could be concluded that all the Weibull values
were the best for 14M of metakaolin and/or fumed silica in all three compositions. In the case
of the 14M samples, consistent with the XRD results, the metakaolin-added pumice revealed
a higher compressive strength of (53.78 ± 33.30 MPa) than the pumice composition
containing fumed silica (10.87 ± 4.04 MPa) and fumed silica plus metakaolin (41.22 ± 5.16

MPa) although their structural integrity for the MK_14M samples was low. The flexural
strengths were correlated with the compressive strengths. The use of varying amounts of
reactive metakaolin and fumed silica additives in pumice resulted in mechanical properties
with different characteristics, and it was concluded that the starting composition could be
designed depending on the mechanical properties expected from the resulting material.
Acknowledgement
The work was funded by Hitit University Scientific Research Projects Unit in Turkey under
the program of MUH19004.21.010 supporting Dogan Kafkas’s master thesis. We gratefully
acknowledge the use of facilities at the center for Microanalysis of Materials, in Frederick
Seitz Research Laboratory at University of Illinois at Urbana-Champaign and the financial
support of the US Army Corps of Engineers under Contract number Army W9132T-21-C-
0005 AH571 through the Engineer Research Development Center (ERDC) and the
Construction Engineering Research Laboratory (CERL) in Champaign, IL, USA.
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List of Tables
Table 1. Experimental design of additives to the pumice
Pumice Si/Al Total amount of NaOH solution Na silicate

Sample additives to the (wt %) solution
(1 Mole) ratio (wt %)
pumice (wt%)
MK_8M* 3.06 21.91 43 -
Metakaolin MK_14M 2.52 32.93 43 -
MK_20M 2.21 41.23 43 -
FS_8M** 5.39 7.07 - 63
Fumed silica FS_14M 5.75 11.76 - 67
FS_20M 6.11 16.00 - 70
FS+MK_8M*** 3.98 35.95 - 63
Fumed silica
FS+MK_14M 3.71 49.55 - 70
+ Metakaolin
FS+MK_20M 3.56 58.38 - 75
* ** **
MK_8M: 8 moles of metakaolin FS_8M: 8 moles of fumed silica, FS+MK_8M: 8 moles of metakaolin
and 8 moles of fumed silica. In the case of MK, fixed 11M NaOH, and in the case of FS and FS+MK, the Na
silicate solution formed by dissolving in additional FS in 11M NaOH was used.
Table 2. Pumice and additives composition from quantitative XRF scan in terms of
constituent oxide compounds.
Oxide Mole %
SiO2 Al2O3 Na2O K2O CaO Fe2O3
Pumice 81.6 8.7 5.0 2.9 1.2 0.6
Metakaolin 73.0 24.5 0.2 0.1 1.6 0.6
Fumed silica 99.99 trace metals basis

Table 3. Compressive properties of the geopolymer from all designed composition
(σo ) (σ) (S.D.) 95%

(m)
Pumice Scale Weibull Standard Confidence
Samples Weibull
(1 Mole) parameter mean deviation interval
Modulus (MPa) (MPa) (MPa) (MPa)
MK_8M 2.73 75.75 67.39 26.62 67±20.8
Metakaolin
MK_14M 1.61 60.10 53.78 33.30 53±26.4
MK_20M 1.28 67.97 62.92 49.31 62±39.2
FS_8M 4.28 11.81 10.75 2.83 10±1.6
Silica fume FS_14M 2.92 12.18 10.87 4.04 10±3.2
FS_20M 3.90 8.08 7.31 2.09 7±1.6
FS+MK_8M 5.42 32.85 30.30 6.44 30±4.8
Metakaolin
+ Silica fume FS+MK_14M 9.58 43.40 41.22 5.16 41±4
FS+MK_20M 4.55 18.7 17.08 4.26 18±3.2
Table 4. Flexural properties of the geopolymer from the 14 M compositions.
(σo ) (σ) (S.D.) 95%

(m)
Pumice Scale Weibull Standard Confidence
Samples Weibull
(1 Mole) parameter mean deviation interval
Modulus (MPa) (MPa) (MPa) (MPa)
MK_14M 6.7 4.98 4.65 0.813 4±0
Flexural FS_14M 4.2 1.24 1.13 0.30 1±0
FS+MK_14M 19.64 2.35 2.28 0.144 2±0
Table 5.
Thermal conductivity and density test results
Thermal resistance, Thermal conductivity ( λ),

Sample Density, g/cm³
m²K/W W/mK
MK_14M 0.013±0.007 0.469±0.328 1.444±0.375
FS+MK_14M 0.024±0.010 0.198±0.097 1.414±0.178

Fig. 1. XRD patterns of as-received and heat-treated pumice.

List of Figures
Fig. 2. 27Al NMR spectra for the as-received and heated pumice samples. Spinning sidebands
appear at 175 and -75 ppm.
Fig. 3. XRD patterns of MK_14 M, FS_14 M, FS+MK_14 M samples and of as-received
pumice. Anorthite (Ca(Al2Si2O8), PDF#89-1459); illite (SiO2, PDF # 00-026-0911); quartz
(SiO2, PDF # 01-078-2315).

Fig. 4. (a) Photograph of some GP samples and (b) SEM image of fracture surface of the

pumice sample without additives.
Fig. 5. Probability plots of compressive strength of some geopolymers from pumice; (a)

MK_14 M, (b) FS_14 M, (c) FS+MK_14 M.
Fig. 6. Load-strain curves from compression test results of 14M specimens.

FS+MK_14M and polished surface of (d) MK_14M (e) FS+MK_14M (f) FS+MK_14M.
Fig. 7. SEM micrographs of samples; fractured surface of (a) MK_14M (b) FS_14M (c)

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Sustainable activation of pumice with partially variable substitutions of metakaolin and/or fumed

Cengiz. Bagci,a,* Dogan Kafkas,a Devon M. Samuelb and Waltraud M. Krivenb,*

University, Corum, 19030, TURKEY

Champaign, Urbana, IL, 61801, USA

* Correspondence: kriven@illinois.edu, cengizbagci@gmail.com

replacement of metakaolin and/or fumed silica additives. Following the characterization of

to undergo additional curing at ambient temperature. The microstructural, mechanical and

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conductivity of metakaolin-based geopolymers.

Key words: Pumice, alkali activation, geopolymer

population growth, urbanization and unconscious use of existing resources.1 Undoubtedly,

Geopolymers (GPs), known as alkali-activated aluminosilicates made at room

temperature, are themselves XRD amorphous, inorganic, polymeric, ceramic-like materials.4-

generally utilized as a substantial solid source as it contains reactive aluminum silicate in

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because of its lightweight, porous, amorphous nature,31, 32 it is directly used as a thermal

which is a waste-reducing approach.36 However its reactivity or dissolution capacity in an

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geopolymerization process. The materials produced were characterized in terms of

geopolymerization, microstructure and Weibull statistical analyses of mechanical and thermal

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and then calcined at 400 °C for 5 h in an open-air furnace. Metakaolin (Al2O3•2SiO2) to be

solution as an activation reagent.

2.2. Sample preparation

according to the ASTM C1424-1052 standard and 10x10x50 mm three-point bending

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mold were then subjected to mechanical tests.

2.3. Sample characterization

The composition of the as-received powder was determined by X-ray fluorescence

spectroscopy (XRF) using a Shimadzu EDX-7000 (rhodium source) spectrometer. The

Crystallinity was examined by X-ray diffraction (Bruker D8 Advance) using Cu Kα

Aluminum coordination was determined by 27Al NMR on a Unity Inova 300

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Scanning electron microscopy (SEM) of the fracture surface of the geopolymer

Samples were imaged at different magnifications using secondary electron imaging at an

accelerating voltage of 20 kV in high vacuum mode.

bending strength equation (2);

width (mm), t= sample thickness (mm).

distribution function was utilized as represented in equation (3).54

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ASTM C518 standard55, samples with a diameter of 60 mm and a thickness of 3 mm were

prepared for the measurements.

3. Results and Discussion

carried out to determine its suitability for geopolymerization.

effect due to their low concentration.

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amount of six-coordinated Al based on the low-intensity peak at about 0 ppm occurring in

FS+MK and only quartz in the case of FS.59

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metakaolin-added samples. This determination is further confirmed by the flexural standard

amount of metakaolin between 20-30 % by weight was used. Agglomeration of metakaolin as

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measured and found to be higher than in the case of FS or MK+FS.

sodium aluminosilicate was enhanced leading to an increase in flexural and compressive

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content and its good structural integrity.

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the final material.

adversely affected their mechanical properties.17,18,19