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Monitoring and Characterization of Creation of

Geopolymers Prepared From Fly Ash and Metakaolin


by X-Ray Photoelectron Spectroscopy Method
M. Kanuchova,a L. Kozakova,a M. Drabova,a M. Sisol,a A. Estokova,b J. Kanuch,c and J. Skvarlaa
a
The Technical University of Kosice, Faculty of Mining, Ecology, Process Control and Geotechnology, Institute of Montaneous
Sciences and Environmental Protection, Park Komenskeho 19, 043 84 Kosice, Slovakia; maria.kanuchova@tuke.sk
(for correspondence)
b
The Technical University of Kosice, Faculty of Civil Engineering, Vysokoskolska 4, 042 00 Kosice, Slovakia
c
The Technical University of Kosice, Faculty of Electrical Engineering and Informatics, Letna 9, 042 00 Kosice, Slovakia
Published online 00 Month 2014 in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/ep.12068

The formation of geopolymers from fly ash (FA) and forming geopolymers, i.e. geopolymerization, aluminosilicate
metakaolin (MK) was investigated. The effect of different materials are dissolved into alkali solution to form free SiO4
reactivity of FA and MK was studied by X-ray photoelectron and AlO4 tetrahedral units.
spectroscopy method. Geopolymer materials were obtained by Several studies have investigated the use of different clays
an alkaline activation of aluminosilicate sources. The aim of for the formulation of geopolymer materials and it has been
this work is to develop methods for working properties predic- shown that metakaolin (MK) is the ideal one because of its
tion of geopolymer materials based on the starting materials. high reactivity and purity compared to other materials [1]. MK
Selection of a geopolymerization scheme is found to be a key is used to replace a part of cement or as a source of new
factor to realize a beneficial effect of improved reactivity. cementless materials. MK reacts chemically with hydrating
Finally, a descriptive model of the mechanism of geopolymer cement to form modified paste microstructure. In addition to
formation, taking into account the quality of starting materi- its positive environmental impact, it improves the concrete
als was proposed. VC 2014 American Institute of Chemical Engineers
workability, mechanical properties, and durability [2].
Environ Prog, 00: 000000, 2014
Alkali activation of MK is a way of making new cementi-
Keywords: XPS measurements, fly ash, geopolymers, tious materials (hydroceramicceramic-like materials synthe-
ecology sized from a solid aluminosilicate and an alkali-rich solution
at low temperatures, <100 C). MK is essentially an anhy-
INTRODUCTION drous aluminosilicate that is produced by thermal decompo-
In the last years, several experimental researches have sition of kaolin, a naturally occurring clay basically
been focused on an efficient low cost valorization of fly containing kaolinite [Al2Si2O5(OH)4] and trace amounts of
ashes in large quantities, released by burning coal in power silica and other minerals. The hydroxyl ions are strongly
stations and/or from storage with negative implications on bonded to the aluminosilicate framework structure so that
the environment. only temperatures in excess of 550 C are capable of eliminat-
There are two main constituents of geopolymers, namely ing them. During the dehydroxylation process, a consider-
the source materials and the alkaline liquids. The source able atomic readjustment occurs. The final result is a partially
materials for geopolymers based on aluminasilicate should ordered structure that cannot rehydrate in the presence of
be rich in silicon (Si) and aluminum (Al). These could be water (or does so very slowly). Due to its disorder and X-ray
natural minerals such as kaolinite, clays, etc. Alternatively, amorphous nature, MK possesses a huge reactive potential
by-product materials such as fly ash (FA), silica fume, slag, when in the presence of an alkali/alkaline earth containing
rice-husk ash, red mud, etc. could be used as an additive or solution [3].
an admixture material. The choice of the source materials for Davidovits [4] described the alkali activation of MK using
making geopolymers depends on factors such as availability, a polymerization model similar to that proposed to describe
cost, type of application, and specific demand of the end the formation of zeolites or zeolite precursors from alkali alu-
users. minosilicate solutions. More recently, Palomo et al. [3] have
The alkaline liquids are soluble alkali metals that are usu- focused on the identification of the fundamental factors that
ally sodium or potassium based. The most common alkaline control the synthesis of MK-based hydroceramics (alkali acti-
liquid used in geopolymerization is a combination of sodium vation at temperatures between 35 and 85 C), their charac-
hydroxide (NaOH) or potassium hydroxide (KOH) and terization, and the evaluation of their usefulness in a
sodium silicate or potassium silicate. During the process of commercial setting.
Geopolymers are members of family of inorganic poly-
mers. The chemical composition of the geopolymer material
C 2014 American Institute of Chemical Engineers
V is similar to natural zeolitic materials, but the microstructure

Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep Month 2014 1
is amorphous. The polymerization process involves a quite
fast chemical reaction under alkaline conditions in SiAl min-
erals that results in a three-dimensional polymeric chain and
ring structure consisting of SiAOAAlAO bonds [5].
Although the exact process of geopolymerization is not
sufficiently understood, often it can be identified with the
proposed mechanism contained in four phases, namely [6]:
1. Dissolution: release of Si and Al aluminosilicate from
solid materials in a strongly alkaline aqueous solution
(e.g., NaOH), 4. Polymerization:
2. Nucleation: formation of Si or Si/Al oligomers in the a. Condensation of ortho-sialate molecules via reactive
aqueous phase, groups of SiAONa and aluminum hydroxyl OHAAl,
3. Gelation: condensation of oligomers and creation of a with production of NaOH and creating cyclo-tri-sialate
three-dimensional aluminosilicate structure, structure, releasing NaOH, which again reacts and thus
4. Polymerization: particles joining to form the geopolymer supports the new polycondensation and formation of
structure and to set the overall strengthening of the solid the poly-sialate chain:
in the final polymer structure.
Chemical mechanisms of a geopolymer can then be
described by the following chemical reactions [6]:
1. Dissolution:
a. Alkalination and creation of tetravalent aluminum in
the next sialate-group:

Si-O-Al (OH)32Na 1
b. Alkaline dissolution by connecting OH2 anion to the
silicon atom, which then changes its coordination of b. Making ortho-sialato-disiloxo cyclic structure in the
valence to the pentavalent: presence of water glass (soluble Na-polysiloxonate),
releasing NaOH which reacts again:

2. Nucleation:Bond cleavage of SiAOASi group to form an


intermediate silanol SiAOH on one hand, and the pro-
duction of basic siloxo SiAOA group on the other hand:
c. Polycondensation into Na-poly(sialate-disiloxo) frame-
work

3. Gelation:
a. Further formation of silanol SiAOH groups and isola-
tion of ortho-sialate molecules as the basic unit in the
formation of geopolymer:

During the chemical reaction occurring in the formation


of geopolymers (reaction 4a), the released of water can be
b. Reaction of the base unit with a cation Na1 and the seen. This water, expelled from the geopolymer matrix dur-
formation of SiAOANa terminal group ing the curing and further drying periods, leaves behind

2 Month 2014 Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep
Table 1. Chemical composition of metakaolin (MK) and fly ash (FA).

Wt % SiO2 Al2O3 Fe2O3 TiO2 MnO CaO MgO K2O Na2O P2O 5 SO3 LOI*
Metakaolin 60.91 38.77 0.68 0.57 0.27 0.56 1.00 0.01 0.10 2.29
Fly ash 44.27 24.01 9.67 2.91 0.13 2.36 0.97 1.18 0.90 0.46 0.40 19.81

*LOI 5 Loss on ignition.

Figure 2. Vibrating table. [Color figure can be viewed in the


online issue, which is available at wileyonlinelibrary.com.]
Figure 1. Prismatic molds of geopolymers from FA (dark)
and MK (light). [Color figure can be viewed in the online an excellent source of aluminosilicate that is very reactive in
issue, which is available at wileyonlinelibrary.com.] the presence of alkali solution. In contrast to MK, FA is an
industrial waste that is very inhomogeneous. Therefore, MK
geopolymers are often used as model systems by which FA-
nanopores in the matrix, which provide benefits to the per- based geopolymers may be better understood. We chose these
formance of geopolymers. The water in a geopolymer mix- materials for better understanding of the processes of geopol-
ture, therefore, plays no role in the chemical reaction; it ymerization. MK was purchased from CLUZ  (Czech Republic)
merely provides the water in a Portland cement concrete under the brand name of Mefisto K05. It was made by calcina-
mixture during the hydration process. tion of kaolin at 750 C in rotary kiln. The calcination period
X-ray photoelectron spectroscopy (XPS) is a highly sensi- cannot be disclosed because it is the intellectual property of
tive technique well suited for examining the composition 
the CLUZ (Czech Republic) company. FA was derived from
and chemical states of a surface. When a material is bom- black coal combusted in melting boilers of a District Heating
barded with X-rays, photoelectrons may be emitted from the Plant in Kosice (Slovakia) at the temperature 14001550 C.
top-most surfaces (typically 110 nm). All elements yield Chemical composition of MK and FA determined by X-ray flu-
photoelectrons of a specific binding energy, enabling ele- orescence (XRF) spectrometer is shown in Table 1. Due to the
mental analysis. Furthermore, small changes in the chemical relatively low calcium content, this FA should be classified as
bonding environments result in small shifts in the photoelec- Class F according to the ASTM C618 definitions. The BET sur-
tron energy, thus allowing chemical information to be face area of MK and FA, as determined by nitrogen adsorption
obtained. Among the chemical properties which may be in Gemini 2360 (Micrometrics, USA) instrument, is 10.65 3
evaluated from the binding energies are the oxidation state, 1023 m2/kg and 3.84 3 1023 m2/kg, respectively. The mean
the nearest neighbor atoms, and a type of bonding [7]. particle size (d50) is equal to 3.87 mm and 19.29 mm, respec-
This article shows that XPS study is capable of providing tively, measured by a Diffraction Spectrometer Helos 12 LA
key information regarding initial setting and later transforma- (Sympatec GmbH, Germany).
tions taking place in geopolymer system. Recent works Sodium hydroxide in a spherical form (Kittfort Praha Co.,
[812] describe process of geopolymerization by FTIR and 9799.5% purity) and sodium water glass (LARO, v.o.s.,
NMR spectroscopy. However, they allow differentiation of molar ratio SiO2-to-Na2O 5 3.37, 3638% of Na2SiO3,
various types of bonds in a material only on a molecular q 5 1336 kg/m3) were used for the synthesis of the geopoly-
level. In the present article, the XPS spectra of the inorganic meric materials in this study.
polymers confirmed previous works and showed the excel-
lence of this method.
In this study, the geopolymerization phenomenon was Geopolymer Preparation
investigated using XPS method to compare geopolymers pre-
Alkaline silicate solution with silicate modulus (SiO2/Na2O)
pared from two different starting materials, namely MK and
of 1.39 was prepared by dissolving the solid sodium hydrox-
FA. The reported experimental work indicated that XPS anal-
ide in sodium water glass until clear. MK or FA was mixed
ysis may be used to obtain detailed information on the
with the alkaline silicate solution in a mechanical mixer for 7
hydrolysis and condensation reactions occurring during syn-
and 10 min respectivelythis time was enough for homoge-
thesis of the inorganic polymers.
neous paste formatting. In order to obtain a good workability
for the next working and manipulation, the liquid/solid bulk
EXPERIMENTAL ratios were 0.23 (MK product) and 0.26. Small samples were
prepared from fresh geopolymer pastes for XPS tests.
Materials and Chemicals The mixtures were molded into prismatic molds with
Two different materials were used in this study. MK is a dimensions 40 mm 3 40 mm 3 160 mm (Figure 1), vibrated
known standard material for formation of geopolymers. It is for 5 min (Figure 2) to remove entrapped air bubbles and

Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep Month 2014 3
Table 2. Values of compressive and flexural strength of MK and FA based geopolymers.

Flexural strength
Compressive strength (MPa) (MPa)
Alkali activated material 1 day 7 days 28 days 1 day 7 days 28 days
Metakaolin* 54.3 69.1 70.2 7.3 8.4 5.5
Fly ash** 43.0 44.6 50.2 7.3 7.2 6.6

*Cured at temperature of 22 C for 20 h.


**Cured at temperature of 22 C for 20 h and next 6 h at temperature 80 C.

cured in a hot-air drying chamber at temperature of 22 C


for 20 h, under atmospheric pressure and uncontrolled
humidity conditions. The FA paste, unlike the MK paste, did
not get hard under the aforementioned curing conditions.
Therefore, it was cured at 80 C for next 6 h, duration of
cured was given by the experimental practice. Hardened
samples were removed from the forms, marked and stored
at ambient temperature until the flexural and compressive
strength test were applied. The flexural and compressive
strength of the hardened samples was measured after 1, 7,
and 28 days using the hydraulic machine Form1Test MEGA Figure 3. Measurement of the flexural and compressive
100200-10D (Table 2, Figure 3). The experimental process strength. [Color figure can be viewed in the online issue,
of preparation is listed in Figure 4. which is available at wileyonlinelibrary.com.]

Sample Characterization by XPS


The surfaces of geopolymers from the FA and MK were RESULTS
analyzed by XPS. XPS measurements were performed using The surface analysis carried out to characterize the C, O,
XPS instrument (SPECS) equipped with PHOIBOS 100 SCD Si, and Al is shown in Figures 5 and 6 for MK and FA,
and non-monochromatic X-ray source. The survey surface respectively. The binding energies for each material reflect
spectrum was measured at 40 eV transition energy and core exactly the chemical nature of the subunits of which it is
spectra at 50 eV at room temperature. All spectra were composed and the position of peaks of Si, Al, C, and O
acquired at a basic pressure of 2 3 1028 mbar with MgKa atoms is very important. The analyzed material contains O
excitation at 10 kV (150 W). The data were analyzed by 1s, C 1s, and two states of atoms SiSi 2s and Si 2p. Alumi-
SpecsLab2 CasaXPS software (Casa Software). A Shirley and num is detected as Al 2s and Al 2p.
Tougaard type baseline was used for all peak-fits. The sam- From Figures 5 and 6, we can see that the MK has higher
ples of geopolymers were first kept in a vacuum chamber proportions of Si and Al than the FA. In addition, the peak
for about one day to remove water and then put into the lines of O 1s, C 1s, Si, and Al atoms in MK are sharper than
detector chamber under high vacuum to start the XPS mea- those of the FA, indicating a greater purity of MK. Peak posi-
surement. The spectrometer was calibrated against silver (Ag tion of Si 2p in MK at 103 eV indicates the presence of SiO2
3d). All samples showed variable degrees of charging due to with good agreement with Barr and Seal [13] where the posi-
their insulating nature. The problem was resolved by the cal- tion of Si 2p is at 102.4 eV. Presence of Al2O3 is indicated by
ibration on carbon. The XPS of Si 2p, O 1s and Al spectra of the peak at 75 eV (74.3 eV for MK in Ref. 13).
the inorganic polymers were recorded in order to obtain The geopolymer prepared from the MK and FA was inves-
information on the elemental and chemical composition. tigated daily for 28 days. As mentioned earlier, the mecha-
nism of the geopolymerization takes place in four steps:
dissolution, nucleation, gelation, and polymerization. When
Sample Characterization by Thermogravimetric dissolving the hydroxide ions, they react with the surface of
Analysis (TGA)/Differential Thermogravimetric the aluminosilicates and disrupt covalent bonds SiAO and
Analysis (DTA) AlAO in SiO2 and Al2O3. There is a gradual release of Si and
Thermal properties of prepared samples were studied by Al into the solution. At the beginning of the creation of geo-
STA 449F3 Thermo-analyser (Netzsch, Germany) in the tem- polymer, aluminum dissolves faster than silicon, resulting in
perature range from 26 to 800 C with the heating rate of the formation of a silica layer on the particles of the material.
10 K/min under nitrogen atmosphere using DSC/TG mode. Aluminum dissolved in water is adsorbed on the surface
The samples of about 18.0 mg in weight were heated in areas of these layers causing passivity of the surface. Also
Al2O3 crucibles. ions of Al and Si dissolved in a solution form
SiAOAAl(OH)32 anions, which subsequently react with the
Measurement Procedure Na1 cations. This process equilibrates the charge balance on
The geopolymer prepared from the MK and FA was inves- the surface, eliminating negative surface charges and ena-
tigated by XPS method daily for 28 days. We determined the bling formation of the monomers M1SiAOAAl(OH)32.
dependence of amount of released electrons from the bind- The coordination of aluminum atoms changes from octa-
ing energy measurements. The amount of released water hedral to tetrahedral. Decomposition of SiO2 and Al2O3 was
was studied by TGA analysis in the second day. The flexural already observed in the first day of the creation of geopoly-
and compressive strength of the hardened samples prepared mer, because the position of peaks of atoms changed (Table
from FA and MK was measured after 1, 7, and 28 days using 3). It is in agreement with the point 1 in process of geopoly-
the hydraulic machine. merizationdissolution (Eqs. 1a and 1b).

4 Month 2014 Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep
Figure 4. The experimental process of geopolymers preparation.

Figure 5. Energy spectrum of MK (magnesium anode). Figure 6. Energy spectrum of FA (magnesium anode). [Color
[Color figure can be viewed in the online issue, which is figure can be viewed in the online issue, which is available
available at wileyonlinelibrary.com.] at wileyonlinelibrary.com.]

In the process of geopolymerization, the amount and ratio Table 3. Core level binding energies (eV) in MK, in geopoly-
of Si and Al plays an important role. As a source of soluble mer prepared from MK, in FA, and in geopolymer prepared
Si we used sodium water glass. The amount and ratio of Si from the FA on the 1st day.
and Al optimizes the speed of response, and can also
increase the level of geopolymerization. The required ratio XPS line MK GP from MK FA GP from FA
of Si/Al has a positive effect on the strength of aluminosili-
cate gel and also it helps to dissipate unreacted ash particles. Si 2p 103.00 101.5 105.5 101.5
In our work, we used different ratios of alkaline silicate solu- Al 2p 75.00 74.00 77.5 74.5
tion/solid bulk0.23 (MK product) and 0.26 (FA product)
for optimizing the preparation of both products. The alumi-
nosilicate gel contains Al atoms with different coordination aqueous phase and new chains. This is in agreement with
numbers. The coordination number of Al can cause different the point 2 in the process of geopolymerizationnucleation
reactivity of materials. Aluminum, which has the tetrahedral and with Eq. 2.
structure, has a lower binding energy than that in the octahe- Oxygen plays an important role in the formation of geo-
dral structure. The lower the binding energy, the smaller the polymer. Four types of bonds exist in the geopolymer:
energy required to break the binding which causes an easier SiAOASi, SiAOH, SiAOANa (only electrostatic interaction
release of atoms [8]. In Table 4 we can see a shift in the forces), and SiAOAAl. The type of bonds changes in the
binding energy toward the lower values. It confirms change process of polymerization and the length of SiAOAAl chains
of coordination of atoms of aluminum. The shift in the bind- increases, in accordance with the results published in Refs.
ing energy toward the higher values was seen on the last [14,15]. Miyaji et al. [16] have investigated the surface of sili-
day of measurement. cone substrates treated with 2, 5, and 10M NaOH using XPS.
From the literature it is known that in terms of geopoly- In their work, the obtained O1s spectra of the silicone sam-
mer formation, the 7th day is characteristic for creation of ples showed a dominant peak located at 532 eV, which was
new structures. In this phase, the amount of silanol groups assigned to siloxane (SiAOASi) bonds in the silicone
increaseswe can observe forming oligomers in the skeleton.

Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep Month 2014 5
Table 4. Positions of peaks of Al 2p (eV) in geopolymer from metakaolin (GPM) and in geopolymer from fly ash (GPF) moni-
tored from the 1st to the 28th day.

XPS line Binding energy (eV) XPS line Binding energy (eV)
Al 2p for MK 75 Al 2p for FA 77.5
Al 2p for GPM in the 1st day 74 Al 2p for GPF in the 1st day 74.5
Al 2p for GPM in the 7th day 74 Al 2p GPF in the 7th day 74
Al 2p for GPM in the 23rd day 74 Al 2p GPF in the 23rd day 73.5
Al 2p for GPM in the 28th day 74.5 Al 2p GPF in the 28th day 75

Figure 7. O 1s of geopolymer from MK (1st day). Figure 9. O 1s of geopolymer from MK (7th day).

Figure 8. O 1s of geopolymer from FA (1st day). Figure 10. O 1s of geopolymer from FA (7th day).

The samples treated with 5 and 10M NaOH for more than by impurities in FA and the peak positions are in good
3 h showed two additional peaks located at 533 and 531 eV, agreement with the results by Miyaji et al. [16]. The differen-
which were assigned to SiAOH and SiAONa, respectively ces in binding energies of SiAOH, SiAOASi, and SiAOANa
[15]. They observed the formed amount of SiAOH and can be understood in terms of simple electrostatic interac-
SiAONa increases with increasing time of NaOH treatment tions. There are, on average, fewer electrons at the oxygen
[15]. In our case for geopolymer from MK in the first day, the atom in SiAOH than in SiAOASi, due to the fact that the
peak position of O 1s is at 531 eV. However, additional hydrogen atom has a larger electronegativity than the silicon
peaks at 529.461 eV and 533.228 eV for SiAOH and atom. Thus, the electronelectron repulsion at the oxygen
SiAOANa, respectively, as well as a peak at 531.336 eV for atom decreases, hence the increase of the binding energy of
O 1s in SiAOASi were also observed. These results are the electrons [11].
shown in Figure 7. For geopolymer from FA positions at The changes between geopolymer from MK and from FA
529.462 eV for SiAOANa, at 533.899 eV for SiAOH, and at on the 7th day are shown in Figures 9 and 10. For geopoly-
531.390 eV for SiAOASi were located. The differences mer from MK, we can see higher content of SiAOH groups
between the geopolymers from MK and FA can be seen by than in geopolymer from FA. It means that geopolymeriza-
comparison of Figures 7 and 8. These differences are caused tion in geopolymer from MK is faster and more active than

6 Month 2014 Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep
Figure 11. TGA of geopolymer from MK (the 2nd day).
Figure 13. Changes of Na 1s for geopolymer from MK.

Figure 12. TGA of geopolymer from FA (the 2nd day).


Figure 14. Changes of Na 1s for geopolymer from FA.

Figure 15. Changes of O 1s of geopolymer from MK in the 1st and 23rd day of geopolymerization. [Color figure can be
viewed in the online issue, which is available at wileyonlinelibrary.com.]

Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep Month 2014 7
Figure 16. Changes of O 1s of geopolymer from FA in the 1st and 23rd day of geopolymerization. [Color figure can be viewed
in the online issue, which is available at wileyonlinelibrary.com.]

Figure 17. Amount of Al 2p and Al 2s (%) for geopolymer


from MK. [Color figure can be viewed in the online issue, Figure 18. Amount of Al 2p and Al 2s (%) for geopolymer
which is available at wileyonlinelibrary.com.] from FA. [Color figure can be viewed in the online issue,
which is available at wileyonlinelibrary.com.]

in geopolymer from FA. This is confirmed also by TGA anal-


ysis in the second day. The amount of released water is tions of aluminum atoms, which can be attributed to the sta-
higher for geopolymer from MK (Figures 11 and 12). Weight bilization of geopolymer structure. Barr et al. [17] reported
loss for geopolymer from MK is 16.36% and for geopolymer that aluminum binding energies depend on coordination
from FA it is only 11.78%. number. Tetrahedrally coordinated aluminum generally has a
The 15th day is also important. We observe a decrease in lower binding energy than octahedrally coordinated alumi-
the content of Na (Figures 13 and 14). There are no changes in num which is in good agreement with our measurements. In
peak positions of Al atoms but in both geopolymers we see a geopolymer made from MK, we measured position for Al 2p
significant decline in size of the peak of aluminum atomsAl at 75.00 eV and it changed to 74.5 eV on the 28th day. For
2p. This indicates a beginning of oligomer condensates and geopolymer made from FA, the position for Al 2p was at
creation of a three-dimensional aluminosilicate structure 77.5 eV and it changed to 75 eV on the 28th day.
(point 3 in the section of polymerization, Eqs. 3a and 3b.
This may be caused by surface passivity due to dissolu- DISCUSSION
tion of aluminum in alkaline solution. On the 23rd day we In our X-ray photoelectron microscopy spectra, we
can see a significant decrease of oxygen, which is related to observed differences in formation of geopolymers from two
water evaporation and to solidification of the geopolymer. different sourcesMK and FA from boilers. Progressive mon-
The changes in content of oxygen in both geopolymers can itoring from the 1st to the 28th day showed that the forma-
be seen in Figures 15 and 16. On the last day of observation tion of the polymer chain is faster in geopolymer prepared
(the 28th day), we see a significant change in the peak posi- from MK. From the obtained spectra of the two samples, we

8 Month 2014 Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep
can say that an important change in reaction mechanism phase supported by the Research & Development Opera-
occurs on the 1st, 7th, 15th, 23th, and 28th day. Already on tional Programme funded by the ERDF.
the first day of formation of geopolymer we can see changes
in the peak positions of Si and Al atoms, which indicate the
dissolution of the elements in alkaline solution (in accord- LITERATURE CITED
ance with Eqs. 1a and 1b). On the seventh day, the peak 1. Autef, A., Joussein, E., Poulesquen, A., Gasgnier, G.,
positions of atoms do not change too much, but the spec- Pronier, S., Sobrados, I., Sanz, J., & Rossignol, S. (2013).
trum changes its shape, suggesting formation of intermediate Influence of metakaolin purities on potassium geopoly-
silanol SiAOH group and production of basic siloxo mer formulation: The existence of several networks, Jour-
SiAOASi group (in accordance with Eq. 2). The significant nal of Colloid and Interface Science, 408, 4353.
decrease of sodium on the fifteenth day indicates formation 2. Rashad, A.M. (2013). Metakaolin as cementitious material:
of polymer chains in oligomers (in accordance with Eqs. 3a History, scours, production and compositionA compre-
and 3b). hensive overview, Construction and Building Materials,
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decrease of oxygen on the 23rd day of geopolymerization 3. Palomo, A., Blanco-Varela, M.T., Granizo, M.L., Puertas,
(Figures 15 and 16). Peak positions of atoms of C, O, Si, and F., Vazquez, T., & Grutzeck, M.W. (1999). Chemical stabil-
Al confirm condensation of ortho-sialat molecules via reactive ity of cementitious materials based on metakaolin,
groups of Si and SiAONaAOAAlAOH, with formation of Cement and Concrete Research, 29, 9971004.
NaOH and creating cyclo-tri-sialat structure by releasing 4. Davidovits, J. (1985). Early high strength mineral poly-
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[6] (in accordance with Eqs. 4a4c). new materials, Journal of Thermal Analysis, 37, 1633
The differences between the two geopolymers are visible 1657.
from differences in their spectra. The biggest difference in 6. Davidovits, J. (2008). Geopolymer: Chemistry and appli-
making the geopolymers is the decline of the size of the peak cations (2nd Edition, p. 584), France: Institut
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7. Black, L., Garbev, K., Stemmermann, P., Hallam, K.R., &
CONCLUSION
Allen, G.C. (2003). Erratum to Characterisation of crystal-
Geopolymers can be considered as promising materials
line C-S-H phases by X-ray photoelectron spectroscopy
satisfying demanding technical criteria. Also they allow
(XPS), Cement and Concrete Research, 33, 899911.
achieving significant environmental benefits; therefore it is
8. Li, Ch., Wan, J., Sun, H., & Li, L. (2010). Investigation on
necessary to know the exact composition and properties of
the activation of coal gangue by a new compound
all their raw materials. Using XPS it is possible to determine
method, Journal of Hazardeous Materials, 179, 515520.
the suitability of fly ashes in the process of
geopolymerization. 9. Feng, D., Provis, J.L., & Van Deventer, J.S.J. (2012). Ther-
In this work, chemical properties of two different geopol- mal activation of albite for the synthesis of one-part mix
ymersmade from FA, and from MKwere studied. Sam- geopolymers, Journal of the American Ceramic Society,
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changes in peak positions of atoms of oxygen, carbon, 10. Raupp-Pereira, F., Ball, R.J., Rocha, J., Labrincha, J.A., &
sodium, and aluminum were observed. These changes were Allen, G.C. (2008). New waste based clinkers: Belite and
visible already from the first day. Changes in peak positions lime formulations, Cement and Concrete Research 38,
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SiO2 and Al2O3 in alkaline solution. It is known from chemi- 11. Simonsen, M.E., Sonderby, C., Li, Z., & Sogaard, E.G.
cal analysis of materials that FA contains much more impur- (2009). XPS and FT-IR investigation of silicate polymers,
ities than MK. These impurities slow down significantly Journal of Materials Science, 44, 20792088.
chemical reactions in the process of geopolymerization and 12. Rees, C.A., Provis, J.L., Lukey, G.C., & van Deventer, J.S.J.
cause insufficient dissolving of aluminum and silicon oxides. (2008). The mechanism of geopolymer gel formation
In terms of forming the geopolymer chains this phenomenon investigated through seeded nucleation, Colloids and
is undesirable. It is because aluminum and silicon atoms Surfaces A: Physicochemical and Engineering Aspects,
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sable building blocks in the polymer structure. The greater 13. Barr, T.L. & Seal, S. (1995). X-ray photoelectron spectro-
purity of MK suggests sharper peaks in the XPS spectra. This scopic studies of kaolinite and montmorillonite, Vacuum,
investigation proved that MK is better than FA in geopoly- 46, 13911395.
mers, but kaolin needs more energy to convert it to MK, 14. Xu, H. & Van Deventer, J.S.J. (2000). The geopolymerisa-
whilst FA is a waste and does not need any energy. So FA is tion of alumina-silicate materials, International Journal of
more cost-effective than MK. Thus, FA may be recommended Mineral Processing, 59, 247266.
for preparation of the geopolymers. It will save energy 15. Xu, H. & Van Deventer, J.S.J. (2003). Effect of source
required for calcination and at the same time it will eliminate materials on geopolymerization, Industrial & Engineering
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ACKNOWLEDGMENTS Chemical surface treatment of silicone for inducing its
The research has been supported by the Slovak Agency bioactivity, Journal of Materials Science-Materials in Medi-
for Research and Development (APPV) (Grant No. 0423-11) cine, 9, 6165.
and by the Scientific Grant Agency (VEGA) of the Ministry of 17. Barr, T.L., Seal, S., Wozniak, K., & Klinowski, J. (1997).
Education of the Slovak Republic and the Slovak Academy of ESCA studies of the coordination state of aluminum in
Sciences, Grant No. 1/1222/12 and Research excellence oxide environments, Journal of Chemical Society, Faraday
centre on earth sources, extraction and treatment - 2nd Transactions, 93, 181186.

Environmental Progress & Sustainable Energy (Vol.00, No.00) DOI 10.1002/ep Month 2014 9