Composites Part B 112 (2017) 213e223

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Composites Part B
journal homepage: www.elsevier.com/locate/compositesb

Immobilization of hexavalent chromium by fly ash-based

geopolymers
c a, *, Miroslav Komljenovi

Violeta Nikoli
c a, Natasa D
zunuzovi

c a, Tijana Ivanovi

c a,
Zoran Miladinovi
cb
a
Institute for Multidisciplinary Research, University of Belgrade, Serbia
b
Institute of General and Physical Chemistry, Belgrade, Serbia

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

Article history: In this paper the immobilization of hexavalent chromium (Cr (VI)) by fly ash (FA)-based geopolymers was
Received 28 June 2016 investigated, depending on FA characteristics, mechanical activation of FA, geopolymer synthesis con-
Received in revised form ditions and concentration of Cr added. The effectiveness of Cr immobilization was determined via
18 November 2016
investigation of geopolymer compressive strength and Cr leaching. Structural changes of geopolymers
Accepted 4 December 2016
Available online 19 December 2016
during the Cr immobilization were assessed by means of gas adsorption, XRD, and NMR analysis. FA
reactivity was a key factor determining both physical-mechanical and immobilizing properties of geo-
polymers. Mechanical activation of FA caused an increase of both geopolymer strength and effectiveness
Keywords:
Mechanical properties
of Cr immobilization. The presence of Cr induced physical-mechanical and structural changes in geo-
Physical properties polymers. The correlation between concentration of Cr leached and geopolymer physical-mechanical and
Environmental degradation structural parameters was established.
Powder processing © 2016 Elsevier Ltd. All rights reserved.
Geopolymers

1. Introduction process of toxic and radioactive elements [3,11]. Significant number

Geopolymers are formed as a product of alkali activation of
aluminosilicate materials, including fly ash (FA) from thermal po-
wer plants [1]. Geopolymer properties depend largely on FA char-
acteristics (chemical composition, content of glassy phase, amount
of soluble silicon and aluminum, particle size distribution, and
presence of inert particles) [2,3]. It is well known that coarser FA
particles represent less reactive material in the process of geo-
polymer synthesis [4]. Mechanical activation of FA in high energy
mills positively affects the particle size distribution of FA, improves
FA reactivity, and accordingly geopolymer properties [5]. Geo-
polymer properties are also significantly influenced by the syn-
thesis conditions (curing temperature and time, and relative
humidity) [6e9]. Elevated curing temperature accelerates process
of alkali activation, while at lower temperatures curing time plays
more important role [10].
Geopolymers are generally referred to as an alternative to
Portland cement binders. Due to their three-dimensional zeolite-
like structure, geopolymers can also be used in the immobilization
of publications indicates the possibility of effective immobilization
of toxic elements by geopolymers [12]. Immobilization of Cr (VI) is
of particular significance because of its extreme toxicity and car-
cinogenicity. However, Cr (VI) immobilization by geopolymers
seems to be difficult [13,14].
Previous investigations showed that mechanical activation of FA
positively influenced the effectiveness of Pb immobilization by
geopolymers [15]. However, to the best of our knowledge, there are
no data regarding the influence of mechanical activation of FA on
the effectiveness of the Cr (VI) immobilization by geopolymers.
Therefore, the aim of this research was to investigate the influence
of FA characteristics, mechanical activation of FA, and geopolymer
synthesis conditions on the effectiveness of Cr (VI) immobilization
by FA-based geopolymers.
2. Experiment design
The process of Cr immobilization was investigated in two
routes:

* Corresponding author. University of Belgrade, Institute for Multidiciplinary

1) Investigation of the influence of physical-mechanical charac-
Research, Kneza Viseslava 1, 11 030 Belgrade, Serbia. teristics of FA and mechanical activation of FA on the effective-
E-mail address: violeta@imsi.bg.ac.rs (V. Nikoli

c). ness of Cr immobilization by geopolymers,

http://dx.doi.org/10.1016/j.compositesb.2016.12.024
1359-8368/© 2016 Elsevier Ltd. All rights reserved.
214 V. Nikoli
c et al. / Composites Part B 112 (2017) 213e223

2) Investigation of the influence of geopolymers synthesis condi- 196-1). Water was added in the amount required to obtain equal
tions on the effectiveness of Cr immobilization by geopolymers. consistency (mortar flow measured on a flow table was
125 ± 5 mm). Mortar prisms of standard dimensions (40 х 40 х
160 mm) were prepared of FA and standard sand in the 1: 3 mass
2.1. Materials ratio on a vibrating table.
Pre-calculated amount of potassium chromate was completely
In this investigation, FA samples from two coal thermal power dissolved in the amount of distilled water required to achieve
plants (PP) were used as the initial materials: appropriate consistency. The order of geopolymers preparation was
as follows: first activator was added to FA, then potassium chro-
1 FA “Morava”, PP Morava, Svilajnac (denoted as FA M) mate solution, and finally sand. The content of Cr accounting for the
2 FA “Kolubara”, PP Kolubara, Veliki Crljani (denoted as FA K) total mass of FA was 0.0%; 0.5%; 1.0% and 2.0%.
Optimal water/binder ratio (water represents the total amount
A solution of sodium silicate was used as an alkali activator of water in the system including water from the activator, while
(”Galenika-Magmasil”; 13.60% Na2O, 26.25% SiO2). The initial so- binder represents the total FA mass and solid part of the activator)
dium silicate modulus n (SiO2/Na2O mass ratio) of 1.93 was further was established in previous investigations: in the case of mortar
adjusted by adding NaOH (“Sigma Aldrich”, p.a. min 98%). Potas- based on the initial FA M and FA K water/binder ratio was 0.46 and
sium chromate (K2CrO4 p.a., “Merck”) was used as a source of 0.61, respectively [10], while for the mortar based on MFA K it was
chromium. Concentrated 65 mass% HNO3 (p.a. “Superlab”) was 0.38 [15].
used to stabilize the solution after leaching and filtration. The influence of FA characteristics and mechanical activation of
Chemical composition, fineness, and glassy phase content of the FA on the Cr immobilization was investigated on geopolymers
initial FA samples are given in Table 1 [10]. based on the initial FA M and FA K (denoted as G-M and G-K), and
Previous investigations showed better reactivity of FA M in the on geopolymers based on MFA K (denoted as G-MK). On the other
alkali activation reaction in comparison to FA K due to the presence hand, the influence of geopolymer synthesis conditions on the Cr
of higher amount of soluble aluminum in alkaline environment that immobilization was investigated on geopolymers based on more
produced geopolymers with higher strength [10]. In order to reactive initial FA M (G-M).
improve FA reactivity, the less reactive FA K was mechanically For the investigation of the influence of FA characteristics on the
activated. Cr immobilization, geopolymers based on G-M, G-K and G-MK
were synthesized at room temperature (20
C) in a humid chamber
(90 ± 5% rel. hum.) for 24 h and 28 days. For the investigation of the
Table 1
influence of geopolymer synthesis conditions on Cr immobilization,
FA chemical composition, fineness and glassy phase content (mass %) [10].
geopolymers based on G-M were synthesized at elevated temper-
Component FA M FA K ature (24 h at 55
C, 4 h at 95
C, and 24 h at 95
C). The preparation
SiO2 55.23 62.13 of geopolymer paste samples was performed in a similar manner to
Al2O3 21.43 17.20 the preparation of mortars. Pastes were prepared by mixing the FA
Fe2O3 7.42 5.95
or MFA, alkali activator and water, and potassium chromate solu-
CaO 7.94 5.67
MgO 2.61 2.00 tion in the case of geopolymers with Cr added. Pastes were poured
SO3 0.81 0.67 into plastic moulds on a vibrating table and synthesized under the
Na2O 0.64 0.58 same conditions as corresponding mortars. After curing, pastes
K2O 1.35 1.04 were crushed and passed through a 4 mm sieve (for leaching
Loss on ignition at 1000
С 1.66 2.88
testing). For other tests, pastes were additionally pulverized in
Total 99.09 98.12
isopropyl alcohol for 1 h in order to stop further reaction, filtered,
Classification according to class class
rinsed with acetone, and dried at 50
C for 2 h.
ASTM C 618-03 F F

Particle size > 63 mm 23.30 42.65 2.4. Methods of characterization

Particle size 43e63 mm 8.05
Particle size < 43 mm 68.65
Glassy phase content 48
2.2. Mechanical activation of FA
Mechanical activation of FA K was carried out in a planetary ball
mill (FRITSCH Pulverisette, Germany) under air atmosphere for
15 min [5]. Mass ratio FA to steel balls was 1: 20, while the rotation
speed was 380 rpm. Hereinafter, mechanically activated FA K will
be referred to as MFA K.
2.3. Synthesis of geopolymers
Previous investigations showed that geopolymer with optimal
physical-mechanical characteristics can be obtained by using so-
dium silicate with modulus 1.5 as alkali activator, whereby optimal
activator concentration is 10 mass% of Na2O with respect to the FA
mass [4]. Geopolymer mortars were prepared by mixing FA or MFA
with alkali activator and water, and then with standard sand (EN
5.30
52.05
Determination of compressive strength of geopolymer mortars,
38 as the mean value obtained from the six samples, was performed
according to SRPS EN 196-1 standard [16] using the CONTROLS
ADVANTEST 9 device.
Testing of Cr leaching from FA samples and geopolymers was
performed according to standard procedure SRPS EN 12457-2 [17].
Standard SRPS EN 12457-2 prescribes the use of deionized water as
leachant at a liquid to solid (L/S) ratio of 10 L/kg for materials with
particle size below 4 mm, for 24 h. During the experiment, 20 g of
samples (dry mass) was mixed with 200 ml of deionized water.
After 24 h of leaching the samples were vacuum filtered through a
membrane filter of 0.45 mm. The eluates were acidified with 65
mass% HNO3 to the value of pH < 2. The inductively coupled plasma
optical emission spectrometer (ICPeOES, SpectroeGenesis EOP II,
Spectro Analytical Instruments GmbH) was used to determine the
concentration of Cr in eluates. The effectiveness of Cr immobiliza-
tion was calculated in relation to the total concentration of Cr
added.
The specific surface area of geopolymers was calculated accord-
ing to the Brunauer-Emmett-Teller (BET) method, from the linear
 V. Nikoli
c et al. / Composites Part B 112 (2017) 213e223
branch of the adsorption isotherm of gaseous nitrogen at tempera-
ture of liquid nitrogen, using the Micromeritics ASAP 2020 instru-
ment. Samples were degassed at 105
C for 10 h under reduced
pressure (vacuum). The mesopore volume was calculated according
to the Barrett-Joyner-Halenda (BJH) method from the desorption
branch of isotherm. Mineralogical characterization of geopolymers
was conducted using X-ray powder diffractometer type Ital Struc-
tures APD 2000 (CuKa radiation). The diffraction patterns were
recorded within 5e60
2q range, with a step of 0.05
and time per
step of 1 s. For the identification of crystalline phases, the
“PCPDFWIN” software (based on JCPDS-ICDD database) was used.
29
Si MAS NMR spectra of geopolymers were obtained at Larmor
frequency of 79.49 MHz using Bruker MSL 400 system, Apollo
console upgraded (Tecmag). Chemical shifts d(29Si) were externally
referenced to 2,2-dimethyl-2-silapentane-5-sulfonate (DSS) stan-
dard. Gaussian peak deconvolution of the obtained spectra was
performed using DMFIT application [18], by employing common
routine for analyzing peak distribution. Prior to 29Si MAS NMR
analysis, iron content in the geopolymer samples was minimized by
exposing the samples to a strong magnetic field [2,19].
Determination of compressive strength was performed on geo-
polymer mortars, while all other tests and characterization of geo-
polymers were performed on geopolymer pastes. Further in text
solely the term geopolymer is used, regardless of the sample type.
3. Results and discussion
3.1. Cr leaching from FAs
FA originally contains a certain amount of Cr (“native” Cr). Some
authors reported that the amount of hexavalent Cr in the total
content of Cr in FA is less than 5%, while significantly higher amount
of Cr is present in trivalent state within the aluminosilicate glass
[20] or within the ferrite spinel [21]. The concentration of Cr
leached from the initial FAs and MFA K was analyzed according to
SRPS EN 12457-2 [17].
The results of leaching of “native” Cr present in the initial FA
samples and MFA K indicated that FAs tested contained minor
amounts of leachable Cr, whereby FA M contained the highest
amount of leachable Cr (Table 2). Based on the criteria referring to the
disposal of waste at landfilles (EU Landfill Waste Acceptance Criteria)
[22] and the Cr concentration of FA eluate, all investigated FA samples
do not exceed the limit value for disposal at landfills for non-
hazardous waste. The list of parameters [22], significant in terms of
risk assessment for the waste disposal, prescribes only the total
concentration of Cr in the eluate, regardless of the Cr valence state.
Table 2
Concentration of Cr leached from different FAs (SRPS EN 12457-2).
Sample Cr leached
(mg/kg)
FA M 3.78
FA K 0.62
MFA K 0.52
EU Landfill Waste Acceptance Limits inert waste 0.5
[22] non-hazardous waste 10
hazardous waste 70
waste unsuitable for >70
EU landfill
3.2. Characterization of geopolymers
3.2.1. Compressive strength
According to the US Environmental Protection Agency [23], a
215
stabilized materials can be considers as satisfactory if it has a
compressive strength of at least 0.35 N/mm2 [24e26]. Based on the
results of compressive strength testing (Table 3) it can be noticed
that all investigated samples, regardless of the FA characteristics,
showed the compressive strength markedly above the recom-
mended value.
After 28 days of curing at 20
C, the compressive strength of G-M
was almost three times higher than the compressive strength of G-
K. The main reason for this is higher reactivity of FA M [10]. Also,
geopolymers based on G-MK showed remarkably higher strength
in comparison to the strength of G-M and G-K. This is the conse-
quence of improved reactivity of MFA K induced by mechanical
activation [5].
It was found previously that the increase in the curing tem-
perature and time leads to the increase in geopolymer strength
[10]. Furthermore, the compressive strength of geopolymer after
24 h at 95
C was more or less similar to the compressive strength
of geopolymer after 28 days at 20
C.
The addition of smaller concentrations of Cr (0.5e1.0%) caused
minor changes in geopolymer strength (increase or decrease up to
5%), while the addition of 2% of Cr caused more evident decrease in
geopolymer strength (5e14%), regardless of the synthesis condi-
tions and FA characteristics. Minor increase in geopolymer strength
due to the addition of 0.5% of Cr was also noticed earlier [14].
However, such increase was observed during this investigation only
after shorter curing time (24 h), and it was not observable after
longer curing time (28 days) at room temperature. It is obvious that
added Cr (VI) had negative influence on the geopolymer strength in
later stages of the reaction probably by creating some defects in the
geopolymer structure-due to its anionic nature and inability to
effectively incorporate into the geopolymer gel. This phenomenon
was more pronounced at elevated temperature (55
C or 95
C). The
reason for more distinctive strength decrease at elevated temper-
atures probably lies in the fact that the reaction takes place more
quickly at elevated temperature, and therefore the likelihood of the
formation of defects in the structure is higher, wherein the pres-
ence of Cr favored the formation of these defects.
3.2.2. X-ray diffraction analysis
XRD patterns of different geopolymers after 28 days at 20
C for
different concentrations of Cr added are given in Fig. 1. X-ray
diffraction analysis confirmed the presence of crystalline phases
typical for the initial FA: quartz (PDF# 46-1045), anhydrite (PDF#
06-0226), feldspar (PDF# 89-1477), hematite (PDF# 88-2359) and
mullite (PDF# 85-1460), as well as secondary calcite (PDF # 72-
1937) formed due to carbonation and the fact that the reaction took
place in a humid chamber. In addition to the identified crystalline
phases, a broad diffuse reflection, stretching between 25 and 35

2q, indicated the presence of the amorphous phase.
In geopolymers with the addition of 2% Cr, besides the observed
crystalline phases, another phase was also detected e tarapacaite
(K2CrO4, PDF # 750920). Formation of this phase is understandable
since during the geopolymer synthesis Cr was added in this form.
Given that the K2CrO4 was completely dissolved, the presence of
K2CrO4 in the XRD diffractograms may be due to sample prepara-
tion for analysis, which includes drying at elevated temperature.
3.2.3. Leaching of Cr
The results of Cr leached from geopolymers depending on the
concentration of Cr added, FA characteristics, and curing time at
20
C are given in Fig. 1. The EU Landfill Waste Acceptance Criteria
[22] are also given in Fig. 2.
Based on the difference in concentrations of Cr leached from
geopolymers G-K and G-MK after 24 h at 20
C (Fig. 2a), a positive
influence of mechanical activation of FA on the decrease of
216 V. Nikoli
c et al. / Composites Part B 112 (2017) 213e223

Table 3
The mean compressive strength of geopolymers with standard deviations.

Cr added 24 h 28 days 24 h 4h 24 h
(%) 20
C 20
C 55
C 95
C 95
C

G-K G-MK G-K G-MK G-M G-M

2
Compressive strength (N/mm )
0.0 2.09 35.55 12.77 67.93 33.14 26.36 20.75 31.79
±0.04 ±0.48 ±0.46 ±2.04 ±1.05 ±0.68 ±0.20 ±0.96
0.5 2.15 37.48 12.08 65.23 e e e e
±0.04 ±1.25 ±0.25 ±3.33
1.0 2.10 34.50 12.34 64.15 32.33 e e e
±0.07 ±0.59 ±0.38 ±2.06 ±0.67
2.0 1.83 32.23 12.08 60.15 29.83 23.95 19.07 27.44
±0.06 ±0.57 ±0.40 ±1.57 ±1.08 ±0.61 ±0.55 ±1.21
Relative strength (%)
0.0 100 100 100 100 100 100 100 100
0.5 102.9 105.4 94.60 96.03 e e e e
1.0 100.5 97.05 96.63 94.44 97.56 e e e
2.0 87.6 90.66 94.60 88.55 90.01 90.86 91.90 86.32

of Cr leached. Thereby, the fact that the concentration of Cr leached

Fig. 1. XRD of geopolymers after 28 days at 20
C.
concentration of Cr leached can clearly be seen. Comparing these
results to the results obtained for G-K and G-M after 28 days
(Fig. 2b), it can be concluded that both mechanical activation of FA
and longer curing time contributed to the decrease of concentration
from G-MK after 24 h was smaller than the concentration of Cr
leached from G-K after 28 days of curing, indicates that mechanical
activation of FA had greater influence on concentration of Cr
leached than curing time. The concentration of Cr leached from G-
MK was even lower than that from geopolymer G-M based on
highly reactive FA M.
However, unlike geopolymers without Cr added, which can be
classified as non-hazardous waste, all geopolymers synthesized at
room temperature, irrespective of the quantity of Cr added
(0.5e2.0%), can be classified as waste unsuitable for landfilling.
The concentration of Cr leached from geopolymer G-M
depending on the synthesis conditions and concentration of Cr
added is given in Fig. 3. The concentration of Cr leached from G-M
without Cr added was very similar, whereby the lowest concen-
tration of Cr leached was detected at geopolymers synthesized at
room temperature (20
C) for 28 days. Other authors have also
noticed that longer curing time at room temperature contributes to
greater stability of geopolymers and more effective immobilization
of Cr [27].
Given that the concentration of Cr in the eluate significantly
exceeded the limit value [22] regardless of the synthesis conditions,
G-M with the addition of 2% Cr synthesized at elevated temperature
(55
C or 95
C) can also be classified as waste unsuitable for
landfilling. Therefore, the results of Cr leaching from G-M with 2%

Fig. 2. Concentration of Cr leached from different geopolymers versus concentration of Cr added.

 V. Nikoli
c et al. / Composites Part B 112 (2017) 213e223 217

[29]. Barrett-Joyner-Halenda method provides information

regarding pores smaller than 100 nm, meaning that larger pores do
not take part in calculated mesopore volume of geopolymers [30].
Mesopore size distribution for different geopolymers and con-
centration of Cr added is given in Fig. 4. Mesopore volume
depending on mesopore diameter is given in Fig. 4a. Although the
mesopore volume of the investigated geopolymers in most cases
was similar, characteristic presence of smaller mesopores in a
higher degree can clearly be seen in the case of G-M, and especially
in the case of G-MK, compared to G-K. The addition of 2% of Cr in
the case of G-K led to a significant increase in mesopore volume,
unlike geopolymers G-M and G-MK where the change in mesopore
volume with the addition of 2% of Cr was less pronounced.
Mesopore size distribution curve of geopolymer G-K was char-
acterized by a single broad peak, indicating a broad mesopore size
distribution, while in the case of G-M, and especially in the case G-
MK, a narrow mesopore size distribution was noticed (Fig. 4b), as
Fig. 3. Concentration of Cr leached from geopolymer G-M versus concentration of Cr previously also observed [15]. The maximum of these peaks reflects
added for different synthesis conditions. the size of the majority of mesopores.
In spite of the limitations of Barrett-Joyner-Halenda method
[30], the results obtained by this method have clearly shown the
Table 4
shifting of the curves maximum towards lower values of the
The effectiveness of Cr immobilization by geopolymers.
mesopore diameter in the case of G-MK in comparison to G-K. It is
Synthesis conditions Cr added Cr immobilized (%) obvious that due to mechanical activation of FA the mesopore
(%)
G-K G-MK G-M diameter of G-MK was significantly reduced. Shifting of the peak
24 h - 20
C 0.5 64.58 76.47 e
maximum from mesopores to micropores suggested the formation
1.0 63.06 70.60 e of larger amounts of the reaction products (gel). Other authors
2.0 62.01 68.88 e [29,30] have also used BJH methods in order to investigate pore
28 days - 0.5 74.80 91.16 e
refinement in alkali activated materials. Physical characteristics of
20
C 1.0 66.20 78.08 71.91 geopolymers based on the initial FAs and MFA depending on the
2.0 63.23 73.48 70.01 concentration of Cr added are given in Table 5.
24 h - 55
C 2.0 e e 70.77 Due to mechanical activation of FA, the average mesopore
4 h - 95
C e e 65.30 diameter of G-MK was three times lower than of G-K. However, the
24 h - 95
C e e 70.09 addition of 2% of Cr did not trigger significant changes in the spe-
cific surface area, mesopore volume, and average mesopore diam-
eter in the case of G-MK. The addition of 2% Cr in the case of
of Cr added showed that the immobilization of Cr by geopolymers geopolymers based on the initial FAs led to the increase in specific
under given experimental conditions was insufficiently successful. surface area and mesopore volume of geopolymers. G-K with 2% of
The highest concentration of Cr leached was in the case of G-M Cr added showed slightly higher specific surface area and signifi-
synthesized at 95
C for 4 h. The reason for this was relatively short cantly larger mesopore volume in comparison to G-M with 2% of Cr
curing time, whereby the diffusion of Cr from incompletely hard- added, probably due to the presence of larger amount of unburned
ened geopolymer was facilitated. With the increase of curing time carbon particles in FA K, i.e. higher loss on ignition at 1000
C
from 4 h to 24 h at 95
C, the effectiveness of Cr immobilization was (Table 1).
increased by approximately 5%. Finally, it can be concluded that Despite the fact that important pore volume appeared to be
geopolymer synthesis conditions had minor influence on the present above the largest measurable pore diameter, BJH method
effectiveness of Cr immobilization. has been applied most widely to the investigation of pore size
Depending on the FA characteristics, geopolymer synthesis distribution for alkali-activated binders [29e33]. In this research, as
conditions, and the concentration of Cr added, the effectiveness of already mentioned, BJH method clearly confirmed the shifting of
Cr immobilization by geopolymers was in the range of 62e91% the mesopore size distribution curve peak towards lower values of
(Table 4). mesopore diameter, as a result of the formation of larger amounts
The major reason for higher effectiveness of Cr immobilization of gel. The formation of larger amounts of gel led to an increase of
by geopolymers G-M and especially G-MK (compared to geo- compressive strength of geopolymers.
polymer G-K) was in higher geopolymer compressive strength The results obtained by Barrett-Joyner-Halenda method are
(Table 3). consistent with the results of the compressive strength of geo-
It is also clear that leaching of Cr from geopolymers depended polymers (Table 3), given that the geopolymers with smaller
on the concentration of Cr added. Higher concentration of Cr added mesopore volume and smaller average mesopore diameter
led to lower effectiveness of Cr immobilization. (Table 5) were characterized by higher compressive strength.
Pore volume alone is insufficient to characterize the function-
ality of porous materials; the size of the pores is critical for con-
3.2.4. Physical characteristics trolling many processes such as mass transfer [30].
According to the IUPAC classification, porosity is generally Kramar and Ducman [32] showed that even small w/s variation
classified as macroporosity, mesoporosity, and microporosity [28]. had a strong influence on the porosity values and consequently to
In geopolymers macropores mainly represent gaps between the compressive strength. Larger w/s ratio increased the porosity
unreacted FA particles, while mesopores are typical pores between and a shift toward larger pore sized. The porosity and compressive
geopolymer phases, and micropores exist within the gel network strength of geopolymers are in negative correlation. The same
218 V. Nikoli
c et al. / Composites Part B 112 (2017) 213e223

Fig. 4. Mesopore size distribution for different geopolymers and concentration of Cr added: a) mesopore volume versus mesopore diameter and b) mesopore size distribution
curve.

Table 5 geopolymers with 2% Cr added after 28 days at 20
C, depending of

Physical characteristics of geopolymers. the average mesopore diameter and mesopore volume are given in
Sample Cr added Specific Mesopore Average mesopore Fig. 5. It can be seen that with the increase of average mesopore
(%) surface volume diameter (nm) diameter the concentration of Cr leached also increased, while the
(m2/g) (cm3/g) geopolymer compressive strength decreased (Fig. 5a). Featuring
G-M 0 47.6 0.153 10.5 diagrams clearly indicate that the effectiveness of Cr immobiliza-
2 60.6 0.162 10.1 tion by geopolymers is directly dependent on physical-mechanical
G-K 0 33.1 0.144 17.9
characteristics of geopolymers, and thus on the FA characteristics.
2 72.7 0.241 12.6
G-MK 0 78.3 0.146 5.6
The more reactive FA led to the more favorable physical-mechanical
2 78.1 0.147 6.3 properties (higher strength and smaller mesopore diameter) of
geopolymers based on such FA, and to the lower concentration of Cr
leached.
trend is observed for average pore diameter, and the smallest In a similar way it can be seen that in the case of geopolymers
average pore diameter is for the lowest w/s ratio. In this investi- with 2% of Cr added, with the increase in the mesopore volume the
gation, the highest water/binder was in the case of geopolymer G-K, concentration of Cr leached from geopolymers increased while the
while the lowest was in the case G-MK. Decreasing the w/s can compressive strength of the appropriate geopolymers decreased
reduce the porosity of the geopolymer, as was also found by Kramar (Fig. 5b).
and Ducman. The mesopores represent the main porous structure, Phair and van Deventer [34] pointed out that matrix perme-
which is the cluster(s) of aluminosilicate particles that constitute ability is one of the most probable physical properties linking
the Si-O-Al network, as shown by Sindhunata et al. [32]. matrix leachability to matrix strength. Cho et al. found a very good
Concentration of Cr leached and compressive strength of relationship between the diffusion coefficient of Cr(VI) and the pore

Fig. 5. Concentration of Cr leached and compressive strength of geopolymers after 28 days at 20
C versus: a) average mesopore diameter and b) mesopore volume.
 V. Nikoli
c et al. / Composites Part B 112 (2017) 213e223 219

Fig. 6. 29
Si MAS NMR spectra deconvolution of geopolymers based on the initial FAs after 28 days at 20
C.

volume [35]. geopolymers based on the initial FAs were centered at

approximately 92 ppm. Generally, 29Si MAS NMR spectra of
geopolymers consist of overlapping resonances attributed to the
3.2.5. NMR analysis silicon sites present in aluminosilicate gel, unreacted crystalline
29
Si MAS NMR spectra deconvolution of geopolymers based on phases, and unreacted glassy phase present in the initial FA [18].
the initial FAs after 28 days at 20
C is given in Fig. 6. The spectra of

Table 6
29
Si MAS NMR spectra deconvolution of geopolymers based on the initial FAs after 28 days at 20
C (Fig. 6).

Geopolymer sample Q1a Q2a Q4(4Al) Q4(3Al) Q4(2Al) Q4(1Al) Q4(0Al) Quartzb Q4b

0% Cr
G-M d (ppm) 72.95 79.00 84.50 89.40 94.00 99.30 106.4 107.0 112.7
Width (ppm) 7 7 7 7 7 7 7 1.2 7
Area (%) 2.99 6.77 19.64 22.99 20.29 13.53 9.39 1.23 3.14
G-K d (ppm) 72.90 79.00 84.70 89.80 94.60 99.80 106.6 107.0 113.8
Width (ppm) 7 7 7 7 7 7 7 1.5 7
Area (%) 2.66 7.23 17.79 24.50 22.15 12.39 9.38 1.79 2.11

2% Cr
G-M d (ppm) 72.90 79.00 84.70 89.60 94.50 99.90 106.9 107.4 113.7
Width (ppm) 7 7 7 7 7 7 7 1.2 7
Area (%) 1.25 4.59 15.35 24.03 20.61 14.87 12.70 1.28 5.32
G-K d (ppm) 72.90 79.00 84.00 89.00 94.00 99.60 106.99 107.4 113.9
Width (ppm) 7 7 7 7 7 7 7 1.5 7
Area (%) 0.46 2.39 11.49 22.71 25.81 17.87 12.18 1.98 5.09
a
Signals associated with less condensed silicon species, Q1 and Q2.
b
Quartz and other Q4 silicon units.
220 V. Nikoli
c et al. / Composites Part B 112 (2017) 213e223

29
Fig. 7. Si MAS NMR spectra deconvolution of geopolymers G-M.
 V. Nikoli
c et al. / Composites Part B 112 (2017) 213e223 221

The deconvolution of broad 29Si MAS NMR spectra of geopolymers
based on the initial FAs with the additions of 0% and 2% Cr, con-
sisting of individual Q4(mAl) silicon species, is given in Fig. 6 and in
Table 6.
It was assumed that 29Si MAS NMR spectrum of geopolymers
consists of all five Q4(mAl, m ¼ 4, 3, 2, 1 or 0) silicon species, with
Q4(4Al), Q4(3Al), Q4(2Al), Q4(1Al) and Q4(0Al) resonating at
approximately 84, 89, 94, 99 and 107 ppm, respectively
[36,37]. In addition to Q4(mAl) silicon peaks, in the 29Si MAS NMR
spectra of all investigated geopolymer samples in this study small
resonances at approximately 73, 79, 107 (sharp peak),
and 112 ppm were observed. Peaks at approximately 73
and 79 can be ascribed to less condensed silicon species Q1 and Q2
[38,39], probably originating from unreacted alkali activator,
although the possibility that some part of these units can originate
from unreacted FA glassy phase should not be excluded. Some
authors also ascribed these signals to the residual and less
condensed species, monomer or dimer units with silanol groups
[2,38]. Sharp peak at approximately 107 ppm indicated an
ordered crystalline structure and can be attributed to quartz orig-
inating from the initial FA [18]. The resonance at 112 ppm is
usually attributed to different SiO2 polymorphs [40,41], i.e.
unreacted fractions from the initial FA or Q4(0Al) units in the
products of alkali activation reaction [39].
29
Si MAS NMR deconvoluted spectra of geopolymers G-M
depending on the synthesis conditions and the concentration of Cr
added are given in Fig. 7 and in Table 7.
As in the case of geopolymers synthesized at room temperature,
the results of deconvolution of 29Si MAS NMR spectra of G-M
synthesized at elevated temperatures indicated that the most
common structural units in geopolymers were Q4(2Al) and Q4(3Al).
The addition of 2% Cr led to the reduction of fraction of Q4(mAl)
structural units richer in aluminum (m ¼ 3, 4) and the increase of
fraction of structural units richer in silicon (m ¼ 0, 1, 2). Given that
the synthesis of geopolymers was performed using sodium silicate
solution with modulus 1.5, i.e. where an excess of soluble silica was
present, the content of soluble aluminum was the dominant
chemical factor that determined the process of geopolymerization,

Table 7
29
Si MAS NMR spectra deconvolution of geopolymers G-Mor (Fig. 7).

Synthesis conditions Q1a Q2a Q4(4Al) Q4(3Al) Q4(2Al) Q4(1Al) Q4(0Al) quartzb Q4b

0% Cr
24 h-55
C d (ppm) 72.90 79.00 84.58 89.40 94.50 99.87 106.9 107.2 113.9
Width (ppm) 7 7 7 7 7 7 7 1.2 7
Area(%) 0.40 3.78 14.72 26.10 24.13 16.26 10.83 1.08 2.67
4 h-95
C d (ppm) 72.07 79.00 84.74 89.98 94.96 99.97 106.8 107.2 113.9
Width (ppm) 7 7 7 7 7 7 7 1.2 7
Area (%) 1.49 4.08 15.89 26.99 21.83 15.17 10.07 1.13 3.32
24 h-95
C d (ppm) 72.99 79.00 84.90 89.99 94.95 99.98 106.7 107.2 112.0
Width (ppm) 7 7 7 7 7 7 7 1.2 7
Area (%) 1.82 5.57 16.86 25.94 22.52 15.04 9.43 0.97 1.84

2% Cr
24 h-55
C d (ppm) 72.00 79.00 84.80 89.00 94.00 99.78 106.9 107.1 113.9
Width (ppm) 7 7 7 7 7 7 7 1.2 7
Area (%) 2.26 5.98 13.82 22.01 23.41 16.20 11.39 1.16 3.75
4 h-95
C d (ppm) 72.07 79.01 84.13 89.00 94.03 99.02 106.3 107.2 112.0
Width (ppm) 7 7 7 7 7 7 7 1.2 7
Area (%) 2.69 6.63 14.77 26.49 20.52 15.07 10.53 1.41 1.89
24 h-95
C d (ppm) 72.95 79.00 84.60 89.00 94.14 99.70 106.4 107.4 112.0
Width (ppm) 7 7 7 7 7 7 7 1.2 7
Area (%) 1.49 5.96 12.34 23.25 25.01 15.57 10.54 1.36 4.47
a
Signals associated with less condensed silicon species, Q1 and Q2.
b
Quartz and other Q4 silicon units.

Fig. 8. The relationship between geopolymer Q4(mAl) structural units and a) concentration of Cr leached and b) compressive strength of geopolymers.
222 V. Nikoli
c et al. / Composites Part B 112 (2017) 213e223
as confirmed by the previous study [10]. Thus the compressive
strength of geopolymers also depends on the amount of aluminum
present, i.e. higher geopolymer strength is the consequence of
larger amount of soluble aluminum in the initial FA [10]. Besides the
physical factors, such as the volume and size of pores, the
compressive strength of geopolymers depends also on the struc-
tural factors, such as the fraction of aluminum rich structural units,
i.e. the fraction of Q4(4Al) and Q4(3Al) units in the structure [10,42].
Thus, the reduction of geopolymer compressive strength was also
the consequence of reduced fraction of structural units richer in
aluminum.
The reduction of fraction of structural units richer in aluminum
with the addition of Cr indicated the formation of Si e O e Al bonds
in geopolymers to a lesser extent, i.e. that there were more Si e O e
Si bonds. It is known [43] that Cr3þ ion can replace Al3þ in alumi-
nosilicate network due to the similarity in ionic radius. However,
the results indicated that during the immobilization of Cr by geo-
polymers based on FA, regardless of the FA characteristics and
synthesis conditions, Cr is likely to remain in the hexavalent
(anionic) state, by which this type of substitution is implausible.
Likewise, given that the chromate ion is present in anionic form, it
can not act either as a compensator of negative charge caused by
aluminum in tetrahedral coordination.
The dependence of the concentration of Cr leached from geo-
polymers with 2% Cr added on the ratio of the fraction of Q4 (mAl)
structural units Su ¼ [Q4(3Al) þ Q4(4Al))]/[(Q4(0Al) þ Q4(1Al) þ
Q4(2Al)], geopolymer synthesis conditions and FA characteristics is
given in Fig. 8. It can be seen from Fig. 8a that there was an optimal
value of the fraction (~0.77) at which the concentration of Cr
leached from geopolymers was minimal. On the other hand, geo-
polymer compressive strength reached its maximum at the same
fraction value (Fig. 8b).
4. Conclusion
This paper examined the effectiveness of hexavalent Cr immo-
bilization by fly ash (FA)-based geopolymers depending on FA
characteristics, geopolymer synthesis conditions, and concentra-
tion of Cr added. Cr was added during the geopolymer synthesis in
the form of soluble salt - potassium chromate. The effectiveness of
Cr immobilization was determined by investigation of geopolymer
compressive strength and leaching behavior according to SRPS EN
12457-2 standard [17].
The addition of Cr generally led to decrease in geopolymer
strength, whereby such decrease was more pronounced with the
increase in concentration of Cr added.
Depending on FA characteristics, geopolymer synthesis condi-
tions, and concentration of Cr added, the effectiveness of Cr
immobilization by geopolymers was between 62% and 91%. Geo-
polymer synthesis conditions influenced the effectiveness of Cr
immobilization to a lesser extent compared to the influence of FA
characteristics.
FA reactivity was a key factor determining geopolymer physical-
mechanical and immobilization properties. However, regardless of
the synthesis conditions, concentration of Cr leached in all cases
significantly exceeded the limit value for safe disposal at landfills
[22].
The concentration of Cr leached from geopolymers also
depended on the structural parameters of geopolymers, i.e. the
fraction of Q4(mAl) structural units. There was an optimal ratio of
Q4(mAl) structural units at which geopolymer compressive
strength was maximal and concentration of Cr leached from geo-
polymers was minimal.
Finally, it should be emphasized that mechanical activation of FA
caused an increase in both geopolymer compressive strength and
effectiveness of Cr immobilization.
Acknowledgements
This research was financially supported by the Ministry of Ed-
ucation, Science and Technological Development of the Republic of
Serbia through TR 34026 project. The authors would like to thank
Dr. Bojan Joki

c (Faculty of Applied Arts) for XRD analysis and Dr.
Slavica Lazarevi

c (Faculty of Technology and Metallurgy, University
of Belgrade) for porosity investigations. The valuable advice of
Professor Dr. Miroslav Nikoli
c (Plant and Soil Laboratory, Institute
for Multidisciplinary Research, University of Belgrade) in ICPeOES
technique and the results interpretation is also acknowledged.
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