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Mechanical Properties of Geopolymers with Iron Rich Precursors

Conference Paper · July 2011

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 Mechanical Properties of Geopolymers with Iron Rich Precursors

1
Gomes KC
1
DSER/CCA- Federal University of Paraiba, Brazil
2
Torres SM*
2
DEMAT/CT- Federal University of Paraiba, Brazil
2
De Barros S; 3 Vasconcelos IF; 4Barbosa NP
2
DEMAT/CT- Federal University of Paraiba, Brazil
3
DEMM/CT- Federal University of Ceara, Brazil
4
DECA/CT- Federal University of Paraiba, Brazil

* sandromardentorres@yahoo.co.uk

Abstract
Alcaline activation of alumino-silicate materials have attracted significant attention of the scientific community. This is
chiefly due to properties such as good thermal stability and high resistance to aggressive environments. Most studies on
this subject are based on traditional precursor materials such as calcined kaolinite clay (metakaolinite) and fly ash. In
the tropical regions of the earth, there are other aluminosilicate containing materials, such as red tropical soils (RTS).
In this type of soil, alongside with the presence of other alumino silicate phases such as kaolinite, the levels of iron
(Fe2O3) are as high as 60%. Their alkaline activation potential is, still, needed of systematic evaluation. The aim of this
work is to evaluate the potential of RTS as a precursor for the development of geopolymers. The mechanical properties
and the structural characteristics of the samples were evaluated by means of compressive strength and x-ray
diffraction, x-ray fluorescence, infrared and Mössbauer spectroscopy. Even with very high levels of iron, RTS presented
a potential for use in the synthesis of geopolymer. The compressive strength of the samples ranged from 20 to 80 MPa.
Considerations will be given on the distribution of iron within the structure of the activated material.

Originality
There is a need for systematic studies in order to explore the potential use of sources of geopolymer precursor other
than the traditional metakaolinite and fly-ash. Given the nature of precursor materials, it is important to evaluate the
distribution of iron in the structure and mechanisms of geopolymer synthesis. This brings an academic challenge with
implications for the scientific community, considering that the vast majority of published material addresses aspects
related to the latter precursors. As Fe (II, III) and Al(III) are interchangeable in some minerals such as goethite
(FeOOH), bohemita (AlOOH) and hematite (Fe2O3). The presence of large amounts of iron in geopolymers results in
NMR data that are less useful to characterize geopolymer structure. This explains why iron is not often discussed in
geopolymer related articles. This is given to the fact that the ferromagnetic nature of iron may compromise data
analysis. In this sense, this work proposes to use 57Fe Mössbauer Spectroscopy as an alternative technique that favors
analyses where NMR fails to provide accurate data. This is because it is based on resonant excitation of nuclear energy
levels which are sensitive to iron local coordination and electronic structure.

Chief contributions
To increase the knowledge for the development of geopolymeric materials from a variety of industrial and natural
precursors.
To contribute towards sustainable engineering solutions once geopolymers contribute less to green gas emissions as
well as incorporates value to industrial waste immobilizations.
Iron is often present in several industrial waste and minerals. As far as structural characteristic of geopolymers are
concerned, it also contributes for understanding of the role of iron in the geopolymer matrixes.
To increase the range of raw useful materials as precursors for alkaline activation.

Keywords: Alcaline activation, tropical soils, Iron, Mössbauer

1. Introduction

Geopolymers are inorganic polymers, constituted of alternating SiO4 and AlO4 tetrahedra chains, connected by a
shared oxygen atom and balanced by cations (Davidovits, 1987; Palomo and De La Fuente, 2003; Palomo and
Glasser, 1992; Palomo et al, 1999). Some precursor materials used to produce geopolymers contain great
amounts of iron. Although the presence of iron might play important roles in the structure and properties of
geopolymers, substitutions of Al by Fe was not yet fully studied even it may occur in clays Bland and Roll,
1998; Gomes eta al, 2008, Gomes et al, 2009). For instance, fly ash, with iron content of about 10%, stands out
among these commonly used iron-rich precursor materials and up to 40% for some low-calcium ferronickel slag
materials (Komnitsas and Zaharaki, 2009).
However, the presence of large amounts of iron in geopolymers results in NMR data that are less useful to
characterize geopolymer structure. This is given to the fact that the ferromagnetic nature of iron may
compromise data analysis. In this sense, 57Fe Mössbauer Spectroscopy is an alternative technique that favours
analyses where NMR fails to provide accurate data (Provis and Rees, 2009), because it is based on resonant
excitation of nuclear energy levels which are sensitive to iron local coordination and electronic structure.
Studies on geopolymers are mostly based on traditional precursor materials like metakaolinte (Fe2O3 content of
2%), fly ash (Fe2O3 content of 10%) and blast furnace slag (Fe2O3 content of 0.5%). Nevertheless, recent studies
have shown that precursors with iron content higher than the usually found in fly ashes may be activated in
alkaline environment (Gomes et al, 2008; Gomes et al, 2009; Komnitsas and Zaharaki, 2009) with applications
in engineering. This work aims to investigate the implications of the presence of iron in the geopolymeric
structure.

2. Experimental

2.1 Materials

The raw precursor materials were Metakaolin (MK), as reference, Red Tropical Soils in natura (RTS-
SL1) and calcined (RTS-SL2), Laterite concretion in natura (RTS-SL3) and calcined (RTS-SL4).
Sodium silicate with SiO2/Na2O ratio = 2.17 was the alkaline activator used.The chemical
composition of the precursor material is presented in Table 01. Molar ratios and curing regimes for
the synthesized geopolymers are shown in Table 02. The precursor materials and corresponding
synthesized geopolymers (GP-MK, GP-SL1, GP-SL2, GP-SL3, GP-SL4) were ground and sieved
through a 45 µm sieve. The H/M varied between 9.5 and 9.8 and M/S varied between 0.11and 0.19.
The samples were cured for 24 hours at 55oC and at 20oC for 48 hours and 168 hours.

Table 1: Chemical composition of geopolymeric precursors

Oxide Content of the Precursor Materials Alcaline

Activation

SiO2 Al2O3 Fe2O3 K 2O Na2O CaO TiO2 S/(A+F)

MK 64.80 29.74 1.72 3.23 0.01 0.12 0.08 6.19

RTS-SL1 47.19 15.98 29.66 0.55 0.01 0.68 4.32 4.04

RTS-SL2 51.38 18.22 23.95 0.38 0.25 0.64 3.77 4.25

RTS-SL3 35.58 6.09 56.67 0.03 0.19 0.06 0.81 1.96

RTS-SL4 32.80 5.82 60.02 0.04 0.02 0.06 0.79 1.70

2.2 Methods

The samples were characterized by powder x-ray diffraction (XRD), multiple internal reflection
Fourier transform infrared spectroscopy (MIR-FTIR), Mössbauer spectroscopy (ME) and identified
using SEM-EDS analysis. XRD measurements were performed with a Siemens D5000. Mössbauer
spectra were measured in standard transmission geometry using a constant acceleration spectrometer
with a radioactive source of 57Co in Rh matrix at 298K. The spectra were evaluated using the fitting
software Normos. All isomer shift values quoted are relative to metallic iron (α-Fe). For microscopic
analysis we used a microscope Electronic LEO1430 with tungsten filament and coupled with a device
for EDS (Energy Dispersive Spectroscopy).

3. Results and Discussion

3.1 X-Ray Diffraction

The Figure 1 and 2 show diffraction patterns obtained from the geopolymeric precursors (in natura
and calcined) and from corresponding synthesized geopolymers.
The crystalline phases present in the in natura precursor are kaolinite, quartz, goethite and hematite.
Quartz and hematite are the only phases present in the calcined precursor and respective geopolymer,
evidencing the kaolinite-to-metakaolin and goethite-to-hematite transformation (Fig. 1).
Patterns for the samples geopolymeric precursor and geopolymers suggest the occurrence of kaolinite
amorphization as seen by the halo between 10o (2 and 20o (2 with the disappearance of the
kaolinite peak (Fig. 2). The only iron bearing phases present are hematite and goethite.

Figure 1. XRD pattern for geopolymeric precursors in natura (SL, SL3) and calcined (MK, SL2, SL4 ): (Q)
Quartz, (K) Kaolinite, (G) Goethite, (H) Hematite; (R) Internal Standard Rutile
 Figure 2. XRD pattern for respective geopolymers: (Q) Quartz, (G) Goethite, (H) Hematite; (R) Internal
Standard Rutile

Diffraction patterns for samples GP-SL2, GP-SL3 and GP-SL4 do not show the presence of kaolinite,
and the halo between 10o (2 and 20 o (2 was also present. In these samples, hematite and goethite
are the only iron-bearing phase, as both kaolinite and goethite undergo amorphisation with the
calcination process.

3.2 Mössbauer Spectroscopy

Figures 5 shows the Mössbauer spectra obtained from precursors (SL3 and SL4) and synthesized
geopolymers (SL3 and SL4) and Table 04 shows the fitting results.

Figure 5: Mössbauer spectra: a) unreacted in natura geopolymeric precursor (SL3), b) geopolymer synthesised
from the in natura precursor (GP-SL3).

Table 4: Hyperfine Parameters obtained fron fitting on Mössbauer spectra.

 Sextet 01 Sextet 02 Dublet
IS QS BHT RA IS QS BHT RA IS QS LW RA
(mm/s) (mm/s) (T) (%) (mm/s) (mm/s) (T) (%) (mm/s) (mm/s) (mm/s) (%)

SL3 0.37 -0.21 51.2 66 0.33 -0.30 33.9 30 0.38 0.61 0.39 4

GP-SL3 0.37 -0.20 51.2 66 0.22 -0.49 33.7 26 0.32 0.59 0.59 7

SL4 0.37 -0.21 51.3 100

GP-SL4 0.37 -0.21 51.5 100

The spectra for samples SL3 and GP-SL3 (top left and right, respectively) shows the presence of at
least three different iron sites. The Analysis of hyperfine parameters obtained from the fitting curves
and listed in Table 04 allows the association of the magnetic subspectra to hematite (sextet 1, red)
(Van Der Marel, 1976) and also to goethite (sextet 2, blue) (Dorman et al, 1991; Broz et al, 1990;
Murad and Schwertmann, 1983). In addition, the hyperfine parameters of the doublet (green line) are
consistent with structural octahedral Fe+3 in alumina-silicate structure such as in kaolinite (Castelein et
al, 2002).
As can be seen in Table 4, a slight increase from 4 to 7% the doublet's spectral area due to the alkaline
activation of the un-reacted precursor in natura. This observation might indicate an increase of the
iron in octahedral sites of alumina-silicate structure as a result of the alkaline activation, corresponded
to an increased amount of iron-doped kaolinte within the geopolymer structure. The Mössbauer
spectra for samples SL4 and GP-SL4 (bottom left and right, respectively) show that sole presence of
hematite without measurable amounts of goethite. This confirms XRD results which indicate that
hematite is the only iron-bearing phase present in these samples.

3.3 SEM-EDS analysis

Figure 7 shows the BEI micrograph and EDS analysis obtained for the geopolymer precursor (SL3).
 Figure 7: Backscattered Electron Image and EDS analysis

It can be observed that the significant presence of iron in the raw material is distributed in basically
two zones: (zone 1 and 2) together with aluminium and silicon containing phases, possibly alumina-
silicate structure of kaolinite or within goethite as well as clusters of hematatite (zone 4).

3.4 Mechanical Properties

Figure 8 shows the compression strength of geopolymers. It is observed that these resistances are
related to the type of precursor used. It can be observed that the greatest resistance were obtained was
for SL3 and MK (reference). As for the SL1, SL2 and SL4 had resistances around 30MPa. It is
observed that the raw material precursors with high contents of iron and have been activated alkaline
products produced with resistance to compression around 20 to 80 MPa.

Figure 8: Compressive strength of geopolymers

4. Conclusions

There is evidence that the red residual soils have potential for use in the synthesis of geopolymer
cement matrix, despite its very low content of alumina.

The compressive strength of the iron rich alkaline activated products ranged from 20 to 80 MPa. The
distribution of iron in geopolymers made with iron-rich precursors has been investigated. There has
been indication of Fe-O bond within the geopolymer matrixes. Iron (Fe+3) occupancies were primarily
octahedral in all mixes. The Mössbauer spectra analyses indicate that the structure of Fe +3 was
associated to the crystalline phases: hematite and goethite. Also, for the uncalcined system, the
hyperfine parameters associated to the doublet suggest the presence of structural Fe +3 within an
alumina-silicate structure. This observation suggests a replacement of Al +3 by Fe+3 in octahedral sites
most likely within the kaolinite phase.

References

- J. Davidovits: Concrete International Vol. 9 (1987), p. 23.

- A. Palomo, J.I.L. De La Fuente: Cement and Concrete Research Vol. 33 (2003), p. 281.
- A. Palomo, F.P. Glasser: British Ceramic Transactions and Journal Vol. 91 (1992), p.107.
- A. Palomo, M.W. Grutzeck, M.T. Blanco: Cement and Concrete Research Vol. 29 (1999), p. 1323.
- W. Bland, D. Roll: Weathering: A introduction of the scientific principles (Arnolds, London 1998).
- K.C Gomes, S.M Torres, S. de Barros, N.P. Barbosa: ETDCM8- 8th Seminar on Experimental Techniques and
Design in Composite Materials (2008).
 - K. C. Gomes, S.M. Torres, S. de Barros, S and N.P. Barbosa, in: Solid Mechanics in Brazil 09 edited by H.
S. C. Mattos, M. Alves, Associação Brasileira de Engenharia e Ciências Mecânicas Vol. 2 (2009)
- K. Komnitsas, D. Zaharaki, in: Structure, processing, properties and industrial applications PART II:
Manufacture and properties of geopolymers, edited by J. Provis and Jannie S.J. van Deventer, CRC Press,
Woodhead Publishing Ltd, Oxford (2009) p. 343.
- J.L. Provis, C.A Rees, in: Structure, processing, properties and industrial applications PART I: Geopolyemer
systhesis kinetics, in Geopolymer synthesis and characterization, edited by J. Provis and Jannie S.J. van
Deventer, Woodhead Publishing Ltd, Oxford (2009) pp. 118.
- H. Van Der Marel: Atlas of infrared spectroscopy of clay minerals and their admixtures (Elsevier,
Amsterdam 1976).
- P. Larese-Casanova, M.M Scherer: Hyperfine Interact Vol. 174 (2007), p.111.
- S.C. Dorman, L.H. Bowen, S.B. Weed: Journal of Magnetism and Magnetic Materials Vol. 98 (1991), p. 28.
- D. Broz, J. Strakova, J. Subrt et al: Hyperfine Interactions Vol. 54 (1990), p. 479.
- E. Murad, U. Schwertmann: Clay Minerals Vol. 18 (1983), p. 301.
- O. Castelein, L. Aldon, J. Olivier-Fourcade et al: Journal of The European Ceramic Society
Vol. 22 (2002) 11, p. 176.

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