Accepted Manuscript

Composition and technological properties of geopolymers based on metakaolin

and red mud
W. Hajjaji, S. Andrejkoviov, C. Zanelli, M. Alshaaer, M. Dondi, J.A.
Labrincha, F. Rocha
PII:
DOI:
Reference:

S0261-3069(13)00490-1
http://dx.doi.org/10.1016/j.matdes.2013.05.058
JMAD 5496

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Materials and Design

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18 March 2013
17 May 2013

Please cite this article as: Hajjaji, W., Andrejkoviov, S., Zanelli, C., Alshaaer, M., Dondi, M., Labrincha, J.A.,
Rocha, F., Composition and technological properties of geopolymers based on metakaolin and red mud, Materials
and Design (2013), doi: http://dx.doi.org/10.1016/j.matdes.2013.05.058

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Composition and technological properties of geopolymers based on metakaolin and

red mud

W. Hajjaji1,2*, S. Andrejkovi ov1,C. Zanelli3, M. Alshaaer4, M. Dondi3, J. A.

Labrincha2, F. Rocha1

1.Geobiotec,
2.Materials

Geosciences Dept, University of Aveiro.3810-193 Aveiro. Portugal

and Ceramic Engineering Dept & CICECO. University of Aveiro.3810-193

Aveiro. Portugal

3.Istituto

di Scienza e Tecnologia dei Materiali Ceramici, CNR-ISTEC, 48018 Faenza,

Italy

4.Materials

Research Laboratory, University of Jordan, Amman 11942, Jordan

* Author to whom correspondence should be addressed; phone: +351-234370250; fax: +351234370204; email: w.hajjaji@ua.pt

Abstract
New geopolymer formulations were designed by sodium silicate/NaOH activation of
metakaolin, iron oxide and red mud mixtures. The effects of source materials on the
microstructure and mechanical properties were studied. Each formulation induces
different degree of geopolymerization reaction as reflected by the phase composition
where the amorphous phase is predominant. These vestiges are related to silica provided
by sodium silicate more reactive in the geopolymerization than the silica of metakaolin.
Moreover, the variation in strength between the geopolymers is attributed to the same
factors, with higher porosity and nonreacted phases found in the red mud based
geopolymer matrix. In function of curing time, the mechanical strength increased from
day 1 to 28 for the samples with a low amount of red mud. In these two cases, longer
curing time improves the geopolymerization state resulting in higher compressive load.
The metakaolin and metakaolin/red mud products exhibited comparable water
absorption and density.

Keywords: Geopolymers, metakaolin, red mud, geopolymerization, compressive

strength.

1. Introduction
In the Bayer process for alumina production, five tons of bauxite are washed and treated
to produce two tons of aluminum metal [1]. The world annual production of 21 million
ton of aluminum generates 82 million ton of sludge. This extraction residue, highly
alkaline (pH=10) and known as red mud, is produced in huge amounts, evacuated and
disposed in huge landfills [2,3]. Red mud could cause serious environmental problems:
i) contamination of surface and underground water resources with NaOH and metallic
oxide-bearing impurities [4]; ii) direct contact with fauna and flora; iii) evaporation that
could originate highly alkaline rainfalls [5]; iv) visual impact on extensive areas. Some
accidents, the most recent one in Ajka (Hungary, 2010) [6,7], provoked irrecoverable
damages to the environment.
Many recent studies and semi-industrial trials were directed to the incorporation of the
red mud in construction materials; traditional ceramics [8,9], clinker [10,11], mortar and
concrete [10,12], cements [13], light weight aggregates [14] etc. The present work is
aimed at assessing red mud as raw material for new geopolymer-like compounds that
could be used for construction or restoration purposes [15-17].
For several considerations, the geopolymers appears to be a potential alternative to the
classic hydraulic binders. Nevertheless, their chemical composition is very different
from that of cements or lime. Cements owe their mechanical properties to the formation
of the hydrated calcium silicates (C-S-H) while the exothermic reaction of
geopolymerisation generates a structure closer to zeolites or aluminosilicate gels [18].
This alkaline aluminosilicate material, generally amorphous is mainly produced from
metakaolin (source of Si and Al) reacting with hydroxides or alkaline silicate solutions

[19,20]. The geopolymerization mechanism involves Si and Al dissolution from the

starting materials generates to make available polysialate units (e.g., sialate
[ Si O Al O],

sialate

siloxo[ Si O Al O Si O]

or

sialate

disiloxo

[ Si O Al O Si O], depending on the Si/Al ratio) cross-linked [AlO4] and [SiO4]

tetrahedral units, with charge balance ensured by Na+ or K+ ions [21].
Moreover, geopolymers have the advantage to be possibly formulated from a wide
range of aluminosilicate minerals, as from industrial wastes (e.g. coal fly ash,
metallurgical sludge) [19,22,23]. This diversity in material sources places it as
interesting solution for red mud incorporation.
Because of its high iron content, this geopolymeric cement products are red in color and
look like quality fired clay bricks. There are evidences that iron is incorporated in the
geopolymeric framework in both octahedral (in substitution of Al3+) and tetrahedral
coordination [24,25]. It seems that the molecular structure be composed by a Ferrosialate geopolymeric sequence [-Fe-O-Si-O-Al-O-] were Fe atoms are found in
tetrahedral coordination [26,27,28]. This red mud that can be recycled in generation of
geopolymers and insure a good storage method to this tricky waste, is also an aluminasilica bearing material combining aluminum hydroxides (hydrargillite, boehmite,
diaspore and at lower rates as corundum), free silica (crystalline and principally
amorphous) and various aluminosilicates [26,29]. Moreover, the highly alkaline nature
of red mud presents high expectations about its role as activator [27].

2. Experimental details

Geopolymers were designed by using metakaolin 1200S (MK) (AGS Mineraux, France)
as source of alumino-silicate and red mud, whose chemical composition is reported in
Table 1. In water medium, alkaline activators NaOH (ACS AR Analytical Reagent
Grade Pellets) and hydrated sodium silicate (Merck, Germany; 8.5 wt.% Na2O, 28.5
wt.% SiO2, 63 wt.% H2O) were used to dissolve aluminosilicate and avoid residual
sodium [30]. The target was the following molar oxide ratios: SiO2/Al2O3 = 1,
Na2O/Al2O3 = 1 [19,31]. The water content for all the samples was kept the same with a
molar ratio of H2O/Na2O = 17. The following compositions were prepared: a
geopolymer with metakaolin (named GMK) and others where metakaolin was
substituted by 1/4, 1/6, 1/8, 1/10 and 1/12 of red mud (named GR4, GR6, GR8, GR10
and GR12, respectively). In addition, 1/12 of Fe2O3 (Sigma-Aldrich, as reference) was
introduced to compare the activation power of red mud (sample GFE).
The mixing of the blends was carried out by Heidolph ST-1 Laboratory stirrer at two
different speeds; 100 rpm for 2 min and 200 rpm for 4 min, to insure their homogeneity
and avoid bubbles and agglomeration into the sample. The pastes were immediately
poured into 20x20x20 mm cubic molds and placed in oven at 50C for 24 h and after
left at room temperature for one day. Curing was carried out by keeping the geopolymer
cubic specimens in distilled water from 1 to 28 days. While standard tests usually
perform curing under controlled relative humidity in environmental chamber [32], we
need extreme conditions (sample immersed in water) to be sure that geopolymers are
fully stable and dissolution does not affect the final properties [33,34].

The X-ray diffraction was conducted on a Rigaku Geigerflex D/max Series instrument
(CuK radiation in the 480 2

range, step of 0.02), and phase identification by

X'Pert HighScore Plus. Moreover, to evaluate the phase content, the powders were
characterized by X-ray diffraction (D8 ADVANCE, LynkEye detector-Bruker AXS,
Germany) using CuKa radiation in the 10-80 2 range, scan rate of 0.02 (2 ), and 185
s equivalent per step. The quantitative phase analysis was performed using TOPAS 4.2 BRUKER software following RIR (Reference Intensity Ratio) and Rietveld refinement
techniques. The samples were admixed with 20 wt.% corundum, used as internal
standard. Each X-ray powder diffraction pattern consists approximately of 7000 data
point and 700 reflections; up to 40 independent variables were refined: phase fractions,
zero point, 2530 coefficients of the shifted Chebyschev function to fit the background,
unit cell parameters, profile coefficients (one Gaussian, Gw, and one Lorentzian term,
Lx). The agreement indices, as defined in TOPAS, for the final least-squares cycles of
all refinements are represented by Rp (%), Rwp (%), GOF. For the refined patterns, they
were found in the following ranges: 2.5%<Rp<4.0%, 3.0%<Rwp<5.0% and
1%<GOF<2%. The experimental error is within 5% relative.
The X-Ray Fluorescence (XRF) was conducted using Philips XUNIQUE apparatus.
The WD-XRF spectrometry was performed on glass beads, obtained from a mixture of
66 wt.% lithium tetra-borate and 34 wt.% lithium meta-borate, where 10 wt.% of the
sample was dissolved at high temperature. The bead was then analysed for elemental
composition, according to the calibrated procedure. The experimental error is within 1%
relative.

The microstructural characterization was carried out by scanning electron microscopy

(SEM - Hitachi, SU 70) and energy dispersive X-ray spectrometry (EDS - EDAX with
detector Bruker AXS, software: Quantax) operated at 3-30 kV. The particle size
distribution was determined using a Laser Coulter LS230.
The compressive strength was measured on a Shimazdu apparatus (Model: AG-X/R
Refresh). We determined the open porosity, water absorption and bulk density
according to ASTM: C373 on 3 fragments after mechanical test. The leaching test was
carried out following the EN 12457-2 standard [35,36] with multiple batches used to
determine the leachable proportion of sodium. Geopolymer bodies were crushed and dry
ground (all passing the sieve of dry ground 200 m). The leaching test was performed
by placing 5 g of powder in 100 ml of deionized water. The suspension was stirred for
24h at 10 rpm speed. The leachate concentration was measured (4 repetitions) with
flame atomic absorption spectroscopy (GBC Avanta, SIGMA).

3. Results and discussion

3.1.

Metakaolin and red mud characterization

The XRD patterns of studied metakaolin (MK) and red mud (RM) are reported in Fig. 1.
MK shows a broad reflection centred at 2 =24 attributable to the amorphous
metakaolinite along with residual quartz, illite and anatase (Fig. 2). The SiO2/Al2O3
weight ratio, which should be close to 1.15 in case of metakaolinite, is higher because of
quartz and illite occurrence. The plate-like morphology, characteristic of metakaolinite
particles, is shown in Fig. 2 (particle A: ratio Si/Al

1 by EDS quantification). The

complete dehydroxylation and breakdown of the original kaolinite sheet-structure leads

to the development of this unstable arrangement [37].

The chemical composition of the red mud (RM), (Table 1) is predominantly iron oxide
and hydroxide (the main crystalline phases being hematite and goethite, Fig. 1) and
aluminium hydroxides (gibbsite and boehmite), while sodium is introduced by
lixiviating agent (caustic soda). The red mud contains also titanium mainly in the form
of rutile, which is a common accessory mineral in bauxite deposits [38] along with
some amorphous compound.
The particle size distribution of MK is coarser (mean size around 5 m) than that of RM
one, whose mean size is below to 1 m) (Fig. 3). The ball-milled red mud presents a
bimodal distribution due to heterogeneity in composition of this sludge.

3.2. Geopolymer tests

The Fig. 4 shows the geopolymers containing variable amounts of metakaolin,
commercial iron oxide and red mud.
XRD patterns of GMK, GFE and GR12 geopolymers and the results of phase
quantification are reported in Fig. 5 and Table 2, respectively. The patterns show a
broad reflection related to the high amorphous content, like that observed for
metakaolin. Nevertheless, the centre of this reflection is shifted to 2 =29 [39] due to
changes in composition and structure when metakaolin is activated by NaOH and
NaSiO2 solutions. This amorphous alkaline aluminosilicate is the dominant product,
corresponding to 90 1 wt.% in all samples (Table 2). This suggests that a similar
degree of geopolymerization occurred, even if the broad hump is slightly more
pronounced in the MK geopolymer. Fig. 6 confirms the advanced stage of

geopolymerization in both GMK and GR samples. The reaction with the alkaline
solution to form a particulate gel network, characteristic of metakaolin geopolymers
[39], took place at the border of particles (Fig. 6a) then involving the entire surface (Fig.
6b). This amorphous matrix is mainly composed by Si, Al and Na, but Fe seems to be
incorporated as occurs in iron rich GFE and GR4-12 binders [28]. This hypothesis is
supported by the EDS microanalysis (Table 3) and by the difference between the initial
amount of iron oxide and the hematite and goethite residual phases that is as high as
almost 5 to 8% Fe2O3. By increasing the red mud content, the amount of non-dissolved
fillers in the geopolymer binder increased from 1.5 to 3.3%.
In addition, the presence of quartz and metakaolinite is observed as partially reacted
vestiges (Fig. 6) suggests that silica provided by sodium silicate is more active in the
geopolymerization process than the silica introduced by metakaolinite. According to
Pimraksa et al. [33], the Si/Al ratio significantly affects the degree of polymerization.
In the case in hand, the SiO2/Al2O3 ratio was determined by EDS (A1 and A2 in Table
3) to be as low as 1.9 (so well below 3). This EDS quantification matches a threedimensional sodium silico-aluminate structure [40] combining poly-sialate (SiOAl
O) with a Si/Al ratio of 1. A structure like this one, formed by linked SiO4 and AlO4
tetrahedra sharing all the oxygen atoms, requires a lower ratio, i. e. Si/Na the half in the
case of GR (1.7) if compared to GMK (3.3) due to the supplementary content of Na
introduced by the red mud.
The compressive strength (Fig. 7) gave initial maximum values (at 1 day curing) around
8 MPa. The amount of RM had a variable effect on the mechanical properties of
geopolymer. The resistance of sample GR4, for instance, decreased to minimum values

below 5 MPa. Hence, the lower the SiO2/Al2O3 ratio, the weaker is the strength of
geopolymer. The same mechanical performance was observed in the GFE sample (i.e.,
MK/commercial iron oxide ratio 1/12) that exhibits the lowest compressive strength. In
the red mud based equivalent sample GR12 (MK/red mud ratio 1/12), the occurrence of
iron was compensated by the highly alkaline nature of the sludge. By growing the RM
content, also the Na2O/SiO2 ratio increased and a higher strength was measured for the
1/10, 1/8 and 1/6 ratios. This trend is consistent with previous works, as Duxson et al.
[41] and Stevenson and Sagoe-Crentsil [42], which showed that the compressive
resistance is maximal when the of Na2O/Al2O3 molar ratios are between 1 and 3. Over
and below this window, as it occurs for GR4 and GFE, respectively, the polymerized
network is less stable and easily disintegrated [27]. Moreover, the values of mechanical
strength of GR6-10-12 are close that of GMK and in the case of GR10 at 28 days even
better (10.8 MPa). Along with the rising Na2O content, it is the fine granulometry of
RM to probably play an important role by ensuring the cohesion of the geopolymeric
paste. This observation stresses the importance of physical characteristics in addition to
chemical effects.
After curing, the GMK sample showed slight variations in mechanical behavior (Fig. 7).
This is likely stemming from the stable structure and higher polymerization degree. By
extending the curing time, the mechanical strength increased considerably from day 1 to
day 28 for the samples GR10 and GR12 and in lower degree for GR6 (that appears to be
nearly stable). In cases of GR10 and GR12, longer curing time improves the
geopolymerization state resulting in higher compressive strength.

10

On other hand, the geopolymer GR8 showed a opposing behaviour. This could be
explained by dissolution of non-complexed species (like Na or sulphate ions) and
gradual destabilization of the framework in presence of water before 28 days. This
presumed lower degree of geopolymer reaction should be promoted by non-controlled
stoichiometry when RM is added.
Table 4 shows the water absorption, open porosity, bulk density and apparent specific
weight of geopolymers cured for 1 day. The metakaolin-based geopolymers (with or
without RM) basically present similar behavior with high values of water absorption
(44-48 %) and open porosity, while low bulk density (1.0-1.1 g/cm3) and apparent
specific weight are displayed.
A relationship arose between leaching results (Table 5) and compressive strength
values: samples with leachate concentrations close to 100 ppm exhibit the best
mechanical performances. However, both low (GR4 and GR8) and high (GFE) leachate
concentrations result in low strength, this trend might be related also to variation of
sodium content in initial formulations and consequent destabilization of geopolymer
stoichiometry by incorporation of commercial or sludge iron sources. Due to the high
porosity, sodium forming part of the geopolymer network is easily extractable by
Na+

H+ exchange in aqueous media.

4. Conclusions

New geopolymer formulations were designed by sodium silicate/NaOH activation of

mixtures of metakaolin and red mud, deomonstrating the feasibility of chemicallybonded materials containing up to 25% of red mud. The well-known geopolymer

11

composition (amorphous phase predominant over residual quartz, illite and anatase) is
slightly affected by the red mud, despite it provides aluminum and iron oxides and oxyhydroxide (hematite, goethite, gibbsite and boehmite). These phases, in fact, are to a
limited extent involved in the geopolymerization process and the alkaline
aluminosilicate amorphous phase is about 90 wt.% in all samples. The structural
features of the amorphous geopolymer, as resumed by the broad hump of XRD patterns,
are not modified by addition of RM.

The physical properties of geopolymers are not significantly affected by RM, as all
samples exhibit high values of water absorption and low apparent density. The
Chemical stability is good: sodium leaching test gave leachate concentrations close to
100 ppm without evidences of deterioration of mechanical performance. Red mud
influences the mechanical strength during curing (especially at the higher amounts of
RM but the lower additions (GR10 and GR12), cured for 28 days showed good
compressive strength.
In general, this study strengthens preliminary observations that red mud constitutes a
suitable material for geopolymer production once applied in reasonable ratios with
respect to metakaolin.

Acknowledgements
The work was supported by FCT-Grant SFRH/BPD/72398/2010 co-financed by
Programa Operacional potencial Humano POPH.

12

References
[1] Liu Yong, Lin Chuxia, Wu Yonggui. Characterization of red mud derived from a
combined Bayer Process and bauxite calcination method. J Hazard Mater 2007;
146:255261.
[2] Rai Suchita, Wasewar KL, Mukhopadhyay J, Kyoo Yoo Chang, Uslu Hasan.
Neutralization and utilization of red mud for its better waste management. Arch
Environ Sci 2012;6:13-33.
[3] Power G, Grfe M, Klauber C. Bauxite residue issues: I. Current management,
disposal and storage practices. Hydrometallurgy 2011;108:33-45.
[4] Ramesh Chandra Sahu, Rajkishore Patel, Bankim Chandra Ray. Neutralization
of red mud using CO2 sequestration cycle. J Hazard Mater 2010;179:2834.
[5] Tamotia SK. Management of Red Mud. In: International Symposium on
Processing of fines - Vol.2. NML Jamshedpur. Jamshedpur, 2000, 430-434.
[6] Burke IT, Mayes WM, Peacock CL, Brown AP, Jarvis AP, Gruiz K. Speciation
of arsenic, chromium and vanadium in red mud samples from the Ajka spill site,
Hungary. Environ Sci Technol 2012;46:3085-3092.
[7] Renforth P, Mayes WM, Jarvis AP, Burke IT, Manning DAC, Gruiz K.
Contaminant mobility and carbon sequestration downstream of the Ajka
(Hungary) red mud spill: The effects of gypsum dosing. Sci Total Environ
2012;421422:253-259.
[8] Amritphale SS, Patel M. Utilisation of red mud, fly ash for manufacturing bricks
with pyrophyllite. Silic Ind 1987;2:31-35.

13

[9] VincenzoMS, Renz C, Stefano M, Giovanni C. Bauxite red mud in the ceramic
industry. Part 2: production of clay based ceramics. J Eur Ceram Soc
2000;20:245252.
[10]

Senff L, Hotza D, Labrincha JA. Effect of red mud addition on the

rheological behaviour and on hardened state characteristics of cement mortars.

Constr Build Mater 2011;25:163-170.
[11]

Senff L, Castela A, Hajjaji W, Hotza D, Labrincha JA. Formulations of

sulfobelite cement through design of experiments. Constr Build Mater

2011;25:3410-3416.
[12]

Ribeiro DV, Labrincha JA, Morelli MR. Effect of the addition of red

mud on the corrosion parameters of reinforced concrete. Cement Concrete Res

2012;42:124133.
[13]

Singh Maneesh, Upadhayay SN, Prasad PM. Preparation of special

cements from red mud. Waste Management 1996;16:665-670.

[14]

Oh JS, Chang PK, Lim YM. A study on the fabrication of lightweight

aggregates using red mud, the by-product from Al2O3 industry. J Korea Solid
Wastes Eng Soc 1998;15:16-23.
[15]

Fabbri B, Gualtieri S. Geopolymers: compatible materials for the

restoration and conservation of natural and artificial stone materials. Proceedings

4th international congress on science and technology for safeguard of cultural
heritage in the Mediterranean basin, Cairo, Egypt, 2009.
[16]

Teixeira Pinto A, Fernandes P, Jalali S. Geopolymer Manufacture and

Application - Main problems When Using Concrete Technology. Geopolymers

International Conference, Melbourne, Australia, Siloxo Pty. Ltd., 2002.

14

[17]

Hanzl ek T, Steinerov M, Straka P, Pern I, Siegl P, varcov T.

Reinforcement of the terracotta sculpture by geopolymer composite. Mater Des

2009;30:32293234.
[18]

Khale D, Chaudhary R. Mechanism of geopolymerization and factors

inuencing its development: a review. J Mater Sci 2007;42:729-746.

[19]

Duxson P, Fernandez-Jimenez A, Provis JL, Lukey GC, Palomo A, Van

Deventer JSJ. Geopolymer technology: the current state of the art. J Mater Sci
2007;42:2917-2933.
[20]

Wang Jing, Zhang Chi, Xu Jing, Qu Peng, Zhou Ye, Min Han Hui. The

Effect of Alkali on Compressive of Metakaolin Based Geopolymeric Cement.

Adv Mater Res 2012;554-556:327-330.
[21]

Giannopoulou I, Pania D. Structure, Design and Applications of

Geopolymeric Materials. 3rd International Conference on Deformation

Processing and Structure of Materials, Belgrade, Serbia, 2007.
[22]

Maragkos I, Giannopoulou IP, Panias D. Synthesis of ferronickel slag-

based geopolymers. Miner Eng 2009;22:196-203.

[23]

Palomo A, Grutzeck MW, Blanco MT. Alkali-activated flyashes. A.

cement for the future. Cement Concrete Res 1999;29:13231329.

[24]

Perera DS, Cashion JD, Blackford MG, Zhang Z, Vance ER. Fe

speciation in geopolymers with Si/Al molar ratio of 2. J Eur Ceram Soc

2007;27:2697-2703.
[25]

Bell JL, Kriven WM. Formation of an Iron-Based Geopolymer

Analogue. Cer Eng and Sci Proceedings 30 Mechanical Properties and

15

Performance of Engineering Ceramics and Composites IV. Edited by Dileep

Singh and Waltraud M. Kriven. Ceram Eng Sci Proc 2009;30:301-312.
[26]

Zhang G, He J, Gambrell RP. Synthesis, Characterization, and

Mechanical Properties of Red Mud-Based Geopolymers. Transport Res Rec

2010;2167;1-9.
[27]

He Jian, Zhang Jianhong, Yu Yuzhen, Zhang Guoping. The strength and

microstructure of two geopolymers derived from metakaolin and red mud-fly

ash admixture: A comparative study. Constr Build Mater 2012;30:80-91.
[28]

Davidovits J. Patent WO/2012/056125, Geopolymer cement of the

calcium ferro-aluminosilicate polymer type and production process, Geneva,

2012.
[29]

Dimas DD, Giannopoulou IP, Panias D. Utilization of alumina red mud

for synthesis of inorganic polymeric materials. Miner Process Extr M

2009;30:211-239.
[30]

Barbosa VFF, Mackenzie KJD. Thermal behaviour of inorganic

geopolymers and composites derived from sodium polysialate. Mater Res Bull
2003;38:319-331.
[31]

De Silva P, Sagoe-Crenstil K. Medium-term phase stability of Na2O-

Al2O3-SiO2-H2O geopolymer systems. Cement Concrete Res 2008;38:870-876.

[32]

Somna Kiatsuda, Jaturapitakkul Chai, Kajitvichyanukul Puangrat,

Chindaprasirt Prinya. NaOH-activated ground fly ash geopolymer cured at

ambient temperature. Fuel 2011;90:2118-2124.

16

[33]

Pimraksa K, Chindaprasirt P, Rungchet A, Sagoe-Crentsil K, Sato T.

Lightweight geopolymer made of highly porous siliceous materials with various

Na2O/Al2O3 and SiO2/Al2O3 ratios. Mater Sci Eng A 2011;528:6616 6623.
[34]

Silva I, Castro-Gomes J, Albuquerque A. Evaluation of the stability of

waste-based geopolymeric artificial aggregates for wastewater treatment

processes under different curing conditions. Adv Sci Tech 2010;69:86-91.
[35]

Izquierdo M, Querol X, Davidovits J, Antenucci D, Nugteren H,

Fernndez-Pereira C. Coal fly ash-slag-based geopolymers: Microstructure and

metal leaching. J Hazard Mater 2009;166:561-566.
[36]

EN 12457, Characterization of waste Leaching Compliance test for

leaching of granular waste materials and sludges, parts 14, CEN, Brussel, 1999.
[37]

Konan KL, Peyratout C, Smith A, Bonnet J-P, Rossignol S, Oyetola S.

Comparison of surface properties between kaolin and metakaolin in concentrated

lime solutions. J Colloid Interf Sci 2009;339:103-109.
[38]

Alien VT. Petrographic relations in some typical bauxite and diaspore

deposits. Bull Geol Soc Amer 1952;63:649-88.

[39]

Zhang Zuhua, Wang Hao, Provis JL, Bullen F, Reid A, Zhu Yingcan.

Quantitative kinetic and structural analysis of geopolymers. Part 1. The

activation

of

metakaolin

with

sodium

hydroxide.

Thermochim

Acta

2012;539:23-33.
[40]

Xu H, Van Deventer JSJ. The geopolymerisation of alumino-silicate

minerals. Int J Miner Process 2000;59:24766.

[41]

Duxson P, Provis JL, Lukey GC, Mallicoat SW, Kriven WM, van

Deventer JSJ. Understanding the relationship between geopolymer composition,

17

microstructure and mechanical properties. Colloid Surf A Physicochem Eng

Asp 2005;269:4758.
[42]

Steveson M, Sagoe-Crentsil K. Relationships between composition,

structure and strength of inorganic polymers Part 2: Flyash-derived inorganic

polymers. J Mater Sci 2005;40:424759.

18

Table captions:
Table 1. Chemical compositions of metakaolin (MK) and red mud (RM).
Table 2. Phase composition of geopolymers (averagestandard deviation).
Table 3. Microchemical analysis of GMK and GR4 samples (see Fig. 6 for spots).
Table 4. Water absorption, open porosity and bulk density of geopolymers.
Table 5. Sodium leaching from samples.

Figure captions:
Fig. 1. XRD patterns of metakaolin (MK) and red mud (RM).
Fig. 2. SEM micrograph (ticks span 8.57 m) and chemical composition (by EDS) at
spots A and B of metakaolin MK.
Fig. 3. Particle size distribution of metakaolin (MK) and red mud (RM).
Fig. 4. Geopolymer cubic specimens (20mm side); from left to right: metakaolin-based
(GMK), with iron oxide (GFE), and mixtures with red mud (GR4, GR6, GR8, GR10
and GR12).
Fig. 5. (a) Plot of Rietveld refinement performed on X-ray powder diffraction data. The
experimental data are indicated by plus signs, the calculated pattern is the continuous
line and the lower curve is the weighted difference between the calculated and observed
patterns. The rows of vertical tick marks shows the allowed reflections for the
crystalline phases present in the sample: 1) Illite, 2) Anatase 3) Corundum (added 20
wt.% as internal Standard 4) Quartz. (b) Comparison of geopolymers based on
metakaolin (GMK) and containing iron-oxide (GFE) or red mud (GR12).
Fig. 6. SEM micrographs of GMK (a) and GR (b) geopolymers.
Fig. 7. Compressive strength of geopolymers at different curing times (1 and 28 days).

Table 1
Oxides (wt.%)

MK

RM

SiO2
TiO2
Al2O3
Fe2O3
MgO
CaO
MnO
Na2O
K 2O
SO3
L.O.I.

54.4
1.55
39.4
1.75
0.14
0.10
0.01
1.03
2.66

5.54
0.23
18.8
51.8
3.27
0.04
6.84
0.08
11.2
1.90

Table 2
% weight
Amorphous phase

GMK

GFE

GR12

GR10

GR8

GR6

GR4

91.5 0.2 91.0 0.5 91.7 0.5 90.9 0.5 89.2 0.6 91.6 0.5 91.4 0.4

Illite

5.6 0.1 4.6 0.2 3.7 0.2 4.2 0.2 6.2 0.3 2.1 0.1 2.5 0.1

Quartz

2.3 0.1 2.4 0.2 2.6 0.2 2.5 0.1 2.3 0.1 3.1 0.2 2.4 0.1

Hematite

absent

1.8 0.1 0.7 0.1 0.9 0.1 1.1 0.1 1.3 0.1 1.5 0.1

Goethite

absent

absent

Anatase

0.6 0.1 0.2 0.1 0.3 0.1 0.2 0.1 0.2 0.1 0.7 0.1 0.4 0.1

1.0 0.1 1.3 0.1 1.0 0.1 1.2 0.1 1.8 0.1

Table 3

Spectrum 1

A1

Spectrum 2

A2

Na
Al
Si
Fe
O

6.2
10.3
21.9
1.6
60

6.1
13.2
19.9
0.4
60.4

8.6
7.9
22.3
0.4
60.8

10.4
11.2
18.2
1
59.2

Na2O
Al2O3
SiO2
Fe2O3

9.1
24.6
64.8
1.5

9.0
32.2
57.3
1.5

13.0
19.7
65.7
1.6

15.6
27.7
53.0
3.6

Si/Al
Si/Na

2.1
3.5

1.5
3.3

2.8
2.6

1.6
1.7

SiO2/Al2O3
SiO2/Na2O

2.6
7.1

1.8
6.4

3.3
5.1

1.9
3.4

Table 4

GMK

GFE

GR12

GR10

GR4

Water absorption (% wt.)

47.2 0.5

44.0 0.5

48.9 0.5

44.3 0.5

44.5 0.5

Open porosity (% vol.)

49.5 0.5

48.2 0.5

50.6 0.5

48.2 0.5

49.3 0.5

Bulk density (g cm-3)

1.05 0.03

1.09 0.03

1.03 0.03

1.09 0.03

1.11 0.03

Apparent specific weight (1)

2.08 0.05

2.11 0.05

2.09 0.05

2.09 0.05

2.19 0.05

Table 5
Samples

Leaching of Na (ppm)

GMK

102

GFE

132

GR12

114

GR10

98

GR8

66

GR6

95

GR4

70

Fig. 1

Fig. 2.

Fig. 3

10

Fig. 4

11

(a)

(b)

Fig. 5

12

Fig. 6

13

Fig. 7

14

Highlights
New geopolymer formulations were designed by mixtures of metakaolin and red
mud.

Water absorption and apparent density are not affected by RM addition.

Na leaching values show that the chemical stability of the geopolymers is good.

RM based geopolymers exhibited good compressive strength after 28 days of curing.

RM constitutes a suitable material once applied in reasonable ratios in geopolymer.

15