Accepted Manuscript

Composition and technological properties of geopolymers based on metakaolin
and red mud
W. Hajjaji, S. Andrejkovičová, 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., Andrejkovičová, 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 ová1,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.

2

The world annual production of 21 million ton of aluminum generates 82 million ton of sludge.11]. This extraction residue. ii) direct contact with fauna and flora. highly alkaline (pH=10) and known as red mud. iv) visual impact on extensive areas. For several considerations. generally amorphous is mainly produced from metakaolin (source of Si and Al) reacting with hydroxides or alkaline silicate solutions 3 . Nevertheless. 2010) [6. iii) evaporation that could originate highly alkaline rainfalls [5]. Some accidents. 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]. evacuated and disposed in huge landfills [2.12]. five tons of bauxite are washed and treated to produce two tons of aluminum metal [1]. the most recent one in Ajka (Hungary. This alkaline aluminosilicate material. provoked irrecoverable damages to the environment. light weight aggregates [14] etc.3]. Introduction In the Bayer process for alumina production. 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].1. Many recent studies and semi-industrial trials were directed to the incorporation of the red mud in construction materials. mortar and concrete [10. their chemical composition is very different from that of cements or lime. traditional ceramics [8.7]. clinker [10. the geopolymers appears to be a potential alternative to the classic hydraulic binders. cements [13]. is produced in huge amounts. Red mud could cause serious environmental problems: i) contamination of surface and underground water resources with NaOH and metallic oxide-bearing impurities [4].9].

g. this geopolymeric cement products are red in color and look like quality fired clay bricks. geopolymers have the advantage to be possibly formulated from a wide range of aluminosilicate minerals. This red mud that can be recycled in generation of geopolymers and insure a good storage method to this tricky waste.20].25].g. metallurgical sludge) [19.28].23]. the highly alkaline nature of red mud presents high expectations about its role as activator [27]. This diversity in material sources places it as interesting solution for red mud incorporation.27. boehmite. Because of its high iron content.. depending on the Si/Al ratio) cross-linked [AlO4] and [SiO4] tetrahedral units. 4 . diaspore and at lower rates as corundum). sialate [ Si O Al O]. is also an aluminasilica bearing material combining aluminum hydroxides (hydrargillite.[19. The geopolymerization mechanism involves Si and Al dissolution from the starting materials generates to make available polysialate units (e. as from industrial wastes (e.29]. 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. Moreover.22. sialate siloxo[ Si O Al O Si O] or sialate disiloxo [ Si O Al O Si O]. with charge balance ensured by Na+ or K+ ions [21]. free silica (crystalline and principally amorphous) and various aluminosilicates [26. Moreover. coal fly ash. There are evidences that iron is incorporated in the geopolymeric framework in both octahedral (in substitution of Al3+) and tetrahedral coordination [24.

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. Germany.5 wt. 100 rpm for 2 min and 200 rpm for 4 min. 28. The following compositions were prepared: a geopolymer with metakaolin (named GMK) and others where metakaolin was substituted by 1/4. to insure their homogeneity and avoid bubbles and agglomeration into the sample.% Na2O.% SiO2.% H2O) were used to dissolve aluminosilicate and avoid residual sodium [30]. respectively). GR8. The mixing of the blends was carried out by Heidolph ST-1 Laboratory stirrer at two different speeds. While standard tests usually perform curing under controlled relative humidity in environmental chamber [32]. GR10 and GR12.5 wt.34]. as reference) was introduced to compare the activation power of red mud (sample GFE). 8. Na2O/Al2O3 = 1 [19. 63 wt. The water content for all the samples was kept the same with a molar ratio of H2O/Na2O = 17. 1/10 and 1/12 of red mud (named GR4. 1/12 of Fe2O3 (Sigma-Aldrich. France) as source of alumino-silicate and red mud. The target was the following molar oxide ratios: SiO2/Al2O3 = 1.31]. In water medium. 1/6. 1/8. In addition. Curing was carried out by keeping the geopolymer cubic specimens in distilled water from 1 to 28 days. whose chemical composition is reported in Table 1. 5 . GR6. The pastes were immediately poured into 20x20x20 mm cubic molds and placed in oven at 50°C for 24 h and after left at room temperature for one day. alkaline activators NaOH (ACS AR Analytical Reagent Grade Pellets) and hydrated sodium silicate (Merck.2. Experimental details Geopolymers were designed by using metakaolin 1200S (MK) (AGS Mineraux.

for the final least-squares cycles of all refinements are represented by Rp (%).% lithium tetra-borate and 34 wt. The quantitative phase analysis was performed using TOPAS 4. Each X-ray powder diffraction pattern consists approximately of 7000 data point and 700 reflections. Moreover. The samples were admixed with 20 wt. LynkEye detector-Bruker AXS. according to the calibrated procedure. and phase identification by X'Pert HighScore Plus.2 BRUKER software following RIR (Reference Intensity Ratio) and Rietveld refinement techniques. 6 . step of 0. obtained from a mixture of 66 wt.% of the sample was dissolved at high temperature. Gw. and 185 s equivalent per step.0% and 1%<GOF<2%. scan rate of 0. The bead was then analysed for elemental composition. where 10 wt. Germany) using CuKa radiation in the 10-80º 2 range. The experimental error is within 5% relative.0%. The agreement indices. The experimental error is within 1% relative. and one Lorentzian term. to evaluate the phase content.02º (2 ). the powders were characterized by X-ray diffraction (D8 ADVANCE. they were found in the following ranges: 2.The X-ray diffraction was conducted on a Rigaku Geigerflex D/max – Series instrument (CuK radiation in the 4–80º 2 range. 25–30 coefficients of the shifted Chebyschev function to fit the background. Rwp (%).% corundum.% lithium meta-borate. zero point. profile coefficients (one Gaussian. as defined in TOPAS.5%<Rp<4. For the refined patterns. up to 40 independent variables were refined: phase fractions. 3.0%<Rwp<5. The WD-XRF spectrometry was performed on glass beads.02º). unit cell parameters. The X-Ray Fluorescence (XRF) was conducted using Philips X’UNIQUE apparatus. GOF. used as internal standard. Lx).

The leachate concentration was measured (4 repetitions) with flame atomic absorption spectroscopy (GBC Avanta. The leaching test was performed by placing 5 g of powder in 100 ml of deionized water. 1. 2). software: Quantax) operated at 3-30 kV. The leaching test was carried out following the EN 12457-2 standard [35. 2 (particle A: ratio Si/Al 1 by EDS quantification). which should be close to 1.EDAX with detector Bruker AXS. The compressive strength was measured on a Shimazdu apparatus (Model: AG-X/R Refresh). characteristic of metakaolinite particles. SIGMA). SU 70) and energy dispersive X-ray spectrometry (EDS . Geopolymer bodies were crushed and dry ground (all passing the sieve of dry ground 200 µm). The suspension was stirred for 24h at 10 rpm speed. water absorption and bulk density according to ASTM: C373 on 3 fragments after mechanical test. MK shows a broad reflection centred at 2 =24º attributable to the amorphous metakaolinite along with residual quartz. The particle size distribution was determined using a Laser Coulter LS230. illite and anatase (Fig. is shown in Fig.Hitachi.15 in case of metakaolinite. The SiO2/Al2O3 weight ratio. 3. We determined the open porosity. is higher because of quartz and illite occurrence.36] with multiple batches used to determine the leachable proportion of sodium. The complete dehydroxylation and breakdown of the original kaolinite sheet-structure leads to the development of this unstable arrangement [37].The microstructural characterization was carried out by scanning electron microscopy (SEM .1. The plate-like morphology. Results and discussion 3. Metakaolin and red mud characterization The XRD patterns of studied metakaolin (MK) and red mud (RM) are reported in Fig. 7 .

The red mud contains also titanium mainly in the form of rutile. 6 confirms the advanced stage of 8 . The patterns show a broad reflection related to the high amorphous content. corresponding to 90 ± 1 wt.The chemical composition of the red mud (RM). Fig. 3. commercial iron oxide and red mud. the centre of this reflection is shifted to 2 =29º [39] due to changes in composition and structure when metakaolin is activated by NaOH and NaSiO2 solutions. XRD patterns of GMK. 1) and aluminium hydroxides (gibbsite and boehmite). which is a common accessory mineral in bauxite deposits [38] along with some amorphous compound. This amorphous alkaline aluminosilicate is the dominant product. The ball-milled red mud presents a bimodal distribution due to heterogeneity in composition of this sludge. even if the broad hump is slightly more pronounced in the MK geopolymer. while sodium is introduced by lixiviating agent (caustic soda). Nevertheless. 3).2. GFE and GR12 geopolymers and the results of phase quantification are reported in Fig. Fig. whose mean size is below to 1 µm) (Fig. The particle size distribution of MK is coarser (mean size around 5 µm) than that of RM one. This suggests that a similar degree of geopolymerization occurred.% in all samples (Table 2). respectively. 5 and Table 2. 4 shows the geopolymers containing variable amounts of metakaolin. Geopolymer tests The Fig. (Table 1) is predominantly iron oxide and hydroxide (the main crystalline phases being hematite and goethite. like that observed for metakaolin.

Al and Na. The amount of RM had a variable effect on the mechanical properties of geopolymer.9 (so well below 3). A structure like this one. the SiO2/Al2O3 ratio was determined by EDS (A1 and A2 in Table 3) to be as low as 1. By increasing the red mud content. but Fe seems to be incorporated as occurs in iron rich GFE and GR4-12 binders [28]. decreased to minimum values 9 . The reaction with the alkaline solution to form a particulate gel network. requires a lower ratio.5 to 3. for instance.geopolymerization in both GMK and GR samples. 7) gave initial maximum values (at 1 day curing) around 8 MPa.3) due to the supplementary content of Na introduced by the red mud. formed by linked SiO4 and AlO4 tetrahedra sharing all the oxygen atoms. the Si/Al ratio significantly affects the degree of polymerization. The resistance of sample GR4.3%. took place at the border of particles (Fig. 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. According to Pimraksa et al. [33]. The compressive strength (Fig. 6a) then involving the entire surface (Fig. e. Si/Na the half in the case of GR (1. characteristic of metakaolin geopolymers [39]. 6b). i.7) if compared to GMK (3. 6) suggests that silica provided by sodium silicate is more active in the geopolymerization process than the silica introduced by metakaolinite. In addition. This EDS quantification matches a threedimensional sodium silico-aluminate structure [40] combining poly-sialate (–Si–O–Al– O–) with a Si/Al ratio of 1. the amount of non-dissolved fillers in the geopolymer binder increased from 1. This amorphous matrix is mainly composed by Si. the presence of quartz and metakaolinite is observed as partially reacted vestiges (Fig. In the case in hand.

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

Conclusions New geopolymer formulations were designed by sodium silicate/NaOH activation of mixtures of metakaolin and red mud. open porosity. Table 4 shows the water absorption. sodium forming part of the geopolymer network is easily extractable by Na+ H+ exchange in aqueous media. 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. bulk density and apparent specific weight of geopolymers cured for 1 day. However. 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.On other hand. Due to the high porosity. The metakaolin-based geopolymers (with or without RM) basically present similar behavior with high values of water absorption (44-48 %) and open porosity. deomonstrating the feasibility of chemicallybonded materials containing up to 25% of red mud. 4. the geopolymer GR8 showed a opposing behaviour. 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. This presumed lower degree of geopolymer reaction should be promoted by non-controlled stoichiometry when RM is added. The well-known geopolymer 11 .1 g/cm3) and apparent specific weight are displayed. both low (GR4 and GR8) and high (GFE) leachate concentrations result in low strength.0-1. while low bulk density (1.

In general. These phases. The Chemical stability is good: sodium leaching test gave leachate concentrations close to 100 ppm without evidences of deterioration of mechanical performance.composition (amorphous phase predominant over residual quartz. The physical properties of geopolymers are not significantly affected by RM. in fact. this study strengthens preliminary observations that red mud constitutes a suitable material for geopolymer production once applied in reasonable ratios with respect to metakaolin. are not modified by addition of RM. The structural features of the amorphous geopolymer. Red mud influences the mechanical strength during curing (especially at the higher amounts of RM but the lower additions (GR10 and GR12). 12 . Acknowledgements The work was supported by FCT-Grant SFRH/BPD/72398/2010 co-financed by Programa Operacional potencial Humano POPH. gibbsite and boehmite). are to a limited extent involved in the geopolymerization process and the alkaline aluminosilicate amorphous phase is about 90 wt. goethite. despite it provides aluminum and iron oxides and oxyhydroxide (hematite. as resumed by the broad hump of XRD patterns.% in all samples. cured for 28 days showed good compressive strength. illite and anatase) is slightly affected by the red mud. as all samples exhibit high values of water absorption and low apparent density.

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

3. 1. XRD patterns of metakaolin (MK) and red mud (RM). (b) Comparison of geopolymers based on metakaolin (GMK) and containing iron-oxide (GFE) or red mud (GR12). 2) Anatase 3) Corundum (added 20 wt.57 µm) and chemical composition (by EDS) at spots A and B of metakaolin MK. 5. Geopolymer cubic specimens (20mm side).% as internal Standard 4) Quartz. 4. GR10 and GR12). SEM micrographs of GMK (a) and GR (b) geopolymers. GR8. Fig. Compressive strength of geopolymers at different curing times (1 and 28 days). Particle size distribution of metakaolin (MK) and red mud (RM). Fig. the calculated pattern is the continuous line and the lower curve is the weighted difference between the calculated and observed patterns. 2. with iron oxide (GFE). The experimental data are indicated by plus signs. from left to right: metakaolin-based (GMK). GR6. and mixtures with red mud (GR4. Fig. Fig. Fig. (a) Plot of Rietveld refinement performed on X-ray powder diffraction data. The rows of vertical tick marks shows the allowed reflections for the crystalline phases present in the sample: 1) Illite. SEM micrograph (ticks span 8. 7. 6.Figure captions: Fig. 2 . Fig.

01 1.90 3 .8 3.04 6.84 0. 54.75 0.66 5.55 39.2 1.23 18.I.8 51.%) MK RM SiO2 TiO2 Al2O3 Fe2O3 MgO CaO MnO Na2O K 2O SO3 L.08 11.O.27 0.4 1.03 2.4 1.10 0.54 0.Table 1 Oxides (wt.14 0.

2 2.5 91.6 ± 0.1 1.2 ± 0.1 2.6 ± 0.5 ± 0.1 4.3 ± 0.1 Quartz 2.1 2.7 ± 0.2 3.1 1.4 ± 0.1 ± 0.5 ± 0.1 3.6 ± 0.6 ± 0.4 ± 0.3 ± 0.1 Hematite absent 1.9 ± 0.1 0.9 ± 0.6 ± 0.Table 2 % weight Amorphous phase GMK GFE GR12 GR10 GR8 GR6 GR4 91.2 2.3 ± 0.1 4 .2 4.2 ± 0.1 0.5 ± 0.1 ± 0.6 91.2 ± 0.2 91.1 0.1 0.8 ± 0.5 89.0 ± 0.1 1.1 1.0 ± 0.1 0.7 ± 0.3 ± 0.1 1.2 2.0 ± 0.1 1.2 ± 0.2 6.7 ± 0.1 ± 0.2 ± 0.3 ± 0.5 90.4 Illite 5.1 1.1 1.1 0.1 2.4 ± 0.5 91.7 ± 0.1 0.1 Goethite absent absent Anatase 0.3 2.4 ± 0.1 0.5 ± 0.2 ± 0.2 ± 0.8 ± 0.

0 19.8 1.6 15.8 10.4 5 .1 1.7 53.8 2.9 0.9 22.0 32.2 Na2O Al2O3 SiO2 Fe2O3 9.2 19.3 21.2 10.8 6.6 7.4 3.6 64.5 9.Table 3 Spectrum 1 A1 Spectrum 2 A2 Na Al Si Fe O 6.7 SiO2/Al2O3 SiO2/Na2O 2.2 1 59.4 60.2 57.4 60.6 1.6 60 6.5 13.7 1.6 1.4 11.1 24.4 8.6 7.0 3.5 3.7 65.3 1.3 0.6 27.1 1.9 3.5 1.1 3.9 1.3 2.3 5.2 18.6 Si/Al Si/Na 2.1 13.

3 0.5 48.05 2.5 44.05 2.5 50.5 44.03 1.2 0.3 0.5 Bulk density (g cm-3) 1.09 0.05 0.05 6 .03 1.03 Apparent specific weight (1) 2.2 0.6 0.05 2.5 44.5 0.11 0.08 0.09 0.19 0.03 1.11 0.5 0.) 47.03 0.5 48.2 0.05 2.03 1.9 0.5 48.0 0.5 Open porosity (% vol.09 0.5 49.) 49.09 0.Table 4 GMK GFE GR12 GR10 GR4 Water absorption (% wt.

Table 5 Samples Leaching of Na (ppm) GMK 102 GFE 132 GR12 114 GR10 98 GR8 66 GR6 95 GR4 70 7 .

1 8 .Fig.

9 .Fig. 2.

3 10 .Fig.

4 11 .Fig.

5 12 .(a) (b) Fig.

6 13 .Fig.

7 14 .Fig.

Na leaching values show that the chemical stability of the geopolymers is good. Water absorption and apparent density are not affected by RM addition.Highlights New geopolymer formulations were designed by mixtures of metakaolin and red mud. RM based geopolymers exhibited good compressive strength after 28 days of curing. 15 . RM constitutes a suitable material once applied in reasonable ratios in geopolymer.