Construction and Building Materials 24 (2010) 19061910

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Construction and Building Materials

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Preparation and characterisation of y ash based geopolymer mortars

J. Temuujin a,*, A. van Riessen a, K.J.D. MacKenzie b
a b

Centre for Materials Research, Department of Imaging and Applied Physics, Curtin University of Technology, GPO Box U1987, Perth, WA 6845, Australia School of Chemical and Physical Sciences, Victoria University of Wellington, New Zealand

a r t i c l e

i n f o

a b s t r a c t
Geopolymer mortars with varying levels of sand aggregate were prepared and their physical and mechanical properties studied. The geopolymer binder to sand aggregate weight ratio was varied from 9 to 1. Compressive strength and Youngs modulus of the y ash based geopolymer paste were 60 MPa and 2.27 GPa and these values did not change signicantly with addition of up to 50 wt.% sand aggregate. Geopolymer binder exhibited strong bonding to the sand aggregate. Increasing sand content without increasing the amount of alkaline activator resulted in a decreasing level of geopolymerisation within the binder system. 2010 Elsevier Ltd. All rights reserved.

Article history: Received 16 December 2009 Received in revised form 12 March 2010 Accepted 1 April 2010 Available online 20 April 2010 Keywords: Geopolymer Fly ash Mortar Compressive strength Bonding

1. Introduction In the last decade y ash based geopolymer has emerged as a promising new cement alternative in the eld of building and construction materials [13]. Geopolymers exhibit many excellent properties such as high compressive strength, low creep, good acid resistance and low shrinkage [3]. Geopolymers described in this paper were manufactured from y ash which is a solid residue arising from coal burning thermal power stations and is thus very benecial in terms of environmental impacts. Hardjito and Rangan [3] demonstrated that one tonne of low-calcium y ash can be used to produce 2.5 m3 of high quality geopolymer concrete that is cheaper than Portland cement concrete. Fly ash geopolymers have been prepared as geopolymer pastes [4], mortars [5] and concretes [2,3]. For the production of mortar and concrete, natural or industrially manufactured aggregate is added as ller as it is less expensive than the paste. The inclusion of naturally occurring materials such as quartz, basalt, granite, sandstone and limestone as aggregates to geopolymer paste is not only economically favourable but also reduces pore density, reduces crack formation and improves durability [6]. In ordinary Portland cement (OPC) concrete and mortar there is a likelihood of an alkali-aggregate reaction between reactive aggregate and alkalis present in cement (Na2O + K2O) and Ca(OH)2. The product of the alkali-aggregate reaction results in expansion and subsequent crumbling of the mortar and concretes. Garcia-Lodeiro et al. found that the calcium in the OPC

mortar plays an essential role in the expansive nature of the gels [7]. Fly ash based geopolymer mortars are less susceptible to alkali-aggregate reaction because the lower calcium content in these systems results in a reaction product that is not expansive [7,8]. Previous researchers have described addition of aggregate to geopolymer with binder: aggregate at constant ratio 0.5 [5]. Determination of the optimal binder: aggregate ratio is important for resource efciency and meeting specied mechanical properties of mortars. The present research reports on the effects of aggregate content on the geopolymerisation process within the binder phase and subsequent mechanical properties of the mortar.

2. Experimental 2.1. Preparation Geopolymer was manufactured from Collie y ash from Western Australia. The y ash consists of wt.%: 60(1) amorphous composition, 20(1) quartz low, 17(1) mullite, 1.7(0.5) maghemite (Q) and 0.9(0.5) hematite [4]. The values in brackets indicate the uncertainty. The median size d50 of the y ash was 14.4 lm. The aggregate used was bricklayers sand purchased from a local hardware store. The granulometry distribution of the sand (aggregate) is shown in Fig. 1. The granulometry distribution was obtained by shaking the sand through a sieve set with sizes of 1180, 750, 600, 425, 250, 150 and 75 lm, respectively. The grading curve of the sand aggregate indicates that the neness of the sand is lower than that specied as the low limit for ne aggregates for concrete according to ASTM C33. Characteristics such as neness modulus and apparent dry density of the aggregate are important factors for determining mortar properties which is usually determined by utilising a standard sieving method with exact mesh sizes [9]. The sieves used for the granulometric distribution of the aggregate were not the same as required for determination of the neness modulus and therefore, the neness modulus was not calculated. The apparent dry density or bulk density of the aggregate was calculated by dividing the mass of non-compacted dry aggregate (dried at

* Corresponding author. Tel.: +61 8 9266 3673. E-mail address: jtemuujin@yahoo.com (J. Temuujin). 0950-0618/$ - see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.conbuildmat.2010.04.012

J. Temuujin et al. / Construction and Building Materials 24 (2010) 19061910 Table 2 Compositions of the geopolymer mortars. Fly ash, wt.% Paste Mortar Mortar Mortar Mortar Mortar 73.91 66.52 59.12 51.74 44.33 36.96 Sodium silicate, PQ, D-51, wt.% 18.63 16.77 14.89 13.04 11.17 9.31 Sodium hydroxide (14 M), wt.% 7.45 6.70 5.95 5.21 4.47 3.72 Sand, wt.% 10 20 30 40 50

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Binder:sand, wt. ratio 9.0 4.0 2.3 1.5 1.0

10% 20% 30% 40% 50%

Fig. 1. Grading curve of sand aggregate.

105 C) to the volume of a 100 ml glass cylinder containing the dried aggregate. The apparent dry density of the sand was 1416(10) kg/m3. The value in the bracket is the standard deviation of three separate measurements. An XRD pattern (not shown here) of the sand revealed the presence of quartz with a minor amount of microcline. The chemical composition of the y ash and aggregate as determined by X-ray uorescence are presented in Table 1. The binder composition of the geopolymer mortar was calculated based on the amorphous composition of the y ash assuming the amorphous alumina and silica of the y ash are the reactive components. The method used to determine the amorphous composition of Collie y ash is described elsewhere [10]. The content of the amorphous Al2O3 and SiO2 in y ash were 11.64 wt.% and 26.49 wt.%, respectively. For geopolymer described in this paper a formulation determined by Hardjito and Rangan was used for the same Collie y ash [3]. However, we have re-calculated the geopolymer formulation using the only the amorphous composition of the y ash and obtained Si:Al = 2.3 and Na:Al = 0.88 [4]. Since we used only the amorphous part of the y ash to determine the geopolymer formulation less alkaline activator is used than that used by the previous authors [3]. The activating solutions used were sodium silicate D-51 from PQ Australia Pty., Ltd. with a chemical composition of (wt.%): Na2O = 14.7, SiO2 = 29.4 and water = 55.9 and 14 M sodium hydroxide solution prepared from analytical grade sodium hydroxide pellets. The compositions of the geopolymer mortars are shown in Table 2. As mentioned above the y ash consists of an amorphous part (60 wt.%) and a crystalline part (40 wt.%). The crystalline part of the y ash has low reactivity and can be considered as ne aggregate. Therefore the geopolymer mortar contains geopolymeric (aluminosilicate) gel, crystalline ne aggregate present in y ash and added sand aggregate. The weighed components for the paste were mixed in a centrifuge mixer (Thinky Co., Japan) at 1300 rpm for 5 min. followed by de-foaming at 2100 rpm for 30 s. The paste was then placed in cylindrical plastic moulds with 25 mm diameter and 50 mm height. The capped moulds were cured at 70 C for 24 h. After curing the moulds were removed from the oven and kept at ambient temperature for 3 days followed by de-moulding. For compressive strength testing the samples were cut at with a diamond saw. Mortars were prepared the same way, however, it was noted that for the 40 and 50 wt.% aggregate samples workability was low.

cycle time of 1 s were used and referenced to AlH2 O3 6 . Seven days compressive strength tested samples were immediately ground and used for NMR analysis. NMR spectra were taken approximately 1 month after preparation of the geopolymer mortar. Seven day compressive strengths of the samples were measured with an EZ-50 Universal testing machine (Lloyd Instruments). ASTM C39 for determination of compressive strength of cylindrical concrete specimens was used as a guide. We followed the standard by using a 2:1 aspect ratio for cylindrical samples (length:diameter) and applying a load rate 0.25 MPa/s. The standard was not strictly adhered to because it was used for mortar rather than concrete and using an instrument without a bearing stage. The compressive strength and Youngs modulus values are thus treated as relative measures enabling us to compare different samples. The uncertainty in the measurements was taken as the standard deviation of the compressive strength of four samples. The Youngs modulus of each sample was calculated from the linear stress/strain response by Lloyd Instruments Nexygen Plus material test data analysis software. Changes of open porosity and density were measured by Archimedes principle using the sectioned samples with height of about 57 mm. For each composition the average of two specimens were used to obtain density and open porosity values. Values in brackets indicate the standard deviation. The measurements were performed 8 days after sample preparation. Since, de-ionized water was used as the liquid medium, the porosity and density should be considered as relative values because of possible leaching of Na ions into the water.

3. Results and discussion Geopolymer mortars with 1030 wt.% of aggregate exhibited acceptable owability while the 40 and 50 wt.% aggregate containing mortars were stiff and difcult to pack into the plastic moulds. An optical micrograph of the 50 wt.% aggregate containing mortar (Fig. 2) revealed that the aggregate was distributed homogeneously within the geopolymer binder. Sectioning of the mortar by diamond saw did not cause any interfacial cracks between sand and geopolymer binder at a macro level. The compressive strength of the mortar remains essentially constant with varying aggregate content (Fig. 3). Differences between the mean values of different mortar samples are not significant when taking into account uncertainties of two standard deviations (2r). The compressive strength of the geopolymer mortar depends on the strength of the geopolymeric gel, the interfacial bonding between the geopolymeric gel and aggregate and to some extent the aggregate itself. The results suggest that the interfacial bonding between aggregate and geopolymer was comparable in strength to the geopolymer and/or the sand aggregate by themselves. Physical and mechanical properties of the geopolymer mortars are summarized in Table 3. As the level of aggregate was increased the open porosity decreased. There is a decrease in open porosity from paste to mortar with 50 wt.% aggregate of 37.8% that is accompanied by an increase in density of 14.5%. The density of a geopolymer gel is reported to

2.2. Test methods The XRD patterns of the y ash and sand (aggregate) were collected on a Bruker D8 Advance Diffractometer using Cu Ka radiation. Diffraction patterns were collected from 10 to 80 2h. The step size was 0.02 2h with a scan rate of 0.6 2h/ min. Geopolymer-aggregate interfaces in the mortars were studied with a Zeiss EVO 40XVP scanning electron microscope on a fracture surface. SEM micrographs were taken within 2 weeks of sample preparation. Aggregate distribution at macroscopic level was observed with a Nikon SMZ 800 light microscope using sectioned geopolymer mortar samples. The 27Al MAS NMR spectra of the samples were acquired at 11.7 T using a Varian Unity 500 MHz spectrometer and 5 mm Doty MAS probe in which the sample was spun at 1012 kHz and a 15 pulse of 1 ls and reTable 1 Chemical composition of y ash and aggregate, wt.%. Al2O3 Aggregate Fly ash 3.59 23.63 CaO 0.02 1.74 Fe2O3 1.29 15.3 K2O 1.08 0.84 MgO 1.2

MnO 0.13

Na2O 0.13 0.38

P2O5 1.31

SiO2 87.05 51.5

SO3 0.28

TiO2 1.32

LOI 1.78

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J. Temuujin et al. / Construction and Building Materials 24 (2010) 19061910 Table 3 Open porosity, density and Youngs modulus of the samples. Open porosity, % Paste Mortar Mortar Mortar Mortar Mortar 10% 20% 30% 40% 50% 9.8 11.6 9.5 9.7 7.7 6.1 (1.3) (0.7) (1.2) (1.7) (0.2) (0.4) Density, g/cm3 2.00 2.02 2.11 2.10 2.19 2.29 (0.02) (0.01) (0.01) (0.03) (0.02) (0.01) Youngs modulus, GPa 2.27 2.30 2.37 2.47 2.45 2.44 (0.14) (0.04) (0.04) (0.09) (0.13) (0.06)

be below 2 g/cm3 depending on its composition [11]. The increase in density of mortar reported in this paper is due to decreased open porosity and also because quartz, the main component of the sand aggregate, has a density of 2.65 g/cm3 [12] raising the overall density of the mortar. There was no difference in Youngs modulus when comparing paste with mortar samples. As with compressive strength, the use of two standard deviations (2r) as an uncertainty for Youngs modulus obscured any variations between values from different samples. SEM micrographs of the 10 and 50 wt.% aggregate mortars are shown in Fig. 4. It is clear that there is an intimate bond between the aggregate and geopolymer binder. No cracks were observed along the interface suggesting a strong bond. A close inspection of the interfacial region suggests that a partial dissolution of the aggregate surface might have occurred producing a smooth intimate interface. Lee and van Deventer noted strong bonding of aggregate with binder in mortar and concretes made with soluble silicate [5]. The aggregategeopolymer interface for both low (10 wt.%) and high (50 wt.%) aggregate mortars are remarkably similar suggesting that the same bonding process occurred in both samples. Barbosa and MacKenzie observed higher compressive strength in geopolymers containing kaolin or powdered stone as llers compared with geopolymers containing corundum or b-Sialon [13]. They concluded that the difference in bonding was due to lack of reactivity of the corundum or b-Sialon in geopolymer so no bond was formed with the matrix. The possibility of partial dissolution of the sand aggregate in geopolymer mortar observed in our work is in agreement with the results of Barbosa and MacKenzie

[13]. Cracks present in the geopolymer gel (Fig. 4) are believed to have arisen during testing for compressive strength or when the sample was placed in vacuum when coating for the SEM. Fig. 5 shows 27Al Solid State MAS NMR spectra of the y ash and selected mortar samples. Solid State MAS NMR results are very sensitive to the presence of iron in the samples. Thus the Collie y ash used in the present experiments with 15 wt.% of amorphous and crystalline iron oxides produces spectra with broad peaks and large spinning side bands. The integrated areas of the tetrahedral and octahedral peaks of the y ash indicate that 66% of Al is in tetrahedrally coordinated and 34% is octahedrally coordinated. Because signal to noise of the spectra is poor plus the presence of large spinning side bands these values should be considered as approximate values. The octahedral component of the Al also has a contribution from the mullite present in the y ash. After 7 days a large proportion of the octahedral coordination is converted to tetrahedral coordination a strong indication of the formation of geopolymer. The coordinations of the Al nuclei based on spectra in Fig. 5 are shown in Table 4. All samples are expected to have some Al in octahedral coordination due to the presence of approximately 20 wt.% mullite in the

Fig. 2. Optical micrograph of the 50 wt.% aggregate mortar, 20.

Fig. 3. Compressive strength of mortar samples.

Fig. 4. SEM micrographs of the aggregate and binder interface of 10 wt.% (a) and 50 wt.% (b) aggregate mortars. In both micrographs the smooth feature on the right side is quartz aggregate.

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y ash. The mullite does not take part in the geopolymerisation reaction so its contribution to the NMR spectra is expected to stay constant. As the amount of aggregate increases the number of Al atoms in octahedral coordination clearly increases from approximately 8% to 22%. It is expected that Al will be in tetrahedral coordination in geopolymer so the increase in octahedral coordination suggests incomplete geopolymerisation as the amount of aggregate increases. Incomplete geopolymerisation is believed to be the result of insufcient alkali being available for dissolution of the reactive aluminosilicates in the y ash. Some alkali may also react with the aggregate, as discussed above, leaving less for dissolution of y ash. The alkali content in the y ash mortar was calculated based on the reactive component of the y ash. Thus increasing the aggregate content leads to insufcient alkali activator for complete geopolymerisation of available y ash. This observation clearly suggests an increase in alkali is warranted to ensure complete dissolution of available reactive aluminosilicate. This step is also expected to lead to greater mechanical properties such as compressive strength. In addition, the presence of extra liquid will improve workability. Determining the optimum amount of alkali is important because any excess will result in unacceptable eforescence, an increase in porosity and a decrease in compressive strength [14]. An alternative approach would be to add water to the original amount of alkali thus decreasing pH and reducing dissolution leading to a reduction in strength but improved workability. This approach would be acceptable if the nal strength was acceptable for specic applications. A more palatable solution might be to add a superplastisizer which would increase workabil-

Table 4 Coordination of Al nuclei in y ash, paste and mortars. Fly ash Tetrahedral Octahedral 66 34 Paste 92 8 Mortar 10 wt.% 91 9 Mortar 30 wt.% 87 13 Mortar 50 wt.% 78 22

ity and maintain strength at current levels while xing costs of alkali activator solutions. The ratio of binder to aggregate depends on the nature of the aggregate, i.e. whether it is amorphous or crystalline; apparent dry density and neness modulus. For instance De Schutter and Poppe found that for Ordinary Portland cement mortar using low apparent dry density sand aggregate (1404 kg/m3) caused an increase in water demand and a decrease of the 28 day compressive strength by about 3-fold [9]. Geopolymer mortars prepared for the experiment presented here used sand with almost similar apparent dry density (1416 kg/m3) and exhibited acceptable compressive strength for all composition ranges. In other words, geopolymer and OPC mortars behaved differently. The apparent dry density is sensitive to close packing of the particles based on their shapes [9]. In general high packing density suggests a wide size range so that smaller particles t in between larger particles, etc. It is likely that low packing density sand has smaller particle size or higher porosity than the high packing density sand aggregates and therefore it has more chance to react with the alkali activator. Fractured surfaces of the mortars at low magnication (not shown here) as well as the surfaces displayed in Fig. 4 show fracture has occurred through the sand aggregate particles. In other words sand aggregate itself shows weaker mechanical properties than geopolymer gel and aggregate geopolymeric gel interface. The strong interfacial bond may be evidence of a chemical reaction between aggregate and alkali. Another possibility of the strong interfacial bonding between sand and geopolymer is mechanical interlocking between the matrix and sand as the surface of sand used for present experiment is porous. However, we do not have direct evidence of the exact bonding mechanism. It is likely that the crystallinity of the aggregates will inuence the degree of dissolution that the aggregate undergoes once exposed to the alkali. Based on our observations the compressive strength of the geopolymer mortars depends on the physical properties of the sand aggregate. The consistent strength across all mortar compositions is believed to be due in part to strong bonding between gel and aggregate. However, the low Ca content is unlikely to result in any additional long term alkali-aggregate reaction. This is a major advantage over the detrimental alkaliaggregate reaction that can occur in ordinary Portland cement mortar [7]. 4. Conclusions Compressive strength of y ash based geopolymer mortar was found to depend on the strength of the geopolymer binder and excellent bonding between the geopolymer binder and aggregate. Increasing the proportion of aggregate in the mortar reduced the amount of geopolymerisation but did not signicantly impact on compressive strength. It is proposed that compressive strength of geopolymer mortars with high levels of aggregate can be increased by optimising the amount of alkali. Acknowledgement

Fig. 5. Al MAS NMR spectra of y ash (A), paste (B), 10 wt.% (C), 30 wt.% (D) and 50 wt.% (E) aggregate containing mortars after 7 days. Asterisks indicate spinning side band.

27

The present research was funded by the Cooperative Research Centre for Sustainable Resource Processing (CSRP).

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J. Temuujin et al. / Construction and Building Materials 24 (2010) 19061910 [8] Fernandez-Jimenez A, Garcia-Lodeiro I, Palomo A. Durability of alkali-activated y ash cementitious materials. J Mater Sci 2007;42:305565. [9] De Schutter G, Poppe AM. Quantication of the water demand of sand in mortar. Construct Building Mater 2004;18:51721. [10] Temuujin J, van Riessen A. Effect of y ash preliminary calcination on the properties of geopolymer. J Hazard Mater 2009;164:6349. [11] Duxson P, Provis JL, Lukey GC, Mallcoat SW, Kriven WM, van Deventer JSJ. Understanding the relationship between geopolymer composition, microstructure and mechanical properties. Colloids Surf A: Physicochem Eng Aspects 2005;269:4758. [12] Deer WA, Howie RA, Zussman J. An introduction rock forming minerals. Longman: Edinburgh Gate; 1966. [13] Barbosa VFF, MacKenzie KJD. Thermal behaviour of inorganic geopolymers and composites derived from sodium polysialate. Mater Res Bull 2003;38:31931. [14] Williams R. Determination of the reactive component of y ashes for geopolymer production. Annual geopolymer meeting geopolymer 2009, Centre for Sustainable Resource Processing, 1516 July, 2009, Perth, Australia.

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