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Construction and Building Materials

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Study on solids-to-liquid and alkaline activator ratios on kaolin-based geopolymers

C.Y. Heah a,, H. Kamarudin a, A.M. Mustafa Al Bakri a, M. Bnhussain b, M. Luqman a, I. Khairul Nizar c, C.M. Ruzaidi a, Y.M. Liew a
a Centre of Excellence Geopolymer System Research, School of Materials Engineering, Universiti Malaysia Perlis (UniMAP), P.O. Box 77, D/A Pejabat Pos Besar, 01000 Kangar, Perlis, Malaysia b King Abdulaziz City Science and Technology, P.O. Box 6086, Riyadh 11442, Saudi Arabia c School of Environmental Engineering, University Malaysia Perlis, P.O. Box 77, D/A Pejabat Pos Besar, 01000 Kangar, Perlis, Malaysia

h i g h l i g h t s
" Solids-to-liquid and activator ratios

g r a p h i c a l a b s t r a c t

affect signicantly the compressive strength. " Strength of kaolin-based geopolymers increased with the ageing time. " The geopolymer do not destroy in water proving the presences of geopolymer bondings.

a r t i c l e

i n f o

a b s t r a c t
Kaolin and alkali activator were mixed with the solids-to-liquid ratios in range of 0.601.20 (Al2O3/Na2O molar ratio of 0.631.27). Sodium silicate and sodium hydroxide ranged between 0.16 and 0.36 (SiO2/ Na2O molar ratio of 3.193.67) were mixed together to prepare alkali activator. The results concluded that compressive strength was affected by both S/L and Na2SiO3/NaOH ratios and strength increased with ageing day. Both these ratio also inuenced the workability of the mixes. Besides, the kaolin geopolymers showed good volume stability in water. Compressive strength was highest at S/L and Na2SiO3/NaOH ratios of 1.00 and 0.32, respectively. In term of molar ratios, optimum was achieved at Al2O3/Na2O of 1.09 and SiO2/Na2O molar ratios of 3.58. Microstructures showed that kaolin particles were slightly activated with large part of unreacted raw materials remained in the system. Geopolymer sample reduced in peak intensities over time as presented by XRD analysis and the presence of crystalline peaks in the kaolin geopolymers was Zeolite X. FTIR analysis showed the presence of geopolymer bonding increased over age. In overall, kaolin geopolymers does not undergo complete geopolymerization and showed slow strength development. Vast research works have to be carried out to further improve the properties of kaolin geopolymers. 2012 Elsevier Ltd. All rights reserved.

Article history: Received 3 February 2012 Received in revised form 19 April 2012 Accepted 29 April 2012

Keywords: Kaolin Geopolymer Alkaline activator Geopolymerization Solids-to-liquid Activator ratio

1. Introduction Glukhovsky and later by Krivenko in the 1950s have developed on the alkali-activated system containing the calcium silicate hydrated (CSH) and aluminosilicate phases. Due to the various catastrophic res in France in 19701973, Davidovits started research on the non-combustible and non-ammable plastic materials. In developing new inorganic polymer materials, Davidovits found
Corresponding author. Tel.: +60 12 5711154.
E-mail address: chengyongheah@hotmail.com (C.Y. Heah). 0950-0618/$ - see front matter 2012 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.conbuildmat.2012.04.102

that the synthesis of both plastic and heat resistant feldspathoids and zeolites was controlled by the similar hydrothermal condition and required high PH, concentrated alkali, atmospheric pressure and thermoset at temperature below 150 C. The development of this technology was based on the geosynthesis of aluminosilicate kaolinite with caustic soda at 100150 C which was then polycondensed into a hydrated sodalite or hydrosodalite [1]. In 1978, Davidovits created the name geopolymers meaning the mineral polymers resulting from geochemistry or geosynthesis. The geopolymer chemistry concept was invented in 1979 [1]. Geopolymerization is a reaction that chemically integrates minerals

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involving silicoaluminates sources. Source of alumina in and silica acts as a source of precursor that readily dissolved in the alkaline solution, and synthesized by alkaline and/or silicate activation which lends itself to the process of geopolymerization [2]. This results in a amorphous to semi-crystalline three dimensional silicoaluminate structure [1] that has signicant similarities to zeolite precursor gels [3]. The SiO4 and AlO4 tetrahedra are linked alternatively by sharing all the oxygens. The negative charges of Al3+ in the IV fold coordination are charge-balanced by the positive ions (Na+, K+, Li+, Ca2+, Ba2+, NH4+, H3O+). Geopolymers have the empirical formula of: Mn{(SiO2)zAlO2}wH2O, where M is a cation (K+, Na+ or Ca2+); n is a degree of polycondensation and z is 1, 2, 3 [4]. Types of geopolymers includes poly(sialate), poly(sialate-siloxo) and poly(sialate-disiloxo) as shown as follows [1]:

Formerly, two alkali-activated binding systems were established: (1) the alkali activation of blast furnace slag (Si + Ca) with mild alkaline solution and (2) alkali activation of metakaolin and Class F y ash (Si + Al) with medium to high alkaline solution [5]. According to Palomo et al. [5], the alkali activation of blast furnace slag has calcium silicate hydrate (CSH) as main products. For alkali activation of metakaolin and y ash, the reaction products were the zeolite-like polymer. Later, plenty researches have been carried out to investigate the physical properties, mechanical properties, characterization and the durability of the geopolymers by using the source materials such as metakaolin [6], y ash [7] and slag [8]. Geopolymers exhibit a wide variety of properties and characteristics depending on the raw material selection and processing conditions. Several well-known benets of these materials include excellent mechanical strength, long term durability [9], low shrinkage [10], fast setting [9], acid resistance [10], re resistance [9] and low thermal conductivity [10]. Alonso and Palomo [11] found that the rate of polymer formation was inuenced by parameters such as curing temperature, alkali concentration, and initial solid content, among others. In particular, the source materials, as well as the curing regime for the geopolymers were important factors that must be taken into consideration during geopolymers synthesis [12]. In addition, the water content, the kaolinite ratio, and the type of metal silicate used also have a substantial effect on the nal properties of the geopolymers. Criado et al. [13] also suggested that the activation rate and the chemical composition of the reaction product depended on the particle size, chemical composition and type of the alumino-silicate source, activator concentration and etc. Even so, the activation mechanism was independent of the variables stated above at any given time. Focusing on the solids-to-liquid (S/L) ratio, which corresponds to the aluminosilicate-to-activator solution ratio, Yao et al. [14] reported that high S/L ratios resulted in low viscosity of the slurry and the lower S/L ratios increased the geopolymerization period.

Zuhua et al. [15], on the other hand, stated that low S/L ratios could accelerate the dissolution of source materials, however, it was not benecial to polycondensation process at high sodium hydroxide (NaOH) concentration. Provis et al. [3] observed that geopolymers with very high S/L ratios generally do not achieve high strength due to low extent of binder formation. There is limited research on the effect of alkaline activator, especially sodium silicate-to-sodium hydroxide (Na2SiO3/NaOH) ratio on geopolymer synthesis. However, Hardjito and Rangan [16] reported that compressive strength increased when Na2SiO3/ NaOH ratio was increased. Both S/L ratio [17] and Na2SiO3/NaOH ratios [18] inuenced the workability of geopolymers. In early study, researchers have focused on metakaolin as the aluminosilicate source [19,20]. Later, the utilization of y ash as aluminosilicate source became major study areas [21,22]. The use of raw kaolin itself in geopolymer has not been studied in detailed. It is important to study on the basic material (kaolin) to address how much kaolin can stand alone in the production of geopolymers. Moreover, the use of basic material led to easy in the interpretation of result and eliminated complex interpretation of results due to the utilization of complex raw material, such as y ash with lots of impurities. which may affect the data interpretation. Kaolin geopolymer is well known by its characteristics of being lightweight and capability to bind materials which makes it ideal for industrial applications such as cementitious materials. If succeeded, this kaolin geopolymers would have wide range of the applications especially in the low strength precast materials eld, not limited to cement board, architectural products, decorative wall or countertop, plasterboard, drains or pipe, wall panel, roof tiles, road barrier and many more. These binders are still in the early stages of development; hence, they need further research to become technically and economically viable materials. In this paper, important parameters, that is, S/L ratio and Na2SiO3/NaOH ratio on the synthesis of kaolin geopolymers were discussed. The effect of S/L and Na2SiO3/NaOH ratios was also discussed in term of relation of various oxide molar ratios (e.g. SiO2/Al2O3, SiO2/ Na2O, H2O/Na2O and Al2O3/Na2O molar ratios). Physical observation, bulk densities as well as the workability of the kaolin geopolymers were reported. In addition, the SEM, XRD and FTIR analyses were performed.

2. Experimental method 2.1. Materials The NaOH powder used was of caustic soda micropearls, 99% purity with brand name of Formosoda-P, made in Taiwan. A technical grade sodium silicate (Na2SiO3) solution was supplied by South Pacic Chemicals Industries Sdn. Bhd. (SPCI), Malaysia. The chemical compositions comprised of 30.1% SiO2, 9.4% Na2O and 60.5% H2O with modulus SiO2/Na2O of 3.2, specic gravity at 20 C = 1.4 g/cm3 and viscosity at 20 C = 0.4 Pa.s. The kaolin was supplied by Associated Kaolin Industries Sdn. Bhd., Malaysia. The general chemical composition is tabulated in Table 1 which obtained from Xray uorescence (XRF) analysis. The physical form of kaolin used was of powder

Table 1 Chemical composition of kaolin. Chemical SiO2 Al2O3 Fe2O3 TiO2 ZrO2 K2O MnO2 LOI Wt (%) 54.0 31.7 4.89 1.41 0.10 6.05 0.11 1.74

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C.Y. Heah et al. / Construction and Building Materials 35 (2012) 912922 2.7. Fourier transform infrared spectroscopy (FTIR) Perkin Elmer FTIR Spectrum RX1 Spectrometer was used to evaluate the functional group of the sample. Small amount of potassium bromide (KBr) and geopolymer powder were put into a mold. By using cold press machine, mold which contains powder and KBr was pressed at 4 ton for 2 min to produce specimens for examination.

type and has minimum 40% of particle size less than 2 lm and maximum 2% of moisture content. It was used as SiAl cementitious materials. Distilled water was used throughout.

2.2. Sample preparation NaOH solution having the concentration of 8 M was prepared in volumetric ask and was allowed to cool down to room temperature. NaOH solution was mixed with Na2SiO3 solution with Na2SiO3/NaOH ratio ranged from 0.16 to 0.36 to prepare alkali activator solution 24 h prior to use. The kaolin powder and alkali activator solution were mixed with the solids-to-liquid ratio ranged from 0.60 to 1.20 and were stirred well for few minutes by using mechanical mixer. The detail of mixture proportions were given in Table 2. The fresh paste was then rapidly poured into 50 50 50 mm steel molds and the samples were compacted approximately one half of the depth (about 1 in. or [25 mm]) of the mold in the entire cube compartments and the paste was tamped in each cube compartment at each layer as described in ASTM C109 [23]. Lastly, the samples were put into the oven at temperature of 80 C for 24 h for curing purpose. The samples were sealed with thin plastic at the exposed portion of the mold during the curing stage.

3. Results and discussion 3.1. Qualitative observation In order to observe the soundness of the kaolin geopolymers, the samples were soaked in water up to 180 days as shown in Fig. 1. It was observed that the kaolin geopolymers with S/L ratio of 0.60 (Mix 1) disintegrated in water at 7 days. This was probably because of the very weak structure as shown by the very low compressive strength reported (Fig. 4). However, kaolin geopolymers with S/L ratio of 1.00 (Mix 3) did not collapse when put in water even after 180 days. No cracks were observed. This kaolin geopolymers was stable in water. Based on Davidovits [1], activation of kaolinite clay produced three dimensional network structure that was stable in water. Even though this kaolin-based geopolymers achieved quite a low strength in range of 56 MPa, however the geopolymer bonding (Figs. 1012) existed in the system made it stable and did not collapse in water [28]. The same observation was recorded for kaolin geopolymers with Na2SiO3/NaOH ratios of 0.16 (Mix 5) and 0.32 (Mix 8). This proved that this kaolin geopolymers formation was relied on the geopolymerization process but not merely relied on the drying and hardening of the waterglass binder. Fig. 2 showed the workability of kaolin geopolymers measured by using mini-slump cone. Workability is a property of fresh binder which measures the ease of the fresh paste can be mixed, placed, consolidated and nished. The slump values suggested the workability decreased with increasing S/L and Na2SiO3/NaOH ratios. As S/L ratios were increased, there were more solid contents than the uid medium within the mixes. Thus, the mixes became stiffer. At this time, the workability was also strongly depended on the particle shape of the solid materials. The kaolin particles decreased the workability due to the plate-like structure which resulted in the inter-particle friction. On the other hand, with the increased of the Na2SiO3/NaOH ratio, the sodium silicate content in the mixes increased. Workability decreased as result of the highly viscous property of sodium silicate than the NaOH solution [29]. Fig. 3 displayed the bulk densities of kaolin geopolymers at 7 and 28 days. The kaolin geopolymers showed bulk densities between 1250 kg/m3 and 1500 kg/m3. The kaolin geopolymers showed no signicant difference in bulk densities among themselves; however kaolin geopolymers with optimum strength exhibited slightly greater bulk densities. This supported that the bulk density increased with the increasing mechanical strength [30]. At 28 days, the bulk densities dropped which were partly resulted from the loss of water due to drying [31]. 3.2. Effect of solids-to-liquid ratio on compressive strength

2.3. Qualitative observation The kaolin geopolymers were soaked in water up to 180 days. The observation of these kaolin geopolymers were recorded at 1, 7 and 180 days to determine the soundness of the geopolymers produced. Workability of the fresh kaolin geopolymers were measured using mini-slump cone as proposed by Kantro [24]. Based on Kantro [24], the test method corresponded to the slump test (ASTM C143) used for concrete mixes. For neat cement paste, this mini-slump test has been devised. The mini-slump cone was placed at the center of the glass plate and lled with geopolymer paste. Gently, the cone was lifted and the diameter of the pat formed was measured. The two perpendicular diameters were recorded and the average diameter was calculated [25,26]. Bulk densities of kaolin geopolymers were determined by measuring the mass and the dimensions of the kaolin geopolymers in accordance to BS EN12390-7 [27].

2.4. Compressive test Compressive strength tests of all specimens were evaluated by using the Instron machine series 5569 Mechanical Tester. The specimens were taken out from oven after 24 h of curing and were put in room temperature until the day of testing. Compressive test was carried out to evaluate the strength development of the specimens. The samples were tested up to 180 days. Three specimens were tested for each ratio.

2.5. Scanning Electron Microscope (SEM) JSM-6460LA model Scanning electron microscope (JEOL) was performed to reveal the microstructure of kaolin geopolymers at different S/L and Na2SiO3/NaOH ratios. The specimens were prepared and coated by using Auto Fine Coater; model JEOL JFC 1600 prior to examination. The chemical composition of the reaction products was determined by an Energy Dispersive X-ray Spectroscopy (EDX).

2.6. X-ray diffraction (XRD) Specimens were prepared in powder form and undergone XRD examination. XRD-6000, Shimadzu X-ray diffractometer equipped with auto-search/match software as standard to aid qualitative analysis was used.

Table 2 Detail of mixture proportions. Mix no. 1 2 3 4 5 6 7 8 9 NaOH molarity (M) 8 8 8 8 8 8 8 8 8 S/L ratio 0.60 0.80 1.00 1.20 1.00 1.00 1.00 1.00 1.00 Na2SiO3/NaOH ratio 0.24 0.24 0.24 0.24 0.16 0.20 0.28 0.32 0.36

Fig. 4 showed the compressive strength of kaolin-based geopolymers at various S/L ratios with constant Na2SiO3/NaOH ratio of 0.24 up to 180 days. Overall result showed that compressive strength increased with the ageing time. However, the strengths achieved were quite low. This was because kaolin-based geopolymers required more time to react in order to become hard solid. A weak structure was formed initially because of its nature of low reactivity which contributes to the low rate of reaction development [9,32].

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Fig. 1. Performance of kaolin geopolymers in water for (a) Mix 1, 1 day, (b) Mix 1, 7 days, (c) Mix 3, 180 days; (d) Mix 5, 180 days and (e) Mix 8, 180 days.

Fig. 2. Mini-slump ow values for kaolin geopolymer mixes at various (a) S/L ratios and (b) Na2SiO3/NaOH ratios.

Fig. 3. Bulk densities of kaolin geopolymers with various (a) S/L ratios and (b) Na2SiO3/NaOH ratios at 7 and 28 days.

Compressive strength increased linearly from day 1 to day 3 [2]. Kaolin geopolymers with S/L ratio of 1.20 (Mix 4) recorded the highest compressive strength while kaolin geopolymers with S/L ratio of 0.60 (Mix 1) showed the lowest compressive strength. Later strength gain after day 3 presented that the compressive strength of kaolin geopolymers with S/L ratio of 1.00 (Mix 3) was most ideal in terms of the strength and the workability of the geopolymer slurry. At high S/L ratio, the geopolymer slurry was less workable [2]. Mix 4 (S/L ratio of 1.20) always has higher compressive strengths than Mix 3 (S/L ratio of 1.00). Even so, S/L ratio of 1.20 was not chosen for the next experiment investigating the effect of Na2SiO3/NaOH ratios. This was owing to the very low workability of the geopolymer slurry (Fig. 2a) which resulted in difculty in compaction during the molding process [14,17]. For samples with S/L ratio of 0.60 (Mix 1), the geopolymer slurry was highly workable (Fig. 2a). The samples displayed no or very little strength increment up to 180 days. In addition, the samples

appeared peeled off. This may probably due to the high amount of activating solution which hinders the geopolymerization process. The result concluded here was in agreement with the previous related studies conducted. In the study of Kong et al. [17] based on metakaolin-based geopolymer, S/L ratio of 0.80 was used in investigation as this ratio gave nearly optimum strength and provided good workability. Higher S/L ratio than 0.80 has very low workability and will deteriorate the properties of the paste produced. In contrast, according to Xu and van Deventer [32], the S/L ratio, by mass should be approximately 3 to produce y ashbased geopolymers to allow for geopolymerization process and alkaline activator solution formed a thick gel instantaneously upon mixing with source material. On the other hand, kaolinite, the major mineral of kaolin, consisted of dioctahedral (1:1) layer silicate. The kaolinite layer com prised of Si2 O5 2 sheet and Al(OH)3 sheet linked by sharing n bridging oxygen atom. The kaolinite layers were linked together

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Fig. 4. Compressive strength of geopolymer samples with various solids-to-liquid (S/L) ratios and constant Na2SiO3/NaOH ratio of 0.24.

Fig. 5. Compressive strength of geopolymer samples with various Na2SiO3/NaOH ratios (at constant S/L ratio of 1.00).

by hydrogen bonds [33]. Based on Davidovits [34], the alkaline attack started from the outer surfaces of the kaolinite crystal and continued layer by layer and from outside to inside. The attack started by the division of Al-OH bond by the OH ions. So, when low S/L ratio was employed, there was more uid medium then the solid content in the mix, the contact between the activating solution and the reacting materials was far and limited due to the large volume of uid medium. The dissolution of aluminosilicate was believed slow. This further explained the reason for the low compressive strength of kaolin geopolymers with S/L ratio of 0.60 (Mix 1). In contrast, when higher S/L ratio was used, the solid contents increased. The contact between the activating solution and the reacting materials were believed improved and hence showed increase in the compressive strength measured. Therefore, 1.00 was chosen as the best S/L ratio and the S/L ratio of a mixture design inuenced the workability of the geopolymer slurry and thus the compressive strength measured. 3.3. Effect of sodium silicate-to-sodium hydroxide ratio on compressive strength Fig. 5 represented the compressive strength of kaolin geopolymers with various Na2SiO3/NaOH ratios at constant S/L ratio of 1.00. Sinusoidal uctuated curve was observed. The strength results uctuated as observed in day 1 to day 3 due to the different reaction rate and formation of the structure within the tested ratio mainly due to the fact that kaolinite has comparatively lower reactivity which needed sufcient time for interactions to occur. The rate of reaction of kaolin depended on the supply of Si and Al to the reacting gel [35]. The reaction of the kaolin could be determined by the compressive strength measured. After 7 days,

a nearly stable parabolic curve observed. In overall, compressive strength increased as the Na2SiO3/NaOH ratio was increased until 0.32 (Mix 8). Mix 8 showed steady and higher strength increment among other ratios. As the Na2SiO3/NaOH ratio increased, the content of the waterglass liquid increased. This waterglass liquid was required for the geopolymerization process and acted as binder, alkali activator and dispersant or plasticizer [9]. However, at higher Na2SiO3/NaOH ratio than 0.32, it was believed that the high amount of waterglass liquid may inhibit the geopolymerization process.

Fig. 6. SEM micrograph of kaolin.

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Due to the low reactivity of the kaolin itself, kaolin faced problem owing to low dissolution of Al and Si ions into the system. Thus, insufcient Al and Si ions were to be taken into reaction to form a rigid network of geopolymers. As the Na2SiO3/NaOH ratio increased, high content of waterglass liquid caused the geopolymer slurry became very sticky due to the viscous nature of the waterglass liquid. This could be clearly showed by the decreased in slump values as the Na2SiO3/NaOH ratio was increased (Fig. 2b). These even worsen the condition where the dissolved Al and Si ions were unable to contact to each other. Thus, 0.32 was chosen as the best Na2SiO3/NaOH ratio for kaolin geopolymers. In previous research, the Na2SiO3/NaOH ratio by mass of 0.24 was reported for metakaolin-based geopolymers [36,37]. However, a higher Na2SiO3/NaOH mass ratio of 1.50 and 2.50 were reported by Chindaprasirt et al. [7] and Hardjito and Rangan [16], respectively for y ash-based geopolymers. It was believed that the Na2SiO3/NaOH ratio chosen depended strongly on the workability of the mixes. Even though both kaolin and metakaolin have plate-like morphology, metakaolin-based geopolymers required lower Na2SiO3/NaOH ratio than kaolin geopolymers due to metakaolin has higher water demands [38] as result of the increased in the surface are after calcination [26,39]. Thus, metakaolin geopolymers required only a lower mass ratio of Na2SiO3/NaOH (lower Na2SiO3 content) as high water demands in addition to the increased in the sodium silicate content declined signicantly the workability of the mixes due to the sticky nature as stated above. Nevertheless, higher ratio was used for the y ash-based geopolymers owing to the y ash could achieved better workability than kaolin and metakaolin. Sphericalshaped particles of y ash enhanced the workability of mixes by reducing the inter-particle friction [40]. In addition, the spherical shape minimized the particles surface to volume ratio, and thus reducing the water demands [26]. Thus, increased in the sodium silicate content would not affect signicantly the workability of y ash geopolymers and hence, higher Na2SiO3/NaOH ratio could be applied for y ash geopolymers. 3.4. Effect of solids-to-liquid and sodium silicate-to-sodium hydroxide ratios based on various molar ratios Table 3 represented the summary of the compressive strength of kaolin geopolymers based on SiO2/Al2O3, SiO2/Na2O, H2O/Na2O and Al2O3/Na2O molar ratios. By concerning the S/L ratios, the Al2O3/Na2O molar ratios increased when S/L ratios were increased. In other words, the aluminosilicate sources increased (or alkali activator liquid decreased) when the S/L ratios were increased. The Al2O3 came from the aluminosilicate source while the Na2O came from the alkali activator solution. In geopolymer chemistry, every Al atom required one Na atom to reach equilibrium [6]. At low S/L ratio, Al2O3/Na2O molar ratio decreased, excess Na content in the geopolymer system may weaken the structure formed. Conversely, the Na content was insufcient in the geopolymer system

at high S/L ratios (high Al2O3/Na2O molar ratio). The Na2O content was very important in geopolymerization process. Na2O content improved the solubility of the aluminosilicate source. However, excess in the Na2O content may degrade the strength of the geopolymers produced. In the contrary, increment in the Na2SiO3/NaOH ratios increased the SiO2/Na2O molar ratios. The compressive strength optimized at SiO2/Na2O molar ratio of 3.58 and decreased for any further rise in the SiO2/Na2O molar ratio. This meant that the SiO2 content was important to provide the silicate species to allow for the rapid exchange and oligomerization reaction between the aluminate and silicate species from the kaolin and the silicate species from the activating solution [41]. At low SiO2/Na2O molar ratio (low Na2SiO3/NaOH ratio), the Na2O was believed to be in excess as in the case of low S/L ratio (low Al2O3/Na2O molar ratio). Thus, from the study here, the optimum Al2O3/Na2O and SiO2/Na2O molar ratios were 1.09 and 3.58, respectively. These optimum values fell into range proposed by Davidovits [42] who stated that the composition of reactant mixture, in term of oxide molar ratios to prepare geopolymers was the following: 3.57 < SiO2/Na2O < 5 and 0.83 < Al2O3/Na2O < 1.25; The SiO2/Al2O3 molar ratio of the kaolin geopolymers of 3.28 was also fell in range of 3.5 < SiO2/ Al2O3 < 4.5. The H2O/Na2O molar ratio fell out the range proposed, that was 15 < H2O/Na2O < 17.5. However, Davidovits and Sawyer [43] has also proposed the range for H2O/Na2O of 1025.0. Based on other researchers doing on metakaolin geopolymers, the Na2O/SiO2 ratio of 0.25, SiO2/Al2O3 ratio of 3.30, H2O/Na2O ratio of 10.0, SiO2/Al2O3 ratio of 3.0 and Na2O/SiO3 ratio of 0.25 were the optimum chemical composition. Based on a study on metakaolin geopolymers, best mechanical performance were achieved when the ratio of SiO2/Al2O3 is 3.0 and Na2O/SiO3 ratio is 0.25 [44]. 3.5. SEM observation Scanning Electron Microscope (SEM) depicted morphological features of geopolymer of different degree of reaction at different ratios of activation medium. The micrographs were taken with the objective of analyzing their microstructural evolution. Dense in appearance reected the advances of geopolymerization reaction of samples activated with alkaline solution. Fig. 6 revealed the microstructure of pure kaolin. Morphological features of kaolin have plate-like structure [45,46] and this platelike structure contributed smaller surface area for geopolymerization process. In addition, as stated above in Section 3.2, kaolin comprised of one tetrahedral silica sheet and one octahedral alumina sheet, joined together by sharing a common layer of oxygen and hydroxyls. These layers were strongly held together by the hydrogen bonding, supplemented by dipoledipole and van der waals interactions. Thus, the layers only allowed very little, if any, substitution of other elements and have layer charge close to zero and thus contributed to low reactivity [47,48]. These were the reason

Table 3 Effect of SiO2/Al2O3, SiO2/Na2O, H2O/Na2O and Al2O3/Na2O molar ratios on compressive strength. Mix no. Molar ratios SiO2/Al2O3 1 2 3 4 5 6 7 8 9 3.41 3.28 3.20 3.15 3.11 3.16 3.24 3.28 3.32 SiO2/Na2O 2.16 2.78 3.39 4.00 3.19 3.29 3.48 3.58 3.67 H2O/Na2O 14.36 14.36 14.36 14.36 14.09 14.23 14.49 14.61 14.73 Al2O3/Na2O 0.63 0.85 1.06 1.27 1.02 1.04 1.07 1.09 1.11 Compressive strength (MPa) 1 day 0.20 0.86 1.42 2.06 2.03 1.31 1.48 1.80 1.53 3 day 0.18 1.09 1.74 2.21 1.71 1.84 1.56 1.68 1.43 7 day 0.15 1.18 2.38 2.29 2.10 1.30 1.77 2.65 1.23 28 day 0.18 1.48 2.65 2.56 1.83 2.88 1.91 3.38 2.26 60 day 0.35 1.78 3.10 2.99 2.28 3.80 2.98 3.93 3.40 90 day 0.46 2.44 4.20 4.60 3.06 3.27 5.15 5.22 3.61 180 day 0.40 3.98 5.34 5.81 3.27 4.48 5.72 6.05 4.57

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Fig. 7. Kaolin geopolymers at days 1, 7 and 60 of ageing for (a) Mix 2, (b) Mix 3 and (c) Mix 4 (constant Na2SiO3/NaOH ratio of 0.24).

Fig. 8. Kaolin geopolymers at days 1, 7 and 60 of ageing for (a) Mix 5 (b) Mix 6 and (c) Mix 7 (constant S/L ratio of 1.00).

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Fig. 9. Kaolin geopolymers at day 180 of ageing for (a) Mix 3 (at Na2SiO3/NaOH ratio of 0.32) and (b) Mix 7 (at S/L ratio of 1.0).

Fig. 10. XRD pattern of pure kaolin and kaolin geopolymers with different (a) x = S/L ratios and (b) y = Na2SiO3/NaOH ratios. D represents day of ageing (K = kaolinite; A = Alunite; Q = Quartz and D = Dickite).

for the very low compressive strength achieved. For y ash-based geopolymers, high compressive strength could be achieved [49] mainly due to the large surface area of spherical y ash particles which allowed for optimum dissolution by alkaline solution and geopolymerization reaction [50]. After activated by alkali activating solution, the edges of the kaolin particles were slightly altered [51]. Fig. 7 displayed the microstructures of kaolin geopolymers with various S/L ratios at constant Na2SiO3/NaOH ratio of 0.24 whereas Fig. 8 showed the SEM micrographs of kaolin geopolymers with various Na2SiO3/NaOH ratios at constant S/L ratio of 1.00. Both gures clearly showed that the kaolin has been activated by the activating solution with changes at the edges of the plate-like particles and became more compact from day 1 to day 60. As shown in Fig. 7, SEM micrograph of kaolin geopolymers with S/L ratio of 1.00 (Mix 3) has more geopolymeric gel than other samples. The microstructure of kaolin geopolymers with S/L ratio of 1.20 (Mix 4) was nearly similar to that with S/L ratio of 1.00 (Mix 3), except that it has larger precipitation. The solids ratio did not inuence the rate of alumino-silicates formation, but larger product precipitation was produced when the solids ratio increased. This was also agreed by Chen et al. [52] where higher S/L ratio favored the formation of precipitations. For Fig. 8, it could be observed that as the Na2SiO3/NaOH ratio increased, the microstructure of the activated kaolin become more compact, which further ascertained that the

presence of more waterglass liquid favored the geopolymer formation as stated above. Fig. 9 revealed the microstructure of kaolin geopolymers at day 180. At longer age, micrograph revealed that numerous kaolin particles being involved in the alkali activation, and coexisting with partially reacted or unreacted particles. The loosely grained structure contributed to the imperfect microstructure of kaolin geopolymers would be one of the main cause of poor compressive strength obtained. Table 4 showed the mass percentage of Si, Al and Na in the kaolin geopolymers as determined by EDX analysis. The result of EDX suggested that the element of kaolin geopolymers were in good agreement with their respective components. The kaolin geopolymers composed mainly of Al, Si and Na. The kaolin geopolymer has Si/Al ratio of 1.50 (Fig. 9a) and 1.60 (Fig. 9b). In summary, the kaolin geopolymers does not undergo complete geopolymerization and are not totally incorporated into the polymeric structure. The low reactivity of kaolin due to the plate-like and the layered structure, the dissolution of kaolin by alkaline solution was extremely slow and caused slow development of geopolymer gel and formation of strong structure. This was in agreement with Xu and van Deventer [53] who stated that the geopolymer structure using kaolinite source material alone produced weak structure. However, when the kaolinite was added to the y ash as minor portion, a strong and low cracking geopolymer was formed. As kaolin needed longer time for the interaction

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Fig. 11. IR spectra of kaolin (1) and geopolymer products with S/L ratio of (2) Mix 3, 1 day; (3) Mix 2, 7 days; (4) Mix 3, 7 days; (5) Mix 4, 7 days; (6) Mix 3, 60 days and (7) Mix 3, 180 days at constant Na2SiO3/NaOH ratio of 0.24.

Fig. 12. IR spectra of kaolin (1) and geopolymer products with Na2SiO3/NaOH ratio of (2) Mix 8, 1 day; (3) Mix 6, 7 days; (4) Mix 3, 7 days; (5) Mix 8, 7 days; (6) Mix 8, 60 days and (7) Mix 8, 180 days at constant S/L ratio of 1.00.

between the source materials, thus it was believed that the strength will be increased if the unreacted part and fastened structure reacted to form denser structure. 3.6. XRD analysis Fig. 10a showed the XRD pattern of geopolymer samples with various S/L ratios while Fig. 10b revealed the XRD pattern of geopolymer samples with various Na2SiO3/NaOH ratios. Pure kaolin comprised of kaolinite (K) as major mineral [51]. The characteristic kaolinite peaks are at 2h values of 12.3, 19.8, 24.9, 45.4, 55.1 and 62.2 [12]. Besides this, kaolin also contained some dickite (D) and quartz (Q). Alunite (A) could be found in trace amount. These alunite mineral and especially quartz phase has been found to be largely unreactive [13]. The reection peak still remained in the system and indicated that they did not take part in the geopolymerization process, but their intensities were slightly lower due to a dilution effect [54,55]. After geopolymerization process, a number of characteristic kaolinite peaks was remained in diffractogram of geopolymer samples due to the lower activities of pure kaolin [33]. However, these kaolinite peaks decreased in intensity in all geopolymer products and the intensity continued to decrease with ageing days as shown in Fig. 10 (spectra 1, 4, 6 and 7 in Fig. 10a and spectra 1, 5, 6 and 7 in Fig. 10b). This meant that the dissolution increased with ageing

Table 4 Mass percentage pure kaolin, and kaolin geopolymer using Energy Dispersive X-ray analysis (EDX). Mass percentage and ratios Si Al Na Pure kaolin (Fig. 6) 26.36 18.33 0.20 Kaolin geopolymers (Fig. 9a) 26.66 17.79 3.04 Kaolin geopolymers (Fig. 9b) 27.39 17.12 4.07

days. The position of halo (2h values between 20 and 30) shifted to higher angular values (Fig. 10) indicating the formation of alkaline aluminosilicate gel [13]. But, the halo was very small in the kaolin geopolymers. According to Cristobal et al. [51], the activation of kaolin with alkaline solution will form an amorphous aluminosilicate gel which acted as precursor for zeolite formation. Zeolite reection peaks were found in all kaolin geopolymer pastes. Peaks at 2h values of 14.0, 32.0, 35.0, 43.5, 50.5, 52.5, 59.0 and 61.0 most properly was corresponding to zeolite X (ICDD# 39-0218) [56] and will only appear in geopolymer samples. Initially, the zeolite X intensity was high but the peak lowered at longer age [45]. For day 1, the XRD pattern for S/L ratio of 1.0 (Spectrum 2 in Fig. 10a) was initially very similar to the raw material (Spectrum 1) due to early strength gain of geopolymer with only 1.42 MPa. Similar observation was found in Na2SiO3/NaOH ratio of 0.32 for day 1 (Spectrum 2 in Fig. 10b), where only 1.79 MPa has been recorded. At day 7, sample of Na2SiO3/NaOH ratio of 0.32 (Spectrum 5 in Fig. 10b) has overall lower intensities of characterized peak compared to the other sample and obtained the highest strength gain in the similar day, with 2.68 MPa. This situation was also appeared in S/L ratio of 1.0 at day 7 (Spectrum 4 in Fig. 10a), with 2.38 MPa being recorded. Another similar observation obtained from XRD pattern was that, all the geopolymer sample reduced in intensities which becoming amorphous at longer age with higher strength gain around 56 MPa at day 180 for both cases. In general, XRD pattern of geopolymer samples showed a large part of unreacted materials remained. These unreacted parts contributed to the low strength of geopolymer products. After alkaline activation, the peak shifted slightly to the right which indicated the occurrence of changes in the raw materials to geopolymers products. 3.7. FT-IR analysis Figs. 11 and 12 presented the IR spectra of kaolin geopolymers with different S/L ratios and Na2SiO3/NaOH ratios, respectively.

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C.Y. Heah et al. / Construction and Building Materials 35 (2012) 912922 Table 5 Peak height of SiOT (T = Al or Si) group (absorption peak at 930965 cm1) for kaolin geopolymers. Ageing day Peak height (%T) S/L ratio 1.0 (Mix 3) 1 7 60 180 26.5 24.0 17.5 15.0 Na2SiO3/NaOH ratio 0.32 (Mix 8) 28.0 27.5 20.0 11.0

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Transformation took place during the synthesis was indicated by the different absorption frequencies of kaolin and the synthesized geopolymers. In IR spectrum of kaolin, bands at 3688 cm1, 3617 cm1 and 1643 cm1 were corresponded to OH vibration. The peak around 1113 cm1 was attributed to SiO symmetrical stretching in tetrahedral, which vanished after geopolymerization reaction. Also, a weak band of SiO symmetrically stretching vibration was observed at 640 cm1. Absorption at 790 cm1 and 749 cm1 were assigned to SiOSi symmetrical stretching [57]. Peak at 995 cm1 was assigned as alternating SiO and AlO bonds. A shift of the asymmetric bending of the bonds OSiO and OAlO to lower frequencies was conrmed by previous ndings [34,58]. Band at 907 cm1 was the Al-OH bending mode. Another band at 544 cm1 was AlIVOSi, where Al3+ is in octahedral coordination [57]. In geopolymer products, major bands were broad band at 3000 3500 cm1 and 16501655 cm1, which were the OH stretching and OH bending, respectively. These peaks indicated the presence of weak H2O bond absorbed in the surface or caught in the cavities of structure [51,55]. From Fig. 11(2)(4) and Fig. 12(2)(5), it was clear that the peaks at 907 cm1 were shifted to higher frequency which was around 937 cm1, due to the alkalination from Al-OH into Al-(OH)(). The geopolymer bonding was lesser; hence, the strength was lower. In Fig. 11(5)(7) and Fig. 12(6)(7), the frequency change to around 967 cm1 which was vibration of asymmetric tension of SiOAl and AlOSi groups [51]. Table 5 represented the peak height in percentage transmittance of these absorption peaks (SiOAl and AlOSi groups) over age. The percentage transmittance was measured directly from the FTIR curves. The lower the percentage transmittance meant the greater the percentage absorption and hence the greater intensities of the peak. From Table 4, it was obvious that the percentage transmittance of the SiOT peak decreased over age for both S/L and Na2SiO3/ NaOH ratios. Thus, this peak increased in intensities over age [59] and contributed to higher strength gain (Figs. 4 and 5). Besides this, peak around 619662 cm1 which corresponded to zeolite [51]. Chandrasekhar and Pramada [45] also reported that the absorption peak near 670 cm1 was a typical band of zeolite X. These peaks showed decrease in intensities at latter age. This was clearly proved by XRD pattern (Fig. 10). It was believed that crystalline phase transformed into amorphous phase over ageing time. In general, large part of unreacted kaolin remained in the system which was shown by peaks at 1400 cm1 and 530 cm1 corresponded to asymmetric stretching vibration of SiO/AlO bonds and AIIVOSi.

kaolin geopolymers. The workability of the kaolin geopolymers mixes decreased with increasing in the ratios. The kaolin geopolymers have relatively low bulk densities (12501500 kg/m3). The bulk densities were consistent with the compressive strength measured. The bulk densities decreased from 7 to 28 days mainly due to the loss of unbound water to the atmosphere during curing process. The S/L and Na2SiO3/NaOH ratios affected compressive strength of kaolin geopolymers. However, the compressive strengths achieved by the kaolin-based geopolymers were quite low. The reason for the low compressive strength achieved was the limitation due to the structure of kaolin with kaolinite stacks and plate of low surface area. In addition, the strongly held alumina and silica sheets avoid the cations exchange and the substitution of elements. In spite of this, the strength of kaolin geopolymers increased with the ageing time but very slowly. From the experimental results, the S/L ratio of 1.00 and Na2SiO3/NaOH ratio of 0.32 were the optimum ratios for kaolin geopolymers. In term of oxide molar ratios, the compressive strength was the best when the Al2O3/Na2O and SiO2/Na2O molar ratios were 1.09 and 3.58, respectively. These values fell in the range proposed by many researchers. SEM analysis of kaolin geopolymers revealed the coexisting of both partially reacted or unreacted particles while EDX results of the reaction products conrmed the Si, Al and Na were the main elements. XRD pattern showed that kaolinite peaks decreased in intensity in all geopolymer products and the intensity continued to decrease with ageing days. The presences of crystalline peaks in the kaolin-based geopolymers were Zeolite X. FTIR spectra emphasized the increased in the intensity of the absorption peaks (SiOSi/SiOAl) and further ascertained the continuous dissolution and polycondensation of the reacting materials over age. Geopolymers possessed the ability to resist chemical attack and weathering and has long term durability. Kaolin geopolymers, like other geopolymers, produced from the activation of kaolinite with alkaline solution. The reaction products consisted SiOSi and Si OT geopolymer bondings. Thus, it was believed that the kaolin geopolymers should also durable. This was one of the characteristic of geopolymer products. However, the actual durability of the kaolin geopolymers should be tested in future work to improve its applications in various elds. Acknowledgment The authors of the present work wish to acknowledge the KACST for the support provided in this study through collaboration between KACST UniMAP. References
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4. Conclusion In this paper, the effect of S/L and Na2SiO3/NaOH ratios on the properties of kaolin geopolymers was investigated. Results concluded that kaolin geopolymers showed good volume stability with no crack and disintegration in water. This proved the existing of geopolymer bonding which hold the geopolymers from collapse. Both S/L and Na2SiO3/NaOH ratios affected the workability of the

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