Geopolymer: green chemistry and sustainable development solutions

Studies on fly ash-bas ed geopolymer concrete

tudes sur le bton gopolymre base de cendres volantes

B. Vijaya Rangan, Djwantoro Hardjito, Steenie E. Wallah, and Dody M.J. Sumajouw Faculty of Engineering and Computing, Curtin University of Technology, GPO Box U 1987, Perth 6845, Australia

Abstract: This paper presents test data on fly ash-based geopolymer concrete. The paper covers the material and the mixture proportions, the manufacturing process, the fresh and hardened state characteristics, the influence of various parameters on the fresh and hardened state concrete, the utilisation of the material in structural members, and the long-term behaviour. Cet article prsente les rsultats des essais sur le bton gopolymre base de cendres volantes, raliss Curtin University, Perth, Australie. Il couvre le matriau en soit, les proportions des mlange, le processus de fabrication, les caractristiques du bton frais et durci, l'influence de divers paramtres sur le bton frais et durci, l'utilisation du matriau dans les pices de structure, et son comportement long terme.

Introduction
Concrete is the most commonly used construction material; its usage by the communities across the globe is second only to water. Customarily, concrete is produced by using the Ordinary Portland Cement (OPC) as the binder. The usage of OPC is on the increase to meet infrastructure developments. The world-wide demand for OPC would increase further in the future. It is well-known that cement production depletes significant amount of natural resources and releases large volumes of carbon-dioxide. Cement production is also highly energy-intensive, after steel and aluminium. On the other hand, coalburning power generation plants produce huge quantities of fly ash. The volume of fly ash would increase as the demand for power increases. Most of the fly ash is considered as waste and dumped in landfills. In order to address the issues mentioned above, it is essential that other forms of binders must be developed to make concrete. The geopolymer technology developed by Davidovits in the 1980s offers an attractive solution (1, 2). In 2001, the authors embraced Davidovits original concept of geopolymers to make fly ash-based geopolymer concrete. This paper presents a summary of the results of this on-going research.

Past research on geopol ymer mat erial

In geopolymers, the polymerisation process involves a chemical reaction under highly alkaline conditions on AlSi minerals, yielding polymeric Si-O-Al-O bonds as proposed by Davidovits (1, 2).

The chemical composition of geopolymers is similar to zeolite, but shows an amorphous microstructure (3). The structural model of geopolymer material is still under investigation; hence the exact mechanism by which geopolymer setting and hardening occur is not yet clear (4). The mechanism of geopolymerisation may consist of dissolution, transportation or orientation, and polycondensation, and takes place through an exothermic process (1, 2). The strength of geopolymer depends on the nature of source materials. Geopolymers made from calcined source materials, such as metakaolin (calcined kaolin), fly ash, slag etc., yield higher compressive strength when compared to those synthesised from non-calcined materials, such as kaolin clay. The source material used for geopolymerisation can be a single material or a combination of several types of materials (5). A combination of sodium or potassium silicate and sodium or potassium hydroxide has been widely used as the alkaline activator, with the activator liquid-to-source material ratio by mass in the range of 0.25-0.30 (1-7). Because heat is a reaction accelerator, curing of fresh geopolymer is carried out mostly at an elevated temperature. When curing at elevated temperatures, care must be taken to minimize the loss of water. However, curing at room temperature has successfully been carried out by using calcined source material of pure geological origin, such as metakaolin (1-7). The geopolymer material can be used in various applications, such as fire and heat resistant fibre composites, sealants, concretes, ceramics, etc., depending on the chemical composition of the source materials and the activators. Davidovits (1, 2) suggested that the atomic 133

Sodium Silicate solution

Mixture No.

Added Water
7.5 14.4 20.7 26.5 10.6 21.3 -

Aggregates

Sodium Hydroxide solution Superplasticiser

Fly Ash

ratio of Si-to-Al of about 2 for making cement and concrete. Geopolymer can also be used as waste encapsulation to immobilise toxic metals (8).

Table 1: Details of the mixtures

Fly ash-based geopo lymer concrete

In the authors experimental work, geopolymer is used as the binder, instead of cement paste, to produce concrete. The geopolymer paste binds the loose coarse aggregates, fine aggregates and other un-reacted materials together to form the geopolymer concrete. The manufacture of geopolymer concrete is carried out using the usual concrete technology methods. As in the Portland cement concrete, the aggregates occupy the largest volume, i.e. about 75-80 % by mass, in geopolymer concrete. The silicon and the aluminium in the low-calcium fly ash are activated by a combination of sodium hydroxide and sodium silicate solutions to form the geopolymer paste that binds the aggregates and other un-reacted materials.

[ kg / m3 ] 1 2 3 4 5 6 7 8 9 10 11 12 13 14 1848 1848 1848 1848 1848 1848 1848 1848 1756 1756 1848 1848 1848 1848 408 408 408 408 408 408 408 408 476 476 408 408 408 408 103 103 103 103 103 103 103 103 120 120 103 103 103 103 41 (8M) 41 (10M) 41 (12M) 41 (14M) 41 (16M) 41 (14M) 41 (14M) 41 (14M) 48 (8M) 48 (14M) 41 (14M) 41 (8M) 55.4 (8M) 55.4 (8M) 6 6 6 6 6 8 8 8 8 6 6 6 60oC Oven 60oC Oven 60oC Oven 60oC Oven 60oC Oven Varied Oven Varied Oven Varied Oven 60oC Oven 60oC Oven 90oC Oven 90oC Oven 60oC Oven 60oC Steam

Materials, mixture compositions, and test specimen s

In the authors experimental work (9-16), low-calcium ASTM Class F dry fly ash obtained from a local power station was used as the source material. Most of the fly ash comprised oxides of silicon (about 50% by mass), aluminium (about 25% by mass), and iron (about 10 to 18% by mass). The calcium content of the fly ash was about 2% by mass. About 80% of the fly ash had particles of less than 38 to 55 micrometer in size. The details of the chemical composition of various batches of the fly ash, as determined by X-Ray Fluorescence (XRF) analysis, are given elsewhere (9-16). Analytical grade sodium hydroxide (NaOH with 98% purity) flakes dissolved in water and sodium silicate solution (Na2O=14.7%, SiO2=29.4% and water=55.9% by mass) were used. Both the liquids were mixed together and the activator solution was prepared at least one day prior to its use. To improve the workability of fresh concrete, a commercially available naphthalene based superplasticiser was used. A combination of locally available aggregates, i.e. granite-type coarse aggregates and fine sand, in saturated surface dry condition, were mixed together. The grading of the combined aggregates had a fineness modulus of approximately 4.5. The details of some of the Mixtures used in authors studies are given in Table 1. Complete details are given in References 9 to 16. The aggregates and the fly ash were mixed dry in a pan mixer for about 3 minutes. At the end of this dry mixing, the activator solution, the super plasticiser, and the extra water (if any) were mixed together, and then added to the solid particles and the mixing continued for another 3 to 5 minutes. The fresh concrete had a stiff consistency and was glossy in appearance. The fresh concrete mixture was then cast in 100x200 mm cylinder steel moulds in three layers. Each layer received 60 manual strokes and vibrated for 10 seconds on a vibrating table. Five cylinders were prepared for each test variable.

Immediately after casting, the samples were covered by a film to avoid the loss of water due to evaporation during curing at an elevated temperature. The specimens were cured in an oven or steamed chamber at a specified temperature for a period of time in accordance with the test variables selected. The details of the authors research have been reported elsewhere (9-12). At the end of the curing period, the 100x200 mm test cylinders were removed from the curing chamber, and were left in the moulds for six hours in order to avoid a drastic change of the environmental conditions. The specimens were then removed from the moulds, and left to air dry at room temperature until loaded in compression at the specified age in a universal test machine. Before testing, the specimens were weighed to determine the density of the material. The loading rate and other test procedures used were in accordance with the details specified in the relevant Australian Standard for testing Portland cement concrete. Each of the compressive strength test data points plotted in various graphs corresponds to the mean value of the compressive strengths of five test cylinders in a series. The standard deviations are plotted on the test data points as the error bar.

Parameters aff ecting fresh an d harden ed concrete

The fresh fly ash-based geopolymer concrete has a stiff consistency and is glossy in appearance. As in the case of Portland cement concrete, water content of the mixture influences the workability of geopolymer

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Curing

Geopolymer: green chemistry and sustainable development solutions

concrete, as measured by the conventional slump test. This is demonstrated in Figure 1.

Figure 1: Slump values for mixtures 1 to 5

In Figure 1, the slumps of various mixtures are plotted. In order to maintain the molar ratio of H2O-to-Na2O constant, the concentration of sodium hydroxide (NaOH) was increased in the mixtures that were added with extra water. The net effect is that higher the water content of the mixture higher is also the Na2O-to-SiO2 molar ratio. It is interesting to note that an increase in the Na2O-to-SiO2 ratio has insignificant effect on the compressive strength of hardened concrete (Figure 2).

With regard to hardened concrete, the molar ratio of H2Oto-Na2O significantly influences the compressive strength of fly ash-based geopolymer concrete. An increase in this ratio decreases the compressive strength (Figure 3). The test results plotted in Figure 3 are recast in Figure 4 in terms of geopolymer solids-to-water ratio by mass versus compressive strength. For a given geopolymer concrete, the total mass of water in the mixture is taken as the sum of the mass of water in the sodium silicate solution, the mass of water in the sodium hydroxide solution, and the mass of extra water, if any, added to the mixture. The mass of geopolymer solids is the sum of the mass of fly ash, the mass of sodium hydroxide flakes, and the mass of sodium silicate solids (i.e. the mass of Na2O and SiO2 in sodium silicate solution). Again, this relation is similar to the relationship between the water-to-cement ratio and the compressive strength of Portland cement concrete. Other important factors that influence the properties of hardened fly ash-based geopolymer concrete are the curing temperature and the curing time. Higher the curing temperature higher is the compressive strength (Figure 5). On the influence of curing time, fly ash-based geopolymer concrete cured for longer periods of time, shows an increase in its compressive strength, at least up to 48 hours (Figure 6).

Figure 2: Effect of molar NaO 2-to-SiO2 ratio on compressive strength

Another important characteristic of fresh concrete state is the setting time. Our laboratory experience showed that fresh fly ash-based geopolymer concrete could be handled at least up to 120 minutes after mixing, without any sign of setting, and without any degradation in compressive strength (11).

Figure 5: Effect of curing temperature on compressive strength

Figure 6: Influence of curing time on compressive strength Figure 3: Effect of the H 2O-to-Na2O molar ratio on compressive strength

Figure 4: Effect of Water-to-Geopolymer Solids ratio by mass on compressive strength

Figure 7: Compressive strength at different ages

In fly ash-based geopolymer concrete, we believe that the curing temperature and the curing time play significant
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roles not only as accelerators of chemical reaction, but also determine the extent of that reaction. Therefore, we found that geopolymer concrete samples cured at 60oC for a period of 24 hours showed very little strength gain after curing (Figure 7).

Elastic constants an d stress-strain relations

To measure the elastic constants and to investigate the stress-strain relations of fly ash based geopolymer concrete, four different mixtures were prepared to obtain four different compressive strengths in the range of 40 to 90 MPa (12). The elastic properties, Youngs modulus and Poissons ratio, were measured in accordance with the relevant Australian Standard. The Youngs modulus was determined as the secant modulus, measured at a stress level equal to 40 percent of the compressive strength of concrete.
Table 2: Youngs Modulus (Ec) and Poissons Ratio (!) of fly ash-based geopolymer concrete

After 52 weeks under sustained load of 40 % of the compressive strength, the drying shrinkage strain measured was approximately 100 x 10-6 and the creep factor (the ratio of creep strain to elastic strain) was found to vary between 0.44 and 0.63 when the compressive strength of concrete was approximately 60 MPa (15). In order to study the effect of chemical attack, specimens of fly ash-based geopolymer concrete were soaked in 5% concentration of sodium sulfate solution (Na2SO4). The variations in the compressive strength, the unit mass, the length change, as well as the physical appearance, were measured. It was found that after 52 weeks exposure, the geopolymer concrete did not show any sign of sulfate attack or degradation in properties. However, the compressive strength significantly decreased when the fly ash-based geopolymer concrete was immersed in 2% concentration of sulfuric acid solution (16).

Mixture No. 11 12 13 14

fcm (MPa) 89 68 55 44

Ec (GPa) 30.84 27.29 26.05 22.95

! 0.16 0.12 0.14 0.13

Manufacture of fly ash-based geopolym er con crete in ambient condition s

In most of our work, we have used heat curing (either steam curing or dry curing) to make the test specimens. However, we have also manufactured fly ash-based geopolymer concrete test specimens and cured them in ambient conditions at room temperature. For instance, the mixture given in Table 3 was used to cast 100mm by 200mm test cylinders. The slump of the fresh concrete was approximately 150 mm. The granite-type coarse aggregates were a combination of three different grades with maximum sizes of 20mm, 14mm, and 7mm. Both coarse and fine aggregates were in a saturatedsurface dry condition.
Table 3: Mixture proportion of geopolymer concrete cured in ambient conditions

The values of Youngs modulus of fly ash- based geopolymer concrete shown in Table 2 are similar to those of Portland cement concrete using the same coarse aggregate type. These values are at the lower end of the values predicted by the empirical expression given in the Australian Standard for Concrete Structures, AS3600. The Poissons ratio falls between 0.12 and 0.16, and is within the range observed for Portland cement concrete. The stress-strain relation in compression of fly ash-based geopolymer concrete is also similar to that of Portland cement concrete (12).

Material Coarse aggregates 20mm 14mm 7mm

Structuural appl ication s

Studies on the utilisation of fly ash-based geopolymer concrete in structural members have been carried out. Twelve 175x175x1500 mm reinforced columns were manufactured and tested. The primary variables of the experimental work were longitudinal reinforcement, load eccentricity, and concrete compressive strength in the range of 40 and 60 MPa to represent concrete with normal and high strength. The authors have also conducted tests on twelve 200x300x3300 mm reinforced geopolymer concrete beams. The test variables were the longitudinal tensile reinforcement ratio and the compressive strength of concrete. The behaviour of these reinforced columns and beams was similar to that of members made of Portland cement concrete. The test results have also shown that the design provisions of the current codes and standards are applicable to reinforced fly ash-based geopolymer concrete members. The details of these works are described elsewhere (13, 14).

Fine sand Fly ash (low-calcium ASTM Class F) Sodium silicate solution ( SiO 2/Na2O=2) Sodium hydroxide solution (8 Molar) Super Plasticiser

Mass, kg/m 3 277 370 647 554 408 103 41 6

Long-term properties
On the long-term properties, our laboratory experiments have shown that the fly ash-based geopolymer concrete undergoes low creep and very little drying shrinkage.
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The cylinders were left in ambient conditions of the laboratory when the room temperature varied between 20 and 25 degree C. The test specimens hardened within 24 hours, and were removed from the moulds three days after casting. The cylinders were tested in compression at various ages. Four cylinders were tested at each age. The mean compressive strength was 35 MPa on the 7th day and 47 MPa on the 28th day, after casting. It must be noted that the mean 7th day compressive strength of test cylinders manufactured using the same mixture and, cured immediately after casting at 60 degree C for 24 hours, ranged between 55 MPa (steam curing) and 65 MPa (dry curing). These heat-cured specimens did not gain strength with age (Figure 7).

Geopolymer: green chemistry and sustainable development solutions

Economic benef its

Fly ash-based geopolymer concrete offers several economic benefits over Portland cement concrete. The cost of one ton of fly ash is only a small fraction, if not free in some parts of the world, of the cost of one ton of Portland cement. Therefore, after allowing for the cost of activator liquids needed to the make the geopolymer concrete, we have estimated that the cost of fly ash-based geopolymer concrete may be about 10 to 30 percent cheaper than that of Portland cement concrete. In addition, we have learnt that the appropriate usage of one ton of fly ash earns one carbon-credit that has a redemption value of about 10 to 20 Euros. Based on the data given in this paper, one ton low-calcium fly ash can be utilised to manufacture approximately 2.5 cubic metres of fly ash-based geopolymer concrete, and hence earn monetary benefits through carbon-credit trade. Furthermore, the very little drying shrinkage, the low creep, and the excellent resistance to sulfate attack offered by the fly ash-based geopolymer concrete may yield additional economic benefits when it is utilised in infrastructure applications.

Concluding remarks
The paper presented a summary of the extensive studies carried out by the authors on the fly ash-based geopolymer concrete. Low-calcium fly ash is used as the source material, instead of the Portland cement, to make concrete. Fly ash-based geopolymer concrete has excellent compressive strength and is suitable for structural applications. The salient factors that influence the properties of the fresh concrete and the hardened concrete have been identified. The elastic properties of hardened concrete and the behaviour and strength of reinforced structural members are similar to those of Portland cement concrete. Therefore, the design provisions contained in the current standards and codes can be used to design reinforced fly ash-based geopolymer concrete structural members. The fly ash-based geopolymer concrete also shows excellent resistance to sulfate attack, undergoes low creep, and suffers very little drying shrinkage. The paper has identified several economic benefits of using fly ashbased geopolymer concrete.

References
1. Davidovits J. Chemistry of Geopolymeric Systems, Terminology. In: Joseph Davidovits, Davidovits R, James C, editors. Geopolymer '99 International Conference; 1999 June 30 to July 2, 1999; France; 1999. p. 9-40. 2. Davidovits J. Properties of Geopolymer Cements. In: First International Conference on Alkaline Cements and Concretes; 1994; Kiev, Ukraine, 1994: SRIBM, Kiev State Technical University; 1994. p. 131-149. 3. Xu H, van Deventer JSJ. The Geopolymerisation of Alumino-Silicate Minerals. International Journal of Mineral Processing 2000;59(3):247-266. 4. van Jaarsveld JGS, van Deventer JSJ, Lukey GC. The Effect of Composition and Temperature on the Properties of Fly Ash and Kaolinite-based Geopolymers. Chemical Engineering Journal 2002;89(1-3):63-73.

5. Xu H, van Deventer JSJ. Geopolymerisation of Multiple Minerals. Minerals Engineering 2002;15(12):1131-1139. 6. Swanepoel JC, Strydom CA. Utilisation of fly ash in a geopolymeric material. Applied Geochemistry 2002;17(8):1143-1148. 7. Barbosa VFF, MacKenzie KJD, Thaumaturgo C. Synthesis and Characterisation of Materials Based on Inorganic Polymers of Alumina and Silica: Sodium Polysialate Polymers. International Journal of Inorganic Materials 2000;2(4):309-317. 8. van Jaarsveld JGS, van Deventer JSJ, Lorenzen L. The Potential Use of Geopolymeric Materials to Immobilise Toxic Metals: Part I. Theory and Applications. Minerals Engineering 1997;10(7):659-669. 9. Hardjito D, Wallah SE, Rangan BV. Study on Engineering Properties of Fly Ash-Based Geopolymer Concrete. Journal of the Australasian Ceramic Society 2002;38(1):44-47. 10. Hardjito D, Wallah SE, Sumajouw DMJ, Rangan BV. Fly Ash-Based Geopolymer Concrete. Australian Structural Engineering Journal, Engineers Australia, 2005. 11. Hardjito D, Wallah SE, Sumajouw DMJ, Rangan BV. On The Development of Fly Ash-Based Geopolymer Concrete. ACI Materials Journal, American Concrete Institute, December, 2004. 12. Hardjito D, Wallah SE, Sumajouw DMJ, Rangan BV. Introducing Fly Ash-based Geopolymer Concrete: Manufacture and Engineering Properties. In Proceedings of the International Conference Our World in Concrete, Singapore, August 2005. 13. Sumajouw DMJ, Hardjito D, Wallah SE, Rangan BV. Behaviour of Geopolymer Concrete Columns Under Equal Load Eccentricities. In: Proceedings of the Seventh International Symposium on Utilisation of High Strength/High Performance Concrete; Washington DC, USA: American Concrete Institute; June 2005. 14. Sumajouw DMJ, Hadrjito D, Wallah SE, Rangan BV. Flexural Behaviour of Reinforced Fly Ash-Based Geopolymer Concrete Beams. In Proceedings of CONCRETE 05 Conference, Melbourne, Concrete Institute of Australia, October 2005. 15. Wallah SE, Hardjito D, Sumajouw DMJ, Rangan BV. Creep and Drying Shrinkage Behaviour of Fly Ash-Based Geopolymer Concrete. In Proceedings of CONCRETE 05 Conference, Melbourne, Concrete Institute of Australia, October 2005. 16. Wallah SE, Hardjito D, Sumajouw DMJ, Rangan BV. Sulfate and Acid Resistance of Fly Ash-Based Geopolymer Concrete. In Proceedings of the Australian Structural Engineering Conference, Newcastle, Engineers Australia, September 2005.

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