Alkali-activated 'geopolymer' concrete has been commercialised in Australia under the trade name E-Crete(TM) and is now

finding acceptance among the end-user community and from regulatory authorities. E-Crete is derived from fly ash and blast furnace slag with proprietary alkali activators and is available in both precast and pre-mix forms. The pre-mix concrete is able to be placed using largely standard concrete processing equipment and expertise. A life-cycle analysis of E-Crete has shown savings of around 80% in CO2 emissions compared to a standard OPC-based binder, which provides the primary driver for the uptake of this technology on a larger scale. Commercialisation of geopolymer technology by Zeobond has been linked closely with both scientific research in this area and a broad process of industry and stake-holder engagement. The combination of these two activities will be highlighted throughout this article.
Introduction Concrete made from OPC including its blends with mineral admixtures is second only to water as the commodity most used by mankind today (1). Global OPC production in 2008 was around 2.6Bnt (2), corresponding to around 11Bnt/yr of concrete (3). The cement industry contributes conservatively 5-8% of global carbon dioxide (CO2) emissions (4), mainly through decomposition of limestone and combustion of fossil fuels during cement production. Grinding and transport are lesser but also significant contributors to the environmental footprint of the cement industry. With rapidly increasing demand for advanced civil infrastructure in China, India, the Middle East and the developing world, the cement and concrete industries are expected to expand significantly (5). The future cement industry is now coming to grips with the fact that meaningful production of alternative binders will form part of a carbon constrained industry, aiding to significantly reduce CO2 emissions and provide some advantages in performance only offered by these alternative binding systems (6 - 7). Usually the driver for competition has been cost reduction, in which case alternative materials starting from a low volume basis can never compete against large-scale OPC production. Abatement of CO2 and technical features are now forming a major role in growth of alternative binder systems. There are various possible alternatives to OPC technology which have attracted attention in different parts of the world (8). Calcium sulphoaluminate cements are increasingly being used and studied and contain binding phases based mainly on Klein's compound (ye'elimite) (9 - 10). In addition, there are two major types of alternative binders that have not been commercialised widely, being the alkali activated material (AAM) system and also magnesium-based systems. In AAM chemistry, the reactive aluminosilicate phases present in materials such as fly ash, slag, calcined clay or volcanic ash are reacted with alkaline reagents including alkali metal silicates, hydroxides, carbonates, and/or sodium aluminate (11). to form zeolite-like aluminosilicate gel phases of varying (but generally low) degrees of crystallinity. AAM concrete has been shown to be quite resistant to attack by acids and by fire and does not produce the high reaction heat associated with OPC concrete, which reduces cost and potential cracking issues when the material is placed in large volumes (12).

research into alkali activation technology then moved eastward for several decades. Both the former Soviet Union and China developed alkali activation as a means of supplementing Portland cement production by utilising alkali activation of various types of slags. However. patented numerous aluminosilicate-based formulations for niche applications from the early 1980s onwards (17) and first applied the name 'geopolymer' to these materials (18). alkali activation research in the Western world was quite limited until the 1980s. His slag-alkali binders displayed rates of strength development and final strengths comparable to Portland cements. which is now available in Australia in precast. working in France. and low heat evolution. with much lower CO2 emissions than OPC. as highlighted in the timeline published in a review by Roy (16). particularly as a repair material for concrete runways (19). and in particular its development via the E-Crete(TM) technology. the sensitivity of the material properties to the amount of water added. Experience over the following 70 years has shown that Purdon was correct in identifying these as issues of concern . The focus of this article will therefore be on the commercial application of AAM technology. but in general the magnesium phosphate system has technical and economic limitations compared with AAMs.and silica-containing solid precursor as a means of forming a solid material comparable to hardened Portland cement was first introduced by the Belgian civil engineer. the low solubility of the hardened binder phases. This report was prepared in conjunction with the commercial producers of an alkali-activated binder which was at the time sold under the name Pyrament. alkali activation research has grown dramatically in all corners of the globe.but it has also been shown that each is able to be remedied by the correct application of scientific understanding to the problems at hand.see the comparable listing of difficulties presented by Wang and co-workers in 1995. was noted as potential problems. After the work of Purdon. Phosphate cements have not been used commercially and require more research and development. He also noted enhanced tensile and flexural strength compared to Portland cements of similar compressive strength. oxychloride and other specific types of phase assemblage) have been used in niche applications and can also give superior fire resistance. many of which are based around the development of sulphate-containing phases for strength development (12). The United States Army published a report in 1985 discussing the potential value of alkali activation technology in military situations. Work in the former Soviet Union was initiated by Glukhovsky at the institute in Kiev which now bears his name15 and focused predominantly on alkali-carbonate activation of metallurgical slags. with more than 100 active research centres (academic and commercial) now operating worldwide. Alkali activation through the 20th Century The reaction of an alkali source with an alumina. as well as the difficulties inherent in handling concentrated caustic solutions. Following this initial investigation in Western Europe. . A O Purdon in 1940 (13). pre-mix and in-situ cast formats. Since the 1990s. Chinese researchers also developed a range of materials throughout the 1980s and subsequently. Davidovits. for example (14) .Magnesium-based cements (including oxide. phosphate.

The Melbourne-based company Zeobond Pty Ltd developed its own pilot-scale production facilities in 2007 and now supplies its concrete. To a large extent though. comprise mainly a low-calcium C-S-H structure with significant Al substitution (sometimes termed C-A-S-H) (12. This means that the N-A-S-H structure is not as tightly space-filling as the C-A-S-H. continues to be the key driver for the short term adoption of geopolymer concrete. Research on the durability of AAM The nano. in particular in the study of areas such as setting time. . workability and durability. E-Crete utilises a blend of fly ash and blast furnace slag as its binder. Alkali activated binders derived from Class F fly ash and other low calcium AAM binders predominantly comprise a sodium aluminosilicate gel. closing this clear and apparent disparity between the laboratory and the real-world has been the focus of Zeobond. Being able to do this has unlocked the commercial value of geopolymer technology. Rather. E-Crete(TM).' (20) parallel to the C-S-H terminology for calcium silicate hydrates. There are numerous technical and commercial factors driving the commercial adoption of AAM technology. molecular water remains within the gel (22). Indeed.AAM research and commercialisation in Australia The commercial implementation of AAM technology in Australia is currently being driven by multiple teams operating in different parts of the country. There is now a growing amount of scientific literature exploring the properties of geopolymeric materials on the laboratory scale. plays an enabling role in the commercialisation process. which takes time and demonstration on a relevant industrial scale to gain practical credibility and the cost implications of non-equitable economies of scale. which incorporates the water into its crystal structure during hydration when filling the pore space. The Centre for Sustainable Resource Processing. based in Perth. It is clear that the development of an understanding of the chemistry and mechanisms of geopolymer synthesis is pivotal to the optimal mix design of 'green' concretes for large-scale applications in industry. 21). The alkali-activated slag sub-class of AAM binders. The main distinction in a microstructural/durability sense between the alkali aluminosilicate (N-A-S-H) and C-A-S-H gels is that the N-AS-H structure does not chemically bind water into a hydrate structure.and micro-structure of AAM binders are essential to the control of durability. has been making advances in this area over the past decade and conducted a number of trial pours in recent years. to major civil infrastructure projects including freeway expansion works and bridge construction and repairs through license. A detailed chemical understanding of the properties of AAM binders. which has been termed by some as 'N-A-S-H. on the other hand. Counter-balancing this demand driver is the inherent resistance of the civil construction industry to new products. Demand pull. Geopolymers that perform according to all standards can be synthesised easily in a laboratory. led by a carbon conscious consumer market. with combinations of proprietary alkaline activating components which are tailored for specific raw materials and products. while it is a much more demanding task to reproduce such performance in a commercially and practically feasible form in real-world applications. this information has extremely limited value.

excellent performance has been shown by samples synthesised in eastern Europe in the 1970s and analysed after more than 20 years of service (12. which further highlights the need to design a low-permeability microstructure to achieve acceptable durability. even in unreinforced materials (26).28). particularly due to chloride attack. even at relatively low chloride levels. which has shown the role of calcium compounds in reducing geopolymer binder permeability by the reduction of porosity and the refinement of pore diameters (23). However. 31). carbonation tends to form sodium carbonates and bicarbonates. 33). mortars and concretes. 24. At longer times the presence of chloride can lead to decreased strength performance. which will be highly significant in determining the ability to resist the loss of pore solution alkalinity. but this is most likely due to the calcium ions (25).Wood's metal intrusion porosimetry has recently been applied for the first time to AAM binders. but it is not clear how these results will transfer to the fly ash system given the differences in gel chemistry. What actually is the effect of carbonation on AAM concrete performance? Particularly in the case of low-Ca AAMs. This excellent performance of alkali-activated slags is related to the highly refined pore network which is generated by alkali activation of blast furnace slag. This has not yet been studied in detail. This is certainly of relevance and importance in the commercial application of AAM technology and the carbonation resistance of existing and recently-placed AAM concrete elements continues to be monitored with interest. depending on other synthesis parameters (35). another critical question must be raised in this discussion. which are more soluble than the CaCO3 formed by carbonation of OPC and may therefore act as an alkali sink and/or play a buffering role in the pore solution. Criado et al. with the performance of these materials in accelerated chloride penetration tests generally observed to be at least comparable to that of Portland cements (29 . The main effect of chloride on AAM concretes is this corrosive effect on embedded steel reinforcing. The carbonation resistance of well-cured alkali-activated slag systems has been claimed to be very good. and showed that the outcome could be either an increase or a reduction in the rate of carbonation. 32. CaCl2 showed an accelerating effect. Lee & van Deventer observed a weak retarding effect upon addition of KCl to fly ash-derived AAM pastes. Fly ash-based AAMs made with chloride-contaminated mix water show a severe effect on the likelihood of electrochemical corrosion on reinforcing steel (27 . which leads eventually to depassivation of reinforcing steel as chloride ions diffuse to reach the metal surface. but may be a point of interest in future studies. There have been a number of studies of chloride diffusion in alkali-activated slag concretes. The study of samples with chloride added in the mixing water is also of value in determining the likely effects of chloride ingress on the AAM binder structure. The effects of carbonation on the structure and properties of AAMs are also very much of interest.30). observed the formation of sodium bicarbonate in their low-calcium fly ash-based AAM samples. Bernal added metakaolin to sodium silicate-activated slag pastes. forming a dense low-calcium C-A-S-H phase (23. This can give a reduction of up to a factor of 10 in effective diffusion coefficients (24). However.34 with long-term curing (and therefore more refined pore structures) giving less carbonation. The path of commercialisation .

Acknowledgements . Conclusions Along with the need to introduce alternative binder systems to complement OPC-based materials and to reduce the environmental footprint of the construction industry. asset management. unlike the non-structural grade concrete used in the paving project in Figures 1 and 2. chemistry and durability of these materials. Following from small paving works. VicRoads Project: 180 Precast panels across Salmon Street Bridge in Port Melbourne. this project required that the concrete meet all of the technical specifications of the local road authority. This small section of work demonstrates the entire process of commercialisation of geopolymer concrete in reality. Moreover. the Port Melbourne City Council and was approved for use by the construction consortium that included numerous national and multinational construction companies and engineering firms. with the aim of using the highest grade concrete specified by VicRoads as a 'stretch target' for trials. Australia. While such technical challenges are sufficient to be insurmountable to many. Here the level of concrete specification and scrutiny was consistent with bridge design. comes the need for a detailed understanding of the structure. Victoria. the toughest challenges in the commercialisation of geopolymer concrete and the development of a geopolymer industry involve the engagement and inclusion of the existing industry in the development process. VicRoads. it is the ability to manage the scale-up of industry participation and acceptance of geopolymer concrete that provides the core challenge to the future world of a geopolymer concrete industry. Figures 1 and 2 shows a small section of paving completed as part of the Victorian Government upgrade of the Westgate Freeway in Melbourne. microstructure and in-service performance. liability and industry stakeholder engagement process that has been undertaken by Zeobond to commercialise geopolymer concrete. VicRoads. i.e. the vast regulatory. in particular the relationship between mix design. Australia. As opposed to focusing on the technical detail of these projects. Figures 3 and 4 shows the installation and final vista of a small project completed using 55MPa E-Crete in Victoria for the local road authority. For Zeobond. The specification of concrete was required to meet the structural concrete code (VicRoads Section 610). the ultimate asset owner. Several key aspects of the characteristics of alkali activated concrete. While small in volume. It is important for commercial alkali activated concrete producers to work closely in partnership with academic research partners to ensure that this understanding is developed and to as far as possible ensure the durability of the materials being produced and marketed. attention is drawn to the fact that these case studies demonstrate something that is rarely seen in geopolymer technology. Port Melbourne.Paving works on Westgate Freeway upgrade. are now beginning to be understood in more detail. Victoria. the shift from the laboratory to the real-world is not a process of scale-up of technology alone.

2009. E.L.' 3rd Ed.Parts of this work have been funded by an Australian Research Council Linkage Project grant co-sponsored by Zeobond Pty Ltd.' Woodhead. Commun. P. D. Yang. 11 (1).K. & Kirkpatrick. Concr. 10.L. 38 (2).-C.. 128. Properties and Industrial Applications. 14. Res. . Properties and Materials. 'Industrially interesting approaches to "low-CO2" cements. Zhang. O..M. 50.L.. 2009. Melbourne.. Mehta.' Adv. 38 (2). 'Geopolymers: Structures.. 1940. Concr. Krivenko. J. R. Chem. 2000. Res.. 'High-performance cement matrices based on calcium sulfoaluminate-belite compositions. K.P. Tam. Wang. Abingdon.. 'Energy efficiency and CO2 emissions from the global cement industry. 2001. van Deventer. 2006. 'Calcium sulfoaluminate cements .M. 34. 1349. J.' Cem.' Taylor & Francis. Scrivener.-D. Sharp. P. 2008. M. 115.. Pu X. 6. International Energy Agency. C. J.freedoniagroup.' Adv. Gartner. 7. K.. 'Low CO2 concrete: Are we making any progress?' Part of: 'BEDP Environment Design Guide. 1881. UK. Damtoft.. Freedonia Group. L. Trans. Duxson.' Australian Institute of Architects..V. 30.' Cem. 11. Purdon. Ind. Taylor. Cem. Sorrentino. 3. 'Alkali-Activated Cements and Concretes. Concr. Res..html. 8. Monteiro..D.S. 3.. 93. 'Cements of yesterday and today. F. 'Concrete: Microstructure.J. Cem. Concr. 2008.' Cem. Lukasik..L.. Res. 4. E. S. C. 1995.L.' 2006. 1999. 2.' J. 2004 1489. Roy. Cambridge..H. Shi. Gartner. Provis. McGraw-Hill. P. J. C. D. P.C. J.' Cem. 2009. Paper PRO24. Pratt. Provis. Aïtcin. J. Lawrence.. Glasser.. D.. J. P. New York.' Cem.' http://www. 'Sustainable development and climate change initiatives. Gielen.. Res. Res.com/World-Cement. D. R.L. 'World Cement to 2012. 191.low-energy cements. Australia.. 31 (12). A. Res. 7.J. Concr. Soc. Processing. 12. P. References 1. 9. 59. UK.' in: Provis. 'Alkali-activated slag cement and concrete: a review of properties and problems. 'The action of alkalis on blast-furnace slag. special cements or what?. 5. 2006. pp. Concrete of tomorrow. Herfort. 'Activating solution chemistry for geopolymers. J. Scrivener. 'Innovation in use and research on cementitious material. 13.S.

.Opportunities and challenges.. Roy.C. 63. Jiang. 832. 'The effect of alkali cations on aluminum incorporation in geopolymeric gels..J. W. 29 (2).. Fernández-Jiménez. blended.A.. (Submitted).. 'The effect of ionic contaminants on the early-age properties of alkaliactivated fly ash-based cements. 16. 2008. 2009.. Concr. A.M.' Ind. Davidovits. V... 17. 21. France. M. Lloyd. Randall. 'Geopolymer Chemistry and Applications.349. Surf.M. J. Malhotra. 35 (6).G. Res. 44 (4). García-Lodeiro.. Roy. J.A. 29. Chem. Kiev.. S. Richardson. I. González. Lloyd. R. J.' J.' Micropor. 2009. T. W. 'Properties and durability of alkali-activated slag concrete. Glukhovsky.W. 'Potential applications of alkali-activated aluminosilicate binders in military operations. J. 23.. J. 1994. Provis. 2005. Saint-Quentin. A. ..T.. A.' Cem. 20. A. Sci. 509. 1959. Lukey.K. 2005. D. Washington DC.S.L. R.. 1999.' Cem.. Department of the Army. 1879.. 18.. Miranda.. 2008. Mater. Res.J. van Deventer. Res. 'The characterisation of hardened alkaliactivated blast-furnace slag pastes and the nature of the calcium silicate hydrate (C-S-H) paste.' Corros. Duxson.' Cem. 32 (4).K. 'Spatial distribution of pores in fly ash-based inorganic polymer gels visualised by Wood's metal intrusion. R. G.' ACI. E. 28... van Deventer. 27.. Technol. Palomo. Separovic. J.. J. 1210. Concr. 89 (5). Concr.. 115. J. Res. A...J.' Institut Géopolymère.R. Blanco.. 1058. Palomo. A.. 32. Palomo. and alkali-activated cement pastes and its relation to other properties. van Deventer. Colloids. J. P. 'A study on the passive state stability of steel embedded in activated fly ash mortars.. R. Malone.' Cem.. F. 50 (4). 'FTIR study of the sol-gel synthesis of cementitious gels: C-S-H and N-A-S-H. A. Kirkpatrick. 577. Mater. Res. 2002.' Cem.. S.. 4. C. Res. G. Sol-Gel Sci. Brough.. Lee.15. 813.386.. V. Mesopor. van Deventer J.. D.S.R.W.. 30.. J.' Cem. 'Mineral polymers and methods of making them. 'Soil Silicates.W. 1992. Dobson. A. J. Concr.L. 2002. 249. Provis.G.' US Patent No... 1985. Geotechnical Laboratory. Lee. 1982.. 24 (5). 24. I. 26. 211 (2-3).. 'Corrosion resistance in activated fly ash mortars.. J... K.. M. 126 (1-2). J. Eng. D. Silsbee.. Groves. Concr. P. van Deventer. 'The effects of inorganic salt contamination on the strength and durability of geopolymers. 22. González.J. J. Res. Fernández-Jiménez.S. 'Chloride diffusion in ordinary. W. 19. 25.' Gosstroyizdat. Bilodeau. Smeaton. J. Bastidas...W. C. 45 (1). A. 'Pore solution composition and alkali diffusion in inorganic polymer cement. 'Alkali-activated cements . 30. 2008. Douglas. 2000. Concr. D. Davidovits..M.. Fernández-Jiménez.

'Alkali activation of fly ashes. van Deventer.31. 34. Mater.V.. M.. Bernal. Industr.R. R.. A. 33. S.. 131. PhD Thesis. Fernández-Jiménez. Xu.' Fuel 84.' Silic.. Provis.. 67 (1) 2002. J.' ACI. 2008. PhD Thesis. J. (16) 2005. 'Characterisation of aged slag concretes.S. H.... Palomo. Colombia. P. 2008. 'Carbonation aspects of alkali activated slag mortars and concretes.A. 105 (2). 35. Universidad del Valle. A. Criado. 37.L. J. University of Melbourne. Deja. J. Lloyd. 2048. . Krivenko.. Part 1: Effect of curing conditions on the carbonation of the reaction products. 2009. 32.J. Cali. Australia.