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).

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

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

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

Paving works on Westgate Freeway upgrade, Port Melbourne, Victoria, Australia. Figures 1 and 2 shows a small section of paving completed as part of the Victorian Government upgrade of the Westgate Freeway in Melbourne. While small in volume, this project required that the concrete meet all of the technical specifications of the local road authority, VicRoads, the ultimate asset owner, 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. This small section of work demonstrates the entire process of commercialisation of geopolymer concrete in reality. VicRoads Project: 180 Precast panels across Salmon Street Bridge in Port Melbourne, Victoria, Australia. Following from small paving works, 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, VicRoads. The specification of concrete was required to meet the structural concrete code (VicRoads Section 610), unlike the non-structural grade concrete used in the paving project in Figures 1 and 2. Here the level of concrete specification and scrutiny was consistent with bridge design, with the aim of using the highest grade concrete specified by VicRoads as a 'stretch target' for trials. As opposed to focusing on the technical detail of these projects, attention is drawn to the fact that these case studies demonstrate something that is rarely seen in geopolymer technology, i.e. the vast regulatory, asset management, liability and industry stakeholder engagement process that has been undertaken by Zeobond to commercialise geopolymer concrete. For Zeobond, the shift from the laboratory to the real-world is not a process of scale-up of technology alone. While such technical challenges are sufficient to be insurmountable to many, 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. 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, comes the need for a detailed understanding of the structure, chemistry and durability of these materials. 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. Several key aspects of the characteristics of alkali activated concrete, in particular the relationship between mix design, microstructure and in-service performance, are now beginning to be understood in more detail. Moreover, 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. Acknowledgements

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