Alkali-activated binders

INTRODUCTION To enhance the environmental and durability performance of future concrete structures, a new binder is required to replace Portland cement. The urge to reduce green house emissions due to cement production and improve the disintegration problems related to ordinary Portland cement (OPC) structures means an alternative binder with different properties to OPC is required. Examples of premature concrete disintegration include foundations of a tunnel in Dubai disintegrating after only 12 years in service [1], and a study of Norway OPC bridges indicating that only 25% of those built after 1970 presented corrosion problems [2]. Another author documented that 40% of the 600,000 bridges in the US were affected by corrosion problems with the cost of repairing operations estimated to be 50 billion dollars [3]. The durability problems of OPC are related to its intrinsic properties relating to a high permeability that allow aggressive elements and water to enter concrete, leading to carbonation and corrosion problems. Research work carried out on alkali-activated binders show enormous potential in becoming an alternative to OPC, with further research still required in order for these binders to become technically and economically viable construction materials. The development of alkali-activated binders had a major contribution in the 1940s, with Purdon [4] activating blast furnace slag with sodium hydroxide, with the process developed in two steps. The first step involved liberation of silica aluminium and calcium hydroxide, and the second step related to the formation of silica and alumina hydrates as well as the regeneration of the alkali solution, leading Purdon to conclude that alkali hydroxides act as catalysts. Since the 1940s, a large part of the investigations about alkali activated binders related to the activation of blast furnace slag, known as alkali-activated slag cement. Blast furnace slag is a by-product of the iron production industry, having a high volume of calcium which is attributed to the use of calcium carbonate in the iron calcination process. Glukhovsky [5] made crucial investigations about the activation of blast furnace slag; identifying hydration products as being composed of calcium and sodium alumino-silicate hydrates, and noticing that clay (alumino-silicate) minerals formed aluminium silicate hydrates (zeolite) when submitted to alkali activation. Alkali-activated binders are also termed geopolymers because they transform, polymerise, and harden at low temperatures, but are also inorganic, hard, and stable at high temperatures [6]. Theoretically, any material composed of silica and aluminium can be alkali activated, such as kaolinitic clays, metakaolin, fly ashes, and the previously mentioned slag. The exact reaction mechanism which explains the setting and hardening of alkaliactivated binders is not yet fully understood, however it does depend on the properties of the geopolymer and alkali activator. According to Glukhovsky [5], the mechanism of alkali-activation is composed of the destruction of the prime material into low stable structural units (breakdown of covalent bonds Si-O-Si and Al-O-Si), the accumulation of destroyed products, and the generation of a condensed structure, indicating an initial phase of silica dissolution, followed by the phases of transportation and polycondensation. According to Palomo [7], two models of alkali activation could be established depending on the prime materials used. The first model relates to activating blast furnace slag (Si + Ca) with a mild alkaline solution, having calcium silica hydrate (CSH) as the main reaction product. In the second model, the general example is the alkali activation of metakaolin (Si+Al) with medium

to high alkaline solutions, with the final product characterised by a zeolite polymeric model and high mechanical strength. Similarly, the alkali activation of fly ashes involves the breakdown of covalent bonds Si-O-Si and Al-O-Al, with the products starting to accumulate before finally condensing in a poorly ordered structure with high mechanical strength. The final reaction products and hence mechanical strength of alkali-activated binders depend on the structural conditions of the alumino-silicate materials, with natural materials leading to lower mechanical strength, while materials submitted to calcination such as fly ashes, slag, and metakaolin have higher mechanical strength. The alkali-activation reactivity depends on the amorphous content of silica and aluminium, with reactivity being higher with higher amorphous content [8]. In terms of the alkaline activators used, the most common types are a mixture of sodium or potassium hydroxide (NaOH, KOH) with sodium waterglass (nSiO2Na2O) or potassium waterglass (nSiO2K2O), which contain soluble silica [7]. Literature on the optimum concentration of using alkali activators differs significantly, with the influence of the different activators depending on the prime materials used [8]. The effect of different curing conditions on strength and other properties of geopolymer concrete depend on the prime materials and activators used. Different curing conditions include air and dry curing, at different temperatures ranging from 20oC to 80oC, with different durations. In terms of the optimum mixing order of the constituents, again depending on the constituents, generally the solids are mixed first, the activator is prepared and put to rest, and finally the activator is mixed with the solids [8].

References: [1] [2] [3] [4] [5] Mehta, P. K. (1991). Concrete in a marine environment, New York, USA: Elsevier Science Publishers. Gjorv, O. E. (1994). Steel corrosion in concrete structures exposed to Norwegian marine environment. ACI Concrete International 16(4), 35-39. Ferreira Rui Miguel. (2000). Tests for evaluation of concrete durability (Masters Thesis). University of Minho. Purdon, A. O. (1940). The action of alkalis on blast furnace slag. Journal of the Society of Chemical Industry 59,191-202. Glukhovsky, V. D., Rostovskaja, G. S., Rumyna, G. V. (1980). High strength slag alkaline cements. In: Proceedings of the seventh international congress on the chemistry of cement, vol. 3, p. 164-168. Davidovits, J. (1979). Synthesis of new high temperature geo-polymers for reinforced plastics/composites. SPE PACTEC 79 Society of Plastic Engineers, Brookfield Center, p.151-154. Palomo, A., Grutzek, M. W., Blanco, M. T. (1999). Alkali-activated fly ashes. A cement for the future. Cement and Concrete Research 29(8), 1323-1329.

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Pacheco-Torgal, F., Castro-Gomes, J., Jalali, S. (2008). Alkali activated binders: A review. Part 2. about materials and binders manufacture. Construction and Building Materials 22(7), 1315-1322.