Advances in understanding alkali-activated materials

The development of new, sustainable, low-CO2 construction materials is essential if the global construction industry is to reduce the environmental footprint of its activities, which is incurred particularly through the production of Portland cement. One type of non-Portland cement that is attracting particular attention is based on alkali-aluminosilicate chemistry, including the class of binders that have become known as geopolymers. These materials offer technical properties comparable to those of Portland cement, but with a much lower CO2 footprint and with the potential for performance advantages over traditional cements in certain niche applications. This review discusses the synthesis of alkali-activated binders from blast furnace slag, calcined clay (metakaolin), and fly ash, including analysis of the chemical reaction mechanisms and binder phase assemblages that control the early-age and hardened properties of these materials, in particular initial setting and long-term durability. Perspectives fo...

Geopolymers and Related Alkali-Activated Materials

The microstructural evolution of alkali-activated binders based on blast furnace slag, fly ash and their blends during the first six months of sealed curing is assessed. The nature of the main binding gels in these blends shows distinct characteristics with respect to binder composition. It is evident that the incorporation of fly ash as an additional source of alumina and silica, but not calcium, in activated slag binders affects the mechanism and rate of formation of the main binding gels. The rate of formation of the main binding gel phases depends strongly on fly ash content. Pastes based solely on silicate-activated slag show a structure dominated by a C–A–S–H type gel, while silicate-activated fly ash are dominated by N–A–S–H ‘geopolymer’ gel. Blended slag-fly ash binders can demonstrate the formation of co-existing C–A–S–H and geopolymer gels, which are clearly distinguishable at earlier age when the binder contains no more than 75 wt.% fly ash. The separation in chemistry between different regions of the gel becomes less distinct at longer age. With a slower overall reaction rate, a 1:1 slag:fly ash system shares more microstructural features with a slag-based binder than a fly ash-based binder, indicating the strong influence of calcium on the gel chemistry, particularly with regard to the bound water environments within the gel. However, in systems with similar or lower slag content, a hybrid type gel described as N–(C)–A–S–H is also identified, as part of the Ca released by slag dissolution is incorporated into the N–A–S–H type gel resulting from fly ash activation. Fly ash-based binders exhibit a slower reaction compared to activated-slag pastes, but extended times of curing promote the formation of more cross-linked binding products and a denser microstructure. This mechanism is slower for samples with lower slag content, emphasizing the correct selection of binder proportions in promoting a well-densified, durable solid microstructure.

Modification of phase evolution in alkali-activated blast furnace slag by the incorporation of fly ash

Influence of slag chemistry on the hydration of alkali-activated blast-furnace slag — Part I: Effect of MgO

Structural models for the primary strength and durability-giving reaction product in modern cements, a calcium (alumino)silicate hydrate gel, have previously been based solely on non-cross-linked tobermorite structures. However, recent experimental studies of laboratory-synthesized and alkali-activated slag (AAS) binders have indicated that the calcium-sodium aluminosilicate hydrate [C-(N)-A-S-H] gel formed in these systems can be significantly cross-linked. Here, we propose a model that describes the C-(N)-A-S-H gel as a mixture of cross-linked and non-cross-linked tobermorite-based structures (the cross-linked substituted tobermorite model, CSTM), which can more appropriately describe the spectroscopic and density information available for this material. Analysis of the phase assemblage and Al coordination environments of AAS binders shows that it is not possible to fully account for the chemistry of AAS by use of the assumption that all of the tetrahedral Al is present in a tobermorite-type C-(N)-A-S-H gel, due to the structural constraints of the gel. Application of the CSTM can for the first time reconcile this information, indicating the presence of an additional activation product that contains highly connected four-coordinated silicate and aluminate species. The CSTM therefore provides a more advanced description of the chemistry and structure of calcium-sodium aluminosilicate gel structures than that previously established in the literature.

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Generalized Structural Description of Calcium–Sodium Aluminosilicate Hydrate Gels: The Cross-Linked Substituted Tobermorite Model

For first time, an experimental and computational study has been conducted to define a structural model for the C-A-S-H gel forming in alkali-activated slag (AAS) pastes that would account for the mechanical properties of these materials. The study involved a comparison with the C-S-H gel forming in a Portland cement paste. The structure of the C-A-S-H gels in AAS pastes depends on the nature of the alkali activator. When the activator is a NaOH, the structure of the C-S-H gel falls in between tobermorite 1.4 nm with a mean chain length of five, and tobermorite 1.1 nm with a mean length of 14. When waterglass is the activator the structure of the C-A-S-H gel is indicative of the co-existence of tobermorite 1.4 nm with a chain length of 11 and tobermorite 1.1 nm with a chain length of 14. This very densely packed structure gives rise to excellent mechanical properties.

A model for the C-A-S-H gel formed in alkali-activated slag cements

Dry sliding wear behaviour of aluminium–lithium alloys reinforced with SiC particles

Thermal barrier coatings (TBC) are extensively used to protect metallic components in applications where the operating conditions include aggressive environment at high temperatures. Isothermal oxidation degrades the performance of these coatings, so this work analyses the mechanical properties (Young's modulus, E, and hardness, H) of TBC and its evolution after thermal exposure in air. ZrO2(Y2O3) top coat and NiCrAlY bond coating were air plasma sprayed onto an Inconel 600 Ni base alloy. The TBC were isothermally oxidized in air at 950 °C and 1050 °C for 72, 144 and 336 h. Depth sensing indentation tests were carried out on the ceramic coating to evaluate E and H in the as-sprayed materials and after isothermal oxidation. An approach based on multiple tests at different loads was used to determine size independent apparent E an H. These mechanical properties, measured perpendicular to the surface, clearly decreased after isothermal oxidation as a consequence of microcracking within the ceramic coating.

Mechanical properties of thermal barrier coatings after isothermal oxidation. Depth sensing indentation analysis

Wear behaviour of nanostructured alumina–titania coatings deposited by atmospheric plasma spray

The evaluation of the fatigue crack propagation at room and low temperature of neat polyamide 12 and its composite reinforced with short fibers processed by selective laser sintering (SLS) has been carried out. The linear fracture mechanics approach was successfully applied. The crack growth rate curves obeyed the Paris law, and their parameters were determined. It was found that at −50 °C fiber reinforcement improves the fatigue resistance of SLS polyamide 12 significantly while at room temperature similar fatigue behavior between the pure polyamide and the composite is observed. The polyamides microstructure and fracture surfaces obtained from the fatigues tests were analyzed using SEM. The differences in fracture micromechanisms at room and low temperatures in the PA12 composite were attributed to the different thermal expansion coefficients of the fibers as well as the crystalline and amorphous regions of the granular structure of the matrix.

A. Rico

Papers

A model for the C-A-S-H gel formed in alkali-activated slag cements

Dry sliding wear behaviour of aluminium–lithium alloys reinforced with SiC particles

Mechanical properties of thermal barrier coatings after isothermal oxidation. Depth sensing indentation analysis

Wear behaviour of nanostructured alumina–titania coatings deposited by atmospheric plasma spray

Fatigue crack growth of SLS polyamide 12: Effect of reinforcement and temperature