Thermodynamic modelling of alkali-activated slag cements

This paper presents a thermodynamic modelling analysis of alkali-activated slag-based cements, which are high performance and potentially low-CO2 binders relative to Portland cement. The thermodynamic database used here contains a calcium (alkali) aluminosilicate hydrate ideal solid solution model (CNASH_ss), alkali carbonate and zeolite phases, and an ideal solid solution model for a hydrotalcite-like Mg-Al layered double hydroxide phase. Simulated phase diagrams for NaOH- and Na2SiO3-activated slag-based cements demonstrate the high stability of zeolites and other solid phases in these materials. Thermodynamic modelling provides a good description of the chemical compositions and types of phases formed in Na2SiO3-activated slag cements over the most relevant bulk chemical composition range for these cements, and the simulated volumetric properties of the cement paste are consistent with previously measured and estimated values. Experimentally determined and simulated solid phase assemblages for Na2CO3-activated slag cements were also found to be in good agreement. These results can be used to design the chemistry of alkali-activated slag-based cements, to further promote the uptake of this technology and valorisation of metallurgical slags

Uptake of chloride and carbonate by Mg-Al and Ca-Al layered double hydroxides in simulated pore solutions of alkali-activated slag cement

Chloride ingress and carbonation are major causes of degradation of reinforced concrete. To enable prediction of chloride ingress, and thus to improve the durability of structural alkali-activated slag cement (AAS) based concretes, it is necessary to understand the ionic interactions taking place between chlorides, carbonates, and the individual solid phases which comprise AAS. This study focused on two layered double hydroxides (LDH) representing those typically identified as reaction products in AAS: an Mg-Al hydrotalcite-like phase, and an AFm structure (strätlingite), in simulated AAS pore solutions. Surface adsorption and interlayer ion-exchange of chlorides occurred in both LDH phases; however, chloride uptake in hydrotalcite-group structures is governed by surface adsorption, while strätlingite shows the formation of a hydrocalumite-like phase and ion exchange. For both Ca-Al and Mg-Al LDHs, decreased chloride uptakes were observed from solutions with increased [CO₃²⁻]/[OH⁻] ratios, due to the formation of carbonate-containing hydrotalcite and decomposition of AFm phases, respectively

The effect of blast furnace slag/fly ash ratio on setting, strength, and shrinkage of alkali-activated pastes and concretes

The aim of this study was to determine the effects of partial fly ash substitution in to a series of alkali-activated concrete based on a high-MgO blast furnace slag BFS. Mixes were activated with various amounts of sodium silicate at alkali modulus (mass ratio SiO2/Na2O) values of 1.0, 0.5, and 0.25. The results showed that, an increase in the fly ash content extended the initial setting time but had very little effect on the final setting time, although the early age compressive strength was decreased. The fly ash addition had no effect on the drying shrinkage but lowered the autogenous shrinkage. The mixes activated with sodium silicate at a lower alkali modulus showed a significantly higher autogenous shrinkage but lower drying shrinkage values. Severe micro cracking of the binder matrix was observed only for mixes without fly ash, activated with sodium silicate solution at higher alkali modulus. Decreasing the alkali modulus resulted in a higher autogenous shrinkage, less micro cracking and a more homogenous structure due to more extensive formation of sodium-aluminate-silicate-hydrate gel (N-A-S-H), promoted by the addition, and more extensive reaction of the fly ash

Recent progress in low-carbon binders

The development of low-carbon binders has been recognized as a means of reducing the carbon footprint of the Portland cement industry, in response to growing global concerns over CO2 emissions from the construction sector. This paper reviews recent progress in the three most attractive low-carbon binders: alkali-activated, carbonate, and belite-ye'elimite-based binders. Alkali-activated binders/materials were reviewed at the past two ICCC congresses, so this paper focuses on some key developments of alkali-activated binders/materials since the last keynote paper was published in 2015. Recent progress on carbonate and belite-ye'elimite-based binders are also reviewed and discussed, as they are attracting more and more attention as essential alternative low-carbon cementitious materials. These classes of binders have a clear role to play in providing a sustainable future for global construction, as part of the available toolkit of cements

Solid-state nuclear magnetic resonance spectroscopy of cements

Cement is the ubiquitous material upon which modern civilisation is built, providing long-term strength, impermeability and durability for housing and infrastructure. The fundamental chemical interactions which control the structure and performance of cements have been the subject of intense research for decades, but the complex, crystallographically disordered nature of the key phases which form in hardened cements has raised difficulty in obtaining detailed information about local structure, reaction mechanisms and kinetics. Solid-state nuclear magnetic resonance (SS NMR)spectroscopy can resolve key atomic structural details within these materials and has emerged as a crucial tool in characterising cement structure and properties. This review provides a comprehensive overview of the application of multinuclear SS NMR spectroscopy to understand composition–structure–property relationships in cements. This includes anhydrous and hydrated phases in Portland cement, calcium aluminate cements, calcium sulfoaluminate cements, magnesia-based cements, alkali-activated and geopolymer cements and synthetic model systems. Advanced and multidimensional experiments probe 1 H, 13 C, 17 O, 19 F, 23 Na, 25 Mg, 27 Al, 29 Si, 31 P, 33 S, 35 Cl, 39 K and 43 Ca nuclei, to study atomic structure, phase evolution, nanostructural development, reaction mechanisms and kinetics. Thus, the mechanisms controlling the physical properties of cements can now be resolved and understood at an unprecedented and essential level of detail

Analysing the relation between pore structure and permeability of alkali-activated concrete binders

Alkali-activated binders are usually porous materials that consist of various scales of pores, gels and residual raw material particles. The importance of pore structure has been highlighted in recent studies as it impacts the permeability of fluids and further impacts the durability of alkali-activated binders. This chapter reviews the pore features of alkali-activated metakaolin (AAM), alkali-activated fly ash (AAFA) and alkali-activated slag (AAS). The water permeability, absorption and chloride iron diffusion are particularly discussed for AAM and AAFA binders, which are two relatively new materials. For comparison purposes, Portland cement binders are also investigated