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Time-resolved in-situ synchrotron X-ray microtomography reveals new levels of detail about the chemical and physical processes that take place as Portland cement hardens. The conversion of a fluid paste into a hardened product can be monitored on a sub-minute time-scale, and with sample movement/settlement corrections applied to enable individual particles to be tracked as they react, hydrate, and become interconnected into a single strong monolith. The growth of the strength-giving hydrate phases surrounding cement grains, and of the fluid-filled pore network that surrounds them, is able to be directly viewed at the level of individual cement particles through the application of this tracking protocol. When cement is brought into contact with water, a layer which differs in density from the bulk of the cement grains becomes observable on the grain surfaces during the induction period (during which time the heat evolution from the paste is relatively low). As hydration continues, reaction products grow both from particle surfaces into the initially fluid-filled region, and also into the space originally occupied by the cement particles, forming a density gradient within the microstructure. As the reaction accelerates and larger volumes of solid phases precipitate, the newly-formed solid structure percolates via interconnection of agglomerated low-density outer hydrates, which then densify as hydration continues. This eventually leads to solidification of the structure into a hardened porous matrix. Graphical abstract

This paper assesses the use and valorisation of two industrial wastes generated at a large scale, which are currently disposed in landfills, as raw materials to produce geopolymers. Specifically, a kaolinitic sludge from the mining industry (CKS), and bottom ash (BA) generated during coal combustion in a thermal power station, were used as aluminosilicate precursors in geopolymer synthesis. The geopolymers were synthesised at 50°C, with a sodium oxide/aluminium oxide (Na2O/Al2O3) molar ratio of 1.0, and different silica/aluminium oxide (SiO2/Al2O3) molar ratios adjusted by manipulating the content of the soluble silicate solution used as the activator. The mechanical strength and reaction products formed during the geopolymerisation process were assessed up to 90 days of curing. The use of CKS as the main component of the precursor blend provides a geopolymer with better mechanical properties due to its higher reactivity than BA. The content of soluble silicates in the alkali activator plays an important role during geopolymerisation, improving the mechanical properties due to the formation of a more reticulated and dense structure. The mortars show a compressive strength higher than 55 MPa after 28 days and low water absorption by capillarity. This elucidates the feasibility of valorising these industrial residues as precursors for geopolymer cements.

Alkali-activated materials (AAMs) are binders that can complement and partially substitute the current use of conventional cement. However, the present knowledge about how AAMs protect steel reinforcement in concrete elements is incomplete, and uncertainties exist regarding the application of electrochemical methods to investigate this issue. The present review by EFC WP11-Task Force ‘Corrosion of steel in alkali-activated materials’ demonstrates that important differences exist between AAMs and Portland cement, and between different classes of AAMs, which are mainly caused by differing pore solution compositions, and which affect the outcomes of electrochemical measurements. The high sulfide concentrations in blast furnace slag-based AAMs lead to distinct anodic polarisation curves, unusually low open circuit potentials, and low polarisation resistances, which might be incorrectly interpreted as indicating active corrosion of steel reinforcement. No systematic study of the influence of the steel–concrete interface on the susceptibility of steel to corrosion in AAMs is available. Less common electrochemical methods present an opportunity for future progress in the field., Materials and Corrosion, 74 (7), ISSN:0947-5117, ISSN:0043-2822, ISSN:1521-4176

Materials and structures 55(3), 92 (2022). doi:10.1617/s11527-022-01928-6 special issue: "RILEM TC-267 TRM: Development and validation of tests for measuring the reactivity of supplementary cementitious materials", Published by Springer, Dordrecht

Alkali-activated materials are promising low-carbon alternatives to Portland cement; however, there remains an absence of a fundamental understanding of the effect of different activator types on their reaction products at the atomic scale. Solid-state 27Al and 29Si magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy and 1H–29Si cross-polarization MAS NMR spectroscopy are used to reveal the effect of the activator anion on the nanostructure, cross-linking, and local hydration of aged alkali-activated slag cements. The main reaction product identified is a mixed cross-linked/non-cross-linked sodium-substituted calcium aluminosilicate hydrate (C–(N)–A–S–H) gel with a structure comparable to tobermorite 11 A. Analysis of cross-polarization kinetics revealed that a higher content of soluble silicate in the activator promoted the incorporation of Al into the aluminosilicate chains of C–(N)–A–S–H gels, charge-balanced preferentially by protons within the gel interlayer. In sodium carbonate-activated slag cements, aluminosilicate chains of C–(N)–A–S–H gels are instead charge-balanced preferentially by Ca2+ or AlV ions. Hydrotalcite was observed as a secondary reaction product independent of the activator used and in higher quantities as the content of sodium carbonate in the activator increases. The presence of soluble silicates in the activator promotes the formation of an Al-rich sodium aluminosilicate hydrate (N–A–S–H) gel which was not identified when using sodium carbonate as the activator. These results demonstrate that the anion type in the activator promotes significant differences in the nanostructure and local hydration of the main binding phases forming in alkali-activated slag cements. This explains the significant differences in properties identified when using these different activators.

The RILEM technical committee 282-CCL: Calcined Clays as Supplementary Cementitious Materials, investigates all the aspects related to calcined clays, from clay exploration and characterization to calcination process, hydration reactions and concrete properties. This white paper focuses on the hydration mechanisms of calcined clay-blended Portland cements, covering both 1:1 and 2:1 calcined clays. The pozzolanic reaction of calcined clay is detailed, and the main reaction products are described. The differences observed depending on the clay type are also discussed, as well as the potential influence of the secondary phases present in calcined clay. The factors controlling and limiting the reaction of calcined clay are investigated, evidencing the role of porosity saturation and refinement of the microstructure. The complete characterisation of the hydration of calcined clay cements is made possible by the determination of the reaction degree of calcined clay. Several methods are compared to estimate the extent of calcined clay reaction. The influence of clinker and limestone mineralogy are also discussed. Finally, guidelines for optimising the mixture design of calcined clay blended cements are provided, with special attention to sulphate adjustment and clinker factor.

Struvite-K (MgKPO4·6H2O) is a magnesium potassium phosphate mineral with naturally cementitious properties, which is finding increasing usage as an inorganic cement for niche applications including...

Materials and structures: = Matériaux et constructions 55(8), 225 (2022). doi:10.1617/s11527-022-02041-4, Published by RILEM Publications SARL, Cachan

The use of calcined clays as supplementary cementitious materials provides the opportunity to significantly reduce the cement industry’s carbon burden; however, use at a global scale requires a deep understanding of the extraction and processing of the clays to be used, which will uncover routes to optimise their reactivity. This will enable increased usage of calcined clays as cement replacements, further improving the sustainability of concretes produced with them. Existing technologies can be adopted to produce calcined clays at an industrial scale in many regions around the world. This paper, produced by RILEM TC 282-CCL on calcined clays as supplementary cementitious materials (working group 2), focuses on the production of calcined clays, presents an overview of clay mining, and assesses the current state of the art in clay calcination technology, covering the most relevant aspects from the clay deposit to the factory gate. The energetics and associated carbon footprint of the calcination process are also discussed, and an outlook on clay calcination is presented, discussing the technological advancements required to fulfil future global demand for this material in sustainable infrastructure development.

Materials and structures = Matériaux et constructions 55(5), 142 (2022). doi:10.1617/s11527-022-01947-3 special issue: "RILEM TC-267 TRM: Development and Validation of Tests for Measuring the Reactivity of Supplementary Cementitious Materials", Published by Springer Netherlands, Dordrecht

Conventional supplementary cementitious materials (SCMs), such as blast furnace slags or fly ashes, have been used for many decades, and a large body of knowledge has been collected regarding their compositional make-up and their impacts on cement hydration and concrete properties. This accumulated empirical experience can provide a solid, confident base to go beyond the status quo and develop a new generation of low-clinker cements composed of new types and combinations of SCMs. The need for new sources of SCMs has never been greater, as supplies of traditional SCMs are becoming restricted, and the demand for SCMs to reduce CO2 emissions from concrete production is increasing. In this paper, recent research on emerging SCM sources is reviewed, along with new developments in characterizing and qualifying SCMs for use and improved knowledge of SCMs on long-term concrete performance and durability.

Alkali-activated metakaolin geopolymers are attracting interest in the conditioning of nuclear wastes, especially for their ability to immobilise cationic species. However, there is limited understanding of the chemical interactions between the encapsulated spent ion-exchangers, used for decontaminating waste water, and the host aluminosilicate matrix. The lack of such understanding makes it difficult to predict the long-term stability of the waste form. In this study, the suitability of using metakaolin based geopolymer as a matrix for encapsulation of titanate-type ion-exchangers loaded with non-radioactive Sr was investigated for the first time, via spectroscopic and microstructural inspection of the encapsulated ion-exchangers and the aluminosilicate gel matrix. The microstructural and chemical properties of metakaolin geopolymers remained stable after encapsulating titanate type spent ion-exchangers, performed desirably as host materials for conditioning of Sr-loaded titanate ion-exchangers.

Intermediate level waste produced in UK nuclear power generation is encapsulated or immobilised in blended cements comprising blast furnace slag (BFS) and Portland cement (PC), to be emplaced in a proposed geological disposal facility (GDF). The wasteforms are expected to be exposed to temperatures from 35 to 80 °C during the initial 150 years of GDF operation. Thermodynamic modelling is applied here to describe the phase assemblages of hydrated 1:1, 3:1 and 9:1 BFS-PC blends, with the participation of hydrogarnet as an important phase above 60 °C. The chemical composition of the main phase forming in these systems, an aluminium rich calcium silicate hydrate (C-A-S-H), was well described by a solid-solution model with explicit Al incorporation, although the Al/Si ratio was systematically slightly under-predicted. The developed thermodynamic model predicts the correct phase assemblage across varying temperature regimes, making it a valuable tool to assess the effects of temperature on cements.

Materials and structures = Matériaux et constructions 54(2), 87 (2021). doi:10.1617/s11527-021-01658-1, Published by Springer Netherlands, Dordrecht

The corrosion of the steel bars of two reinforced concrete specimens subjected to different chloride ingress environments for 13 years was evaluated by scanning electron microscopy. A multi-peak Gaussian model has been applied for the distinctive shape of the corrosion layer observed in these systems. The influence of macroscopic voids (10−5–10−2 m in diameter) at the steel–concrete interface (SCI) on the corrosion process and the relationship between the shape of the corrosion layer and the location of the cracks are discussed. The width-to-height ratio Rwh of the corrosion layer is proposed, according to the calculation of coefficients of the multi-peak Gaussian model to describe the shape of the corrosion products at the SCI. The distinctive influence of natural and artificial chloride environment on the corrosion process are quantified by this model, demonstrating the applicability of the model to reinforced concrete exposed for long durations to severed corrosive environments.

The production of nonferrous metals, including aluminium, copper, manganese, zinc, lead, nickel, and tin, is forecasted to increase in the mid-21st century, and consequently, the amount of slags derived from their processing will significantly rise. Nonferrous metal slags are industrial waste streams produced in large volumes, whose disposal poses environmental hazards due to potential release of toxic elements. New technologies to enable their sustainable management are urgently needed, and alkali-activation technology offers a route to transform nonferrous slags into value-added cementitious products for construction. This chapter provides an overview of recent advances in the understanding of relationships between slag composition and hardened cement properties, as well as their long-term safety and durability. Beyond purely material aspects, this chapter puts these developments into context of the circular economy and discusses the opportunities and barriers for greater adoption of alkali-activation technology to valorize nonferrous slags.

Materials and structures 53(6), 136 (2020). doi:10.1617/s11527-020-01558-w, Published by Springer, Dordrecht

Carbonation of cementitious materials induced by their interaction with atmospheric CO2 is one of the main degradation mechanisms threatening their durability. In this study, a novel thermodynamic model to predict the phase evolution of alkali-activated slags exposed to an accelerated carbonation environment is presented. This model predicts the phase assemblages of carbonated alkali-activated slag cements, as a function of CO2 uptake under 1 v/v % CO2 conditions, considering the bulk slag chemistry and activators used. The changes taking place during the carbonation process regarding the physicochemical properties of the main binding gel, an alkali calcium aluminosilicate hydrate (C-(N)-A-S-H), the secondary reaction products CaAl and MgAl layered double hydroxides, and amorphous aluminosilicate gels, were simulated and discussed. The predictions of the thermodynamic model are in good agreement with experimental data retrieved from the literature, demonstrating that this is a valuable tool for predicting long-term performance of alkali-activated slag cements.

This study evaluates the freeze-thaw performance of steel fibre reinforced rubberised concretes (SFRRuC) engineered for flexible concrete pavements. The effect of large volumes of fine and coarse rubber particles (i.e. 30% and 60% volumetric replacement of natural aggregates) is determined for concretes reinforced with 40 kg/m3 of a blend of manufactured steel fibres and recycled tyre steel fibres. The freeze-thaw performance is assessed through surface scaling, internal damage, residual compressive strength and flexural behaviour. The results show that SFRRuC are able to withstand 56 freeze-thaw cycles with acceptable scaling and without presenting internal damage or degradation in mechanical performance. This indicates that SFRRuC can perform well under extreme freeze-thaw conditions and can be used to construct long-lasting flexible pavements as a sustainable alternative to asphalt concretes.

To minimise disruption due to repairs of concrete pavements, rapid hardening and tough materials need to be used. This paper investigates the flexural performance of rapid hardening mortar mixes made with two commercial cement types, calcium sulfo-aluminate cement and calcium aluminate cement, for thin concrete repair applications. Three-point bending tests are performed on plain and steel fibre reinforced concrete specimens containing 45 kg/m3 of recycled clean steel fibres to characterise the flexural performance of notched and unnotched prisms at different ages, ranging from one hour up to one year. The recycled fibers are shown to enhance both the flexural strength and toughness of FRC prisms, leading to hardening behaviour. Constitutive equations based on the RILEM and Model Code 2010 recommendations are found to overestimate the loading capacity of the bending tests. FE analyses using multilinear σ-ɛ tensile curves obtained by employing inverse analysis can capture better the post cracking strength and cracking pattern of the tested prisms.

To future-proof alkali-activation technology, there is a need to look beyond well-established precursors such as fly ash and blast furnace slag, due to resource competition, geographical distribution and technical limitations. Clay minerals are abundant and diverse aluminosilicate resources available around the world. However, due to the mineralogical complexity amongst the most common 1:1 (kaolinite, halloysite) and 2:1 (montmorillonite, illite) clay minerals, and practical issues such as workability, their use has been more limited. Recent advances have improved understanding both of pre-activation treatments (thermal, mechanical, chemical), and of the factors influencing clay reactivity, phase assemblages and properties of final products. This opens new opportunities for the exploitation of these resources to produce sustainable cements. A one-size-fits-all approach for processing and activating clay minerals is not viable. Instead, activation routes need to be tailored according to the clay mineralogy to achieve the binder properties required for key applications. Published with golden open access ispartof: Cement And Concrete Research vol:132 status: published

This study assesses the durability and transport properties of low water/binder ratio (0.35) steel fibre reinforced rubberised concrete (SFRRuC) mixes, which are proposed to be used as flexible concrete pavements. Waste tyre rubber is incorporated in concrete as fine and coarse aggregate replacement and blends of manufactured steel fibres and recycled tyre steel fibres are used as internal reinforcement. The fresh, mechanical and transport properties of plain concrete are compared with those of SFRRuC mixes having different substitutions of rubber aggregates (0, 30 and 60% by volume). The chloride corrosion effects due to exposure to a simulated accelerated marine environment (intermittent wet-dry cycles in 3% NaCl solution) is also evaluated. The results show that, although water permeability (e.g. volume of permeable voids and sorptivity) and chloride ingress increase with rubber content, this increase is minor and water and chlorides permeability are generally within the range of highly durable concrete mixes. No visual signs of deterioration or cracking (except superficial rust) were observed on the surface of the concrete specimens subjected to 150 or 300 days of accelerated chloride corrosion exposure and a slight increase in the mechanical properties is observed. This study shows that the examined low water/binder SFRRuC mixes promote good durability characteristics, making these composite materials suitable for flexible concrete pavement applications.

We recently reported the first comprehensive investigation of magnesium potassium phosphate cements (MKPCs) blended with supplementary cementitious materials (pulverized fuel ash and granulated blast furnace slag) for the encapsulation of radioactive wastes [Gardner et al., Cem. Concr. Res. 74 (2015) 78–87]. Using a combination of characterization techniques, we demonstrated the important role of the reaction of the supplementary cementitious materials in contributing to the development of the microstructure and strength of MKPC composites. Here, we clarify aspects of our experimental design, and elaborate on the interpretation of our data, following discussion by Ma and Li.

The structural evolution of a sodium carbonate activated slag cement blended with varying quantities of Mg(OH)2 was assessed. The main reaction products of these blended cements were a calcium-sodium aluminosilicate hydrate type gel, an Mg-Al layered double hydroxide with a hydrotalcite type structure, calcite, and a hydrous calcium aluminate phase (tentatively identified as a carbonate-containing AFm structure), in proportions which varied with Na2O/slag ratios. Particles of Mg(OH)2 do not chemically react within these cements. Instead, Mg(OH)2 acts as a filler accelerating the hardening of sodium carbonate activated slags. Although increased Mg(OH)2 replacement reduced the compressive strength of these cements, pastes with 50 wt% Mg(OH)2 still reached strengths of ∼21 MPa. The chemical and mechanical characteristics of sodium carbonate activated slag/Mg(OH)2 cements makes them a potentially suitable matrix for encapsulation of high loadings of Mg(OH)2-bearing wastes such as Magnox sludge.

The development of alkali-activated materials (AAMs) as an alternative to Portland cement (PC) has seen significant progress in the past decades. However, there still remains significant uncertainty regarding their long term performance when used in steel-reinforced structures. The durability of AAMs in such applications depends strongly on the corrosion behaviour of the embedded steel reinforcement, and the experimental data in the literature are limited and in some cases inconsistent. This letter elucidates the role of the chemistry of AAMs on the mechanisms governing passivation and chloride-induced corrosion of the steel reinforcement, to bring a better understanding of the durability of AAM structures exposed to chloride. The corrosion of the steel reinforcement in AAMs differs significantly from observations in PC; the onset of pitting (or the chloride ‘threshold’ value) depends strongly on the alkalinity, and the redox environment, of these binders. Classifications or standards used to assess the severity of steel corrosion in PC appear not to be directly applicable to AAMs due to important differences in pore solution chemistry and phase assemblage., RILEM Technical Letters, 20, ISSN:2518 -0231

Stoichiometrically controlled alkali-activated materials within the system CaO-MgO-Na2O-Al2O3-SiO2 are produced by alkali-activation of high-purity synthetic powders chemically comparable to the glass in ground granulated blast furnace slag, but without additional minor constituents. Mg content controls the formation of hydrotalcite-group and AFm-type phases, which in turn strongly affects C-(N)-A-S-H gel chemistry and nanostructure. Bulk Mg content and the Mg/Al ratio of hydrotalcite-group phases are strongly correlated. With sufficient Ca, increased bulk Mg promotes formation of low-Al C-(A)-S-H and portlandite, due to formation of hydrotalcite-group phases and a reduction in available Al. Hydrotalcite-group phase formation is linked to increased C-(N)-A-S-H gel polymerisation, decreased gel Al uptake and increased formation of the ‘third aluminate hydrate’. These findings highlight the importance of considering available chemical constituents rather than simply bulk composition, so that the desired binder structure for a particular application can be achieved.

Many standardised durability testing methods have been developed for Portland cement-based concretes, but require validation to determine whether they are also applicable to alkali-activated materials. To address this question, RILEM TC 247-DTA ‘Durability Testing of Alkali-Activated Materials’ carried out round robin testing of carbonation and chloride penetration test methods, applied to five different alkali-activated concretes based on fly ash, blast furnace slag or metakaolin. The methods appeared overall to demonstrate an intrinsic precision comparable to their precision when applied to conventional concretes. The ranking of test outcomes for pairs of concretes of similar binder chemistry was satisfactory, but rankings were not always reliable when comparing alkali-activated concretes based on different precursors. Accelerated carbonation testing gave similar results for fly ash-based and blast furnace slag-based alkali-activated concretes, whereas natural carbonation testing did not. Carbonation of concrete specimens was observed to have occurred already during curing, which has implications for extrapolation of carbonation testing results to longer service life periods. Accelerated chloride penetration testing according to NT BUILD 443 ranked the tested concretes consistently, while this was not the case for the rapid chloride migration test. Both of these chloride penetration testing methods exhibited comparatively low precision when applied to blast furnace slag-based concretes which are more resistant to chloride ingress than the other materials tested.

The RILEM technical committee TC 247-DTA ‘Durability Testing of Alkali-Activated Materials’ conducted a round robin testing programme to determine the validity of various durability testing methods, originally developed for Portland cement based-concretes, for the assessment of the durability of alkali-activated concretes. The outcomes of the round robin tests evaluating sulfate resistance, alkali-silica reaction (ASR) and freeze–thaw resistance are presented in this contribution. Five different alkali-activated concretes, based on ground granulated blast furnace slag, fly ash, or metakaolin were investigated. The extent of sulfate damage to concretes based on slag or fly ash seems to be limited when exposed to an Na2SO4 solution. The mixture based on metakaolin showed an excessive, very early expansion, followed by a dimensionally stable period, which cannot be explained at present. In the slag-based concretes, MgSO4 caused more expansion and visual damage than Na2SO4; however, the expansion limits defined in the respective standards were not exceeded. Both the ASTM C1293 and RILEM AAR-3.1 test methods for the determination of ASR expansion appear to give essentially reliable identification of expansion caused by highly reactive aggregates. Alkali-activated materials in combination with an unreactive or potentially expansive aggregate were in no case seen to cause larger expansions; only the aggregates of known very high reactivity were seen to be problematic. The results of freeze–thaw testing (with/without deicing salts) of alkali-activated concretes suggest an important influence of the curing conditions and experimental conditions on the test outcomes, which need to be understood before the tests can be reliably applied and interpreted.

The aim of RILEM TC 247-DTA ‘Durability Testing of Alkali-Activated Materials’ is to identify and validate methodologies for testing the durability of alkali-activated concretes. To underpin the durability testing work of this committee, five alkali-activated concrete mixes were developed based on blast furnace slag, fly ash, and flash-calcined metakaolin. The concretes were designed with different intended performance levels, aiming to assess the capability of test methods to discriminate between concretes on this basis. A total of fifteen laboratories worldwide participated in this round robin test programme, where all concretes were produced with the same mix designs, from single-source aluminosilicate precursors and locally available aggregates. This paper reports the mix designs tested, and the compressive strength results obtained, including critical insight into reasons for the observed variability in strength within and between laboratories., The participation of J. L. Provis and S. A. Bernal (at U. Sheffield), S. Nanukuttan and D. Bondar (at Queen’s University) in this research was sponsored by the Engineering and Physical Sciences Research Council (EPSRC; UK) under Grant Number EP/M003272/1. Participation of V. Ducman was financially supported by the Slovenian Research Agency Programme Group P2-0273. The work and research of K. Dombrowski-Daube in RILEM TC-247 DTA was supported by ZIM - Central Innovation Program, German Federal Ministry of Economic Affairs and Energy (BMWi) by order of the German Bundestag. The contribution of the team at TU Delft led by G. Ye was supported by the Materials innovation institute M2i/Netherlands Organisation for Scientific Research (STW/M2i Project 13361). The contributions of K. Arbi were also supported by Delta Concrete Consult BV.

The ability of Nirex Reference Vault Backfill (NRVB), a cement backfill material, to capture carbon dioxide from Intermediate Level Radioactive waste packages after repository backfilling, has been assessed. Large-scale trials assessed the physical and chemical reaction of carbon dioxide with the hardened backfill grout. A carbonation front, radial in nature, was observed extending into the grout and three distinct regions were identified in the hardened grouts. A carbonated region, a carbonation front, and a partially carbonated zone were discerned. Potassium, and to a lesser extent sodium, were concentrated in the carbonated region just behind of the main reaction front. The area just ahead of the carbonation front was enriched in both sulphur and aluminium, while sulphur was found to be depleted from the carbonated material behind the main reaction front. Within the main carbonated region, virtually all of the hydrated cement phases were found to be carbonated, and carbonation extended throughout the grout, even within material indicated by phenolphthalein solution to be uncarbonated. Importantly, carbonation was observed to impact both the mineral assemblage and porosity of the cement backfill; it is therefore important to understand these characteristics in terms of the long term evolution of NRVB and its groundwater buffering safety function within the geological disposal facility near-field.

Radioactive waste streams containing 90Sr, from nuclear power generation and environmental cleanup operations, are often immobilised in cements to limit radionuclide leaching. Due to poor compatibility of certain wastes with Portland cement, alternatives such as alkali aluminosilicate ‘geopolymers’ are being investigated. Here, we show that the disordered geopolymers ((N,K)-A-S-H gels) formed by alkali-activation of metakaolin can readily accommodate the alkaline earth cations Sr2+ and Ca2+ into their aluminosilicate framework structure. The main reaction product identified in gels cured at both 20 °C and 80 °C is a fully polymerised Al-rich (N,K)-A-S-H gel comprising Al and Si in tetrahedral coordination, with Si in Q4(4Al) and Q4(3Al) sites, and Na+ and K+ balancing the negative charge resulting from Al3+ in tetrahedral coordination. Faujasite-Na and partially Sr-substituted zeolite Na-A form within the gels cured at 80 °C. Incorporation of Sr2+ or Ca2+ displaces some Na+ and K+ from the charge-balancing sites, with a slight decrease in the Si/Al ratio of the (N,K)-A-S-H gel. Ca2+ and Sr2+ induce essentially the same structural changes in the gels. This is important for understanding the mechanism of incorporation of Sr2+ and Ca2+ in geopolymer cements, and suggests that geopolymer gels are excellent candidates for immobilisation of radioactive waste containing 90Sr.

The impact of adding two types of layered double hydroxides (LDHs), commercial hydrotalcite (HT) and its thermally treated form (CLDH), on the reaction kinetics and phase assemblage development of a sodium silicate-activated slag cement was investigated. The reaction kinetics of LDH-modified cements was assessed by isothermal calorimetry, and the results were correlated with in situ attenuated total reflection Fourier transform infrared spectroscopy results collected over the first days of reaction, to identify the structural evolution of the main binding phase forming in these cements: a sodium-containing calcium aluminosilicate hydrate (C-(N)-A-S-H)-type gel. The addition of either HT or CLDH into sodium silicate-activated slag paste accelerates the precipitation of reaction products and increases the formation of HT in these cements, without causing significant changes to the C-(N)-A-S-H binding phase. This is extremely relevant in terms of the durability of alkali-activated slag cements, as a higher content of the HT-like phase has the potential to reduce their chloride permeability and enhance carbonation resistance.

In this study, a multi-technique approach was utilised to determine the high temperature performance of magnesium potassium phosphate cement (MKPC) blended with fly ash (FA) or ground granulated blast furnace slag (GBFS) with respect to nuclear waste immobilisation applications. Conceptual fire conditions were employed (up to 1200 °C, 30 min) to simulate scenarios that could occur during interim storage, transportation or within a final geological disposal facility. After exposure up to 400 °C, the main crystalline phase, struvite-K (MgKPO4·6H2O), was dehydrated to poorly crystalline MgKPO4 (with corresponding volumetric and mass changes), with MgKPO4 recrystallisation achieved by 800 °C. XRD and SEM/EDX analysis revealed reaction occurred between the MgKPO4 and FA/GBFS components after exposure to 1000–1200 °C, with the formation of potassium aluminosilicate phases, leucite and kalsilite (KAlSi2O6 and KAlSiO4), commensurate with a reduced relative intensity (or complete elimination) of the dehydrated struvite-K phase, MgKPO4. This was further supported by solid-state NMR (27Al and 29Si MAS), where only residual features associated with the raw FA/GBFS components were observable at 1200 °C. The high temperature phase transformation of blended MKPC binders resulted in the development of a glass/ceramic matrix with all existing porosity infilled via sintering and the formation of a vitreous phase, whilst the physical integrity was retained (no cracking or spalling). This study demonstrates that, based on small-scaled specimens, blended MKPC binders should perform satisfactorily under fire performance parameters relevant to the operation of a geological disposal facility, up to at least 1200 °C.

Co-fired fly ash, derived from the co-combustion of coal and biomass, is examined as a potential precursor for geopolymers. Compared to a coal fly ash, two co-fired fly ashes have a lower vitreous content and higher carbon content, primarily due to differing combustion processing variables. As a result, binders produced with these co-fired fly ashes have reduced reaction potential. Nevertheless, compressive strengths are generally highest for all ashes activated with solutions with a molar ratio of SiO₂/(Na₂O + K₂O) = 1, and these mixes reach the highest extent of reaction among those studied. Activation with sodium hydroxide solution forms zeolitic phases for all ashes. The thermal and dilatometric behavior of the coal and co-fired fly ash geopolymers is similar between equivalent mix designs. These results indicate that co-fired fly ashes can be viably used to form alkali-activated geopolymers, which is a new beneficial end-use for these emerging waste materials.

Calcium sulfoaluminate-belite cement (CSAB) offers lower CO2 emissions in its production, compared with Portland cement. However, for the production of CSAB a high amount of alumina is required, and the scarcity and high cost of high-purity bauxite make these cements costly at present. In this study, the use of uncalcined aluminium anodising sludge (AAS) as the main source of alumina to produce CSAB clinkers, replacing bauxite, was assessed. The CSAB clinkers produced were mainly composed of ye’elimite and belite, along with minor traces of alite, and/or brownmillerite, depending on the alumina source. Clinkers derived from AAS as a source of aluminium showed a lower content of ye’elimite (35.5%), as well as the formation of alite (8.2%) when compared to a reference clinker produced with reagent-grade materials. Comparable hydration products were identified in the hydrated cements independent of the alumina source used. The use of AAS to produce CSAB cement was proven to be technically feasible, and the cement thus produced has desirable technical characteristics, presenting high mechanical strength (>40 MPa in paste samples).

There is growing global interest in maximising the re-use and recycling of waste, to minimise the environmental impacts associated with waste treatment and disposal. Use of high-volume wastes in the production of blended or novel cements (including alkali-activated cements) is well known as a key pathway by which these wastes can be re-used. This paper presents a critical overview of the urban, agricultural, mining and industrial wastes that have been identified as potential precursors for the production of alkali-activated cement materials, or that can be effectively stabilised/solidified via alkali activation, to assure their safe disposal. The central aim of this review is to elucidate the potential advantages and pitfalls associated with the application of alkali-activation technology to a wide variety of wastes that have been claimed to be suitable for the production of construction materials. A brief overview of the generation and characteristics of each waste is reported, accompanied by identification of opportunities for the use of alkali-activation technology for their valorisation and/or management. © 2016 Society of Chemical Industry

This paper assesses the feasibility of using a kaolinitic sludge, which is a residue from the mining industry, is available in large volumes and is currently landfilled, as a raw material for the production of geopolymer binders. The geopolymers were synthesized at 50 °C with an overall Na 2 O/Al 2 O 3 molar ratio of 1.0, and overall SiO 2 /Al 2 O 3 molar ratios between 3.1 and 4.5. The content of soluble silicates, associated with the SiO 2 /Al 2 O 3 molar ratio, was identified by calorimetric and spectroscopic techniques to play an important role in determining the nature of the reaction products formed. A highly dense and cross-linked Si-rich gel was identified as the main reaction product when an increased content of soluble silicates was used. Geopolymers based on kaolinitic sludge waste developed compressive strengths of up to 70 MPa after one day of curing. This elucidates that geopolymerization can be a feasible technological solution for the valorization and exploitation of kaolinitic sludge waste from the mining industry for the production of cementitious matrices.

This study reports the development and application of a digital image cross correlation based approach to resolve contiguous microstructural volumes of interest in X-ray microtomography data, collected in fluid suspensions that undergo significant microstructural changes over time, using fresh cementitious pastes as an example. This computational method provides a high precision both for cementitious pastes that sediment only slightly (i.e. are cohesive), and for those that undergo significant sedimentation and/or settlement within the first few minutes of reaction. The normalised cross correlation algorithm presented here enables the observation of an identical volume of interest, i.e., one which contains a contiguous particle group, from the first seconds of observation onwards with excellent accuracy. This method enables segmentation of the same cluster of particles to be almost entirely automated and resolved in large sets of sequentially collected data, therefore enabling particle reaction to be observed directly while removing effects due to sedimentation.

The service-life of steel-reinforced concrete structures is primarily determined by the ability of the concrete cover to resist chloride ingress. With limited literature available on the ingress of chloride into alkali-activated slags (AAS) under service conditions, it is critical that this is described by appropriate models. This paper describes an interactive software framework to relate chloride ingress into AAS with the chemistry of the concrete cover, by considering the chloride binding capacity and porosity of the binder as a function of time, based on thermodynamic calculations of the phase assemblage as a function of slag and activator composition. This provides a major step towards developing the ability to predict the ingress of chlorides in alkali-activated concretes from a sound theoretical basis, which is essential in providing confidence in the durability of these materials in essential infrastructure applications.

This article belongs to the Special Issue Sustainable Cementitious Materials for the Construction Industry., The reaction kinetics of four commercial ground granulated blast furnace slags with varying percentages of MgO (6 to 14 wt.%), activated with four different doses of sodium metasilicate, were evaluated using isothermal calorimetry. The reaction kinetics were strongly dependent on the dose of the alkaline activator used, and the chemical and physical properties of the slag. When using low concentrations of sodium metasilicate as an activator, the MgO content in the slag influences the kinetics of the reaction, while the CaO content plays a more significant role when the concentration of metasilicate is increased. This study elucidated a close relationship between the dose of the alkali-activator and the chemistry of the slag used, although it was not possible to identify a clear correlation between any of the published chemically-based “slag quality moduli” and the calorimetry results, highlighting the complexity of blast furnace slag glass chemistry, and the importance of the physical properties of the slag in defining its reactivity., This research was funded in part by the European Research Council under the European Union’s Seventh Framework Program (FP7/2007–2013)/ERC Grant Agreement #335928 (GeopolyConc), and in part by the Engineering and Physical Sciences Research Council (EP/P013171/1). Participation of SAB in this study was sponsored by EPSRC through ECF EP/R001642/1.