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Many (inter)national standards exist to evaluate the resistance of mortar and concrete to carbonation. When a carbonation coefficient is used for performance comparison of mixtures or service life prediction, the applied boundary conditions during curing, preconditioning and carbonation play a crucial role, specifically when using latent hydraulic or pozzolanic supplementary cementitious materials (SCMs). An extensive interlaboratory test (ILT) with twenty two participating laboratories was set up in the framework of RILEM TC 281-CCC 'Carbonation of Concrete with SCMs'. The carbonation depths and coefficients determined by following several (inter)national standards for three cement types (CEM I, CEM II/B-V, CEM III/B) both on mortar and concrete scale were statistically compared. The outcomes of this study showed that the carbonation rate based on the carbonation depths after 91 days exposure, compared to 56 days or less exposure duration, best approximates the slope of the linear regression and those 91 days carbonation depths can therefore be considered as a good estimate of the potential resistance to carbonation. All standards evaluated in this study ranked the three cement types in the same order of carbonation resistance. Unfortunately, large variations within and between laboratories complicate to draw clear conclusions regarding the effect of sample pre-conditioning and carbonation exposure conditions on the carbonation performance of the specimens tested. Nevertheless, it was identified that fresh and hardened state properties alone cannot be used to infer carbonation resistance of the mortars or concretes tested. It was also found that sealed curing results in larger carbonation depths compared to water curing. However, when water curing was reduced from 28 to 3 or 7 days, higher carbonation depths compared to sealed curing were observed. This increase is more pronounced for CEM I compared to CEM III mixes. The variation between laboratories is larger than the potential effect of raising the CO 2 concentration from 1 to 4%. Finally, concrete, for which the aggregate-to-cement factor was increased by 1.79 in comparison with mortar, had a carbonation coefficient 1.18 times the one of mortar., Supplementary Information: The online version contains supplementary material available at 10.1617/s11527-022-01927-7., Competing Interests: Conflict of interestThe authors declare that they have no conflict of interest., (© RILEM 2022.)

The CASH+ sublattice solid solution model of C-S-H aims to predict the composition of C-S-H and its ability to take up alkalis. It was originally developed for dilute systems with high water-solid ratios, and thus in this paper further optimized and benchmarked against measured pore solution compositions of hydrated Portland cement (PC) and PC blended with silica fume (SF) at realistic water-binder ratios. To get an improved agreement with the pore solution data, the stability of two CASH+ model endmembers, TCKh and TCNh, has been fine-tuned with standard Gibbs energy corrections of + 7.0 and + 5.0 kJ·mol -1 , respectively (at 1 bar, 25 °C). The agreement was maintained with the experiments used to originally parameterize the CASH+ model for the uptake of K and Na in dilute systems. The K and Na concentrations predicted using the fine-tuned CASH+NK model are in a good agreement with the measured values for PC and PC + SF system at different water to binder ratios, silica fume additions, and at temperatures up to 80 °C., Supplementary Information: The online version contains supplementary material available at 10.1617/s11527-022-02045-0., Competing Interests: Conflict of interestThe authors have no relevant financial or non-financial interests to disclose. The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© The Author(s) 2022.)

Production of blended cements in which Portland cement is combined with supplementary cementitious materials (SCM) is an effective strategy for reducing the CO 2 emissions during cement manufacturing and achieving sustainable concrete production. However, the high Al 2 O 3 and SiO 2 contents of SCM change the chemical composition of the main hydration product, calcium aluminate silicate hydrate (C-A-S-H). Herein, spectroscopic and structural data for C-A-S-H gels are reported in a large range of equilibration times from 3 months up to 2 years and Al/Si molar ratios from 0.001 to 0.2. The 27 Al MAS NMR spectroscopy and thermogravimetric analysis indicate that in addition to the C-A-S-H phase, secondary phases such as strätlingite, katoite, Al(OH) 3 and calcium aluminate hydrate are present at Al/Si ≥ 0.03 limiting the uptake of Al in C-A-S-H. More secondary phases are present at higher Al concentrations; their content decreases with equilibration time while more Al is taken up in the C-A-S-H phase. At low Al contents, Al concentrations decrease strongly with time indicating a slow equilibration, in contrast to high Al contents where a clear change in Al concentrations over time was not observed indicating that the equilibrium has been reached faster. The 27 Al NMR studies show that tetrahedrally coordinated Al is incorporated in C-A-S-H and its amount increases with the amount of Al present in the solution., Supplementary Information: The online version contains supplementary material available at 10.1617/s11527-022-02080-x., Competing Interests: Conflict of interestThe authors have no competing interests to declare that are relevant to the content of this article., (© The Author(s) 2022.)

Alkali-silica reaction (ASR) causes severe degradation of concrete. The mechanical property of the ASR product is fundamental to the multiscale modeling of concrete behavior over the long term. Despite years of study, there is a lack of consensus regarding the structure and elastic modulus of the ASR product. Here, ASR products from both degraded field infrastructures and laboratory synthesis were investigated using high-pressure X-ray diffraction. The results unveiled the multiphase and metastable nature of ASR products from the field. The dominant phase undergoes permanent phase change via collapsing of the interlayer region and in-planar glide of the main layer, under pressure >2 GPa. The bulk moduli of the low- and high-pressure polymorphs are 27±3 and 46±3 GPa, respectively. The laboratory-synthesized sample and the minor phase in the field samples undergo no changes of phase during compression. Their bulk moduli are 35±2 and 76±4 GPa, respectively. The results provide the first atomistic-scale measurement of the mechanical property of crystalline ASR products.

To reduce the CO 2 emissions from cement production, Portland cement (PC) is partially replaced by supplementary cementitious materials (SCM). Reactions of SCM with PC during hydration leads to the formation of CSH with more silicon and aluminum than in PC, which affects the stability and durability of such concrete. Therefore, it is crucial to determine the role of aluminum on CSH properties to predict the formed hydrate phase assemblages and their effects on durability. Aluminum sorption isotherms including very low Al concentrations have been determined for CSH with Ca/Si ratios from 0.6 to 1.4. Elemental measurements were performed with ICP-MS and ICP-OES. The presence of secondary phases was investigated by using thermogravimetric analysis and XRD. Higher dissolved concentrations of Al were observed at increased alkali hydroxide concentrations and thus higher pH values. High alkali hydroxide led to an increased Al(OH) 4 - formation, which reduced the Al uptake in CSH. This comparable behavior of Al and Si towards changes in pH values, points toward the uptake of aluminum within the silica chain both at low and high Ca/Si ratios. A higher Al uptake in CSH was observed at higher Ca/Si ratios, which indicates a stabilizing effect of calcium in the interlayer on Al uptake., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 The Author(s). Published by Elsevier Inc. All rights reserved.)

Mortars and concretes are ubiquitous materials with very complex hierarchical microstructures. To fully understand their main properties and to decrease their CO 2 footprint, a sound description of their spatially resolved mineralogy is necessary. Developing this knowledge is very challenging as about half of the volume of hydrated cement is a nanocrystalline component, calcium silicate hydrate (C-S-H) gel. Furthermore, other poorly crystalline phases ( e.g. iron siliceous hydrogarnet or silica oxide) may coexist, which are even more difficult to characterize. Traditional spatially resolved techniques such as electron microscopy involve complex sample preparation steps that often lead to artefacts ( e.g. dehydration and microstructural changes). Here, synchrotron ptychographic tomography has been used to obtain spatially resolved information on three unaltered representative samples: neat Portland paste, Portland-calcite and Portland-fly-ash blend pastes with a spatial resolution below 100 nm in samples with a volume of up to 5 × 10 4  µm 3 . For the neat Portland paste, the ptychotomographic study gave densities of 2.11 and 2.52 g cm -3 and a content of 41.1 and 6.4 vol% for nanocrystalline C-S-H gel and poorly crystalline iron siliceous hydrogarnet, respectively. Furthermore, the spatially resolved volumetric mass-density information has allowed characterization of inner-product and outer-product C-S-H gels. The average density of the inner-product C-S-H is smaller than that of the outer product and its variability is larger. Full characterization of the pastes, including segmentation of the different components, is reported and the contents are compared with the results obtained by thermodynamic modelling.

The interplay between the solubility, structure and chemical composition of calcium (alkali) aluminosilicate hydrate (C-(N,K-)A-S-H) equilibrated at 50 °C is investigated in this paper. The tobermorite-like C-(N,K-)A-S-H products are more crystalline in the presence of alkalis, and generally have larger basal spacings at lower Ca/Si ratios. Both Na and K are incorporated into the interlayer space of the C-(N,K-)A-S-H phases, with more alkali uptake observed at higher alkali and lower Ca content. No relationship between Al and alkali uptake is identified at the Al concentrations investigated (Al/Si ≤ 0.1). More stable C-(N,K-)A-S-H is formed at higher alkali content, but this factor is only significant in some samples with Ca/Si ratios ≤1. Shorter chain lengths are formed at higher alkali and Ca content, and cross-linking between (alumino)silicate chains in the tobermorite-like structure is greatly promoted by increasing alkali and Al concentrations. The calculated solubility products do not depend greatly on the mean chain length in C-(N,K-)A-S-H at a constant Ca/(Al + Si) ratio, or the Al/Si ratio in C-(N,K-)A-S-H. These results are important for understanding the chemical stability of C-(N,K-)A-S-H, which is a key phase formed in the majority of cements and concretes used worldwide.

Chromate is a toxic contaminant of potential concern, as it is quite soluble in the alkaline pH range and could be released to the environment. In cementitous systems, CrO4(2−) is thought to be incorporated as a solid solution with SO4(2−) in ettringite. The formation of a solid solution (SS) could lower the soluble CrO4(2−) concentrations. Ettringite containing SO4(2−) or CrO4(2−) and mixtures thereof have been synthesized. The resulting solids and their solubility after an equilibration time of 3 months have been characterized. For CrO4-ettringite at 25 °C, a solubility product log K(S0) of −40.2 ± 0.4 was calculated: log K(CrO4−ettringite) = 6log{Ca2+} + 2log{Al(OH)4(−)} + 3log{CrO4(2−)} + 4log{OH−} + 26log{H2O}. X-ray diffraction and the analysis of the solution indicated the formation of a regular solid solution between SO4- and CrO4-ettringite with a miscibility gap between 0.4 ≤ XCrO4 ≤ 0.6. The miscibility gap of the SO4- and CrO4-ettringite solid solution could be reproduced with a dimensionless Guggenheim fitting parameter (a0) of 2.03. The presence of a solid solution between SO4- and CrO4-ettringite results in a stabilization of the solids compared to the pure ettringites and thus in an increased uptake of CrO4(2−) in cementitious systems.

A thermodynamic approach is used to model changes in the hydrate assemblage and the composition of the pore solution during the hydration of calcite-free and calcite-containing sulphate-resisting Portland cement CEM I 52.5 N HTS. Modelling is based on thermodynamic data for the hydration products and calculated hydration rates for the individual clinker phases, which are used as time-dependent input parameters. Model predictions compare well with the composition of the hydrate assemblage as observed by TGA and semi-quantitative XRD and with the experimentally determined compositions of the pore solutions. The calculations show that in the presence of small amounts of calcite typically associated with Portland cement, C-S-H, portlandite, ettringite and calcium monocarbonate are the main hydration products. In the absence of calcite in the cement, however, siliceous hydrogarnet instead of calcium monocarbonate is observed to precipitate. The use of a higher water-to-cement ratio for the preparation of a calcite-containing cement paste has a minor effect on the composition of the hydrate assemblage, while it significantly changes the composition of the pore solution. In particular, lower pH value and higher Ca concentrations appear that could potentially influence the solubility and uptake of heavy metals and anions by cementitious materials.

Mechanistic model calculations for the migration of Cs, Ra, Am and Pb in compacted bentonite have been carried out to evaluate sensitivities with respect to different parameter variations. A surface chemical speciation/electric double layer model is used to calculate: (i) porewater composition and radionuclide speciation in solution and at the bentonite surface, yielding the distribution of mobile and sorbed species and (ii) interaction of diffusing species with negatively charged pore walls to obtain diffusion parameters. The basic scenario considers the interaction of compacted bentonite with a fresh-type groundwater; variations include the presence of bentonite impurities and saline groundwater. It is shown that these scenarios result in significant variations of porewater composition that affect migration via three mechanisms that can partly compensate each other: (1) effects on sorption through radionuclide complexation in solution, and competition of major cations for surface sites; (2) changes in radionuclide solution speciation leading to different diffusing species under different conditions; (3) effects on diffusion through changes in the electric double layer properties of the clay pores as a function of ionic strength., (Copyright 2002 Elsevier Science B.V.)

A thermodynamic sorption model and a diffusion model based on electric double layer (EDL) theory are integrated to yield a surface chemical model that treats porewater chemistry, surface reactions, and the influence of charged pore walls on diffusing ions in a consistent fashion. The relative contribution of Stern and diffuse layer to the compensation of the permanent surface charge represents a key parameter; it is optimized for the diffusion of Cs in Kunipia-F bentonite, at a dry density of 400 kg/m3. The model is then directly used to predict apparent diffusivities (Da) of Cs, Sr, Cl-, I- and TcO4- and corresponding distribution coefficients (Kd) of Cs and Sr in different bentonites as a function of dry density, without any further adjustment of surface chemical and EDL parameters. Effective diffusivities (De) for Cs, HTO, and TcO4- are also calculated. All calculated values (Da, De, Kd) are fully consistent with each other. A comparison with published, measured data shows that the present model allows a good prediction and consistent explanation of (i) apparent and effective diffusivities for cations, anions, and neutral species in compacted bentonite, and of (ii) Kd values in batch and compacted systems.