Thermodynamic equilibrium calculations in cementitious systems

This review paper aims at giving an overview of the different applications of thermodynamic equilibrium calculations in cementitious systems. They can help us to understand on a chemical level the consequences of different factors such as cement composition, hydration, leaching, or temperature on the composition and the properties of a hydrated cementitious system. Equilibrium calculations have been used successfully to compute the stable phase assemblages based on the solution composition as well as to model the stable phase assemblage in completely hydrated cements and thus to asses the influence of the chemical composition on the hydrate assemblage. Thermodynamic calculations can also, in combination with a dissolution model, be used to follow the changes during hydration or, in combination with transport models, to calculate the interactions of cementitious systems with the environment. In all these quite different applications, thermodynamic equilibrium calculations have been a valuable addition to experimental studies deepening our understanding of the processes that govern cementitious systems and interpreting experimental observations. It should be carried in mind that precipitation and dissolution processes can be slow so that thermodynamic equilibrium may not be reached; an approach that couples thermodynamics and kinetics would be preferable. However, as many of the kinetic data are not (yet) available, it is important to verify the results of thermodynamic calculations with appropriate experiments. Thermodynamic equilibrium calculations in its different forms have been applied mainly to Portland cement systems. The approach, however, is equally valid for blended systems or for cementitious systems based on supplementary cementitious materials and is expected to further the development of new cementitious materials and blend

Determination of the degree of reaction of fly ash in blended cement pastes

This paper gives a review over methods to determine the degree of reaction for supplementary cementitious materials (SCMs) with focus on Portland cement - fly ash blends only and summarizes and highlights the most important findings which are detailed in a parallel paper published in Materials and Structures. Determination of the extent of the reaction of SCMs in mixtures is complicated for several reasons: (1) the physical presence of SCMs affects the rate and extent of the reaction of the ground clinker component – the so called “filler effect”; (2) SCMs are usually amorphous with complex and varied mineralogy which make them difficult to quantify by many classical techniques such as X-ray diffraction; (3) the rate of reaction of SCMs in a cement blend may be quite different from its rate of reaction in systems containing simply alkali or lime. From this review it is clear that measuring the degree of reaction of SCMs remains challenging. Nevertheless progress has been made in recent years to offer alternatives to the traditional selective dissolution methods. Unfortunately some of these – image analysis and EDS mapping in the scanning electron microscope, and NMR - depend on access to expensive equipment and are time consuming. With regard to fly ashes, NMR seems to be reliable but limited to fly ash with low iron content. New methods with quantitative EDS mapping to segment fly ash particles from the hydrated matrix and to follow the reaction of glass groups of disparate composition separately look very promising, but time consuming. Sources with a high proportion of fine particles will have higher errors due to lower limit of resolution (1-2 μm). Whereas for SCMs which react relatively fast (e.g. slag, calcined clay) the methods based on calorimetry and chemical shrinkage seem promising on a comparative basis, the very low reaction degree of fly ashes before 28 days means that the calorimetry method is not practical. There is a lack of data to assess the usefulness of long term chemical shrinkage measurements. The possibility to quantify the amorphous phase by XRD is promising as this is a widely available and rapid technique which can at the same time give a wealth of additional information on the phases formed. However, the different reaction rates of different glasses in compositionally heterogeneous fly ashes will need to be accounted for and may strongly reduce the accuracy of the profile decomposition method. This paper is the work of working group 2 of the RILEM TC 238-SCM “Hydration and microstructure of concrete with supplementary cementitious materials”

Quantitative disentanglement of nanocrystalline phases in cement pastes by synchrotron ptychographic X-ray tomography

Mortars and concretes are ubiquitous materials with very complex hierarchical microstructures. To fully understand their main properties and to decrease their CO2 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 x 104 mm3. 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.This work has been supported by MINECO through BIA2014-57658 and BIA2017-82391-R research grants, which are cofunded by FEDER. Instrumentation development was supported by SNF (R’EQUIP, No. 145056,‘OMNY’) and the Competence Centre for Materials Science and Technology (CCMX) of the ETH-Board, Switzerland

NEA TDBIV project : preparation of a state-of-the-art report on thermodynamic data for cement

The program of work of the fourth phase of the OECD NEA Thermochemical Database Project (TDB-IV) contemplates a line of activity on the preparation of a state of the art report on cements. The present work aims at presenting the project, its aims and its limits

Thermodynamic modeling of sulfate-resistant cements with addition of barium compounds

Comunicación presentada en el International Congress Science and Technology for the Conservation of Cultural Heritage (TechnoHeritage), celebrado en Santiago de compostela del 2 al 5 de octubre de 2012.Sulfate attack by ground waters, soils, etc. is one of the threats to the built heritage in concrete. This study validated through thermodynamic modeling with GEMS geochemical code a new sulfate-resistant formulation based on the addition of BaCO3 and BaO to ordinary Portland cement (OPC), which could be used to replace weathered concrete. The thermodynamic calculations pointed out that Ba ions were able to form an insoluble salt, barite (BaSO4) with the dissolved sulfate which inhibited the formation of ettringite, the latter oc- curred when the concentrations of BaCO3 and BaO were ≥ 6 and ≥ 4 wt.%, respectively. The results of a simulated sulfate a ttack revealed that ettringite precipitated upon ingression of ≥46 ml of a Na2SO4 solution (44 wt.%) in OPC blends with 20 wt.% of BaCO3; whereas with 20 wt.% of BaO, the sulfate that precipitated besides ba rite was monosulfoaluminate when sulfate solution was ≥40 ml (tested up to 52 ml).Funding from the Spanish Ministry of Education and Science (Project CONSOLIDER CSD2007-00058) and the Regional Government of Madrid (Geomaterials Programme) is gratefully acknowledged.Peer Reviewe

Coupling thermodynamics and digital image models to simulate hydration and microstructure development of portland cement pastes

Equilibrium thermodynamic calculations, coupled to a kinetic model for the dissolution rates of clinker phases, have been used in recent years to predict time-dependent phase assemblages in hydrating cement pastes. We couple this approach to a 3D microstructure model to simulate microstructure development during the hydration of ordinary portland cement pastes. The combined simulation tool uses a collection of growth/dissolution rules to approximate a range of growth modes at material interfaces, including growth by weighted mean curvature and growth by random aggregation. The growth rules are formulated for each type of material interface to capture the kinds of cement paste microstructure changes that are typically observed. We make quantitative comparisons between simulated and observed microstructures for two ordinary portland cements, including bulk phase analyses and two-point correlation functions for various phases. The method is also shown to provide accurate predictions of the heats of hydration and 28 day mortar cube compressive strengths. The method is an attractive alternative to the cement hydration and microstructure model CEMHYD3D because it has a better thermodynamic and kinetic basis and because it is transferable to other cementitious material system

TC 238-SCM: hydration and microstructure of concrete with SCMs State of the art on methods to determine degree of reaction of SCMs

This paper is the work of working group 2 of the RILEM TC 238-SCM. Its purpose is to review methods to estimate the degree of reaction of supplementary cementitious materials in blended (or composite) cement pastes. We do not consider explicitly the wider issues of the influence of SCMs on hydration kinetics, nor the measurement of degree of reaction in alkali activated materials. The paper categorises the techniques into direct methods and indirect methods. Direct methods attempt to measure directly the amount of SCM remaining at a certain time, such as selective dissolution, microscopy combined with image analysis, and NMR. Indirect methods infer the amount of SCM reacted by back calculation from some other measured quantity, such as calcium hydroxide consumption. The paper first discusses the different techniques, how they operate and the advantages and limitations along with more details of case studies on different SCMs. In the second part we summarise the most suitable approaches for each SCM, and the paper finishes with conclusions and perspectives for future work

The combined effect of potassium, sodium and calcium on the formation of alkali-silica reaction products

Both alkalis and calcium play essential roles in the formation of alkali-silica reaction (ASR) products. Investigation of their combined effect helps to better understand the conditions of ASR. In this study, samples with a constant Ca/Si ratio of 0.3 but different K(or Na)/Si and K/Na ratios have been synthesized at 80 °C. Experimental studies and thermodynamic modelling show that a sufficient amount of K or Na is essential to initiate ASR; at low alkali concentrations C-S-H is stabilized instead. However, too high alkaline concentrations (≥900 mM at K(or Na)/Si ≥ 1) also favor C-S-H formation and suppress ASR product formation. The results reveal a strong effect of the alkalis (K and/or Na) on calcium concentrations and on the formation of ASR products; a maximum ASR product formation is observed at Na or K concentrations between 200 and 500 mM and at initial Ca/Si ratio between 0.1 and 0.4.acceptedVersio

Synthesis, characterization, and thermodynamic study of selected K-based zeolites

Potassium-rich zeolites often occur in cementitious systems, as K+ is widespread in various cementitious materials, such as Portland, blended and alkali-activated cements. The knowledge of their stability and of thermodynamic models for solid solutions with Na+ and Ca2+ are critical to understand long-term development and durability in such cements. Completing previous studies on Na- and Ca-based zeolites, the current work aims to determine the thermodynamic data of 14 types of K-based zeolites, which could possibly form in cementitious systems. The zeolites were synthesized hydrothermally, exchanged with K+, and characterized thoroughly with respect to framework structures, elemental compositions, water contents, and bond variations. Their thermodynamic properties were derived from the experimental solubility data, which allowed establishing predominance diagrams in the K2O-SiO2-Al2O3-H2O system. The K-based zeolites typically showed the lowest solubility between 0 and 100 °C, with the notable exception of Ca-gismondine and two Na-based zeolites: natrolite and Na-mordenite.publishedVersio

Synthesis, characterization, and thermodynamic study of selected Na-based zeolites

Zeolites are crystalline aluminosilicates with three-dimensional framework structures that can form in alkali-activated cements, Roman cements, and the interaction zone of cements and clays. However, their stability domains are uncertain due to their high structural variability and the lack of experimental solubility data. Thermodynamic data were here determined for selected Na-based zeolites built from six different secondary building units that could possibly form in the interaction zones of cement/clay. The zeolites were synthesized by hydrothermal methods and full-scale characterized with respect to framework structures, extra-framework cations, Si/Al ratios, and water contents. Their thermodynamic properties were determined based on the experimental solubility products at different temperatures using GEMS. Predominance diagrams of zeolite-clay/mica-SiO2/Al(OH)3 minerals in the chemical sub-systems of Na2O-SiO2-Al2O3-H2O were successfully established using PHREEQC-PhreePlot code. The experimentally derived thermodynamic data provide insights on the early stage of the zeolite ageing and predicting zeolite stability domains during cementitious material hydration.acceptedVersio