Nanoscale modelling of ionic transport in the porous C-S-H network

To reduce the CO2 footprint of construction materials, concrete producers blend their cement with Supplementary Cementitious Materials (SCMs). SCMs such as fly ash or blast furnace slag are mostly the byproducts of other industries. And while SCMs are chosen to match the properties of the common Ordinary Portland cement (OPC), their addition to the cement recipe may alter the chemistry of the system. These changes may lead to different mechanical and transport properties of the cement-based structure which may, in turn, affect its long-term resistance to harmful external agents. Therefore, understanding the relationship between cementâs microstructure and the degradation mechanisms is key for optimizing the design of new cementitious materialsIn this context, chloride attack is the most common reason for steel rebars to corrode especially when exposed to external chloride (seawater, deicer saltsâŠ). At low w/c ratios (typically 13) pore solution, the C-S-H surface develops a negative surface charge density. Electrostatic interactions between the surface and the ions in the pore solution result in a redistribution of the ionic species in two layers of charge at the interface of the solid i.e. the Electrical double layer (EDL). In nanoscopic pores, the EDL is dominated by atomic phenomena which are thought to interfere with the mobility of ions and chloride in particular. In order to understand and quantify the surface effects and their influence on ionic transport, we firstly propose an atomistic model of the EDL formation based on the use of the Metropolis Monte Carlo algorithm. This model is used to compute the ionic distributions and electrochemical potentials of electrolytes at equilibrium in nanoscopic pores. These quantities constitute the main driving forces of ionic transport at the pore scale. The microstructure parameters including the surface charge density of C-S-H, the ionic strength (and pH) of the pore solution, and the pore size are equally investigated and their effect on chlorideâs behavior quantified. Among the other parameters, the model also provides quantitative information on the effect of calcium ions which are thought to play a major role in the binding of chloride on C-S-H. The next step consists in using the calculated atomic-scale properties of the EDL in order to resolve the transport problem at the pore scale and compute microscopic diffusivities of chloride. This is achieved by using the molecular computations from the Monte Carlo (MC) engine in order to implement a modified version of the classical Poisson-Boltzmann system. The method is compared to the classical Finite element analysis of the Poisson-Nernst-Planck (PNP) equations and the data are discussed in the light of established experimental results in the literature.

Aluminium and alkali uptake in calcium silicate hydrates (C-S-H)

Calcium silicate hydrate (C-S-H) is the main hydrate phase in Portland cements. Its composition varies depending on the Ca/Si ratio and on the presence of other ions such as aluminium (called CA- S-H) or alkalis. This thesis aimed to study the composition and the structure of C-S-H. An experimental data base was realised on the effect of different Ca/Si and Al/Si ratios, alkali concentrations (potassium and sodium hydroxide) and of different temperatures on C-S-H after equilibration times up to 1 year. The composition of the solid phases was analysed by TGA, XRD/Rietveld analysis and 29Si and 27Al MAS NMR. The solutions were analysed by ionic chromatography and pH measurements. In the absence of alkali, only C-A-S-H is formed at Al/Si ≤ 0.1. At higher Al/Si ratios, katoite, stratlingite and/or AH3 precipitate in addition to C-A-S-H, such that a part of the aluminium is consumed and limits the Al/Si ratio in C-S-H to 0.15±0.05 regardless of the Ca/Si ratios. A strong correlation between the aqueous aluminium concentration and the aluminium uptake in the solid phase is observed. Aluminium in C-S-H is observed mainly as tetrahedrally, Al(IV) or octahedrally coordinated, Al(VI) aluminium. At high Ca/Si ratios, Al(VI) is favoured and the aluminium uptake in C-S-H increases with the aqueous aluminium concentration. At low Ca/Si ratio (≤ 0.8), aluminium is observed mainly as Al(IV) and the low aqueous aluminium concentrations (below detection limit) indicate a higher affinity of aluminium towards C-S-H. The uptake of aluminium increases slightly the mean basal spacing slightly at low Ca/Si ratio and up to ≈2Å at higher Ca/Si ratios due to incorporation of aluminium and calcium in the interlayer. The presence of alkali hydroxide increases the pH leading (i) to a destabilisation of stratlingite and (ii) to higher aqueous silicon and aluminium concentrations and to lower calcium concentrations. As the aluminium uptake in C-S-H is strongly related to the aqueous aluminium concentrations, the aluminium uptake in the C-S-H increases significantly in the presence of alkali hydroxides, as aluminium is more soluble at higher pH. The increase of the temperature from 7 to 80 °C increases the phase-purity and long-range order of the C-S-H. The mean chain length remains stable up to 50°C, while at 80°C chain length increases and crosslinking is observed in the presence of aluminium. At all temperatures studied, the presence of aluminium has little effect on the calculated solubility of C(-A)-S-H. The incorporation of alkali ions in C-S-H increases with the initial concentration of alkali and with the decrease of Ca/Si ratio. The aqueous calcium concentration play a dominant role in alkali uptake, as calcium competes with the alkali ions to charge balance the negatively charged silanol groups of the C-S-H. A low concentration of calcium favours the alkali uptake in C-S-H. The uptake of alkali ions shortens the silica chain length as calcium is redistributed from the interlayer to the main sheet. The alkali uptake is not significantly influenced by the presence of aluminium in C-S-H, the hydration time or the type of cation (sodium or potassium).

EPFL2014

Adsorption de polycarboxylates et de lignosulfonates sur poudre modèle et ciments

François Perche

Placing concrete requires much more water than the cement needs for its hydration. This results in an important porosity in the hardened concrete, which accentuates the degradation of this material. By adding small amounts of polymeric admixtures, called superplasticizers, to the fresh concrete one can significantly reduce the amount of water required to obtain the suitable workability. The plasticizing effect of superplasticizers has been studied for many years, and remains today, an ongoing field of research. This research led to a better understanding of the forces that act during the deflocculation and dispersion of cement grains induced by superplasticizers. This research work was performed within the framework of the "Superplast" European project. Its main objective has been to determine which parameters (molecular structure, induced charge, adsorption mode, molar mass) influence the plasticizing effects of superplasticizers. The results of this study will allow synthesis new polymeric admixtures with better performances than those currently available. For this study, two types of superplasticizers were selected: lignosulfonates and polycarboxylates. For each one, different samples were synthesised and characterised. For each sample, adsorption, rheological and interaction forces measurements were performed by our partners while we have performed adsorption and electroacoustic measurements on model powder suspensions. Different cement model powders were investigated and a magnesium oxide was selected. The particle size distribution and reactivity were carefully characterized. The inert model system (MgO) allowed us to study adsorption mechanisms without the complexity linked to cement hydration reactions that modify surface and solution of the suspension. Particle surface charge and pH are the two main parameters that influence the polymer adsorption and the polymer conformation. Magnesium oxide which has a high isoelectric point (around at pH 12.4) allows a surface charge similar to cement suspensions at high pH. First, we have measured the adsorption isotherms of all superplasticizers on model suspensions in NaOH (0.01M). This study allowed us to evaluate the affinity of each polymer for MgO and its adsorption plateau. These measurements showed that the lignosulfonates have a higher affinity than the polycarboxylates. They also showed that lignosulfonate adsorption is mainly influenced by their molar mass and their carboxylic group content (for similar sulfonate group content) while polycarboxylate adsorption is mainly driven by the backbone length, the side chain length and the carboxylic group content. Adsorption plateaux allowed us to calculate the surface coverage ratio and to estimate the superplasticizer conformation on the surface. Adsorption isotherms were finally measured on a Portland cement. The polymer adsorption is influenced by the same parameters as on MgO. The model system MgO is representative for the polymer adsorption on cement. In a second step, different electrolytes were added to model suspensions. This practice allowed us to study separately the effect of the main ions present in cement suspensions (Na+, Ca2+, SO42-, OH-) and to mimic the ionic composition of the aqueous phase of the cement suspension. Lignosulfonate adsorption is neither influenced by the studied ions or the pH. Only an increase of ionic strength increases the adsorbed polymer mass. Polycarboxylate adsorption is influenced by calcium and sulfate ions and by the particle surface charge. Finally, superplasticizer adsorption was studied on different cements by our partners and on a fly ash and a silica fume by ourselves. Lignosulfonate adsorption isotherms on cements showed that affinity and adsorbed polymer mass increases with the C3A content and decreases with the alkalis content. The isotherms measured on industrial by-products showed that superplasticizers adsorb on fly ash, but not on silica fume.

EPFL2004

Durability Of Field Concrete Made Of Portland Cement And Supplementary Cementitious Materials Under Several European Exposure Conditions

Aude Chabrelie, Emmanuel Gallucci, Karen Scrivener

Deterioration of cementitious materials by sulfate ions is a concern for concrete in contact with ground water (and in a lesser extent sea water) in many parts of Europe, and is an important issue for underground construction identified as a major area for progress in the construction industry. Sulfate resistance relates closely to testing and standardization and therefore to prescriptive approaches. The lack of feed back oil the durability of structures made of blended cements makes it difficult to fit these new concretes with existing test methods and performance criteria. This paper concerns the microstructural Study of field samples and structures made of blended concretes available across Europe. This concerns several materials exposed to various climate regimes, ranging from Southern to Northern Europe (Spain, Germany, United Kingdom, Denmark and Norway). Complementary techniques Such as SEM, micro-XR-F, XR-D and PIXE are used to evaluate the microstructural performance and stability of the phase assemblage of those blended concretes in the case of sulflate (and chloride in some instances) ingress, compare to pure Portland concrete.

R I L E M Publications, 91 Ave President Wilson, 94235 Cachen, France2008

Adsorption de polycarboxylates et de lignosulfonates sur poudre modèle et ciments

François Perche

EPFL2004

Aluminium and alkali uptake in calcium silicate hydrates (C-S-H)

EPFL2014