The influence of aluminium on the dissolution of amorphous silica and its relation to alkali silica reaction

It is known that the addition of supplementary cementitious materials (SCMs) in concretes reduces or even stops expansion due to alkali silica reaction (ASR). It has been widely shown that the main mechanism controlling ASR in blends is the alkali fixation capacity of silica rich C-S-H, which lowers the pH of the pore solution. The role of alumina additions is less clear. It was shown in a previous paper [1] that the alumina present in certain SCMs does not further reduce the alkalinity of the paste pore solution. It is proposed here that aluminium acts directly on the reactive phases of the aggregates. Aluminium species, present in the pore solution, are absorbed on the silica surface and limit the dissolution of amorphous silica of the aggregates, restricting ASR. The effect of aluminium was demonstrated through a study of mortar expansion and SEM image analysis of reactive aggregates in simulated pore solutions. (C) 2012 Elsevier Ltd. All rights reserved.

Alkali fixation of C-S-H in blended cement pastes and its relation to alkali silica reaction

Theodor Alexandre Emmanuele Chappex, Karen Scrivener

Supplementary cementitious materials (SCM) are known to reduce or even stop expansion due to alkali silica reaction (ASR) in concretes with reactive aggregates. Studies indicate that the main reason for this is the decrease in alkalinity of the pore solution of the cement paste, which in turn is attributed to the change in composition of the C-S,H. In this paper we study the effect of aluminium and silicon incorporation in C-S-H on the composition of the pore solution in cement pastes containing SCMs. Different blended pastes of silica fume and metakaolin were cast, in order to obtain the same Si/Ca ratio of the C-S-H but with different aluminium contents. EDS micro analysis was made to determine the C-S-H compositions. In parallel pore solutions were extracted and analysed. It is found that the incorporation of aluminium does not increase the alkali fixation of the C-S-H found in real cementitious materials, suggesting that the greater effectiveness of SCMs containing alumina is due to other reasons. (C) 2012 Elsevier Ltd. All rights reserved.

Elsevier2012

The effect of paste composition, aggregate mineralogy and temperature on the pore solution composition and the extent of ASR expansion

Mahsa Bagheri, Barbara Lothenbach, Karen Scrivener

The reaction kinetics of the alkali silica reaction depends on the composition of the pore solution. The evolution of the pore solution composition in different cement pastes and concretes was studied. Pastes containing silica fume or metakaolin had the lowest amount of alkalis in the pore solution. In addition, metakaolin increased the aluminium concentrations. The lowest expansion was measured for the concretes made of blended cement pastes with low alkali and hydroxide content in their pore solution, for the duration of the present study, no additional aluminium effect was observed due to the already low pH. Addition of 400 mM of Li slowed down expansion rate of concrete prisms at 40 and 60 degrees C, however, similar expansion was observed for samples with and without Li at 60 degrees C after 1 year. Temperature, alkali concentration and pH of pore solution all have a major effect on ASR expansion.

SPRINGER2022

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

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

EPFL2014