The role of aluminium from supplementary cementitious materials in controlling alkali-silica reaction

Alkali silica reaction (ASR) is a long-term reaction between certain aggregates containing amorphous silicate phases and the alkalis from the cement paste. These silicates react with the alkalis present in the pore solution of the cement paste and form an expansive gel in the presence of water, resulting in the macroscopic expansion and cracking of concrete. Supplementary cementitious materials (SCM), replacing a part of the Portland cement (PC) in blended pastes, are known to reduce or even stop expansion due to ASR. 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, the main cement hydrate. However, knowledge on the effect of SCMs on ASR control is incomplete, especially the role of aluminium. The first part of this work focuses on the effect of aluminium and silicon incorporation in C-S-H, provided by SCMs, on the composition of the pore solution of blended pastes. It was found that, contrary to the common idea, the incorporation of aluminium in C-S-H does not increase its alkali fixation capacity, suggesting that the greater effectiveness of SCMs containing alumina is due to other reasons. In a second part, it is proposed that the additional aluminium acts directly on the reactive phases of the aggregates. Marine chemistry and geology theories about the dissolution mechanisms of amorphous silicates were applied to cementitious systems. Aluminium species, provided by certain SCMs and present in the pore solution, are incorporated in the silica surface and limit the dissolution of amorphous silica of the aggregates, limiting ASR. The effect of aluminium was shown through a study of reactive aggregates in simulated pore solutions. The mechanism was explained through a more fundamental study with pure amorphous silica plates put in simulated pore solutions. Finally, the impact of various alkali cations on ASR was studied to better understand the reactions inducing gel formation

Sudden cardiac death among general population and sport related population in forensic experience.

PURPOSE: The goal of the study was to assess the causes and analyze the cases of sudden cardiac death (SCD) victims referred to the department of forensic medicine in Lausanne, with a particular focus on sports-related fatalities including also leisure sporting activities. To date, no such published assessment has been done nor for Switzerland nor for the central Europe. METHODS: This is a retrospective study based on autopsy records of SCD victims, from 10 to 50 years of age, performed at the University Centre of Legal Medicine in Lausanne from 1995 to 2010. The study population was divided into two groups: sport-related (SR) and not sport-related (NSR) SCDs. RESULTS: During the study period, 188 cases of SCD were recorded: 166 (88%) were NSR and 22 (12%) SR. The mean age of the 188 victims was 37.3 ± 10.1 years, with the majority of the cases being male (79%). A cause of death was established in 84%, and the pathology responsible for death varied according to the age of the victims. In the NSR group, the mean age was 38.2 ± 9.2 years and there was 82% of male. Coronary artery disease (CAD) was the main diagnosis in the victims aged 30-50 years. The majority of morphologically normal hearts were observed in the 15-29 year age range. There was no case in the 10-14 year age range. In the SR group, 91% of victims died during leisure sporting activities. In this group the mean age was 30.5 ± 13.5 years, with the majority being male (82%). The main cause of death was CAD, with 6 cases (27%) and a mean age of 40.8 ± 5.5 years. The youngest victim with CAD was 33 years old. A morphologically normal heart was observed in 5 cases (23%), with a mean age of 24.4 ± 14.9 years. The most frequently implicated sporting activities were hiking (26%) and swimming (17%). CONCLUSION: In this study, CAD was the most common cause of death in both groups. Although this pathology most often affects adults over 35 years of age, there were also some victims under 35 years of age in both groups. SCDs during sport are mostly related to leisure sporting activities, for which preventive measures are not yet usually established. This study highlights also the need to inform both athletes and non athletes of the cardiovascular risks during sport activities and the role of a forensic autopsy and registries involving forensic pathologists for SR SCD

Composition-solubility-structure relationships in calcium (alkali) aluminosilicate hydrate (C-(N,K-)A-S-H)

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

Solid-state nuclear magnetic resonance spectroscopy of cements

Cement is the ubiquitous material upon which modern civilisation is built, providing long-term strength, impermeability and durability for housing and infrastructure. The fundamental chemical interactions which control the structure and performance of cements have been the subject of intense research for decades, but the complex, crystallographically disordered nature of the key phases which form in hardened cements has raised difficulty in obtaining detailed information about local structure, reaction mechanisms and kinetics. Solid-state nuclear magnetic resonance (SS NMR)spectroscopy can resolve key atomic structural details within these materials and has emerged as a crucial tool in characterising cement structure and properties. This review provides a comprehensive overview of the application of multinuclear SS NMR spectroscopy to understand composition–structure–property relationships in cements. This includes anhydrous and hydrated phases in Portland cement, calcium aluminate cements, calcium sulfoaluminate cements, magnesia-based cements, alkali-activated and geopolymer cements and synthetic model systems. Advanced and multidimensional experiments probe 1 H, 13 C, 17 O, 19 F, 23 Na, 25 Mg, 27 Al, 29 Si, 31 P, 33 S, 35 Cl, 39 K and 43 Ca nuclei, to study atomic structure, phase evolution, nanostructural development, reaction mechanisms and kinetics. Thus, the mechanisms controlling the physical properties of cements can now be resolved and understood at an unprecedented and essential level of detail

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