Influence of temperature on the hydration products of low pH cements

2012

International audience; The chemical evolution of two hydrated "low pH" binders prepared from binary (60% Portland cement + 40% silica fume) or ternary (37.5% Portland cement +32.5% silica fume + 30% fly-ash) mixtures was characterized over one year at 20 degrees C. 50 degrees C, and 80 degrees C. The main hydrates were Al-substituted C-S-H. Raising the temperature from 20 to 80 degrees C caused a lengthening and cross-linking of their silicate chains. Ettringite that formed in pastes stored at 20 degrees C was destabilized. Only traces of calcium sulfate (gypsum and/or anhydrite) reprecipitated after one year in some materials cured at 50 degrees C and 80 degrees C. The sulfates released w…

Retention of alkali ions by hydrated low-pH cements: Mechanism and Na+/K+ selectivity

2013

Low-pH cements, also referred to as low-alkalinity cements, can be designed by replacing significant amounts of Portland cement by pozzolanic materials. Their pore solution is characterized by a pH near 11, and an alkali concentration much lower than that of Portland cement. This work investigates the retention of sodium and potassium by a hydrated low-pH cement comprising 60% Portland cement and 40% silica fume. It is shown that sorption of potassium is higher than that of sodium and mainly results from counterion charge balancing of the C-S-H negative surface charge. To explain the greater retention of potassium compared to sodium, it is postulated that potassium, unlike sodium, may enter…

Structure and Yielding of Colloidal Silica Gels Varying the Range of Interparticle Interactions.

2016

The relationship between interaction range, structure, fluid-gel transition, and viscoelastic properties of silica dispersions at intermediate volume fraction, Φv ≈ 0.1 and in alkaline conditions, pH = 9 was investigated. For this purpose, rheological, physicochemical, and structural (synchrotron-SAXS) analyses were combined. The range of interaction and the aggregation state of the dispersions were tuned by adding either divalent counterions (Ca(2+)) or polycounterions (PDDA). With increasing calcium chloride concentration, a progressive aggregation was observed which precludes a fluid-gel transition at above 75 mM of calcium chloride. In this case, the aggregation mechanism is driven by s…

Al-27 and Si-29 Solid-State NMR Characterization of Calcium-Aluminosilicate-Hydrate

2012

International audience; Calcium silicate hydrate (C-S-H) is the main constituent of hydrated cement paste and determines its cohesive properties. Because of the environmental impact of cement industry, it is more and more common to replace a part of the clinker in cement by secondary cementitious materials (SCMs). These SCMs are generally alumina-rich and as a consequence some aluminum is incorporated into the C-S-H. This may have consequences on the cohesion and durability of the material, and it is thus of importance to know the amount and the location of Al in C-S-H and what the parameters are that control these features. The present paper reports the Si-29 and Al-27 MAS NMR analyses of …

The electrostatic role in the retention of sulfate in cement systems

2008

Surface charge, effective charge and dispersion/aggregation properties of nanoparticles

2003

A careful investigation of the relationship between surface properties and colloidal behaviour of nanometric particles in concentrated media has shed some light on the important parameters that must be controlled in order to improve the dispersion of mineral particles. Experimental methods such as rheology and osmometry reveal that the aggregation/dispersion process is not only a matter of electrostatics as stated by classical theories. In practice, the relationship between the surface charge and the state of dispersion is probably much less straightforward than generally assumed by the classical argument stating that the higher the surface charge, the higher the electrostatic repulsion bet…

Prediction of Long-Term Chemical Evolution of a Low-pH Cement Designed for Underground Radioactive Waste Repositories

2012

Low-pH cements, also referred as low-alkalinity cements, are binders with a pore solution pH ≤ 11. They can be designed by replacing significant amounts of Portland cement (OPC) (≥40 %) by silica fume, which can be associated in some cases to low-CaO fly ash and/or ground granulated blast furnace slag to decrease the heat output during hydration by dilution of OPC and improve the mechanical strength of the final material. With the prospect of using these materials in a geological repository, it is of main importance to estimate their long-term properties and the influence of external and internal factors (chemical composition of the binder, storage temperature) on their characteristics. For…

C-S-H/solution interface: Experimental and Monte Carlo studies

2010

International audience; The surface charge density of C-S-H particles appears to be one of the key parameters for predicting the cohesion strength, understanding the ion retention, the pollutant leakage, and admixture adsorption in hydrated cement pastes. This paper presents a Monte Carlo simulation of the surface-ions interactions that permits the prediction of surface charge density (σ), electrokinetic potential (ζ) and ions adsorption of mineral surfaces in equilibrium with a given electrolyte solution. Simulated results are compared to experimental data obtained by titration, electrokinetic potential measurements and ions uptake in the case of C-S-H suspensions. An excellent agreement i…

Experimental and theoretical evidence of overcharging of calcium silicate hydrate

2007

International audience; Electrokinetic measurements such as electrophoresis may show an inversion of the effective surface charge of colloidal particle called overcharging. This phenomenon has been studied by various theoretical approaches but up to now very few attempts of confrontation between theory and experiment have been conducted. In this work we report electrophoretic measurements as well as Monte Carlo simulations of the electrokinetic potential for the surface of calcium silicate hydrate (Csingle bondSsingle bondH), which is the major constituent of hydrated cement. In the simulations, the surface charge of Csingle bondSsingle bondH nanoparticles in equilibrium with the ionic solu…

Ettringite surface chemistry: Interplay of electrostatic and ion specificity

2011

International audience; This paper presents a detailed experimental study combined with Monte Carlo (MC) simulations within the primitive model of the physical chemistry at the ettringite-water interface over a wide range of pH and bulk conditions for which ettringite exists thanks to its solubility in aqueous solutions. Ettringite, which is an important phase in hydrated cement-based systems, bears a permanent and positive structural charge. In contrast with previous studies, electrokinetic measurements together with the careful chemical analysis of the equilibrium solutions of the dispersions have brought strong support to designate sulfate as being the ion determining the potential. Simu…

Surface Charge Density and Electrokinetic Potential of Highly Charged Minerals: Experiments and Monte Carlo Simulations on Calcium Silicate Hydrate

2006

International audience; In this paper, we are concerned with the charging and electrokinetic behavior of colloidal particles exhibiting a high surface charge in the alkaline pH range. For such particles, a theoretical approach has been developed in the framework of the primitive model. The charging and electrokinetic behavior of the particles are determined by the use of a Monte Carlo simulation in a grand canonical ensemble and compared with those obtained through the mean field theory. One of the most common colloidal particles has been chosen to test our theoretical approach. That is calcium silicate hydrate (C−S−H) which is the main component of hydrated cement and is known for being re…

The effect of polycations on early cement paste

2010

International audience; This paper studies the possibility for improving the ductility of cement based materials by means of oligocationic additives. Actually, the setting of cement is due to ionic correlation forces between highly negatively charged C-S-H nanoparticles throughout a calcium rich solution. The main drawback of this strong attraction is its very short range that results in low elastic deformation of hydrated cementitious materials. A way to enlarge the attraction range between C-S-H particles would be to add cationic oligomers that would compete with calcium ions modifying the ionic correlation forces via a bridging mechanism of longer range, which could lead to a more ductil…

Engineering Photocatalytic Cements: Understanding TiO2 Surface Chemistry to Control and Modulate Photocatalytic Performances

2010

The present work addresses the aggregation/dispersion properties of two commercial titanias for application as photocatalysts in concrete technology. A microsized m-TiO2 (average particle size 153.7 ± 48.1 nm) and a nanosized n-TiO2 (average particle size 18.4 ± 5.0 nm) have been tested in different ionic media (Na+, K+, Ca2+, Cl−, SO42−, synthetic cement pore solution) at different pHs and in real cement paste specimens. Results highlighted that ion–ion correlations play a fundamental role in TiO2 particles aggregation in the cement environment. A particle aggregation model derived from TiO2 surface chemistry is proposed here and used to justify such aggregation phenomena in real cement pa…

Experimental study of Si–Al substitution in calcium-silicate-hydrate (C-S-H) prepared under equilibrium conditions.

2009

International audience; C-A-S-H of varying Al/Si and Ca/(Al+Si) ratios have been prepared introducing C-S-H (Ca/Si=0.66 and 0.95) at different weight concentrations in a solution coming from the hydration of tricalcium aluminate (Ca3Al2O6) in water. XRD and EDX (TEM) analyses show that using this typical synthesise procedure, pure C-A-S-H is obtained only for calcium hydroxide concentrations below 4.5 mmol L−1. Otherwise, calcium carboaluminate or strätlingite is also present beside C-A-S-H. The tobermorite-like structure is maintained for C-A-S-H. A kinetic study has shown that the formation of C-A-S-H is a fast reaction, typically less than a few hours. The Ca/(Al+Si) ratio of C-A-S-H mat…