Mesocrystalline calcium silicate hydrate: A bioinspired route toward elastic concrete materials

Controlled aggregation of polymer-stabilized calcium silicate hydrate nanoparticles leads to elastic cementitious materials.

Calcium mediated polyelectrolyte adsorption on like-charged surfaces.

International audience; Monte Carlo simulations within the primitive model of calcium-mediated adsorption of linear and comb polyelectrolytes onto like-charged surfaces are described, focusing on the effect of calcium and polyion concentrations as well as on the ion pairing between polymers and calcium ions. We use a combination of Monte Carlo simulations and experimental data from titration and calcium binding to quantify the ion pairing. The polymer adsorption is shown to occur as a result of surface overcharging by Ca2+ and ion pairing between charged monomers and Ca2+. In agreement with experimental observations, the simulations predict that the polymer adsorption isotherm goes through …

Mechanism of aluminium incorporation into C–S–H from ab initio calculations

Blended cements have great potential to reduce the CO2 footprint due to cement production. C(alcium)–S(ilicate)–H(ydrate) in these novel materials is known to incorporate a considerable amount of Al. We have for the first time applied large-scale first principles calculations to address the mechanism of Al incorporation into low C/S ratio C–S–H. In agreement with state-of-the-art NMR information, our calculations show that Al substitutes Si in bridging tetrahedra only, and that substitutions in pairing tetrahedra are strongly disfavoured in a wide range of conditions. In broad terms, the energy penalty for having an Al atom in a pairing position is of about 20 kcal mol−1. Al in bridging tet…

Identification of binding peptides on calcium silicate hydrate: a novel view on cement additives.

Cement is the most used industrial product in the world. Although the chemical composition of the material has stayed more or less the same since its discovery by the Romans around 2000 years ago, [ 1 ] the performance has been increased by chemical additives. Spectacular buildings like the Willis Tower in Chicago, Taipei 101 or lately the over 800 m high Burj Khalifa in Dubai were realizable thanks to the development of high performance building materials. [ 2 ] Not only for such prestige objects but also in daily building processes, the trend goes towards always higher buildings because of the continued urbanization which was identifi ed already in 1982 as one of the so-called “megatrends…

Effective pair potential between charged nanoparticles at high volume fractions

Simulations of charged colloidal dispersions are technically challenging. One possible workaround consists in reducing the system to the colloids only, whose interactions are described through an effective pair potential, wf. Still, the determination of wf is difficult mainly because it depends on the colloidal density, ϕ. Here we propose to calculate wf from simulations of a pair of colloids placed in a cubic box with periodic boundary conditions. The variation in ϕ is mimicked by an appropriate change in the concentration of counterions neutralized by an homogeneous background charge. The method is tested at the level of the primitive model. A good description of the structure of the coll…

Monte Carlo Simulations of a Clay Inspired Model Suspension: The Role of Rim Charge

International audience; We present a theoretical investigation of a model clay dispersion in 1-1 salt solutions by varying the particle volume fraction and ionic strength as well as the charge distribution on the clay platelets. The platelets are modeled as discs with charged sites distributed on a hexagonal lattice. The edge sites can be positively charged while the remaining sites are negative giving rise to a strong charge anisotropy. Simulations are carried out using a Monte Carlo method in the canonical ensemble. The interactions between the platelet sites are described with a screened Coulomb potential plus a short range repulsive potential. Simulations show a complex phase behavior. …

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

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…

Impact of gluconate and hexitol additives on the precipitation mechanism and kinetics of C-S-H

The present paper investigates the influence of gluconate and hexitol additives on the precipitation mechanism and kinetics of C-S-H. To this end, wet chemistry C-S-H precipitation experiments were performed under controlled conditions of solution supersaturation, under varying silicate concentration, while the transmittance of the solution was followed. This allowed determining induction times for the formation of C-S-H precursors in the presence and absence of gluconate and three hexitol molecules. Characterization of the precipitates was performed via small angle X-ray scattering and cryo-transmission electron microscopy experiments, which allowed the identification of a multi-step nucle…

Interaction of Nanometric Clay Platelets

International audience; The free energy of interaction between two nanometric clay platelets immersed in an electrolyte solution has been calculated using Monte Carlo simulations as well as direct integration of the configurational integral. Each platelet has been modeled as a collection of charged spheres carrying a unit chargethe face of a platelet contains negative charges, and the edge, positive charges. The calculations predict that a configuration of “overlapping coins” is the global free energy minimum at intermediate salt concentrations (10−100 mM). A second weaker minimum, corresponding to the well-known “house of cards” configuration, also appears in this salt interval. At low sal…

Nanoscale Investigation of Particle Interactions at the Origin of the Cohesion of Cement

International audience

Ion-ion correlation and charge reversal at titrating solid interfaces

Confronting grand canonical titration Monte Carlo simulations (MC) with recently published titration and charge reversal (CR) experiments on silica surfaces by Dove et al. and van der Heyden it et al, we show that ion-ion correlations quantitatively explain why divalent counterions strongly promote surface charge which, in turn, eventually causes a charge reversal (CR). Titration and CR results from simulations and experiments are in excellent agreement without any fitting parameters. This is the first unambiguous evidence that ion-ion correlations are instrumental in the creation of highly charged surfaces and responsible for their CR. Finally, we show that charge correlations result in "a…

On the origin of the halo stabilization

Monte Carlo simulations show that charge-regulation alone can cause highly charged zirconium nanoparticles to adsorb to a similarly charged or neutral silica particle and thereby stabilizing the latter. This mechanism, referred to as halo stabilization, is quite general and applicable in a range of systems provided that pH, van der Waals forces, and dissociation constants of the charge-regulating particles are properly chosen. In our modeling we see an overall attraction at low volume fractions of nanoparticles, while at higher a repulsive barrier is created, stabilizing the microparticles and protecting them from aggregation. The charge-regulation mechanism also turns the silica surface fr…

A New Monte Carlo Method for the Titration of Molecules and Minerals

The charge state of molecules and solid/liquid interfaces is of paramount importance in the understanding of the reactivity and the physico-chemical properties of many systems. In this work, we porpose a new Monte Carlo method in the grand canonical ensemble using the primitive model, which allows us to simulate the titration behavior of macromolecules or solids at constant pH. The method is applied to the charging process of colloidal silica particles dispersed in a sodium salt solution for various concentrations and calcium silicate hydrate nano-particles in a calcium hydroxide solution. An excellent agreement is found between the experimental and simulated results.

Two-Step Nucleation Process of Calcium Silicate Hydrate, the Nanobrick of Cement

Despite a millennial history and the ubiquitous presence of cement in everyday life, the molecular processes underlying its hydration behavior, like the formation of calcium–silicate–hydrate (C–S–H), the binding phase of concrete, are mostly unexplored. Using time-resolved potentiometry and turbidimetry combined with dynamic light scattering, small-angle X-ray scattering, and cryo-TEM, we demonstrate C–S–H formation to proceed via a complex two-step pathway. In the first step, amorphous and dispersed spheroids are formed, whose composition is depleted in calcium compared to C–S–H and charge compensated with sodium. In the second step, these amorphous spheroids crystallize to tobermorite-typ…

The electrostatic role in the retention of sulfate in cement systems

Gel, glass and nematic states of plate-like particle suspensions: charge anisotropy and size effects

The influence of the charge anisotropy and platelet size on the formation of gel and glass states and nematic phases in suspensions of plate-like particles is investigated using Monte Carlo simulations in the canonical ensemble. The platelets are modeled as discs with charged sites distributed on a hexagonal lattice. The edge sites can carry a positive charge, while the remaining sites are negatively charged giving rise to a charge anisotropy. A screened Coulomb potential plus a short range repulsive potential are used to describe the interactions between the sites of the platelets. The liquid–gel transition is found to be favored by a high charge anisotropy and by large particles. Opposite…

Monte Carlo Simulations of Parallel Charged Platelets as an Approach to Tactoid Formation in Clay

The free energy of interaction between parallel charged platelets with divalent counterions has been calculated using Monte Carlo simulations to investigate the electrostatic effects on aggregation. The platelets are primarily intended to represent clay particles. With divalent counterions, the free energy for two platelets or two tactoids (clusters of parallel platelets) shows a minimum at a short separation due to the attraction caused by ion-ion correlations. In a salt-free system, the free energy of interaction has a long-range repulsive tail beyond the minimum. The repulsion increases for tactoids with larger aggregation numbers, whereas the depth of the free-energy minimum is graduall…

Gluconate and hexitols effects on C-S-H solubility

This study investigates the effect of gluconate, a carboxylate ion, and three uncharged hexitols, D-sorbitol, D-mannitol and D-galactitol on the solubility of C-S-H. Thermodynamic modeling was used to determine the kind and amount of Ca-organic-silicate-OH complexes that potentially form in the conditions studied. All the organics form complexes with calcium and hydroxide, In addition, heteropolynuclear organics complexes with calcium, hydroxide and silicate are observed at high pH values and high calcium concentrations with the exception of mannitol. The strength of complexation with silicate decreases from gluconate > sorbitol > galactitol. The adsorption of the selected organics on…

Intrinsic Acidity of Surface Sites in Calcium Silicate Hydrates and Its Implication to Their Electrokinetic Properties

Calcium Silicate Hydrates (C–S–H) are the major hydration products of portland cement paste. The accurate description of acid–base reactions at the surface of C–S–H particles is essential for both understanding the ion sorption equilibrium in cement and prediction of mechanical properties of the hardened cement paste. Ab initio molecular dynamics simulations at the density functional level of theory were applied to calculate intrinsic acidity constants (pKa’s) of the relevant ≡SiOH and ≡CaOH2 groups on the C–S–H surfaces using a thermodynamic integration technique. Ion sorption equilibrium in C–S–H was modeled applying ab initio calculated pKa’s in titrating Grand Canonical Monte Carlo simu…

Coarse-Graining Intermolecular Interactions in Dispersions of Highly Charged Colloids

International audience; Effective pair potentials between charged colloids, obtained from Monte Carlo simulations of two single colloids in a closed cell at the primitive model level, are shown to reproduce accurately the structure of aqueous salt-free colloidal dispersions, as determined from full primitive model simulations by Linse et al. (Linse, P.; Lobaskin, V. Electrostatic Attraction and Phase Separation in Solutions of Like-Charged Colloidal Particles. Phys. Rev. Lett.1999, 83, 4208). Excellent agreement is obtained even when ion-ion correlations are important and is in principle not limited to spherical particles, providing a potential route to coarse-grained colloidal interactions…

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

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

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

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…

Packing polydisperse colloids into crystals: when charge-dispersity matters

Monte-Carlo simulations and small-angle x-ray scattering experiments were used to determine the phase diagram of aqueous dispersions of titratable nano-colloids with a moderate size polydispersity over a broad range of monovalent salt concentrations, 0.5 mM $\leq c_s \leq$ 50 mM and volume fractions, $\phi$. Under slow and progressive increase in $\phi$, the dispersions freeze into a face-centered-cubic (fcc) solid followed unexpectedly by the formation of a body centered cubic (bcc) phase before to melt in a glass forming liquid. The simulations are found to predict very well these observations. They suggest that the stabilization of the bcc solid at the expense of the fcc phase at high $\…

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

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…

Size dependent surface charging of nanoparticles

International audience; Experimental interest in the possible curvature dependence of particle charging in electrolyte solutions is subjected to theoretical analysis. The corrected Debye−Hückel theory of surface complexation (CDH-SC) and Monte Carlo (MC) simulation are applied to investigate the dependence of surface charging of metal oxide nanoparticles on their size. Surface charge density versus pH curves for spherical metal oxide nanoparticles in the size range of 1−100 nm are calculated at various concentrations of a background electrolyte. The surface charge density of a nanoparticle is found to be highly size-dependent. As the particle diameter drops to below 10 nm there is considera…

Long-ranged and soft interactions between charged colloidal particles induced by multivalent coions

Forces between charged particles in aqueous solutions containing multivalent coions and monovalent counterions are studied by the colloidal probe technique. Here, the multivalent ions have the same charge as the particles, which must be contrasted to the frequently studied case where multivalent ions have the opposite sign as the substrate. In the present case, the forces remain repulsive and are dominated by the interactions of the double layers. The valence of the multivalent coion is found to have a profound influence on the shape of the force curve. While for monovalent coions the force profile is exponential down to separations of a few nanometers, the interaction is much softer and lo…

Hiding in plain view: Colloidal self-assembly from polydisperse populations.

We report small-angle x-ray scattering (SAXS) experiments on aqueous dispersions of colloidal silica with a broad monomodal size distribution (polydispersity 18%, size 8 nm). Over a range of volume fractions the silica particles segregate to build first one, then two distinct sets of colloidal crystals. These dispersions thus demonstrate fractional crystallization and multiple-phase (bcc, Laves AB$_2$, liquid) coexistence. Their remarkable ability to build complex crystal structures from a polydisperse population originates from the intermediate-range nature of interparticle forces, and suggests routes for designing self-assembling colloidal crystals from the bottom-up.

Acid-Base Properties of 2:1 Clays. I. Modeling the Role of Electrostatics

We present a theoretical investigation of the titratable charge of clays with various structural charge (sigma(b)): pyrophyllite (sigma(b) = 0 e x nm(-2)), montmorillonite (sigma(b) = -0.7 e x nm(-2)) and illite (sigma(b) = -1.2 e x nm(-2)). The calculations were carried out using a Monte Carlo method in the Grand Canonical ensemble and in the framework of the primitive model. The clay particle was modeled as a perfect hexagonal platelet, with an "ideal" crystal structure. The only fitting parameters used are the intrinsic equilibrium constants (pK(0)) for the protonation/deprotonation reactions of the broken-bond sites on the lateral faces of the clay particles, silanol, =SiO(-) + H(+) --=…

The effect of polycations on early cement paste

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…

Liquid Crystal Phases in Suspensions of Charged Plate-Like Particles

International audience; Anisotropic interactions in colloidal suspensions have recently emerged as a route for the design of new soft materials. Nonisotropic particles can form nematic, smectic, hexatic, and columnar liquid crystals. Although the formation of these phases is well rationalized when excluded volume is solely at play, the role of electrostatic interactions still remains unclear and even less so when particles present a charge heterogeneity, for example, clays. Here, we use Monte Carlo simulations of concentrated suspensions of charged disk-like particles to reveal the role of Coulomb interactions and charge anisotropy underlying liquid crystal formation and structures. We obse…

The growth of charged platelets.

Growth models of charged nanoplatelets are investigated with Monte Carlo simulations and simple theory. In a first model, 2-dimensional simulations in the canonical ensemble are used to demonstrate that the growth of a single weakly charged platelet could be limited by its own internal repulsion. The short range attractive interaction in the crystal is modeled with a square well potential while the electrostatic interactions are described with a screened Coulomb potential. The qualitative behavior of this case can also be described by simply balancing the attractive crystal energy with the screened Coulomb repulsion between the crystal sites. This repulsion is a free energy term dominated b…

Stability of negatively charged platelets in calcium-rich anionic copolymer solutions.

Controlling the stability of anisotropic particles is key to the development of advanced materials. Here, we report an investigation, by means of mesoscale molecular dynamics simulations, of the stability and structural change of calcium-rich dispersions containing negatively charged nanoplatelets, neutralized by calcium counterions, in the presence of either comb copolymers composed of anionic backbones with attached neutral side chains or anionic-neutral linear block copolymers. In agreement with experimental observations, small stacks of platelets (tactoids) are formed, which are greatly stabilized in the presence of copolymers. In the absence of polymers, tactoids will grow and aggregat…

Electrostatics for a better understanding of the acid-base chemistry of montmorillonite

International audience

Factors influencing the cohesion forces

Adsorption of sulfate ions on negatively charged surfaces

International audience

Controlling the cohesion of cement paste

The main source of cohesion in cement paste is the nanoparticles of calcium silicate hydrate (C-S-H), which are formed upon the dissolution of the original tricalcium silicate (C(3)S). The interaction between highly charged C-S-H particles in the presence of divalent calcium counterions is strongly attractive because of ion-ion correlations and a negligible entropic repulsion. Traditional double-layer theory based on the Poisson-Boltzmann equation becomes qualitatively incorrect in these systems. Monte Carlo (MC) simulations in the framework of the primitive model of electrolyte solution is then an alternative, where ion-ion correlations are properly included. In addition to divalent calciu…

Portlandite solubility and Ca 2+ activity in presence of gluconate and hexitols

The current paper investigates the impact of gluconate, D-sorbitol, D-mannitol and D-galactitol on calcium speciation at high pH values by i) solubility measurements of portlandite (Ca(OH)2) and ii) potentiometric titration measurements of calcium salt solutions. Thermodynamic modeling was used to fit the chemical activities of Ca2+ and OH- ions and thus to determine the strength and kind of the different Ca-organic-hydroxide complexes. The strength of complex formation with Ca decreases in the order gluconate >> sorbitol > mannitol > galactitol, which follows the same order as sorption on portlandite. Heteropolynuclear gluconate complexes with calcium and hydroxide dominate the…