Surface Relaxivity of Cement Hydrates

Numerous aspects of the physical chemistry of colloidal systems are conditioned by the solid–liquid interface, and this is also the case for hydrated cement systems. Estimating the surface area is thus essential for studying the kinetics of cement hydration and admixture adsorption. Proton nuclear magnetic resonance (NMR) relaxation techniques have already proven useful for this objective, but, for hydrating cements at early ages, it is necessary to know the surface relaxivities of all of the individual phases present to correctly interpret the relaxation data. This paper reports the results of a comparison of NMR relaxometry and Brunauer–Emmett–Teller gas adsorption measurements on various…

From C–S–H to C–A–S–H: Experimental study and thermodynamic modelling

Abstract It has long been known that the stoichiometry of C–S–H varies with the calcium hydroxide concentration in solution. However, this issue is still far from understood. We revisit it in both experimental and modelling aspects. A careful analysis of the solubility confirms the existence of three different C–S–H phases, defined as Ca 4 H 4 Si 5 O 16 , Ca 2 H 2 Si 2 O 7 and Ca 6 (HSi 2 O 7 ) 2 (OH) 2 , respectively. The variation of the Ca/Si ratio of the three phases has been described by surface reactions: the increase of the Si content is accounted for by silicate bridging, the increase of calcium content and the surface charge are accounted for by reactions involving silanol groups v…

Atomistic modeling of crystal structure of Ca1.67SiHx

The atomic structure of calcium-silicate-hydrate (C-1.67-S-H-x) has been investigated by theoretical methods in order to establish a better insight into its structure. Three models for C-S-H all derived from tobermorite are proposed and a large number of structures were created within each model by making a random distribution of silica oligomers of different size within each structure. These structures were subjected to structural relaxation by geometry optimization and molecular dynamics steps. That resulted in a set of energies within each model. Despite an energy distribution between individual structures within each model, significant energy differences are observed between the three m…

The Structure, Stoichiometry and Properties of C-S-H Prepared by C3S Hydration Under Controlled Condition

Hydrations of tricalcium silicate undertaken by keeping constant lime concentration in solution in an open system and in diluted suspensions for different values of [CaO] ranging between 6.5 and 30 mmol/1 show that the lime concentration in solution is the parameter which determines the main characteristics of the reaction and products. The stoichiometry of C3S hydration products vanes with lime concentration in the same way as synthetic C-S-H until C/S c.a. 1.5 corresponding to about [CaO] =20 mmol/1. Beyond this concentration, single phase C-S-H samples were obtained with 1.8<C/S<2. The discontinuity of the variation of stoichiometry with concentration is characteristic of an invariant po…

Mechanisms and parameters controlling the tricalcium aluminate reactivity in the presence of gypsum.

International audience; To understand the mechanisms and the parameters controlling the reactivity of tricalcium aluminate in the presence of gypsum at an early age, a study of the hydration of the “C3A–sulphate” system by isothermal microcalorimetry, conductimetry and a monitoring of the ionic concentrations of diluted system suspensions have been carried out with various gypsum quantities. The role of C3A source and its fineness were also studied. This work shows the fast initial formation of AFm phase followed by ettringite formation during the period when the sulphate is consumed. It has been highlighted that the time necessary to consume all the gypsum varies with the type of C3A and i…

Study of alite containing aluminium hydration

International audience

Calcium silicate hydrates: Solid and liquid phase composition

© 2015 Elsevier Ltd. This paper presents a review on the relationship between the composition the structure and the solution in which calcium silicate hydrate (C S H) is equilibrated. The silica chain length in C S H increases with the silicon concentration and the calcium content in the interlayer space with the calcium concentrations. Sodium and potassium are taken up in the interlayer space preferentially at low calcium concentrations and thus by low Ca/Si C S H. Aluminium uptake in C S H increases strongly at higher aluminium concentrations in the solution. At low Ca/Si aluminium substitutes silica in the bridging position at Ca/Si. > 1 aluminium is bound in TAH. Recently developed ther…

Aggregation Processes and Formation of Silico-calco-alkaline Gels under High Ionic Strength

This paper presents a systematic in situ study of the process of formation of silico-calco-alkaline gels starting from a liquid colloidal solution containing different alkaline ions and different calcium concentration until the final gel state. The combined use of X-ray and neutron small-angle scattering (SAS) and dynamical rheometry techniques lead to a consistent description of the structure of the aggregates and of the mechanisms of aggregation involved in gel formation. SAS results indicate that the aggregates are fractal objects, their structure strongly depending on calcium ion concentration. The differences in gelation kinetics for systems containing different alkaline ions were attr…

Identification des phases sous-hydratées du sulfate de calcium

L'utilisation de moyens et de procedures experimentales adaptees a permis d’identifier chimiquement et structuralement deux formes sous-hydratees de sulfate de calcium : CaSO 4 , 0,5 H 2 O et CaSO 4 , 0,6 H 2 O.Avec l’hanhydrite soluble - γ-CaSO 4 - a laquelle elles s'apparentent structuralement ce sont les trois phases distinctes entrant dans la constitution du plâtre.

Natural fluorapatite as a raw material for Portland clinker

Abstract The present work focuses on the mineralogy and the reactivity of clinkers made from the integration of natural fluorapatite in the raw meals with percentages ranging from 0 up to15%. The samples were characterized by infrared spectrometry, X-ray diffraction and microscopy techniques. The distribution of phosphorous and fluorine into clinkers minerals was determined by MEB/EDS mapping. The mineralogical composition was determined by XRD/Rietveld and the samples reactivity followed by isothermal microcalorimetry. It has been found that fluorine stabilizes C3S and β-C2S which still are found with high levels of P2O5. Cements obtained from up to 8% natural fluorapatite incorporation st…

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.

Study of the hydration of cement with high slag content

International audience; The physico-chemical properties of cementitious materials, such as transport properties or porosity are established during the hydration process. The latter which involves dissolution and precipitation reactions, is characterized by the mineralogical and structural changes associated to water state (evolution from evaporable water to chemically bound water and physically absorbed water) and chemical shrinkage. These physico-chemical properties are modified by the addition of supplementary cementitious materials like slag. Powers' model, based on the water state repartition, was initially developed to describe the hydration of Portland cement. This work aims to apply …

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 …

Observation directe de la croissance d'hydrosilicate de calcium sur des surfaces d'alité et de silice par microscopie à force atomique

Direct observation of the growth of calcium silicate hydrates, the tricalcium silicate hydration products, at the solid-solution interface were performed by atomic force microscopy. The covering of the surface of alite or silica by a three-dimensional oriented aggregation of nano particles of calcium silicate hydrate is always observed whatever the sample. All observations and quantifications made on calcium silicate growth at the submicronic level are in agreement with the data deduced from the study of the system evolution at the macroscopic level.

Influence of temperature on the hydration products of low pH cements

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…

Structural model of gelation processes of a sodium silicate sol destabilized by calcium ions: combination of SAXS and rheological measurements

This study deals with the physico-chemical processes involved in the formation of basic fractal silica gels derived from a sodium silicate sol destabilized by calcium ions. Using small-angle X-ray scattering and dynamic rheological measurements, structural and viscoelastic properties have been investigated in situ during aggregation and gelation processes. The experimental results lead to a consistent model that describes the structural features and aggregation mechanisms involved in the formation of these gels.

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…

Early C3A hydration in the presence of different kinds of calcium sulfate.

International audience; Hydration reactions of C3A with various amounts of calcium sulfate hemihydrate, gypsum or a mixture of two, were investigated by isothermal microcalorimetry, and a monitoring of the ionic concentrations of diluted suspensions. This study shows that sulfate type used modifies the early C3A-CaSO4 hydration products and the rate of this hydration. The fast initial AFm formation observed before ettringite precipitation in the C3A-gypsum system is avoided as soon as hemihydrate is present in the suspension. This was attributed to.higher super saturation degrees and then higher nucleation frequency with regard to the ettringite obtained in the presence of hemihydrate. More…

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

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…

Hydration of alite containing alumimium

International audience; The most important phase in cement is tricalcium silicate which leads during its hydration to the nucleation and growth of calcium silicate hydrate (referred to C-S-H (CaO)x-SiO2-(H2O)y). The development of this hydrate around the cement grains is responsible for the setting and hardening of cement pastes The general term for designating the tricalcium silicate in cements is alite. This name relates to all polymorphs containing various foreign ions inserted in their structure. These ions may influence the intrinsic reactivity and once released during the dissolution, they may interact also with C-S-H. The melt phase during clinkering is rich in aluminium and moreover…

Rate-limiting reaction of C 3 S hydration - A reply to the discussion “A new view on the kinetics of tricalcium silicate hydration” by E. Gartner

Abstract In the case of coupled solids-solution reactions, any mean accelerating or decelerating one of the reaction, will also change the other reaction(s) in the same way, through the coupling mediated by the solution. The observation of any kinetic change by one of these means should not lead to too rapid conclusion on the limitation of kinetics and it must be done with great caution. Contrary to what Gartner mentioned, the acceleration of C3S hydration by the addition of calcium silicate hydrate seeds, is not a trivial evidence suggesting that hydration kinetics “has to be” limited by the C-S-H precipitation and that the C3S dissolution can be neglected. In our paper, efforts have been …

Influence of orthophosphate ions on the dissolution of tricalcium silicate

International audience; Tricalcium silicate dissolution in the presence of orthophosphate ions was monitored by measuring the concentrations of calcium and silicate ions in dilute suspensions using a special dissolution cell coupled to an optical emission spectrometer. Results show that increasing adsorption of orthophosphate ions slows down the dissolution of Ca3SiO5 and that a calcium-phosphate precipitate may form at certain orthophosphate concentrations. These observations are correlated with results of calorimetric experiments carried out during the hydration of silica-rich cement pastes in the presence of the same salts.

Physico-chemical parameters determining hydration and particle interactions during the setting of silicate cements

Abstract Hydration of tricalcium silicate (Ca 3 SiO 5 ), the pure phase used as a model of the portland cements, is the chemical process leading to the formation of hydrates, while setting is a definite time event corresponding to the change of the paste from the soft to the hard state. Setting results from interactions between anhydrous or very partially hydrated particles. The analysis of these interactions leads to the identification of two fundamental steps: the coagulation of cement grains during the first minutes following the mixing and the rigidification of the coagulated structure which arises simultaneously with the acceleration of the calcium silicate hydrates (CSH) formation. …

Du gâchage à l'état durci, ce sont les mêmes liaisons qui sont à l'œuvre

(1998). Du gâchage a l'etat durci, ce sont les memes liaisons qui sont a l'œuvre. Revue Francaise de Genie Civil: Vol. 2, No. 7, pp. 759-765.

Nucleation and growth of hydration products of cement.

International audience

A new calcium sulfate hemi-hydrate

Calcium sulfate hydrates receive significant attention due to numerous large scale industrial applications. There has been a long debate on the possible existence of two gypsum hemi-hydrate polymorphs, denoted alpha- and beta-CaSO(4).0.5H(2)O. In this work, a new crystal structure of calcium sulfate hemi-hydrates is presented, denoted beta-CaSO(4).0.5H(2)O. The structure was solved using powder neutron diffraction data, the space group is P3(1) and the unit cell in a hexagonal setting a = 6.9268(1), c = 12.7565(3) A. The structure has two calcium-oxygen coordination polyhedra: Ca1 is eight coordinated and has Ca-O bond lengths in the range 2.31(3) to 2.89(2) A and Ca2 is nine coordinated an…

Hydration of a CEM V Blended Cement: Characterization of PFA and BFS Reactivity and Evolution of the Porosity

The long term behaviour of cement based materials is strongly influenced by the internal chemistry and the paste microstructure. The industrial byproduct additives like pulverised fly ash (PFA) or blastfurnace slag (BFS) used in blended cement influence together the paste microstructures and the chemistry. A blended cement, designated CEM V in the European standard, containing PFA and BFS has been studied in order to understand processes involved during hydration. Several techniques as Xrays diffraction (XRD), solid-state NMR, thermogravimetry analysis (TGA) have been used to characterize the hydration of the PFA, BFS and the components (C2S, C3S) of the clinker. Such types of characterizat…

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

International audience

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

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 …

Structure et propriétés de surface des C-S-H.

National audience

Hydrated Layer Formation on Tricalcium and Dicalcium Silicate Surfaces: Experimental Study and Numerical Simulations

In this paper, an original approach is used to study the calcium silicate hydrate (C−S−H) layer formation on the surface of grains of anhydrous silicate during tricalcium and dicalcium silicate hydration from the variation of the rate of hydration with lime concentration. The effects of C−S−H nucleation and growth on the curves for the degree of reaction against time have been separated in both experimental study of the rate of hydration in controlled conditions and numerical simulation of the growth of C−S−H on a surface from a particle aggregation model. The influence of the number of nuclei and of the different growth modes has been quantified.

Hydration of alite containing aluminium

Abstract The most important phase in Portland cement is tricalcium silicate, which leads during its hydration to the nucleation and growth of calcium silicate hydrate [referred to as C–S–H, (CaO)x–SiO2–(H2O)y]. The development of this hydrate around the cement grains is responsible for the setting and hardening of cement pastes. The general term for designating the tricalcium silicate in cements is alite. This name relates to all polymorphs containing various foreign ions inserted in their structure. These ions may influence the intrinsic reactivity, and once released during the dissolution, they may interact also with C–S–H. One of the most likely species to be inserted in the alite struct…

Characterization by solid-state NMR and selective dissolution techniques of anhydrous and hydrated CEM V cement pastes.

International audience; The long term behaviour of cement based materials is strongly dependent on the paste microstructure and also on the internal chemistry. A CEM V blended cement containing pulverised fly ash (PFA) and blastfurnace slag (BFS) has been studied in order to understand hydration processes which influence the paste microstructure. Solid-state NMR spectroscopy with complementary X-ray diffraction analysis and selective dissolution techniques have been used for the characterization of the various phases (C3S, C2S, C3A and C4AF) of the clinker and additives and then for estimation of the degree of hydration of these same phases. Their quantification after simulation of experime…

The electrostatic role in the retention of sulfate in cement systems

Study of nucleation and growth processes of ettringite in diluted conditions

Abstract Ettringite is a key compound of cementitious materials, formed during hydration that influences the rheological behavior of the cement paste. Despite its importance, ettringite formation has been poorly studied. In this work, nucleation and growth processes of ettringite were separately investigated. Ettringite nucleation was described using the Classical Nucleation Theory and an interfacial crystal-solution energy was determined. After the initial primary homogeneous nucleation, when the surface of already formed crystals was still low, the precipitation rate was shown to depend almost exclusively on the solution supersaturation. When the surface of crystals in suspension was gett…

Effect of temperature on the development of C-S-H during early hydration of C3S

International audience; It is known that accelerating or retarding hydration of OPC by temperature has consequences on the final properties of concrete, the lower the temperature the higher the final compressive strength. It seems that this effect is related to the properties of the hydration layer formed at early age. Early hydration of C3S has then been studied at temperature ranging from 5 to 45°C in isothermal conditions. The percentage of hydration is estimated from calorimetric measurements and the surface developed by the growth of C-S-H is estimated from Nuclear Magnetic Relaxation Dispersion method. Both data are numerically simulated according to a C-S-H growth model described pre…

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

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…

Modification of the rate of formation and surface area of ettringite by polycarboxylate ether superplasticizers during early C3A–CaSO4 hydration

Abstract Early C3A–CaSO4 hydration was studied in the presence of various amounts of two polycarboxylate ether superplasticizers differing in their grafting degree. Hydration and surface area developments were investigated by in-situ NMR relaxometry coupled with BET and DSC during the first 2 h after mixing. This study enables a quantitative comparison of the amount and the specific surface area of the ettringite precipitated along the C3A–CaSO4 hydration with or without PCE. The main effect of PCE is to strongly increase ettringite specific area for a variable period. These effects are clearly dependent on the PCE charge and dosage and are reduced when using delayed addition. In this conte…

Hydration of cementitious materials, present and future

This paper is a keynote presentation from the 13th International Congress on the Chemistry of Cement. It discusses the underlying principles of hydration and recent evidence for the mechanisms governing this process in both Portland cements and other cementitious materials. Given the overriding imperative to improve the sustainability of cementitious materials, routes to reducing CO2 emissions are discussed and the impact of supplementary materials on hydration considered. (C) 2011 Elsevier Ltd. All rights reserved.

Effect of blastfurnace slag addition to Portland cement for cationic exchange resins encapsulation

In the nuclear industry, cement-based materials are extensively used to encapsulate spent ion exchange resins (IERs) before their final disposal in a repository. It is well known that the cement has to be carefully selected to prevent any deleterious expansion of the solidified waste form, but the reasons for this possible expansion are not clearly established. This work aims at filling the gap. The swelling pressure of IERs is first investigated as a function of ions exchange and ionic strength. It is shown that pressures of a few tenths of MPa can be produced by decreases in the ionic strength of the bulk solution, or by ion exchanges (2Na + instead of Ca 2+ , Na + instead of K + ). Then,…

Zeta-Potential Study of Calcium Silicate Hydrates Interacting with Alkaline Cations

An investigation into the interaction between alkaline cations and calcium silicate hydrates (CSH) was conducted by electrokinetic measurements, which provided information on the nature of the interface between the solid and its equilibrium solution. Calcium constitutes for the CSH surface a potential-determining cation. A model of the CSH surface could be proposed, accounting for the experimental evolution of the CSH zeta potential. The necessity of studying the zeta-potential evolution of the system as a function of the calcium activity, instead of its concentration, was underlined. The results obtained suggest a specific interaction between cesium and the CSH surface, whereas sodium and …

Hydration process and rheological properties of cement pastes modified by orthophosphate addition

Abstract The use of cement by nuclear industry for confining low radioactive waste knows a constant increase. The interest bore to this material is due to its mechanical and chemical properties. However, these properties may be modified by the nature and the amount of wastes introduced with the mixing solution especially with large amount of phosphate. Precipitation of hydroxylapatite in the cement paste at the very beginning after mixing was emphasized from a particular concentration of orthophosphate. It was also found that this phenomenon leads to an early rigidification of the cement paste. From a kinetics point of view, the evolution of hydration was both delayed and slowed down accord…

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…

Fluidizing efficiency of comb-like superplasticizers: The effect of the anionic function, the side chain length and the grafting degree

Superplasticizers and especially polycarboxylate grafted polyethylene oxide (PCE) demonstrated their efficiency to fluidify concrete. The aim of this work is to investigate the evolution of the fluidity as a function of adsorption in a sulfated solution with a wide variety of comb-like superplasticizers and at incomplete adsorption rate. Polymers with various side chain lengths, grafting ratios and also with modified anionic functions (carboxylate, dicarboxylate and phosphate) were synthesized. Inert calcite suspensions were used to mimic early age cementitious materials avoiding the cement hydration. Models of polymer conformation and yield stress prediction have been tested. But the most …

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…

NMR and Infrared Spectroscopies of C-S-H and Al-Substituted C-S-H Synthesised in Alkaline Solutions

(C,N)-(S,A)-H samples have been synthesised from mixes of different CaO/SiO2 and AI(OH)3/SiO2 ratios in stirred suspensions in more or less concentrated soda solutions. The stoichiometry and spectroscopic characteristics of samples have been studied by FTIR, 27A1 and 29Si MAS NMR spectroscopies. The structural changes induced by substitutions have been discussed on the basis of the dreiketten structure of the tobermorite silicate chains.

The particulate nature of C-S-H from AFM and the growth of C-S-H.

International audience

Onset of cohesion in cement paste

It is generally agreed that the cohesion of cement paste occurs through the formation of a network of nanoparticles of a calcium-silicate-hydrate ("C-S-H"). However, the mechanism by which these particles develop this cohesion has not been established. Here we propose a dielectric continuum model which includes all ionic interactions within a dispersion of C-S-H particles. It takes into account all co-ions and counterions explicitly (with pure Coulomb interactions between ions and between ions and the surfaces) and makes no further assumptions concerning their hydration or their interactions with the surface sites. At high surface charge densities, the model shows that the surface charge of…

The structural properties of soda–silicate sols and of the lime–soda–silicate gel formation

Abstract Alkaline silicate solutions were prepared with varying SiO 2 –Na 2 O ratios, Rm=[SiO 2 ]/[Na 2 O]=2 or 3, with a constant silica concentration equal to 1.5 M. The structure and the number fraction of different silicate molecular species present in the solutions were classically determined for molar ratio Rm=2 using 29 Si nuclear magnetic resonance ( 29 Si NMR). In the case of the sample with Rm=3, for which no NMR data was available, we used small-angle X-ray scattering (SAXS) experiments to get this information. The SAXS model was previously tested with Rm=2 silicate solution. When Ca ++ is added to alkaline silicate solutions, a gel is obtained under well-defined conditions. The …

A new view on the kinetics of tricalcium silicate hydration

Abstract C3S hydration is an interesting example of chemical coupling between C3S dissolution, C–S–H and portlandite precipitation. It occurs because Ca2 +, OH− and silicate ions are present in C3S, in both hydration products and in the surrounding solution. Various experimental data sets reveal that the undersaturation with respect to C3S always increases when C3S hydration enters into the deceleratory phase, leading to the conclusion that C3S dissolution is at the origin of this deceleration, not C–S–H growth. In addition, as soon as portlandite precipitates, the dissolution limits the hydration already in the acceleratory hydration step. The evolution of the undersaturation cannot accoun…

Mechanisms of cement hydration

Abstract The current state of knowledge of cement hydration mechanisms is reviewed, including the origin of the period of slow reaction in alite and cement, the nature of the acceleration period, the role of calcium sulfate in modifying the reaction rate of tricalcium aluminate, the interactions of silicates and aluminates, and the kinetics of the deceleration period. In addition, several remaining controversies or gaps in understanding are identified, such as the nature and influence on kinetics of an early surface hydrate, the mechanistic origin of the beginning of the acceleration period, the manner in which microscopic growth processes lead to the characteristic morphologies of hydratio…

Formation of the C−S−H Layer during Early Hydration of Tricalcium Silicate Grains with Different Sizes

Portland cement is a mixture of solid phases which all react with water. Tricalcium silicate (Ca3SiO5) is its main component and is often used in model systems to study cement hydration. It is generally recognized that setting and hardening of cement are due to the formation, by a dissolution-precipitation process, of a calcium silicate hydrate (C-S-H) on anhydrous grains during Ca3SiO5 hydration. The purpose of this paper is to study the effect of Ca3SiO5 particle size on the nucleation-growth process of C-S-H. An experimental study of the rate of hydration by using different grain sizes under controlled conditions has been performed. The experimental data have been compared with results o…

Surface and Intercalation Chemistry of Polycarboxylate Copolymers in Cementitious Systems.

International audience; The Ca–Al-layered double hydroxide, the so-called AFm phase, is a product of cement hydration. It is shown that the interaction of this phase with anionic polycarboxylate ether (PCE)-based dispersant polymers is not a simple adsorption but a more complex intercalation phenomenon leading to the transient sequestration of the PCE within the AFm crystallites. As a result, part of the PCE is immobilized, forming a layered organo-mineral composite, and does not play its role of a dispersing agent. This article presents, along general considerations on the links between cement chemistry and rheology, a detailed investigation of the formation, structure, and stability of a …

Experimental investigation of calcium silicate hydrate (C-S-H) nucleation

Due to the importance of calcium silicate hydrate (C-S-H) in cement chemistry, its nucleation mode and parameters influencing it were investigated. It has been observed that the C-S-H nucleation follows the general laws governing the nucleation. The degree of supersaturation has been found to be the main parameter controlling homogeneous nucleation rates. The lime concentration in solution, well known to be the most important parameter determining the kinetic, morphological and structural features of C-S-H, also controls the nucleation characteristics of heterogeneous nucleation, i.e. during hydration of cement. The correlation between heterogeneous nucleation of C-S-H and possible final me…

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…

Changes in Cement Paste and Mortar Fluidity after mixing induced by PCP: A parametric study

International audience; The interaction mechanism between polycarboxylate-type superplasticizer (PCP) and cement hydration is not fully understood and incompatibilities between concrete and additive are sometimes observed. In some cases, the fluidity tends to increase (“overfluidification”) few minutes after mixing. This is a problem because the overfluidification leds to bleeding of the concrete which could be critical on job site. Our study consisted first in highlighting the phenomenon of “over-fluidification” by slump flow tests on mortar. Next, the time evolution of the rheological behaviour of cement pastes in the presence of PCP was analysed thanks to a rheometry protocol in order to…

Tailoring the anionic function and the side chains of comb-like superplasticizers to improve their adsorption

Nowadays admixtures and especially superplasticizers are unavoidable components of the concrete formulation. The high fluidizing efficiency of the comb-like superplasticizers must not overshadow their high costs. This study aims to determine the PCE structure parameters which influence their adsorption in order to enhance their resistance to sulfate competitive adsorption and thus minimize their dosage. The PCE adsorption has been studied on calcite and ettringite which are both surfaces representative of early hydrating cement. The effect of the POE side chain length and density and also of the PCE anionic function i.e. carboxylate, dicarboxylate or phosphate on the adsorption has been ana…

Revised Atomistic Models of the Crystal Structure of C–S–H with high C/S Ratio

Abstract The atomic structure of calcium-silicate-hydrate (C1.67–S–H x ) has been studied. Atomistic C–S–H models suggested in our previous study have been revised in order to perform a direct comparison of energetic stability of the different structures. An extensive set of periodic structures of C–S–H with variation of water content was created, and then optimized using molecular dynamics with reactive force field ReaxFF and quantum chemical semiempirical method PM6. All models show organization of water molecules inside the structure of C–S–H. The new geometries of C–S–H, reported in this paper, show lower relative energy with respect to the geometries from the original definition of C–S…

Early hydration of calcium silicates.

International audience

Dynamic mode rheology of cement and tricalcium silicate pastes from mixing to setting

Dynamic mode rheometry was used to study the evolution of the structure of cement and pure tricalcium silicate pastes from mixing up to setting and even after setting, together with the nature of the forces responsible for the mechanical properties of the pastes. A special mixer-type tool was used to study rheology during the very first minutes following the end of mixing, which are out of reach with classical tools. Both kinds of pastes have the same behavior. It was found that the main evolution of the structure of the pastes occurs during the very first minutes following the end of mixing, while there is no change in interparticular forces up to setting and even a few hours later. Settin…

UNDERSTANDING OF REACTIONAL SEQUENCES AND LIMITING STAGES DURING TRICALCIUM ALUMINATE HYDRATION WITH AND WITHOUT GYPSUM.

International audience; The tricalcium aluminate reacts very quickly with water to form calcium hydroaluminates while the addition of calcium sulphate, leads to the formation of ettringite, with a slower process. The systematic study of the systems: “C3A” and “C3A-sulphate” by isothermal microcalorimetry and a follow up of ionic concentrations of diluted system suspensions made it possible to understand the sequence of the reactions and the limiting stages in both systems. In all cases, as it is in contact with the solution, the C3A dissolves what leads to the instantaneous precipitation of a certain quantity of calcium hydroaluminate. In case of only C3A hydration, there is then a decrease…

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…

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

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…

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…

Investigation of the swelling behavior of cationic exchange resins saturated with Na+ ions in a C3S paste

Ion exchange resins (IERs) are widely used by the nuclear industry to decontaminate radioactive effluents. Spent products are usually encapsulated in cementitious materials. However, the solidified waste form can exhibit strong expansion, possibly leading to cracking, if the appropriate binder is not used. In this work, the interactions between cationic resins in the Na+ form and tricalcium silicate are investigated during the early stages of hydration in order to gain a better understanding of the expansion process. It is shown that the IERs exhibit a transient swelling of small magnitude due to the decrease in the osmotic pressure of the external solution. This expansion, which occurs jus…

The structure and stoichiometry of C-S-H

Abstract This review relates to the models describing the structural evolution of calcium silicate hydrate (C-S-H) at the crystal–chemical level as a function of composition in terms of calcium to silicon ratio. The different models are compared and discussed in the light of recent spectroscopic and microscopic data. Taking into account the structure and the morphological properties of C-S-H, a surface reaction thermodynamic model has been proposed and discussed to predict and correlate the chemical and structural evolution of C-S-H with solution chemistry.

Does phosphorus affect the industrial Portland cement reactivity?

Abstract The effect of phosphorous on the mineralogy and reactivity of Portland cement has been investigated through an industrial clinkers series. The samples were collected from the same Tunisian cement plant and classified according to the content of P2O5 from 0.5% to 1.1%. All samples were manufactured at the same thermal and cooling conditions as well as possible. The specimens were characterized by X-ray fluorescence spectrometry and optical microscopy techniques and their mineralogy was determined by X-ray powder diffraction coupled to the Rietveld analysis. The cements reactivity prepared from the clinkers was followed by means of isothermalcalorimetry. The compressive strength of t…

Adsorption of sulfate ions on negatively charged surfaces

International audience

Influence of three types of superplasticizers on tricalciumaluminate hydration in presence of gypsum.

International audience; Different types of superplasticizers have been widely used over the past few decades in order to produce a more fluid or very high strength and durable concrete. These chemical admixtures interfere with the various physico-chemical processes occurring in early cement paste. In this paper we present results from a study on the influence of superplasticizers on pure tricalciumaluminate hydration in presence of gypsum. The suspensions hydration has been investigated by conductimetry, isothermal calorimetry and total organic carbon analysis of the liquid phase. The time taken for ettringite formation has been determined without superplasticizer and in presence of three d…

Studies on mechanism and physico-chemical parameters at the origin of the cement setting. I. The fundamental processes involved during the cement setting

Abstract The mechanical evolution and the structure of the cement paste have been analysed in relation with the chemical evolution of the system. The setting process can be described as following two fundamental steps: the coagulation of cement grains during the first minutes following the mixing, and the rigidification of the coagulated structure which arises simultaneously with the acceleration of the hydrates formation During the coagulation step, the structure formed is proved to be mechanically reversible. The rigidification of the coagulated structure is provided by the hydrates formation in the contact zone. The increase of the paste cohesion at this stage is proportional to the quan…

Interactions between chemical evolution (hydration) and physical evolution (setting) in the case of tricalcium silicate

This paper describes recent experimental results concerning investigation of the parameters which determine, on the one hand, the kinetics of hydration of tricalcium silicate and the thermodynamic, morphological and structural characteristics of C-S-H and, on the other hand, the evolution of the particle interactions at the origin of setting. It is shown that, in both cases, lime concentration in solution is the most important parameter. As a consequence, the chemical evolution of the system, which controls the lime concentration in solution, determines the nature of particle interactions and the physical evolution of the suspension or paste. In return, the contacts, between particles, resu…

Studies on mechanism and physico-chemical parameters at the origin of the cement setting II. Physico-chemical parameters determining the coagulation process

The physico-chemical parameters determining the coagulation of cements grains previously identified as the first fundamental process of cement setting have been investigated in diluted suspensions using an adapted granulometric method. The analysis of the influence of the ionic concentration in solution on the coagulation reveals that calcium concentration is the parameter which determines the particle interactions. There exists a minimum critical concentration of calcium ions in solution which is required to occur the coagulation of cement particles and a dispersive effect appears for very high concentrations. The results are discussed in relation with DLVO theory and specific interactions.

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

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…

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…

Electrokinetic Properties which Control the Coagulation of Silicate Cement Suspensions during Early Age Hydration

The coagulation of cement particles during early age hydration has been previously identified as the first step of the setting and hardening of cement pastes. By hydrating Ca3SiO5and a silicate-rich clinker under controlled conditions, a correlation between the coagulation of the suspensions and the electrokinetic properties of particles is established. The zeta potential, and hence the surface charge, of particles in suspension depends on the calcium content of the medium. At low concentrations of Ca2+, the zeta potential of Ca3SiO5particles, calcium silicate hydrate (C–S–H), and clinker is negative (<−30 mV) and the suspensions are well dispersed. A strong coagulation occurs at intermedia…