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

Neoformation of DLH During Impregnation of α-Alumin

The adsorption of Co(II) or Ni(II) ammine complexes from aqueous solutions onto α-alumina at neutral pH and ambient temperature was investigated. The formation of coprecipitates including Al (III) ions extracted from the support was demonstrated by EXAFS for contact times and Ni or Co loadings higher than 0.5 h and about 2.0 wt %, respectively. The EXAFS technique makes it possible to distinguish the Ni or Co hydroxides and basic nitrates from coprecipitates with a double layer hydroxide (DLH) structure. Not only is EXAFS shown to be sensitive to the presence of aluminum in the coprecipitates, but in most cases, the M(lI)/Al(III) ratio (M= Ni or Co) in the supported coprecipitates can be estimated. Thus, alumina should not be considered systematically as inert even at pH values close to its isoelectric point. It is suggested that a dissolution-precipitation mechanism is involved and that the rate of alumina dissolution is promoted by adsorbed Ni(II) or Co(II) ions. Site-binding models have a considerable value for the early stages of impregnation, whereas a geochemical approach involving surface rehydration and coprecipitation have probably a greater validity for the later stages

Surface and Intercalation Chemistry of Polycarboxylate Copolymers in Cementitious Systems.

International audienceThe 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 pure poly(methacrylate- g-PEO)/hydrocalumite composite obtained by coprecipitation. The predictions of scaling laws derived from models of conformation of comb copolymers in solution were tested against small-angle X-ray diffraction, transfer of populations by double-resonance nuclear magnetic resonance, and small-angle neutron scattering experimental results. A model of adsorbed polymers in a configuration of a flexible chain of hemispheric cores is proposed and appears to be compatible with the observed interlayer spacings in the range of several nanometers. Finally, these phases are shown to persist for several hours in the presence of sulfate ions

Formation Mechanism of the Ga 13 Keggin Ion: A Combined EXAFS and NMR Study

International audienc

Interactions between chloride ingress and carbonation in cementitious materials

The 13th International Congress on Chemistry of Cement, MADRID, ESPAGNE, 04-/07/2011 - 08/07/2011Carbonation and chloride attacks are the major causes of reinforced concrete (RC) structure deterioration by initiation of steel rebar corrosion. These attacks are usually studied separately in the literature. Chloride-induced corrosion takes place mainly in marine environment or in the case of contact with deicing salts, while carbonation is systematically present in all RC structures at a variable degree. Since carbonation leads to significant microstructure changes, the effect of chloride ingress will be different in carbonated and noncarbonated materials. In this paper, combined effects of carbonation and chloride ingress on various physical or chemical properties of cementitious materials (OPC alone or with SCM) are studied. For example, carbonation effects have been investigated experimentally on the chloride binding isotherm and on apparent chloride diffusion coefficients. The materials were carbonated after exposure in natural environment or in accelerated conditions (1.5% CO2). Chloride binding isotherms were assessed by the equilibrium method after exposure to alkaline NaCl solutions. Apparent chloride diffusion coefficients were assessed from migration tests under an electrical field in nonsteady-state conditions. The microstructure was characterized not only by usual techniques such as XRD and TGA-DTA, but also by 29Si and 27Al NMR spectroscopy for a more precise understanding