No abstract

Although Portland cement concrete is the world's most widely used manufactured material, basic questions persist regarding its internal structure and water content, and their effect on concrete behaviour. Here, for the first time without recourse to drying methods, we measure the composition and solid density of the principal binding reaction product of cement hydration, calcium-silicate-hydrate (C-S-H) gel, one of the most complex of all gels. We also quantify a nanoscale calcium hydroxide phase that coexists with C-S-H gel. By combining small-angle neutron and X-ray scattering data, and by exploiting the hydrogen/deuterium neutron isotope effect both in water and methanol, we determine the mean formula and mass density of the nanoscale C-S-H gel particles in hydrating cement. We show that the formula, (CaO)1.7(SiO2)(H2O)1.80, and density, 2.604 Mg m(-3), differ from previous values for C-S-H gel, associated with specific drying conditions. Whereas previous studies have classified water within C-S-H gel by how tightly it is bound, in this study we classify water by its location-with implications for defining the chemically active (C-S-H) surface area within cement, and for predicting concrete properties.

C-S-H, the poorly crystalline calcium silicate hydrate formed in cement paste and aqueous suspension, is characterized by extensive disorder and structural variations at the nanometer scale. An analysis of new and published solubility data for C-S-H formed by different preparation methods and with a broad range of compositions illustrates a previously unrecognized family of solubility curves in the CaO-SiO 2 -H 2 O system at room temperature. As demonstrated by 29 Si magic-angle spinning (MAS) NMR data and by charge balance calculations, the observed differences in solubility arise from systematic variations in Ca/Si ratio, silicate structure, and Ca-OH content. Based on this evidence, the family of solubility curves are interpreted to represent a spectrum of metastable C-S-H phases whose structures range from purely tobermorite-like to largely jennite-like. These findings give an improved understanding of the structure of these phases and reconcile some of the discrepancies in the literature regarding the structure of C-S-H at high Ca/Si ratios.

The fundamental chemical hydration process of portland cement and its main mineral component, tricalcium silicate, was studied by investigating the effects of various additives. A relatively small amount (1-4 wt %) of well-dispersed calcium silicate hydrate (C-S-H), a pure form of the main hydration product, significantly increases both the early hydration rate and the total amount of hydration during the early nucleation and growth period (the first ∼24 h), as measured by calorimetry. This is attributed to a seeding effect whereby the C-S-H additive provides new nucleation sites within the pore space away from the particle surfaces. This mechanism is verified by a digital simulation of the hydration process that reproduces key features of the hydration kinetics. The results provide strong evidence that the hydration process is autocatalytic such that the C-S-H gel product stimulates its own formation. The seeding effect of C-S-H also provides a new explanation of the hydration-accelerating effects of various forms of reactive silica because these additives form C-S-H by reacting with aqueous calcium ions released by cement dissolution. Experiments involving sucrose, a hydration retarder, confirm that sucrose interferes with the normal nucleation process on the particle surface.

The hydration kinetics of tricalcium silicate (C 3 S), the main constituent of portland cement, were analyzed with a mathematical ''boundary nucleation'' model in which nucleation of the hydration product occurs only on internal boundaries corresponding to the C 3 S particle surfaces. This model more closely approximates the C 3 S hydration process than does the widely used Avrami nucleation and growth model. In particular, the boundary model accounts for the important effect of the C 3 S powder surface area on the hydration kinetics. Both models were applied to isothermal calorimetry data from hydrating C 3 S pastes in the temperature range of 101-401C. The boundary nucleation model provides a better fit to the early hydration rate peak than does the Avrami model, despite having one less varying parameter. The nucleation rate (per unit area) and the linear growth rate of the hydration product were calculated from the fitted values of the rate constants and the independently measured powder surface area. The growth rate follows a simple Arrhenius temperature dependence with a constant activation energy of 31.2 kJ/mol, while the activation energy associated with the nucleation rate increases with increasing temperature. The start of the nucleation and growth process coincides with the time of initial mixing, indicating that the initial slow reaction period known as the ''induction period'' is not a separate chemical process as has often been hypothesized.