C–S–H (I)—A Nanostructural Model for the Removal of Water from Hydrated Cement Paste?

Helium gas is used as a nanostructural probe to investigate the structural changes in C–S–H (I) due to the removal of interlayer water. Changes in the 002 basal spacing are correlated with helium inflow characteristics. Similarities to helium inflow experiments conducted on hydrated Portland cement and C₃S pastes are discussed. Conclusions are drawn with respect to the viability of considering C–S–H (I) as a physical model for the drying of Portland cement and C₃S pastes.     

Limited-Dose Electron Microscopy Reveals the Crystallinity of Fibrous C–S–H Phases

Using electron diffraction, we demonstrate that the fibrous calcium–silicate–hydrates (C–S–H) of tricalciumsilicate (C₃S) hydration possess a crystalline structure. The crystalline nature was revealed by limiting the electron dose, which is common in electron microscopy of biomacromolecules. Compared with room temperature, the fading of the electron diffraction patterns at −175°C occurs at an electron dose that is about one order of magnitude higher. A combination of low-dose and cryo-protection methods offers the possibility to investigate the structures of water-containing cement phases by high-resolution electron microscopy in a close-to-native state.     

Effects of Saccharide Set Retarders on the Hydration of Ordinary Portland Cement and Pure Tricalcium Silicate

The effects of aliphatic sugar alcohols (e.g., threitol, xylitol, sorbitol) on the hydration of tricalcium silicate (C₃S) and ordinary portland cement (OPC) were investigated and compared with those of sucrose, a well-established cement set retarder. Only sugar alcohols which contain threo diol functionality retarded the setting of C₃S and OPC, their efficacy increasing with the number of threo hydroxy pairs and, to a smaller extent, with the overall population of hydroxy groups. None, however, were as effective as sucrose. The initial and final setting times increased exponentially with the concentration of saccharide, although the hydration of OPC was less inhibited than that of C₃S. Saccharides function as "delayed accelerators," that is, cement hydration is first inhibited and then proceeds faster than in saccharide-free cement. This behavior is consistent with the theory that the induction period is controlled by slow formation and/or poisoning of the stable calcium silicate hydrate (CSH) nuclei. The early inhibiting influence of saccharides on CSH precipitation is apparently stronger than on the growth of crystalline calcium hydroxide. Saccharides did not negatively affect the degree of hydration and compressive strength of fully set OPC paste; on the contrary, sorbitol yielded modest increases.     

Slurry Consistency and In Situ Synchrotron X-Ray Diffraction During the Early Hydration of Portland Cements With Calcium Chloride

Class A and H oil well cements are compared at 25° and 50°C with 0%, 1%, 2%, and 4% CaCl₂. Up to 4% CaCl₂ accelerated Class A thickening, but 4% led to slower thickening than 2% for Class H. C₃S hydration in the two cements responded differently to CaCl₂. CaCl₂ always accelerated aluminate hydration. For Class A, CaCl₂ accelerated early Ca(OH)₂ precipitation, but sometimes reduced the amount at longer times. This may be coupled to C–S–H gel composition changes. For Class H, Ca(OH)₂ precipitation changes nonlinearly with CaCl₂ concentration. Ettringite to monosulfate conversion and Friedel's salt formation were sometimes seen.     

Adsorption of Admixtures on Portland Cement Hydration Products

The adsorption of calcium lignosulfonate and salicylic acid was studied on the hydration products of the four principal components of portland cement. To investigate the adsorption as a function of development of hydration product, the determinations were made after varying hydration times. The times allowed were from 5 min to 24 hr for tricalcium aluminate (C₃A) and tetracalcium aluminoferrite (C₄AF) and from 1 hr to 28 days for β-dicalcium silicate (β-C₂S) and tricalcium silicate (C₃S). Samples were characterized with respect to surface area and poresize distribution. The effect of gypsum on the adsorption was also investigated. The results indicate that the amounts of salicylic acid and calcium lignosulfonate adsorbed on the hydration products of C₃A, and of calcium     

Coarsening Behavior of Tricalcium Silicate (C3S) and Dicalcium Silicate (C2S) Grains Dispersed in a Clinker Melt

Microstructural evolution during the heat treatment of cement clinker was investigated. Two model specimens, which consisted of faceted tricalcium silicate (C₃S) and spherical dicalcium silicate (C₂S) grains dispersed in a liquid matrix, were prepared with 5 wt% of large seed particles. The seed particles of faceted C₃S grains grew extensively, whereas those of the spherical C₂S grains grew rather slowly, relative to the matrix grains. As a consequence, C₃S grains exhibited a bimodal size distribution that was typical of exaggerated grain growth, whereas C₂S grains retained a uniform and normal size distribution. These results suggest that the growth of faceted C₃S grains was controlled by the interface atomic attachment, such as two-dimensional nucleation, and that of spherical C₂S grains was controlled by diffusion through the liquid matrix. The dependence of growth mechanisms on grain morphology has been explained in terms of the atomistic structure of the solid/liquid interface.     

The Pore Structure of Hydrated Cementitious Compounds of Different Chemical Composition

The pore structure ofβ-C₂S, C₃S, and portland cement pastes was investigated using mercury porosimetry and H₂O and N₂ adsorption. The β-C₂S had more total macro- and mesoporosities than C₃S and portland cement pastes of a similar degree of hydration. C₃S and portland cement pastes had similar total porosities but differed in the porosity size distribution. In the mesopore range, the various test methods gave different results. These differences are discussed on the basis of the various models proposed for cement paste. It is shown that shrinkage could be correlated with the volume of pores <0.03 μm, but not with total porosity.     

Synthesis and Hydration Characteristics of Alinite Cement

A chlorine-bearing alinite cement was synthesized using reagent-grade chemicals, and the phase evolution and hydration behavior of the alinite clinker were examined. The effects of the MgO content on alinite formation and hydration also were investigated. Alinite began to appear at 1000°C from β-C₂S, C₁₁A₇CaCl₂, and unreacted raw materials, and an almost single-phase alinite was obtained at 1300°C. The alinite phase also was produced without MgO addition. However, CaO, β-C₂S, and C₁₁A₇CaCl₂ phases were present. Alinite cements hydrated rapidly after a short incubation period, and the hydration products were C-S-H gels, Ca(OH)₂, and a Fridel's saltlike phase. The local environmental changes of silicon and aluminum during the formation and hydration of alinite were determined using magic-angle-spinning nuclear magnetic resonance spectroscopy. The Cl⁻-ion exsolution from the alinite paste during hydration was measured using ion chromatography.     

MAS NMR Studies of Partially Carbonated Portland Cement and Tricalcium Silicate Pastes

²⁹Si, ²⁷Al, and ¹H MAS NMR studies of partially carbonated mature ordinary Portland cement (OPC) and tricalcium silicate (C₃S) pastes have been carried out. The water-to-solid ratios ( W/S ) have been varied between 0 and 1 at hydration temperatures of 23^o and 90^oC. Various Q ⁿi units with n =0, 1,2,3, and 4, and a Q³ (1Al) group have been identified using ²⁹Si NMR. Cross-polarization experiments, in addition, have made it possible to assign the OH groups. Two types of fourfold- and one type sixfold-coordinated aluminum have been distinguished using ²⁷Al NMR. In C₃S pastes for w/s >0.7, progressive carbonation leads to a nearly perfect three-dimensional network consisting of Q³ and Q⁴only. In contrast, in OPC pasted only about 40% of the highly polymerized silicate units are formed, partially copolymerized with AlO₄ tetrahedra.     

Effect of Phosphorus Impurity on Tricalcium Silicate T1: From Synthesis to Structural Characterization

Alite is the major compound of anhydrous Portland cement: it is composed of tricalcium silicate Ca₃SiO₅ (C₃S) modified in composition and crystal structure by ionic substitutions. Alite is also the main hydraulic phase of cement and the most important for subsequent strength development. Using raw meals (rich in Ca₃P₂O₈) as alternative fuels in cement plants raises the question about the effect of phosphorus on C₃S and its consequences on reactivity with water. This paper deals with a systematic study of C₃S triclinic T₁ polymorph doped with P₂O₅ in the range 0–0.9 wt%. All the samples were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and electron-microprobe analysis. The appearance of a phase rich in phosphorus is shown. It displays a structure derivative of the α'_H–Ca₂SiO₄ polymorph, noted α'_H–C₂S(P). As phosphorus content increases, C₃S is more and more decomposed into free lime and α'_H–C₂S(P). The α'_H phase was detected from 0.1 wt% P₂O₅ and located at the interfaces of C₃S grains. Two identification keys are proposed in order to highlight the α'_H–C₂S(P) phase: the XRD angular window at 2θ_Cu=32.8°–33.2° and a smooth aspect on SEM micrographs.     

Structure and Hydration Kinetics of Silica Particles in Rice Husk Ash Studied by 29Si High-Resolution Nuclear Magnetic Resonance

The structure, surface fractal dimension, and global hydration kinetics of silica particles obtained from rice husk ashes (RHAs) were studied with ²⁹Si-NMR spectroscopy and spin–lattice relaxation techniques. Silica particles presented an amorphous fraction higher than 93%, with traces of silica-organic bonding and crystal-like domains. Fe-impurities are located preferentially on the surface of the particles. From the effect of these paramagnetic ions on the spin–lattice relaxation of Q³ and Q⁴ silicate groups, the surface of the particles was characterized as being effectively two-dimensional ( D =1.9±0.1). The hydration kinetics of the particles during the reaction with lime and water was monitored from 8 to 706 days. The process can be described by a power law, with the characteristic exponent higher than those measured for other cements. Also, Johnson–Mehl–Avrami expressions reproduce equally well the experimental data, with parameters compatible with growth habits and morphology known for C–S–H. Two types of Q² tetrahedra were identified in C–S–H, which can be attributed to the bridging and nonbridging silicate groups predicted by the "dreier-kette" structural model of C–S–H.     

A New Approach to Modeling the Nucleation and Growth Kinetics of Tricalcium Silicate Hydration

The hydration kinetics of tricalcium silicate (C₃S), 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 C₃S particle surfaces. This model more closely approximates the C₃S hydration process than does the widely used Avrami nucleation and growth model. In particular, the boundary model accounts for the important effect of the C₃S powder surface area on the hydration kinetics. Both models were applied to isothermal calorimetry data from hydrating C₃S pastes in the temperature range of 10°–40°C. 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.     

Early Hydration of Tricalcium Silicate

The hydration of tricalcium silicate (C₃S) in the preacceleration stages was studied. The C₃S particles carry a positive charge during the early stages of hydration. Following a rapid hydrolysis of C₃S, calcium ions adsorbed on the Si-rich surface of C₃S particles, greatly reducing their further dissolution, thus initiating the induction period. The [Ca²⁺] and [OH^-] continue to increase at lower rates and, because Ca(OH)₂ crystal growth is inhibited by silicate ions, become supersaturated with respect to Ca(OH)₂. When the supersaturation reaches a value of ∼1.5 to 2.0 times the saturation concentration, nuclei are formed, and rapid growth of Ca(OH)₂ and C-S-H is initiated. These products act as sinks for the ions in solution, thus enhancing the further dissolution of C₃S.     

Hydration of Beta Dicalcium Silicate Alone and in the Presence of CaCl2 or C2H5OH

Beta C₂S was hydrated at room temperature with and without added CaCl₂ or C₂H₅OH by methods previously studied for the hydration of C₃S, i.e. paste, bottle, and ball-mill hydration. The amount of reacted β-C₂S, the Ca(OH)₂ concentration in the liquid phase, the CaO/SiO₂ molar ratio, and the specific surface area of the hydrate were investigated. A topochemical reaction occurs between water and β-C₂S, resulting in the appearance of solid Ca(OH)₂ and a hydrated silicate with a CaO/SiO₂ molar ratio of ≃1. As the liquid phase becomes richer in Ca(OH)₂, the first hydrate transforms to one with a higher CaO/SiO₂ ratio. Addition of CaCl₂ increases the reaction rate and the surface area of the hydrate but to a much lesser extent than in the hydration of C₃S, whereas C₂H₆OH strongly depresses the hydration rate of β-C₂S, as observed for C₃S hydration.     

Thermal Study of the Effect of Additives on the Hydration of Tricalcium Silicate

The rate of paste hydration of 3C_aO·SiO₂ (C₃S) and the effects of additions of CaCl₂, CdI₂, and CrCl₃, were studied by differential thermal analysis and thermogravimetry. X-ray analyses were used to identify the synthesized C₃S. The salts CaCl₂, CdI₂, and CrCl₃, accelerated the hydration of C₃S. The degree of hydration was estimated by the amount of Ca(OH)₂, formed, as determined by TG.     

Composition and Morphology of Hydrated Tricalcium Silicate

Hardened C₃S paste cured for 1 year at 20°C was examined to confirm the composition and the morphology of hydrated tricalcium silicate. A new technique was used in which the samples for scanning electron microscopy (SEM) and electron probe microanalysis (EPMA) were etched in 1% HNO₃-alcohol or in glycerol-alcohol (4:6 by volume). After the surface was etched in 1% HNO₃-alcohol, SEM clearly showed the difference in texture in the outer and inner C-S-H products. The existence of a zonal texture within the inner C-S-H products was shown, in addition to the unreacted core; particles 0.1 to 0.2 μm in diameter were observed. After free CH extraction with glycerol-alcohol, two new types of C-S-H grains could be identified. One type has a smooth surface, which seems to be produced from C₃S grains trapped within the growing CH crystals in the early stage of hydration, the C/S mol ratio for these being >3. The other type is covered with many acicular outer C-S-H gel hydration products and has a C/S mol ratio >3.     

Morphological Development of Hydrating Tricalcium Silicate as Examined by Electron Microscopy Techniques

This study of C₃S hydrates used a high-voltage electron microscope equipped with a gas reaction cell that allows the specimen to be kept moist, and high-resolution scanning and scanning transmission microscopes. Mechanical thinning and ion-beam thinning coupled with fractography allowed this study of microstructural development with time, enabling both the morphologies and the spatial relations of the morphologies to be observed. The combination of several microscopic techniques allowed the hydration products of C₃S to be classified and compared with those of Diamond for portland cement hydrates.     

Effect of Carbonation on Alkali-Activated Slag Paste

Carbonation on waterglass- and NaOH-activated slag pastes was analyzed and compared with carbonation in Portland cement pastes to determine possible differences. Thermogravimetry-differential thermal analysis (TG/DTA), Fourier-transform infrared spectrometry, and nuclear magnetic resonance were used to determine the effects on the main reaction products. According to the TG/DTA results, carbonate precipitation following carbonation is much more intense in Portland cement pastes than in alkali-activated slag pastes. This may be attributed to the fact that in Portland cement paste both the portlandite and the C–S–H gel can be carbonated, whereas in alkali-activated slag pastes, only the C–S–H gel is carbonated directly. In both systems, carbonation leads to the formation of CaCO₃, Si-rich C–S–H gel, silica gel, and alumina. The carbonation of waterglass-activated slag pastes is not altered by the presence of either of the organic additives used in the study.     

Influence of Minor Ions on the Stability and Hydration Rates of β-Dicalcium Silicate

The effects of Al³⁺, B³⁺, P⁵⁺, Fe³⁺, S⁶⁺, and K⁺ ions on the stability of the β-phase and its hydration rate were studied in reactive dicalcium silicate (C₂S, Ca₂SiO₄) synthesized using the Pechini process. In particular, the dependences of the phase stability and degree of hydration on the calcination temperature (i.e., particle size) and the concentration of the stabilizing ions were investigated. The phase evolution in doped C₂S was determined using XRD, and the degree of hydration was estimated by the peak intensity ratio of the hydrates to the nonhydrates in ²⁹Si MAS NMR spectra. The stabilizing ability of the ions varied significantly, and the B³⁺ ions were quite effective in stabilizing the β-phase over a wide range of doping concentrations. The hydration results indicated that differently stabilized β-C₂S hydrated at different rates, and Al³⁺- and B³⁺-doped C₂S exhibited increased degree of hydration for all doping concentration ranges investigated. The effect of the doping concentration on degree of hydration was strongly dependent on the stabilizing ions.     

Structural Properties of Calcium Silicate Pastes: I, Effect of the Hydrating Compound

The chemical and physical properties of C₃S, β-C₂S, a C₃S/C₂S blend, and portland cement pastes cured at 25°C were investigated. The H₂O specific surface areas of the calcium silicate samples follow a common linear relation when plotted against a CIS ratio. The β-C₂S had higher capillary porosity and N2 surface area, resulting from increased mesopore volume at the expense of micropores. All calcium silicate pastes had similar polysilicate content vs time curves, indicating an aging process which is not sensitive to the starting composition of the hydrating calcium silicate. The polysilicate content of portland cement was much lower than that of the corresponding calcium silicate pastes. Strength-capillary porosity relations for the various systems are discussed.