Early hydration of tricalcium silicate I. Kinetics of the hydration process and the stoichiometry of the hydration products

The initial hydration of C₃S in paste form at room temperature was studied. The process is initiated by a short lasting rapid hydration in which about 1 – 2% of C₃S is hydrated and a hydrate with low C/S and high H/S ratio is formed. After a subsequent induction period of 4 hours a renewed rapid hydration is observed in which a hydrate of constant stoichiometric composition, independent on the time of hydration is formed. This hydrate has a higher C/S and lower H/S ratio than the one formed initially. The liquid phase stays supersaturated with respect to calcium hydroxide for several hours after the induction period is terminated.     

Hydration of tricalcium silicate

Results of following the quantities of free Ca(OH)₂ and of tricalcium silicate (C₃S) during the hydration of C₃S, and also the influence of the presence of free CaO on this reaction are in accordance with the hypothesis of Stein & Stevels with regard to the hydration of C₃S. at the first contact between C₃S and water, a surface hydrate, invisible by electron microscope methods, is considered to be formed and to retard the reaction strongly. This hydrate is thought to change into one which retards the hydration reaction less and changes later into a third hydrate, tobermorite gel.     

高炉镍铁渣粉在水泥基复合胶凝材料中的水化特性研究

通过对不同高炉镍铁渣掺量的水泥-高炉镍铁渣粉复合胶凝材料水化放热速率、高炉镍铁渣粉的反应程度、硬化浆体化学结合水含量以及水化产物中C-S-H凝胶Ca/Si的测定,分别研究了水泥-高炉镍铁渣粉复合胶凝材料的早期、中长期水化进程、浆体微观形貌以及水化产物特点等水化特性.研究结果表明:高炉镍铁渣的掺入会降低水化放热速率,并推迟水化加速期放热峰的出现时间;在复合胶凝体系中,随着高炉镍铁渣粉掺量的增大,其反应程度和硬化浆体中化学结合水含量将降低.复合胶凝材料水化生成的C-S-H凝胶的Ca/Si低于水泥,且随着水化的进行呈降低趋势;高炉镍铁渣粉中的Al,在水化过程中会取代部分Si进入C-S-H凝胶中,形成C-A-S-H凝胶.     

Analyses of the aqueous phase during early C3S hydration

The concentrations of calcium and silica in solution during the first 4 hours of C₃S hydration were measured. The results of these analyses indicate that a solid calcium silicate hydrate forms within 30 seconds of the start of hydration and that an equilibrium between the solution and the solid hydrate is rapidly established. A strong dependence of the rate of early hydration on the w:C₃S ratio was observed, while the dependence on the surface area of the C₃S was minimal.     

Pastes of tricalcium silicate with rice husk ash

Pastes of tricalcium silicate with rice husk ash (RHA) were cured at 25°C for 1–245 days and examined by XRD, analytical electron microscopy, TG, acid extractions to determine unreacted rice husk ash, and trimethylsilylation. The rice husk ash was highly reactive, and contents of calcium hydroxide, referred to the ignited weight, never exceeded 3%. Initially, a product having a Ca/Si atom ratio of 0.1–0.2 was formed, but this was later replaced by one having a Ca/Si ratio of approximately 1.3. The proportion of the Si in the hydration products that was present as polymeric ions was greater than that found in pure C₃S or C₃S-fly ash pastes of similar age, but the anion size distributions within the polymer were all broadly similar.     

Soft X‐ray Spectromicroscopic Investigation of Synthetic C‐S‐H and C3S Hydration Products

Calcium silicate hydrates (C‐S‐H), the primary binding phase in concrete, is the most prominent physiochemical factor controlling the mechanical and chemical properties in the production of concrete. This paper reports the local‐binding structure and morphological details of C‐S‐H as determined by high‐resolution X‐ray spectromicroscopy. Hydrated tricalcium silicate (C₃S) was used to determine the properties and role of the outer products (Op) of C₃S. C‐S‐H with different molar ratios of Ca/Si, were synthesized (Syn‐CSH) to quantitatively evaluate the effect of silicate polymerization on Ca L and Si K edge of C‐S‐H. Near edge X‐ray absorption fine structure (NEXAFS) spectroscopy of Syn‐CSH showed no variation in peak positions and energy separation for CaL_{III, II} edge for the Ca/Si ratios investigated. Compared to Syn‐CSH, C₃S, when hydrated for 17 d, had a similar local structure around Ca. Si K edge NEXAFS analysis on Syn‐CSH showed a tendency for the peak positions of both the Si K edge and the peak induced by multiple scattering to shift to higher energy levels. The results also indicated that the distance between the two peaks increased with a decrease of the Ca/Si ratio in Syn‐CSH. Silicate polymerization influenced the multiple scattering of distant shell atoms more than the binding energy of the core atoms. Op of C₃S had a uniform and higher degree of silicate polymerization compared to the core area. The results imply that Op reduces the hydration process of C₃S into the core area thereby playing a key role on the properties of concrete upon formation.     

A Reaction Zone Hypothesis for the Effects of Particle Size and Water‐to‐Cement Ratio on the Early Hydration Kinetics of C3S

The hydration kinetics of tricalcium silicate (C₃S) has been the subject of much study, yet the experimentally observed effects of the water‐to‐cement (w/c) ratio and particle size distribution have been difficult to explain with models. Here, we propose a simple hypothesis that provides an explanation of the lack of any significant effect of w/c on the kinetics and for the strong effect of the particle size distribution on the amount of early hydration associated with the main hydration peak. The hypothesis is that during the early hydration period the calcium–silicate–hydrate product forms only in a reaction zone close to the surface of the C₃S particles. To test the hypothesis, a new microstructure‐based kinetics (MBK) model has been developed. The MBK model treats the C₃S particle size distribution in a statistical way to save computation time and treats the early hydration as essentially a boundary nucleation and growth process. The MBK model is used to fit kinetic data from two published studies for C₃S with different size distributions, one for alite (impure C₃S) pastes and one for stirred C₃S suspensions. The model is able to fit all the data sets with parameters that show no significant trend with particle size, providing support for the reaction zone hypothesis.     

Effect of the densification of C–S–H on hydration kinetics of tricalcium silicate

Effect of water to cement (w/c) ratio and temperature profiles on the densification of C–S–H (calcium silicate hydrate gel) and hydration kinetics of triclinic tricalcium silicate (C₃S) is studied beyond the first day of hydration. Calorimetry and quantitative X‐ray diffraction/Rietveld analysis show that degree of hydration is unaffected by w/c up to 7 days and marginally thereafter. Coupling the degree of hydration with the portlandite content measured from thermal analysis indicate that C/S ratio of C–S–H decreases with increasing w/c. There is a clear increase in the portlandite content with increasing w/c, even though the degree of hydration is unchanged, due to the variations in C/S ratio of C–S–H. On the other hand, when C₃S is initially cured at a lower temperature (20°C) and then at a higher temperature (40°C), there is a significant increase in the reactivity even until 28 days and vice versa. These experimental results were explained using the densified volumetric growth hypothesis, which assumes that hydration kinetics are dependent on the internal surface area of C–S–H.     

A high resolution 29Si NMR study of the hydration of tricalciumsilicate

A new method for the determination of the structure of silicate anions, formed during hydration of tricalciumsilicate Ca₃SiO₅ (C₃S), is presented. High resolution solid state ²⁹Si NMR spectra of C₃S and its hydration products, formed during selected reaction times from 6 hours to 130 days, provide the kinetics of formation of the end groups and of the middle groups in silicate chains.     

水泥–矿渣复合胶凝材料中矿渣的水化特性

通过对不同矿渣掺量时水泥–矿渣复合胶凝材料中矿渣的反应程度、硬化浆体中Ca（OH）2含量以及水化硅酸钙（C–S–H）凝胶的Ca/Si比（Ca和Si的摩尔比）的测定,研究复合胶凝材料体系中矿渣的水化特性。结果表明：在水泥–矿渣复合胶凝材料中,矿渣掺量越大,矿渣反应程度越低,但矿渣掺量≤70%时,对矿渣的反应程度影响不大。高温养护可提高早期矿渣的反应程度,但阻碍其后期的进一步水化。矿渣早期水化生成外部水化产物时消耗一定的Ca（OH）2,使硬化浆体中Ca（OH）2含量降低,矿渣水化吸收Ca（OH）2中的Ca2＋,使生成的C–S–H凝胶的Ca/Si比降低较少;在水化后期,矿渣生成内部水化产物不再消耗较多的Ca（OH）2,使C–S–H凝胶的Ca/Si比降低相对较多,硬化浆体中Ca（OH）2含量有增加的趋势,保证硬化浆体的长期稳定性。     

Hydration of C3S thin films

Thin films of C₃S of a few tens of nanometers were produced by electron beam evaporation. After verification that the chemical composition of the bulk material remained unchanged, the samples were hydrated with water vapor in a reaction chamber under saturated pressure and temperature conditions, and were kept isolated from atmospheric exposure throughout the whole duration of the experiment. Analyses by X-ray photoelectron spectroscopy at different stages of hydration evidence a shift of the Si peaks to higher energies and a subsequent decrease of the Ca–Si binding energy distance, indicating silicate polymerization expected upon formation of C–S–H. The measured molar Ca/Si ratio evolves from that of a jennite-like material, of about 1.55, at the beginning of the experiment (attributed to pre-hydration of the thin films), to a tobermorite-like ratio of 0.85 after 3 h of hydration.     

Hydration of β-dicalcium silicate at high temperatures under hydrothermal conditions

Hydration of β-dicalcium silicate was carried out under hydrothermal conditions at different temperatures from 50 °C to 400 °C up to 5 days by using two methods to start the reactions at room temperature or at a desired reaction temperature. 9 C-S-H phases with the same Ca/Si ratio as precursor (γ-dicalcium silicate hydrate and α-dicalcium silicate hydrate and dellaite), Ca-rich compositions (jaffeite and reinhardbraunsite), Si-rich compositions (Ca₈Si₅O₁₈, kilchoanite and foshagite), and C-S-H gel were obtained at the initial stage of the hydration of β-dicalcium silicate. The reaction products were different in dependence in the hydrothermal processes. It was found that α-dicalcium silicate hydrate was directly formed from β-dicalcium silicate at low temperatures below 220 °C. The products obtained at above 240 °C were different in dependence in the hydrothermal processes, due to the different decomposition route of γ-dicalcium silicate hydrate, the initial product from β-dicalcium silicate. The room temperature mixing method gave reinhardbraunsite and kilchoanite through Ca₈Si₅O₁₈. In the case of the high temperature mixing method, γ-dicalcium silicate hydrate decomposed to from Ca₈Si₅O₁₈ and reinhardbraunsite with jaffeite, then Ca₈Si₅O₁₈ decomposed to from jaffeite and kilchoanite, and final products at 400 °C were reinhardbraunsite and foshagite which was formed from kilchoanite.     

Time dependent driving forces and the kinetics of tricalcium silicate hydration

Simulations of tricalcium silicate (C₃S) hydration using a kinetic cellular automaton program, HydratiCA, indicate that the net rate depends both on C₃S dissolution and on hydration product growth. Neither process can be considered the sole rate-controlling step because the solution remains significantly undersaturated with respect to C₃S yet significantly supersaturated with respect to calcium silicate hydrate (C–S–H). The reaction rate peak is attributed to increasing coverage of C₃S by C–S–H, which reduces both the dissolution rate and the supersaturation of C–S–H. This supersaturation dependence is included in a generalized boundary nucleation and growth model to describe the kinetics without requiring significant impingement of products on separate cement grains. The latter point explains the observation that paste hydration rates are insensitive to water/cement ratio. The simulations indicate that the product layer on C₃S remains permeable; no transition to diffusion control is indicated, even long after the rate peak.     

Class H cement hydration at 180 °C and high pressure in the presence of added silica

Under deep oil-well conditions of elevated temperature and pressure, crystalline calcium silicate hydrates are formed during Portland cement hydration. The use of silica rich mineral additives leads to the formation of crystalline hydrates with better mechanical properties than those formed without the additive. The effects of silica flour, silica fume (amorphous silica), and a natural zeolite mixture on the hydration of Class H cement slurries at 180 °C under externally applied pressures of 7 and 52 MPa are examined in real time using in-situ synchrotron X-ray diffraction. For some compositions examined, but not all, pressure was found to have a large effect on the kinetics of crystalline hydrate formation. The use of silica fume delayed both C₃S hydration and the formation of crystalline silicate hydrates compared to what was seen with other silica sources.     

Highly Reactive β-Dicalcium Silicate: I, Hydration Behavior at Room Temperature

The hydration behavior at 25°C of β-dicalcium silicate synthesized from hillebrandite (Ca₂,(SiO₃)(OH)₂) at 600°C was studied over a period of 224 d. The hydration rate of the β-dicalcium silicate having fibrous crystals with specific surface area of 7 m²/g is extremely rapid. For water/solids ratios of 0.5 and 1.0, the hydration reaction is completed in 28 and 14 d, respectively. The hydrate contains almost no Ca(OH)₂, and its Ca/Si ratio is close to 2. SEM observations indicate that the hydrate forms an outer shell on the surface of β-dicalcium silicate and grows inwards. The silicate anion structure is considered to consist of dimers and single-chain structures from ²⁹Si MAS NMR. Variations of physical properties of press-formed bodies have also been discussed.     

Aluminum Incorporation in the C–S–H Phase of White Portland Cement–Metakaolin Blends Studied by 27Al and 29Si MAS NMR Spectroscopy

The composition and structure of the calcium‐silicate‐hydrate (C–S–H) phases formed by hydration of white portland cement–metakaolin (MK) blends have been investigated using ²⁷Al and ²⁹Si MAS NMR. This includes blends with 0, 5, 10, 15, 20, 25, 30 wt% MK, following their hydration from 1 d to 1 yr. ²⁹Si MAS NMR reveals that the average Al/Si ratio for the C–S–H phases, formed by hydration of the portland cement–MK blends, increases almost linearly with the MK content but is invariant with the hydration time for a given MK content. Correspondingly, the average aluminosilicate chain lengths of the C–S–H increase with increasing MK content, reflecting the formation of a C–S–H with a lower Ca/Si ratio. The increase in Al/Si ratio with increasing MK content is supported by ²⁷Al MAS NMR which also allows detection of strätlingite and fivefold coordinated aluminum, assigned to AlO₅ sites in the interlayer of the C–S–H structure. Strätlingite is observed after prolonged hydration for MK substitution levels above 10 wt% MK. This is at a somewhat lower replacement level than expected from thermodynamic considerations which predict the formation of strätlingite for MK contents above 15 wt% after prolonged hydration for the actual portland cement–MK blends. The increase in fivefold coordinated Al with increasing MK content suggests that these sites may contribute to the charge balance of the charge deficit associated with the incorporation of Al³⁺ ions in the silicate chains of the C–S–H structure.     

Influence of triethanolamine on the hydration characteristics of tricalcium silicate

The hydration characteristics of 3CaO.SiO₂ or β2CaO.SiO₂ are studied by an addition of 0.0, 0.1, 0.5 or 1.0% triethanolamine. The amount of Ca(OH)₂ found at 1, 3, 7 or 28 days was in the order C₃S + 0% TEA > C₃S +0.1% TEA > C₃S + 0.5% TEA > C₃S+1.0% TEA, irrespective of whether lime was estimated by X-ray, DTA, TGA or chemical analysis. The rate of hydration, in terms of the disappearance of 3CaO.SiO₂, showed that hydration proceeded faster in the presence of TEA after 1 day. Additions of TEA increase the induction period, promote the formation of a C-S-H with higher CaO/SiO₂ ratio, increase the formation of non-crystalline Ca(OH)₂ and enhance the surface area of the hydrated silicate product.     

Low pressure steam hydration of tricalcium silicate

Pastes of C₃S (w/c ratio = 0.5) were steam cured at 25, 40, 60 and 90°C for 1 hour to 30 days. The results obtained have shown that, as the curing temperature rises, the induction period is shortened and the initial rate of hydration of C₃S is increased; at longer curings, on the other hand, such hydration rate is considerably lowered. In order to explain the influence of temperature on the hydration reaction a new hypothesis has been proposed, which takes into account the C/S molar ratio as well as the surface properties of the hydrated silicate.     

Highly Reactive β-Dicalcium Silicate: II, Hydration Behavior at 25°C Followed by 29Si Nuclear Magnetic Resonance

The hydration behavior at 25°C of highly reactive β-dicalcium silicate synthesized from hillebrandite (Ca₂(SiO₃)(OH)₂) was studied over a period of 7 to 224 d using ²⁹Si magic-angle spinning nuclear magnetic resonance (MAS NMR). The hydration product, C-S-H, contains Q² and Q¹ silicate tetrahedra, the chemical shifts of which are independent of the water/solid (w/s) ratio and curing time. Until the reaction is completed, the amounts of Q¹ and Q² formed are independent of the w/s ratio, being determined only by the degree of reaction. The ratio Q²/Q¹ increases as the reaction progresses and as the curing time becomes longer. From the values of Q²/Q¹, it appears that the hydrate is a mixture of dimers and short single-chain polymers. The Ca/Si ratio of the hydrate is high, taking values close to 2.0, but the Ca/Si ratio does not influence the Q²/Q¹ ratio. It was also found that the NMR peak intensities allow quantitative assessment similar to XRD.     

Hydration of C3S-pozzolana paste estimated by trimethylsilylation

The structure, quantity and the degree of polycondensation of silicate ion in C₃S-pozzolana pastes were examined and discussed in relation to the strenght and the rate of hydration of C₃S and pozzolana. Gel permeation chromatography was adopted to prepare the standard pure sample for the calibration curves and to determine the distribution of molecular weight of silicates. A small amount of monomer was found in the hydrates of C₃S and C₃S-pozzolana. Dimer decreased after a definite period and polysilicate increased gradually with age. The quantity and the degree of polycondensation of polysilicate in hydrate depend roughly on the silica content of pozzolana and the reactivity of silicate in pozzolana. Double chain structure of polysilicate was supported from the infra-red absorption spectra and the basic structure of polysilicate in hydrate was supposed to be identical regardless of the kinds of pozzolana and curing age.