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.     

The effects of seeding C3S pastes with afwillite

The addition of 1–4% s/s (dry solids by mass of C₃S) of afwillite (C₃S₂H₃) seeds to C₃S pastes made with two different commercial polyacrylate-based superplasticizers (SP) allows the pastes to be cast at low water/C₃S mass ratios (w/c) and overcomes the hydration retardation produced by the SPs. SP-free C₃S pastes seeded with afwillite at an initial w/c of 0.50 gave about 30% lower 28-day compressive strengths than the unseeded controls, due to higher porosities. However, at w/c = 0.35, with the addition of 0.4% s/s SP, the afwillite-seeded pastes gave similar or higher strengths than the unseeded controls at all ages tested. Hydration rate data obtained by chemical shrinkage measurements suggest that this is because the degrees of hydration of the C₃S in the low w/c afwillite-seeded pastes made with added SP reach higher values than in the unseeded controls, compensating for the difference in density of the hydrates.     

In‐Situ XRD Measurement and Quantitative Analysis of Hydrating Cement: Implications for Sulfate Incorporation in C–S–H

The study of hydration kinetics by in‐situ X‐ray powder diffraction can provide fundamental details on the time evolution of the phase assemblage in hydrating cement pastes. The main limit of the technique is the lack of quantitative information about the amount of C–S–H and unbound water, which cannot be measured directly by conventional quantitative phase analysis procedures based on X‐ray diffraction, due to their X‐ray amorphous nature. Here, a mass balance algorithm, which can be used to determine the amount of both C–S–H and capillary water, is presented and compared with methods based on standards. This method can also provide information about the stoichiometry of C–S–H formed by the reaction of C₃S, hydrated in the presence of gypsum, suggesting the incorporation of 0.3 mol of sulfate per mole of C–S–H precipitated. In addition, the results show a significant increase in the rate of C₃S hydration, when gypsum is added to the system.     

Physicochemical effects of nanosilica on C3A/C3S hydration

In this paper, C₃A-gypsum and C₃A-C₃S-gypsum model cement systems with and without nanosilica were studied. The effects of nanosilica on the early stage cement hydration, particularly C₃A hydration, were assessed through the heat of hydration (isothermal calorimetry), phase assemblage (quantitative X-ray diffraction), zeta potential, ion concentration measurements, and morphology (scanning electron microscopy) examinations. The results indicate that while promoting C₃S hydration, nanosilica retarded C₃A hydration in both the systems studied. The retardation was caused by the adsorption and coverage of nanosilica on C₃A surfaces through the electrostatic interaction, thus decreasing the C₃A dissolution rate and hindering the precipitation of hydration products. Consequently, the reduced gypsum consumption rate and the seeding effect of nanosilica further promoted C₃S hydration. These findings suggest that nanosilica and other silica-based nanoparticles can physicochemically influence hydration of cement-based materials, and a better understanding of these influencing mechanisms can help optimize performances of nanoparticle-modified cement-based materials.     

Portlandite content and ionic transport properties of hydrated C3S pastes

This paper presents the results of a C₃S paste characterization study. The objective was to determine the parameters needed to model the process of degradation. The experimental study focused on determining the portlandite content and the ionic diffusion coefficients of C₃S paste. The molar C/S ratio of C–S–H in hydrated C₃S pastes was also investigated. The portlandite content was determined with an experimental method based on an electron microprobe analysis.This method leads to a portlandite mass content of 24.4 ± 2.3%. The diffusion coefficient of each ionic species was determined by inverse analysis of diffusion test data performed on hydrated C₃S samples using a multiionic transport model.     

Hydration of calcium aluminates at 60°C – Development paths of C2AHx in dependence on the content of free water

The influence of water loss during the hydration of calcium aluminates on the phase development is investigated at 60°C. This is relevant for applications in which calcium aluminate cement (CAC) based formulations are exposed to quick drying during hydration. The presented results provide new insights into the well-known conversion processes occurring in CAC pastes. Using in situ XRD two different routes of the development of initially formed C₂AH₈ are determined: (a) transformation to C₃AH₆ + AH₃ in the presence of sufficient free water and (b) dehydration to C₂AH₅ at a lack of free water. Moreover, the influence of precuring of the pastes at 23°C before heating to 60°C is investigated. The increasing loss of free water with increasing precuring time resulting from both, precipitation of hydrate phases and evaporation, causes incomplete hydration of CA or CA₂ as well as dehydration of C₂AH₈ instead of conversion into C₃AH₆. Comparative investigations of sealed samples always revealed complete hydration of CA and CA₂ as well as complete conversion of C₂AH₈.     

Hydration of C3S in presence of CA: Mineral-pore solution interaction

C₃S and CA are the main phases of OPC and Fe-rich CAC, respectively. The objective of this research was to investigate the influence of CA on C₃S hydration, representing an under sulfated OPC-rich binder, and to shed light on the underlying hydration mechanisms. To this end, C₃S was blended with 1-30 wt-% CA and the pastes (w/c 0.5) were investigated by heat flow calorimetry, in situ X-ray diffraction and analysis of the pore solution chemistry. CA additions ≥5 wt-% reveal a separation into three distinct heat flow maxima, whereas additions ≤3 wt-% just retard the start of the main reaction. The silicate reaction (dissolution of C₃S and precipitation of C–S–H with or without CH) can be retarded for 4 to ≥22 hours in comparison to pure C₃S depending on the admixed CA content. The start of the silicate reaction seems to be related to a decrease in Al- and increase in Ca-concentration in the pore solution. However, it can be shown in this study that C₃S is able to dissolve even at high Al concentrations in the pore solution.     

Effect of particle size distribution of metakaolin on hydration kinetics of tricalcium silicate

The focus of this study is to elucidate the role of particle size distribution (PSD) of metakaolin (MK) on hydration kinetics of tricalcium silicate (C₃S–T₁) pastes. Investigations were carried out utilizing both physical experiments and phase boundary nucleation and growth (pBNG) simulations. [C₃S + MK] pastes, prepared using 8%_mass or 30%_mass MK, were investigated. Three different PSDs of MK were used: fine MK, with particulate sizes <20 µm; intermediate MK, with particulate sizes between 20 and 32 µm; and coarse MK, with particulate sizes >32 µm. Results show that the correlation between specific surface area (SSA) of MK's particulates and the consequent alteration in hydration behavior of C₃S in first 72 hours is nonlinear and nonmonotonic. At low replacement of C₃S (ie, at 8% _mass), fine MK, and, to some extent, coarse MK act as fillers, and facilitate additional nucleation and growth of calcium silicate hydrate (C–S–H). When C₃S replacement increases to 30% _mass, the filler effects of both fine and coarse MK are reversed, leading to suppression of C–S–H nucleation and growth. Such reversal of filler effect is also observed in the case of intermediate MK; but unlike the other PSDs, the intermediate MK shows reversal at both low and high replacement levels. This is due to the ability of intermediate MK to dissolve rapidly—with faster kinetics compared to both coarse and fine MK—which results in faster release of aluminate [Al(OH)₄⁻] ions in the solution. The aluminate ions adsorb onto C₃S and MK particulates and suppress C₃S hydration by blocking C₃S dissolution sites and C–S–H nucleation sites on the substrates’ surfaces and suppressing the post-nucleation growth of C–S–H. Overall, the results suggest that grinding-based enhancement in SSA of MK particulates does not necessarily enhance early-age hydration of C₃S.     

Creep and drying shrinkage of calcium silicate pastes IV. Effects of accelerated curing

The dependent deformations and evidence of structural changes were measured on pastes of C₃S containing CaCl₂, and on pastes of C₃S or a C₃S/C₂S blend cured at 65°C. It was concluded that the addition of CaCl₂ enhances the role of the “pore component” in controlling irreversible strains even when well-hydrated pastes are dried. The formation of ore stable CSH at 65°C can explain the reduction in time-dependent deformations observed for these pastes. Even though a change in pore size distribution occurs at 65°C, it is not considered to affect irreversible strains in well-hydrated pastes.     

Conversion of calcium aluminate cement hydrates at 60°C with and without water

There have been different hypotheses about the transformation mechanisms of calcium aluminate cement hydrates and this work aims to clarify the long‐running debate about the conversion approaches. In this work, CAH₁₀ and C₂AH₈ were produced from the pastes of calcium aluminate cement (CAC) cured for 24 hours at 10 and 20°C separately. And the cured pastes were continually cured at 60°C for 3 days with water and without water, respectively. The hydration of the pastes was halted by freeze‐drying, and the phases and microstructure of hydrates were investigated by XRD and SEM, respectively. The results indicate that CAH₁₀ and C₂AH₈ converted into C₃AH₆ and AH₃ in water presence at 60°C, but did not transform into C₃AH₆ and AH₃ without water. It is confirmed that the conversion of CAH₁₀ and C₂AH₈ to C₃AH₆ and AH₃ happens through preceding solution of CAH₁₀ and C₂AH₈ and subsequent precipitation of C₃AH₆ and AH₃.     

Soft X‐ray Ptychographic Imaging and Morphological Quantification of Calcium Silicate Hydrates (C–S–H)

Morphological details of calcium silicate hydrate (C–S–H) stemming from the hydration process of Portland cement (PC) phases are crucial for understanding the PC‐based systems but are still only partially known. Here we introduce the first soft X‐ray ptychographic imaging of tricalcium silicate (C₃S) hydration products. The results are compared using both scanning transmission X‐ray and electron transmission microscopy data. The evidence shows that ptychography is a powerful method to visualize the details of outer and inner product C–S–H of fully hydrated C₃S, which have fibrillar and an interglobular structure with average void sizes of 20 nm, respectively. The high‐resolution ptychrography image enables us to perform morphological quantification of C–S–H, and, for the first time, to possibly distinguish the contributions of inner and outer product C–S–H to the small angle scattering of cement paste. The results indicate that the outer product C–S–H is mainly responsible for the q^?3 regime, whereas the inner product C–S–H transitions to a q^?2 regime. Various hypotheses are discussed to explain these regimes.     

The role of alumina on performance of alkali-activated slag paste exposed to 50 °C

The strength and microstructural evolution of two alkali-activated slags, with distinct alumina content, exposed to 50 °C have been investigated. These two slags are ground-granulated blast furnace slag (containing 13% (wt.) alumina) and phosphorous slag (containing 3% (wt.) alumina). They were hydrated in the presence of a combination of sodium hydroxide and sodium silicate solution at different ratios. The microstructure of the resultant slag pastes was assessed by X-ray diffraction, differential thermogravimetric analysis, and scanning electron microscopy. The results obtained from these techniques reveal the presence of hexagonal hydrates: CAH₁₀ and C₄AH₁₃ in all alkali-activated ground-granulated blast-furnace slag pastes (AAGBS). These hydrates are not observed in pastes formed by alkali-activated ground phosphorous slag (AAGPS). Upon exposure to 50 °C, the aforementioned hydration products of AAGBS pastes convert to C₃AH₆, leading to a rapid deterioration in the strength of the paste. In contrast, no strength loss was detected in AAGPS pastes following exposure to 50 °C.     

The Effect of Magnesium and Zinc Ions on the Hydration Kinetics of C3S

Impure tricalcium silicate (C₃S) in portland cement may contain various foreign ions. These ions can stabilize different polymorphs of C₃S at room temperature and may affect its reactivity. In this paper, the effects of magnesium and zinc on the polymorph type, hydration kinetics, and the hydrate morphology of C₃S were investigated. The pure C₃S has the T1 structure while magnesium and zinc stabilize polymorphs M3 and T2/T3, respectively. The two elements have distinct effects on the hydration kinetics. Zinc increases the maximum heat released. Magnesium increases the hydration peak width. The C–S–H morphology is modified, leading to longer needles in the presence of zinc and thicker needles in the presence of magnesium. Zinc is incorporated into C–S–H, while magnesium is only incorporated slightly, if at all, but rather seems to inhibit nucleation. Implementing experimentally measured parameters for C–S–H nucleation and growth in the μic hydration model captured well the observed changes in hydration kinetics. This supports C–S–H nucleation and growth to be rate controlling in the hydration of C₃S.     

Atomic and nano-scale characterization of a 50-year-old hydrated C3S paste

This paper investigates the atomic and nano-scale structures of a 50-year-old hydrated alite paste. Imaged by TEM, the outer product C–S–H fibers are composed of particles that are 1.5–2 nm thick and several tens of nanometers long. ²⁹Si NMR shows 47.9% Q₁ and 52.1% Q₂, with a mean SiO₄ tetrahedron chain length (MCL) of 4.18, indicating a limited degree of polymerization after 50 years' hydration. A Scanning Transmission X-ray Microscopy (STXM) study was conducted on this late-age paste and a 1.5 year old hydrated C₃S solution. Near Edge X-ray Absorption Fine Structure (NEXAFS) at Ca L_3,2-edge indicates that Ca^2 + in C–S–H is in an irregular symmetric coordination, which agrees more with the atomic structure of tobermorite than that of jennite. At Si K-edge, multi-scattering phenomenon is sensitive to the degree of polymerization, which has the potential to unveil the structure of the SiO₄^4 − tetrahedron chain.     

Influence of silica fume on the microstructure of cement pastes: New insights from 1H NMR relaxometry

¹H NMR has been used to characterise white Portland cement paste incorporating 10 wt.% of silica fume. Samples were measured sealed throughout the hydration without sample drying. Paste compositions and C–S–H characteristics are calculated based on ¹H NMR signal intensities and relaxation analysis. The results are compared with a similar study of plain white cement paste. While the presence of silica fume has little influence on C–S–H densities, the chemical composition is impacted. After 28 days of sealed hydration, the Ca/(Si + Al) ratio of the C–S–H is 1.33 and the H₂O/(Si + Al) ratio is 1.10 when 10% of silica fume is added to the white cement. A densification of the C–S–H with time is observed. There are no major changes in capillary, C–S–H gel and interlayer pore sizes for the paste containing silica fume compared to the plain white cement paste. However, the gel/interlayer water ratio increases in the silica fume blend.     

Alkaline Hydration Of C2S and C3S

This study analyzed the behavior of two laboratory‐synthesized calcium silicates, C₃S and C₂S, after hydration in 8‐M NaOH and in water as a control. Two‐ and 28‐d mechanical strength values were determined and the products were characterized with XRD, TEM, and ²⁹Si and ²³Na MAS NMR. The results showed that hydrating C₃S in a highly alkaline medium had no significant effect on the mechanical development of the material, whereas in C₂S hydration, that medium hastened hydration substantially, impacting setting and hardening times. This finding has technological implications, given the low early‐age reactivity of dicalcium silicate under normal hydration conditions.     

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.     

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 kinetics of cements by Time-Domain Nuclear Magnetic Resonance: Application to Portland-cement-derived endodontic pastes

Time-Domain Nuclear Magnetic Resonance (TD-NMR) of ¹H nuclei is used to monitor the maturation up to 30 days of three different endodontic cement pastes. The “Solid–liquid” separation of the NMR signals and quasi-continuous distributions of relaxation times allow one to follow the formation of chemical compounds and the build-up of the nano- and subnano-structured C–S–H gel. ¹H populations, distinguished by their different mobilities, can be identified and assigned to water confined within the pores of the C–S–H gel, to crystallization water and Portlandite, and to hydroxyl groups. Changes of the TD-NMR parameters during hydration are in agreement with the expected effects of the different additives, which, as it is known, can substantially modify the rate of reactions and the properties of cementitious pastes. Endodontic cements are suitable systems to check the ability of this non-destructive technique to give insight into the complex hydration process of real cement pastes.     

Evolution of Mineralogical Phases by 27Al and 29Si NMR in MK‐Ca(OH)2 System Cured at 60°C

The evolution of the metastable phases in metakaolin/Ca(OH)₂ systems cured at high temperatures, remains mostly unknown, newer techniques may now help to establish both the kinetic mechanism of the pozzolanic reaction and the thermodynamic stability of the main hydrated hexagonal phases: Stratlingite (C₂ASH₈) and tetra calcium aluminate hydrate (C₄AH₁₃). For this reason this work examines the kinetics of the pozzolanic reaction in the MK/Ca(OH)₂ system over 123 d at 60°C using nuclear magnetic resonance spectroscopy (²⁷Al and ²⁹Si NMR). The results obtained by ²⁷Al and ²⁹Si NMR show that during the first 30 h, the metastable phases C₂ASH₈ and C₄AH₁₃, coexist with the cubic phase (C₃ASH₆) obtained directly from the pozzolanic reaction. The gel C–S–H is clearly identified after 21 h of reaction, whereas at shorter times the C–S–H bands overlap those with the unreacted metakaolin ones. After 123 d of pozzolanic reaction, the first signs of the cubic phase are detected, a consequence of the conversion reaction of the metastable phases, and a phenomenon not previously identified.