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.     

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.     

An Ideal Solid Solution Model for C–S–H

A model for an ideal solid solution, developed by Nourtier‐Mazauric et al. [Oil & Gas Sci. Tech. Rev. IFP, 60 [2] (2005) 401], is applied to calcium–silicate–hydrate (C–S–H). Fitting the model to solubility data reported in the literature for C–S–H yields reasonable values for the compositions of the end‐members of the solid solution and for their equilibrium constants. This model will be useful in models of hydration kinetics of tricalcium silicate because it is easier to implement than other solid solution models, it clearly identifies the driving force for growth of the most favorable C–S–H composition, and it still allows the model to accurately capture variations in C–S–H composition as the aqueous solution changes significantly at early hydration times.     

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.     

Sodium silicate activated slag‐fly ash binders: Part I – Processing,microstructure, and mechanical properties

Alkali silicate activated slag and class F fly ash‐based binders are ambient curing, structural materials that are feasible replacements for ordinary Portland cement (OPC). They exhibit advantageous mechanical properties and less environmental impact than OPC. In this work, five sodium silicate activated slag‐fly ash binder mixtures were developed and their compressive and flexural strengths were studied as a function of curing temperature and time. It was found that the strongest mixture sets at ambient temperature and had a Weibull average flexural strength of 5.7 ± 1.5 MPa and Weibull average compressive strength of 60 ± 8 MPa at 28 days. While increasing the slag/fly ash ratio accelerated the strength development, the cure time was decreased due to the formation of calcium silicate hydrate (C–S–H), calcium aluminum silicate hydrate (C–A–S–H), and (Ca,Na) based geopolymer. The density, microstructure, and phase evolution of ambient‐cured, heat‐cured, and heat‐treated binders were studied using pycnometry, scanning electron microscopy, energy dispersive X‐ray spectroscopy (SEM‐EDS), and X‐ray diffraction (XRD). Heat‐cured binders were more dense than ambient‐cured binder. No new crystalline phases evolved through 28 days in ambient‐ or heat‐cured binders.     

C–(N)–S–H and N–A–S–H gels: Compositions and solubility data at 25°C and 50°C

Calcium silicate hydrates containing sodium [C–(N)–S–H], and sodium aluminosilicate hydrates [N–A–S–H] are the dominant reaction products that are formed following reaction between a solid aluminosilicate precursor (eg, slags, fly ash, metakaolin) and an alkaline activation agent (eg NaOH) in the presence of water. To gain insights into the thermochemical properties of such compounds, C–(N)–S–H and N–A–S–H gels were synthesized with compositions: 0.8≤Ca/Si≤1.2 for the former, and 0.25≤Al/Si≤0.50 (atomic units) for the latter. The gels were characterized using thermogravimetric analysis (TGA), scanning electron microscopy with energy‐dispersive X‐ray microanalysis (SEM‐EDS), and X‐ray diffraction (XRD). The solubility products (K_S0) of the gels were established at 25°C and 50°C. Self‐consistent solubility data of this nature are key inputs required for calculation of mass and volume balances in alkali‐activated binders (AABs), and to determine the impacts of the precursor chemistry on the hydrated phase distributions; in which, C–(N)–S–H and N–A–S–H compounds dominate the hydrated phase assemblages.     

The Effect of Alkali Ions on the Incorporation of Aluminum in the Calcium Silicate Hydrate (C–S–H) Phase Resulting from Portland Cement Hydration Studied by 29Si MAS NMR

The incorporation of aluminum in the calcium–silicate–hydrate (C–S–H) phases formed by hydration of three different white Portland cements has been investigated by ²⁹Si MAS NMR. The principal difference between the three cements is their bulk Al₂O₃ contents and quantities of alkali (Na⁺ and K⁺) ions. ²⁹Si MAS NMR allows indirect detection of tetrahedral Al incorporated in the silicate chains of the C–S–H structure by the resonance from Q²(1Al) sites. Analysis of the relative ²⁹Si NMR intensities for this site, following the hydration for the three cements from 0.5 d to 30 weeks, clearly reveals that the alkali ions promote the incorporation of Al in the bridging sites of the dreierketten structure of SiO₄ tetrahedra in the C–S–H phase. The increased incorporation of Al in the C–S–H phase with increasing alkali content in the anhydrous cement is in accord with a proposed substitution mechanism where the charge deficit, obtained by the replacement of Si⁴⁺ by Al³⁺ ions in the bridging sites, is balanced by adsorption/binding of alkali ions in the interlayer region most likely in the near vicinity of the AlO₄ tetrahedra. This result is further supported by similar ²⁹Si MAS NMR experiments performed for the white Portland cements hydrated in 0.30M NaOH and NaAlO₂ solutions.     

Preparation of a Novel Cementitious Material from Hydrothermally Synthesized C–S–H Phases

New cementitious materials based on calcium hydrosilicate hydrates were recently developed as potential substitutes for ordinary portland cement, but with a reduced CO₂ footprint. The materials are produced by hydrothermal processing of SiO₂ and Ca(OH)₂, giving rise to calcium silicate hydrates, followed by mechanical activation of the latter via cogrinding with various siliceous materials. Thus, the chemical composition in terms of C/S ratio could be adjusted over a broad range (1–3). In this study the synthesis of a previously unknown cementitious material produced via the combination of mechanical activation in a laboratory mill and thermal treatment of a mixture of quartz and hydrothermally synthesized calcium silicate hydrates: α‐Ca₂[HSiO₄](OH) (α‐C₂SH) and Ca₆[Si₂O₇](OH)₆ (jaffeite) are reported. It forms independently of the type of mill used (eccentric vibrating mill, vibration grinding mill) after thermal treatment of the ground materials at 360°C–420°C. The new material is X‐ray amorphous and possesses a CaO/SiO₂ ratio of 2. A characteristic feature in regards to the silicate anionic structure is the increased silicate polymerization (up to 27% Si₂O₇ dimers) as revealed by the trimethylsilylation method. Infrared (IR) spectra show a very broad absorption band centered at about 935 cm^?1. Another characteristic feature is the presence of ~2.5 wt% H₂O as shown by thermogravimetry (TG) coupled with IR spectroscopy. As this water is bound mostly as hydroxyl to Ca, we refer to this new cementitious material as calcium‐oxide–hydroxide–silicate (C–CH–S). Calorimetric measurements point to a very high hydraulic reactivity which is beyond that for typical C₂S materials. The influence of the type of grinding on the thermal behavior of α‐C₂SH upon its transformation into water‐free Ca₂SiO₄ modifications is discussed.     

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.     

High‐Resolution X‐ray Diffraction and Fluorescence Microscopy Characterization of Alkali‐Activated Slag‐Metakaolin Binders

The effect of the activator concentration on the structure of alkali silicate‐activated slag/metakaolin pastes is assessed through synchrotron radiation‐based X‐ray techniques. As main reaction products, both calcium aluminosilicate hydrate (C–A–S–H) and sodium/calcium aluminosilicate hydrate [(C,N)–A–S–H] type gels are formed in activated binders solely based on slag, along with the zeolitic products gismondine and garronite. In activated blended pastes, the inclusion of metakaolin in the binder hinders the formation of zeolite products, instead favoring the formation of a (C,N)–A–S–H type gel consistent with the activation of metakaolin in the presence of high concentrations of Ca. The formation of the two distinct binding products is confirmed by high‐resolution X‐ray fluorescence microscopy, where the “inner” products and the “outer” products have compositions consistent with (C,N)–A–S–H and C–A–S–H type gels, respectively. These results provide important new insights into the gel chemistry and micro/nanostructure of blended alkali‐activated binder systems.     

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.     

Effect of synthesis procedure on carbonation of calcium‐silicate‐hydrate

Carbonation of synthesized calcium‐silicate‐hydrate (C–S–H) is difficult to avoid and can have significant impact on the molecular structure. Considerable carbonation was observed in C–S–H synthesized from the double decomposition of sodium silicate and calcium nitrate solutions but not in C–S–H synthesized from the direct reaction of fumed silica and calcium hydroxide solution. In order to isolate the cause of the greater carbonation in C–S–H synthesized by double decomposition, carbonation was induced in phase‐pure C–S–H by reaction with four different water‐based solutions containing dissolved CO₂ with varying pH and alkali content. Powder X‐ray diffraction, thermogravimetric analysis, and ²⁹Si nuclear magnetic resonance were used to probe the carbonation and the resulting changes in molecular structure. The pH of the solution was seen to strongly influence the degree of carbonation, while the alkali content had much less effect.     

Calcium silicate hydrate (II) (“C-S-H(II)”)

This semicrystalline phase, originally named ‘calcium silicate hydrate(II)’ by Taylor (1950), has been studied with X-rays, electron optics, chemical investigation of silicate anion type, infrared spectra, and thermal methods. It is structurally related to jennite (C₉S₆H₁₁) and probably also to the fibrous CSH of cement pastes, the three phases forming a sequence of decreasing crystallinity. The specimen studied had approximate composition C₂SH_3.2 after standing over saturated CaCλ₂ at about 15°C. CSH(II) contains metasilicate chains and pyrosilicate groups and has a disordered layer structure. Much of the water can be lost reversibly without significant change in lattice parameters.     

钢渣水化产物的特性(英文)

用X射线衍射分析、水化热的测量、化学结合水量的测定、孔结构的测定、扫描电镜观察及强度测试研究了钢渣的水化产物的特性。结果表明:钢渣硬化浆体中主要含有水化硅酸钙(C–S–H)凝胶、Ca(OH)2、惰性组分[RO相、铁酸二钙(C2F)和Fe3O4]和未水化的胶凝相[硅酸三钙(C3S)和硅酸二钙(C2S)];总体而言,钢渣的水化过程与水泥的水化过程相似;钢渣早期的水化速率远低于水泥,但钢渣后期,尤其是90d之后的水化速率高于水泥的。钢渣水化产生的C–S–H凝胶不具有良好的胶凝性能,凝胶之间的相互黏结也不牢固,因此钢渣砂浆的强度很低。     

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.     

Proton Spin–Spin Relaxation Study of the Effect of Temperature on White Cement Hydration

The chemical and microstructural changes within a white cement paste were characterized in situ using proton nuclear magnetic resonance spin–spin relaxation at 30 MHz, and X-ray diffraction. Paste samples with a water-to-cement ratio of 0.42 were cured at constant temperatures of 2°, 20°, 60°, and 100°C. Proton nuclear magnetic resonance spin–spin relaxation allows tracking the evolution of the mixing water into the solid fractions of calcium silicate hydrate, calcium hydroxide, and monosulfate, and the liquid phases: the calcium silicate hydrate interlayer water, gel pore water, and capillary pore water. It is shown that the hydration process is markedly accelerated with increasing hydration temperature, and that proton nuclear magnetic resonance relaxation measurements can quantitatively determine the proportions of water phases, their magnetic resonance characteristics, as well as the setting times of the cement during the hydration process.     

Crystallization of calcium silicate hydrates on the surface of nanomaterials

The poorly crystalline calcium silicate hydrate (C‐S‐H) is the primary binding phase in portland cement concrete. In this paper, the influence of adding anatase phase nano‐TiO₂, nano‐SiO₂, graphene oxide (GO), and multiwalled carbon nanotubes (CNT) on the crystallization and morphology of C‐S‐H are systematically investigated through tests. C‐S‐H gels were prepared using the double decomposition method, and the nanomaterial additions of nano‐TiO₂, nano‐SiO₂, GO, and CNT were 2 wt%, 2 wt%, 0.5 wt%, and 0.5 wt%, respectively. X‐ray diffraction (XRD) results show that a more crystalline nanostructure of C‐S‐H is induced by the addition of nano‐TiO₂ or GO. This phenomenon is further confirmed by the transmission electron microscopy (TEM) observations. The TEM observations demonstrate that C‐S‐H would grow on the crystal face of TiO₂ to form nanocrystalline regions with a lattice fringe spacing of 3.0 Å. When incorporated with GO, it will form a square lattice structure with a lattice constant of 3.1 Å on the surface of GO and later change to the lattice fringe structure with a spacing of 3.1 Å on the region bit away the GO surface. However, when adding nano‐SiO₂ or CNT, these nanocrystalline regions are not observed. Further characterization through scanning electron microscopy (SEM) and atomic force microscopy (AFM) has been performed to investigate the effect of nanomaterials on C‐S‐H morphology. Different nanomaterials take a different morphology of C‐S‐H: sheet‐shape structures for pure C‐S‐H, rod‐shape with for C‐S‐H with nano‐TiO₂, and granular agglomeration for C‐S‐H with nano‐SiO₂. C‐S‐H with GO or CNT forms a structure of C‐S‐H growing on the templates.     

高温条件下G级油井水泥原浆及加砂水泥的水化和硬化

利用X射线衍射仪和扫描电子显微镜研究了80～240℃温度范围内温度、硅砂对G级油井水泥水化硬化的影响,检测和分析了硬化体的水化产物、微观结构和强度,揭示了水化产物组成、微观结构及硬化体抗压强度的变化特点.结果表明:当养护温度超过110℃时,不添加硅砂的水泥原浆的主要水化产物由CSH(Ⅱ),C2SH2,C3S2H3转变为C2SH,硬化体微观结构由三维网络状结构转变为板快状或团块状结构,原浆水泥石抗压强度随温度升高而降低;在相对较高的温度条件下,添加硅砂的水泥主要水化产物则分别转变为C5S6H5,C6S6H(>150℃),C5S5A0.5H5.5,C3.2S2H0.8及其他类型的水化硅酸钙晶体,硬化体的微观结构相应地变为纤维网状、粗框架、短平行针状及团块状,在温度为100～150℃范围时,添加硅砂的水泥硬化体抗压强度随温度升高而增加,而在温度为150～240℃范围时.抗压强度随温度升高而降低.对于温度超过120℃的深井,合理的硅砂加量为30%～40%.     

Influence of portlandite on Pyrex glass dissolution and the formation of alkali‐silica chemical reaction products

The dissolution behavior of Pyrex glass in a model system consisting of 1‐M NaOH with varying amounts of portlandite, representing the glass dissolution in alkaline environment and alkali‐silica reaction (ASR) in cementitious materials, is studied. The Pyrex glass dissolution and the reaction products were characterized using X‐ray diffraction (XRD), ²⁹Si nuclear magnetic resonance (²⁹Si‐NMR), and scanning electron microscopy with energy dispersive X‐ray (SEM/EDX), and the silica and calcium concentrations in the liquid phase were determined using inductively coupled plasma atomic emission spectroscopy (ICP‐AES). The experimental results show that the dissolution of the Pyrex glass continued until it consumed the portlandite and then reached a constant rate, with a linear relationship with the amount of portlandite. The absence of calcium and reduction of silica concentration in the liquid phase with the increase in portlandite indicate the formation of high‐reaction products with portlandite, confirmed by XRD and ²⁹Si‐NMR. The calcium sodium silicate hydrate (C–N–S–H) and sodium silicate hydrate (N–S–H) are the main ASR products; their composition and proportions strongly depend on the reaction time and the amount of portlandite added. A thermodynamic model, which couples geochemical code (PHREEQC) and the experimental silica dissolution rate, was used to predict ASR products and the remaining portlandite. The simulation results predicted the experimental data fairly well for different portlandite additions. The mechanism for Pyrex glass dissolution in the presence of varying portlandite additions is discussed with regard to experimental data and simulation results.     

Evolution of C–S–H in lime mortars with nanoparticles: Nanostructural analysis of afwillite growth mechanisms by HRTEM

This work studies the formation of calcium–silicate–hydrates (C–S–H) in lime mortars prepared with additions of nano-Ca(OH)₂ and nano-SiO₂ at 23.3°C. Mineral identification was carried out by X-ray diffraction after 10, 30, 90, and 120 days of curing. The nanoscale study starts from the generation of amorphous phases until the development of crystalline phases. Observations of binder mortar made by transmission electron microscopy (low magnification and high resolution TEM) after 30 and 110 days of curing showed the formation of two types of C–S–H with different degrees of crystallinity depending on the curing time. The development of short-range order C–S–H globular phases was visible after 30 days. C–S–H evolved into lamellar crystalline phases visible after 110 days of curing. The crystalline phase corresponds to the C–S–H known as afwillite (Ca₃(SiO₃OH)₂·2H₂O), first reported to affect cement and concrete's mechanical and hydration properties. It appears as isolated fibers, growing epitaxially along the edges of the calcite (product of the carbonation of Ca(OH)₂), and advancing inward aided by atomic defects (grain boundaries, stacking faults). In addition, high-resolution transmission electron microscopy tools and electron diffraction simulation confirmed a monoclinic symmetry for afwillite crystals. These results contribute to analyzing the presence of crystalline/amorphous C–S–H in lime mortars, providing information on the structure of afwillite and its possible effects on the binder materials.