Rietveld refinement of the structures of 1.0 C-S-H and 1.5 C-S-H

Low-Q region Rietveld analyses were performed on C-S-H synchrotron XRD patterns, using the software MAUD. Two different crystal structures of tobermorite 11 Å were used as a starting model: monoclinic ordered Merlino tobermorite, and orthorhombic disordered Hamid tobermorite. Structural modifications were required to adapt the structures to the chemical composition and the different interlayer spacing of the C-S-H samples. Refinement of atomic positions was done by using special constraints called fragments that maintain interatomic distances and orientations within atomic polyhedra. Anisotropic crystallite size refinement showed that C-S-H has a nanocrystalline disordered structure with a preferred direction of elongation of the nanocrystallites in the plane of the Ca interlayer. The quality of the fit showed that the monoclinic structure gives a more adequate representation of C-S-H, whereas the disordered orthorhombic structure can be considered a more realistic model if the lack of long-range order of the silica chain along the c-direction is assumed.     

3D Nanotomography of calcium silicate hydrates by transmission electron microscopy

Calcium silicate hydrate (C-S-H), is the principal hydration product of Portland cement that mainly contributes to the physical and mechanical properties of concrete. This paper aims to investigate the three-dimensional structure of C-S-H with Ca/Si ratios of 1.0 and 1.6 at the nanoscale using electron tomography. The 3D reconstructions and selected region of interest analysis confirm that the morphology of both C-S-H materials are foil-like structures. The difference between the two materials is the density of elongated structures. C-S-H with Ca/Si ratio 1.6 is clearly composed of denser particles compared to the other C-S-H material due to overlapping of the foil-like structure. Pore analysis shows that C-S-H 1.0 and C-S-H 1.6 have porosities 69.2% and 49.8% respectively. Pore size distribution also reveals that C-S-H 1.0 has pore size range between 0-250 nm and C-S-H 1.6 between 0-100 nm. The pore network's size of C-S-H 1.0 is significantly larger than 1.6. This study illustrates the capability of using electron tomography to determine the 3D nanoscale structure of cementitious products and to distinguish between C-S-H 1.0 and 1.6.     

Tobermorite/jennite- and tobermorite/calcium hydroxide-based models for the structure of C-S-H: applicability to hardened pastes of tricalcium silicate, β-dicalcium silicate, Portland cement, and blends of Portland cement with blast-furnace slag, metakaolin, or silica fume

The purpose of this article is to discuss the applicability of the tobermorite-jennite (T/J) and tobermorite-‘solid-solution’ calcium hydroxide (T/CH) viewpoints for the nanostructure of C-S-H present in real cement pastes. The discussion is facilitated by a consideration of the author's 1992 model, which includes formulations for both structural viewpoints; its relationship to other recent models is outlined. The structural details of the model are clearly illustrated with a number of schematic diagrams. Experimental observations on the nature of C-S-H present in a diverse range of cementitious systems are considered. In some systems, the data can only be accounted for on the T/CH structural viewpoint, whilst in others, both the T/CH and T/J viewpoints could apply. New data from transmission electron microscopy (TEM) are presented. The ‘inner product’ (Ip) C-S-H in relatively large grains of C₃S or alite appears to consist of small globular particles, which are ≈4-8 nm in size in pastes hydrated at 20 °C but smaller at elevated temperatures, ≈3-4 nm. Fibrils of ‘outer product’ (Op) C-S-H in C₃S or β-C₂S pastes appear to consist of aggregations of long thin particles that are about 3 nm in their smallest dimension and of variable length, ranging from a few nanometers to many tens of nanometers. The small size of these particles of C-S-H is likely to result in significant edge effects, which would seem to offer a reasonable explanation for the persistence of Q⁰(H) species. This would also explain why there is more Q⁰(H) at elevated temperatures, where the particles seem to be smaller, and apparently less in KOH-activated pastes, where the C-S-H has foil-like morphology. In blended cements, a reduction in the mean Ca/Si ratio of the C-S-H results in a change from fibrillar to a crumpled-foil morphology, which suggests strongly that as the Ca/Si ratio is reduced, a transition occurs from essentially one-dimensional growth of the C-S-H particles to two-dimensional; i.e., long thin particles to foils. Foil-like morphology is associated with T-based structure. The C-S-H present in small fully hydrated alite grains, which has high Ca/Si ratio, contains a less dense product with substantial porosity; its morphology is quite similar to the fine foil-like Op C-S-H that forms in water-activated neat slag pastes, which has a low Ca/Si ratio. It is thus plausible that the C-S-H in small alite grains is essentially T-based (and largely dimeric). Since entirely T-based C-S-H is likely to have different properties to C-S-H consisting largely of J-based structure, it is possible that the C-S-H in small fully reacted grains will have different properties to the C-S-H formed elsewhere in a paste; this could have important implications.     

Solubility and structure of calcium silicate hydrate

The poorly crystalline calcium silicate hydrate (C-S-H) phases that form near room temperature, which include the technically important C-S-H gel phase formed during the hydration of Portland cement, have a broad similarity to the crystalline minerals tobermorite and jennite, but are characterized by extensive atomic imperfections and structural variations at the nanometer scale. Relationships between the aqueous solubility and chemical structure are reported for specimens formed by different preparation methods and with a broad range of compositions. Both new and previously published data show that these phases generate a family of solubility curves in the CaO-SiO₂-H₂O system at room temperature. As demonstrated by ²⁹Si magic-angle spinning (MAS) NMR data and by charge balance calculations, the observed solubility differences arise from systematic variations in Ca/Si ratio, silicate structure, and Ca-OH content. Based on this evidence, the solubility curves are interpreted as representing a spectrum of metastable 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.     

A multi-technique investigation of the nanoporosity of cement paste

The nanometer-scale structure of cement paste, which is dominated by the colloidal-scale porosity within the C-S-H gel phase, has a controlling effect on concrete properties but is difficult to study due to its delicate structure and lack of long-range order. Here we present results from three experimental techniques that are particularly suited to analyzing disordered nanoporous materials: small-angle neutron scattering (SANS), weight and length changes during equilibrium drying, and nanoindentation. Particular attention is paid to differences between pastes of different ages and cured at different temperatures. The SANS and equilibrium drying results indicate that hydration of cement paste at 20 °C forms a low-density (LD) C-S-H gel structure with a range of gel pore sizes and a relatively low packing fraction of solid particles. This fine structure may persist indefinitely under saturated conditions. However, if the paste is dried or is cured at elevated temperatures (60 °C or greater) the structure collapses toward a denser (less porous) and more stable configuration with fewer large gel pores, resulting in a greater amount of capillary porosity. Nanoindentation measurements of pastes cured at different temperatures demonstrate in all cases the existence of two C-S-H structures with different characteristic values of the indentation modulus. The average value of the modulus of the LD C-S-H is the same for all pastes tested to date, and a micromechanical analysis indicates that this value corresponds to the denser and more stable configuration of LD C-S-H. The experimental results presented here are interpreted in terms of a previously proposed quantitative “colloid” model of C-S-H gel, resulting in an improved understanding of the microstructural changes associated with drying and heat curing.     

A thermodynamic model of dissolution and precipitation of calcium silicate hydrates

A thermodynamic incongruent dissolution/precipitation model of calcium silicate hydrate (C-S-H) is proposed, assuming a binary nonideal solid solution of Ca(OH)₂ and SiO₂. Using this model, both dissolution and precipitation of the C-S-H phase, with a continuous change in the Ca / Si ratio of the solid phase, can be predicted. The notable features of the model are its good continuity and simplicity so that calculation can be easily compiled in a calculation code. A series of experiments were carried out. C-S-H precipitates were prepared using two techniques: precipitation by contacting Ca(OH)₂ solution with C-S-H gel and hydrolysis in a mixture of Ca and Si solutions. The equilibria in these experiments were predicted well by the proposed model. A calculation using the model also predicted well the dissolution of ordinary Portland cement hydrate with water exchange.     

Binding of chloride and alkalis in Portland cement systems

A thermodynamic model for describing the binding of chloride and alkalis in hydrated Portland cement pastes has been developed. The model is based on the phase rule, which for cement pastes in aggressive marine environment predicts multivariant conditions, even at constant temperature and pressure. The effect of the chloride and alkalis has been quantified by experiments on cement pastes prepared from white Portland cements containing 4% and 12% C₃A, and a grey Portland cement containing 7% C₃A. One weight percent calcite was added to all cements. The pastes prepared at w/s ratio of 0.70 were stored in solutions of different Cl (CaCl₂) and Na (NaOH) concentrations. When equilibrium was reached, the mineralogy of the pastes was investigated by EDS analysis on the SEM. A well-defined distribution of chloride was found between the pore solution, the C-S-H phase, and an AFm solid solution phase consisting of Friedel's salt and monocarbonate. Partition coefficients varied as a function of iron and alkali contents. The lower content of alkalis in WPC results in higher chloride contents in the C-S-H phase. High alkali contents result in higher chloride concentrations in the pore solution.     

湿度对水化硅酸钙力学性能影响的分子动力学模拟

水化硅酸钙(C-S-H)是水泥水化产物中最重要的组成成分,是水泥基材料的主要胶凝相。C-S-H层间水对其纳米结构和力学性能会产生显著影响。利用分子动力学研究了不同湿度C-S-H在结构和力学性能方面的差异。通过原子径向分布函数和浓度分布、弹性常数以及应力应变关系分析了湿度对C-S-H结构和弹性性质以及拉伸、压缩、剪切力学性能和变形性能的影响。结果表明:湿度增加会导致C-S-H中Si、Ca原子近程范围内的O原子集聚增多,还会导致C-S-H层间距离增大,分层更加明显,同时会降低C-S-H的弹性性质;湿度的增加会降低C-S-H拉伸、压缩、剪切力学性能和变形性能;湿度对抗拉与抗剪强度影响较大,对抗压强度影响较小,对拉伸时的变形性能影响最大,对压缩时的变形性能影响最小。     

Conditional generative adversarial network driven approach for direct prediction of thermal stress based on two-phase material SEM images

A conditional generative adversarial network (cGAN)-driven approach for the direct prediction of thermal stress is proposed. Synthetic two-phase structure images of ceramic top coat (TC) with CaO–MgO–Al₂O₃–SiO₂ (CMAS) inclusions are established, and the TC matrix and CMAS inclusions are semantically segmented by grayscale. The thermal stresses of the two-phase structure are calculated using image-restoration finite element models (FEMs) under the isothermal process. The training database is established based on a small-scale original dataset of integral structures and their stresses. Each integral TC–CMAS structure and its corresponding stress distribution are partitioned into many local images, using which the cGAN model is trained. The model stresses are generated by the trained cGAN directly from the structure images. The deviations between the predicted stress and the FEM stress are small in most areas of the images. In terms of computing time, the proposed approach has higher stress evaluation efficiency than does the FEM.     

The structure of alkali silicate gel by total scattering methods

The structure of the alkali silicate gel (ASR) collected from the galleries of Furnas Dam in Brazil was determined by a pair distribution function (PDF) analysis of high energy X-ray diffraction data. Since this method is relatively new to concrete structure analysis a detailed introduction on the PDF method is given for glassy SiO₂. The bulk amorphous structure of the dam material is confirmed as no Bragg peaks are observed in the scattered intensity. The real space results show that the local structure of the amorphous material is similar to kanemite (KHSi₂O₅:3H₂O) however the long range layer structure of the crystal is broken up in the amorphous state, so that ordering only persists of the length scale of a few polyhedra. The silicate layer structure is a much more disordered than predicted by molecular dynamics models. The X-ray results are consistent with the molecular dynamics model of Kirkpatrick et al. (2005) [1] which predicts that most of the water resides in pores within the amorphous network rather than in layers. The total scattering data provide a rigorous basis against which other models may also be tested.     

First principles study of the structure and stability of carbynes

Possible structures for carbynes are investigated by a first principles study and their free energy as a function of temperature and pressure is examined. A possible model combining elements from previous models is proposed for carbyne structures. Simulations show that structures can be constructed which agree well with results previously proposed in characterization work. The free energy of carbynes is calculated within wide ranges of temperature and pressure (1000-4000 K and 0-18 GPa) for 12 different structures. Results indicate that it is higher than the free energy of graphite in the whole studied region. Therefore, it seems that carbon-only carbynes are meta-stable structures. Introducing additional elements to stabilize the carbyne structures is discussed. Our calculations confirm that a solid consisting of carbyne chains can be stabilized by 3 CH₃ end groups.     

The calcium silicate hydrates

This article is concerned with the calcium silicate hydrates, including crystalline minerals and the extremely variable and poorly ordered phase (C-S-H) that is the main binding phase in most concrete. Up-to-date composition and crystal-structure information is tabulated for the most important crystalline calcium (alumino) silicate hydrates and related phases. A number of models for the nanostructure of C-S-H are summarized and compared and it is shown that there is much more of a consensus than might seem apparent at first sight. The value of the recently solved structures of 1.4 nm tobermorite and jennite, together with those of jaffeite and metajennite, for visualizing the nanostructural elements present in the models is demonstrated. The importance of Hal Taylor's contribution to the solution of the structure of jennite is highlighted. The applicability of Richardson and Groves' model is demonstrated using experimental composition-structure observations on the nature of C-S-H in a Portland cement-fly ash blend.     

The structure and stoichiometry of C-S-H

This review relates to the models describing the structural evolution of calcium silicate hydrate (C-S-H) at the crystal-chemical level as a function of composition in terms of calcium to silicon ratio. The different models are compared and discussed in the light of recent spectroscopic and microscopic data. Taking into account the structure and the morphological properties of C-S-H, a surface reaction thermodynamic model has been proposed and discussed to predict and correlate the chemical and structural evolution of C-S-H with solution chemistry.     

Hydrodynamics in a jet bubbling reactor: Experimental research and mathematical modeling

The radial distribution of liquid velocity in the axial direction of a jet bubbling reactor has been measured by experimentation. Three different typical flow structures controlled by liquid jet, gas bubbling, and liquid jet coupled with bubbling are observed. A tank in series model is established on this basis. Calculated values in each region are in good agreement with measured values in jet, bubbling, and wall effect controlled areas. Axial flow rate, radial exchange rate, and jet controlled volume η are analyzed from energy input aspect under different u_g and u_j. Simulation results indicate that under the synergetic action of the liquid jet and gas bubbling effect, jet controlled area exhibits a “spindle” structure, and its size decreases with the increase of u_g. When gas input power occupies about 67% of total energy consumption, the best synergy of liquid jet and gas bubbling is obtained. © 2017 American Institute of Chemical Engineers AIChE J, 64: 1814–1827, 2018     

Influence of activator type on hydration kinetics, hydrate assemblage and microstructural development of alkali activated blast-furnace slags

The hydration of two slags with different Al₂O₃ contents activated with sodium hydroxide and hydrous sodium metasilicate (commonly named water glass) is studied using a multi-method approach. In all systems, C-S-H incorporating aluminium and a hydrotalcite-like phase with Mg/Al ratio ~ 2 are the main hydration products. The C-S-H gels present in NaOH activated pastes are more crystalline and contain less water; a calcium silicate hydrate (C-S-H) and a sodium rich C-N-S-H with a similar Ca content are observed at longer hydration times. The activation using NaOH results in high early strength, but strength at 7 days and longer is lower than for the sodium metasilicate systems. The drastic difference in C-S-H structure leads to a coarser capillary porosity and to lower compressive strength for the NaOH activated than for the sodium metasilicate activated slags at the same degree of slag reaction.     

Composition, morphology and nanostructure of C-S-H in white Portland cement pastes hydrated at 55 °C

The C-S-H present in water- and alkali-activated hardened pastes of white Portland cement hydrated at 55 °C has been characterized. The mean length of the aluminosilicate anions in the C-S-H was similar in both systems and increased with age. Inner product C-S-H generally had a fine scale, homogeneous morphology. Outer product C-S-H was generally fibrillar with water, and foil- or lath-like with alkali. There were some regions of C-S-H with coarse morphology. It was not possible to determine the chemical composition of C-S-H using the SEM; TEM-EDX was necessary. The C-S-H formed in the alkali-activated paste had a lower mean Ca/(Al + Si) ratio than that formed with water, which was offset by a larger quantity of calcium hydroxide. The potassium in the KOH-activated paste was present either within the C-S-H structure charge balancing the substitution of Al³⁺ for Si⁴⁺, or adsorbed on the C-S-H charge balancing sulfate ions.     

Alkali binding in hydrated Portland cement paste

The alkali-binding capacity of C-S-H in hydrated Portland cement pastes is addressed in this study. The amount of bound alkalis in C-S-H is computed based on the alkali partition theories firstly proposed by Taylor (1987) and later further developed by Brouwers and Van Eijk (2003). Experimental data reported in literatures concerning thirteen different recipes are analyzed and used as references. A three-dimensional computer-based cement hydration model (CEMHYD3D) is used to simulate the hydration of Portland cement pastes. These model predictions are used as inputs for deriving the alkali-binding capacity of the hydration product C-S-H in hydrated Portland cement pastes. It is found that the relation of Na⁺ between the moles bound in C-S-H and its concentration in the pore solution is linear, while the binding of K⁺ in C-S-H complies with the Freundlich isotherm. New models are proposed for determining the alkali-binding capacities of C-S-H in hydrated Portland cement paste. An updated method for predicting the alkali concentrations in the pore solution of hydrated Portland cement pastes is developed. It is also used to investigate the effects of various factors (such as the water to cement ratio, clinker composition and alkali types) on the alkali concentrations.     

Surface jumping in a harmonic model of trans-octatetraene: Franck—condon factors and accepting vibrational modes in s1→S0 non-vertical radiationless transition

A phase-space method for finding the accepting modes in a non-vertical radiationless vibronic transition and for recognizing the final state with the largest Franck—Condon factor is applied to a harmonic model of the S₁ → S₀ relaxation in trans-octatetraene. Input required for the analysis includes the energy gap between S₁ and S₀, normal mode frequencies, reduced masses, and eigenvectors (including the Duschinsky rotation matrix), and the molecule equilibrium configurations (bond lengths and angles) in S₁ and S₀. Some of these data are taken from published experimental results and some are calculated in this work. The energy gap of 0.132 au is much larger than the energy of a vertical transition, which is only 0.047 au. The phase-space method gives a closed-form analytic solution for how to divide the excess energy between the accepting modes. The final distribution includes a large excitation of the two CH₂ end groups, where the motion of the two hydrogen atoms within each quasilocal CH₂ group is antisymmetric; a symmetric stretch of the two central C-H bonds of the molecule; and small totally symmetric bending of the whole molecule. Comparison of Franck-Condon factors (exact within the harmonic model) of the final state obtained by the phase-space analysis and of other similar isoenergetic states shows that the phase-space method indeed chooses the most probable final energy distribution. Possible modifications of these results due to anharmonic effects are discussed.     

Formation of ASR gel and the roles of C-S-H and portlandite

Experimental investigations of the reactions between silica, alkali hydroxide solution, and calcium hydroxide show that alkali-silicate-hydrate gel (A-S-H) comparable to that formed by the alkali-silica reaction (ASR) in concrete does not form when portlandite or the Ca-rich, Si-poor C-S-H of ordinary portland cement (OPC) paste is available to react with the silica. Under these conditions, we observe either the formation of additional C-S-H by reaction of Ca(OH)₂ with the dissolving silica or the progressive polymerization of C-S-H. The A-S-H dominated by Q³ polymerization forms only after portlandite has been consumed and the C-S-H polymerized. These conclusions are consistent with previously published results and indicate that the ASR gel of concrete forms only in chemical environments in which the pore solution is much lower in Ca and higher in Si than bulk pore solution of OPC paste. These results highlight the similarity between ASR and the pozzolanic reaction and are supported by data for mortar bar specimens.