Effects of decalcification on the microstructure and surface area of cement and tricalcium silicate pastes

Thin coupons of white portland cement (WPC) and tricalcium silicate paste were decalcified by leaching in concentrated ammonium nitrate solutions, resulting in calcium-to-silicon molar ratios (C/S) ranging from 3.0 (control) down to 0.3. The microstructure and surface area were measured using both small-angle neutron scattering (SANS) and nitrogen gas sorption. The intensity in the SANS data regime corresponding to the volume fractal C-S-H gel phase increased significantly on leaching, and the total surface area per unit specimen volume measured by SANS doubled on leaching from C/S=3.0 to near C/S=1.0. The nitrogen BET surface area of the WPC pastes, expressed in the same units, increased on decalcification as well, although not as sharply. The primary cause of these changes is a transformation of the high-density “inner product” C-S-H gel, which normally has a low specific surface area as measured by SANS and nitrogen gas sorption, into a morphology with a high specific surface area. The volume fractal exponent corresponding to the C-S-H gel phase decreased with decalcification from 2.3 to 2.0, indicating that the equiaxed 5 nm C-S-H globule building blocks that form the volume fractal microstructure of normal, unleached cement paste are transformed by decalcification into sheetlike structures of increasing thickness.     

Analytical Electron Microscopy of Cement Pastes: III, Pastes Hydrated for Long Times

Analyses of 131 particles of C-S-H in several mature tricalcium silicate pastes hydrated for 1 to 30 years gave a mean Ca/Si ratio of 1.46 with a range of 1.2 to 1.8. Similar analyses of 152 particles in mature cement pastes hydrated for 2 to 3 years gave a mean Ca/ Si ratio of 1.53 with a range of 1.0 to 2.8. Taken together with similar, previously published data for younger pastes, these findings indicate that the mean Ca/Si ratio does not change significantly after 1 day in tricalcium silicate pastes but decreases significantly with time in cement pastes; after several years, the mean Ca/Si ratios are similar in the two cases, despite the presence of other components in the C-S-H formed from cement. For the C-S-H of cement pastes, the mean Al/(Ca plus; Mg) and Fe/(Caplus;Mg) ratios increase with time but the mean S/(Caplus;Mg) ratio decreases. The composition of the AFm phase does not change greatly after 28 days.     

Progressive Changes in the Structure of Hardened C3S Cement Pastes due to Carbonation

The structures of partially carbonated hardened C₃S cement pastes have been investigated by a combination of ²⁹Si magic angle spinning nuclear magnetic resonance spectroscopy and analytical transmission electron microscopy, supported by X-ray diffraction and thermogravimetric analysis. Progressive changes in structure are reported for thin slices for a paste carbonated in pure CO₂ for times from 1 to 16 h, and the results are compared with those for a paste carbonated for 2 months in air. C-S-H gel of reduced Ca:Si ratio and increased silicate polymerization was formed during the early stages of carbonation. The morphology of the original C-S-H was, in the main, retained. A cross-linked silica-rich gel formed at later times in paste carbonated in CO₂ but not up to the time of 2 months in air. Calcium carbonate took the form of microcrystals of vaterite and calcite which formed dense masses between gel fibrils and around partially reacted CH crystals, possibly accounting for the observed slowing in the rate of reaction of CH with time.     

Microstructural and microanalytical studies of sulfate attack. I. Ordinary portland cement paste

Portland cement pastes that had been stored for 6 months in solutions of sodium or magnesium sulfate were examined by scanning electron microscopy using backscattered electron imaging and X-ray microanalysis. For a paste stored in Na₂SO₄ solution, successive changes were observed on passing from the unaltered material in the interior towards the surface. These were (1), replacement of monosulfate by ettringite, which was closely mixed with the C-S-H gel, (2), disappearance of calcium hydroxide, partial decalcification of C-S-H and precipitation of gypsum and (3), further decalcification and leaching. Much of the gypsum occurred in veins sub-parallel to the surface, with which were associated cracks. A paste stored in MgSO₄ solution showed broadly similar effects, as well as a largely continuous surface layer of gypsum and brucite, except at the cube edges, where a gel high in magnesia and silica was formed. This was probably cryptocrystalline serpentine. Neither specimen contained massive deposits of ettringite.     

硅酸盐水泥混凝土的碳化分析

介绍了硅酸盐水泥混凝土的碳化反应和碳化过程,分析了Ca(OH)_2与水化硅酸钙(C-S-H)的碳化作用.Ca(OH)_2发生碳化反应的同时,C-S-H也会发生碳化反应;Ca(OH)_2的碳化产物是方解石,而C-S-H碳化后会转变成无定形硅胶,可能形成稳定性差、结晶度差的球霰石、文石,其分解温度低于方解石的分解温度;C/S低、结晶度差的C-S-H凝胶易于碳化;水泥浆体孔隙溶液中的碱含量越高,碳化速度越快,深度越大.     

How carbonation curing influences ca leaching of Portland cement paste: Mechanism and mathematical modeling

Carbonation curing provides a promising method for both CO₂ sequestration and strength improvement of cement-based materials. To date, there is little knowledge about the influence of carbonation curing on Ca leaching resistance of cement-based materials due to the occurrence of both physical and chemical transformation. It was the first time that Ca solid-liquid equilibrium curves were experimentally established for cement pastes with different carbonation degrees in this paper. Experimental results demonstrated that on the one hand, carbonation curing improves the leaching resistance of cement paste by sequestrating Ca in insoluble CaCO₃; on the other hand, potential negative effects may occur due to the accelerated decalcification and increased solubility of C–S–H after carbonation curing. Results of NMR showed that both carbonation curing and Ca leaching can increase the Si chain length and polymerization degree of C–S–H. Additionally, a modified mathematical model was established to simulate the leaching process of carbonation-cured cement paste and it was also verified by energy-dispersive spectroscopy (EDS) results. Therefore, the long-term leaching resistance of cement-based materials is possibly degraded by the carbonation curing treatment.     

Impact of accelerated carbonation on OPC cement paste blended with fly ash

Cement is a huge carbon dioxide producer. Supplementary cementitious materials can help reduce this outcome. However, carbonation of these blended cements remains an active subject of research. Accelerated carbonation tests (10% CO₂, 25 °C and 62% RH) are performed on fly ash blended cement pastes. Experiments are performed at varying ages of carbonation (1 to 16 weeks) to measure the evolution of the carbonation depth over time and to quantify key parameters: thermogravimetric analysis (TGA), mercury intrusion porosimetry (MIP) and gamma ray attenuation method (GRAM). The total porosity decreases with a rearrangement of the microstructure due to carbonation and the creation of big capillary pores for the paste with the highest contents of fly ash (60 vol.%). The C-S-H molar volume evolution during fly ash-blended cement carbonation is calculated using a method combining MIP, TGA and GRAM formerly successfully applied to OPC paste in a paper published in the same journal.     

Analytical Electron Microscopy of Cement Pastes: II, Pastes of Portland Cements and Clinkers

Three hundred sixty-five particles of C-S-H, Ca(OH)₂, AFm phase, and AFt phase from pastes of normally ground portland cements and of finely ground cements and clinkers were analyzed. All the phases, except the Ca(OH)₂, showed significant variation in composition among paste specimens and among particles within each specimen. The C-S-H contains significant amounts of Al, Fe, and S; for that of a normally ground portland cement paste, cured for 28 days, the median Si:AI, Si:Fe, and Si:S ratios were 11, 43, and 15, respectively, whereas the mean Ca:Si ratio for all the particles analyzed was 2.0. The AFm phase in cement pastes is not pure monosulfate but has a mixture of sulfate, hydroxide, and Al- and Si-bearing ions in its interlayer sites; the AFt phase is not pure ettringite but contains Si and its sulfate is probably partly replaced by hydroxide. The Al and Fe contents in the C-S-H and the Si contents in the AFm and AFt phases are greater when finely ground starting materials are used. This fact, together with the marked variation among particles, emphasizes the difficulty of ionic transport in cement pastes.     

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.     

Identification of viscoelastic C-S-H behavior in mature cement paste by FFT-based homogenization method

A powerful and robust numerical homogenization method based on fast Fourier transform (FFT) is formulated to identify the viscoelastic behavior of calcium silicate hydrates (C-S-H) in hardened cement paste from its heterogeneous composition. The identification is contingent upon the linearity of the creep law. To characterize cement paste microstructure, the model developed by Bentz at the National Institute of Standards and Technology, which has the resolution of 1 μm, is adopted. Model B3 for concrete creep is adapted to characterize the creep of C-S-H in cement paste. It is found that the adaptation requires increasing the exponent of power law asymptote of creep compliance. This modification means that the rate of attenuation of creep with time is lower in C-S-H than in cement paste, and is explained by differences in stress redistribution. In cement paste, the stress is gradually transferred from the creeping C-S-H to the non-creeping components. The viscoelastic properties of C-S-H at the resolution of 1 μm were identified from creep experiments on cement pastes 2 and 30 years old, having the water-cement ratio of 0.5. The irreversible part of C-S-H creep, obtained from these old specimens at almost saturated state, is found to be negligible unless the specimens undergo drying and resaturation prior to the creep test.     

Solubility behavior of Ca-, S-, Al-, and Si-bearing solid phases in Portland cement pore solutions as a function of hydration time

The concentrations of Ca, S, Al, Si, Na, and K in the pore solutions of ordinary Portland cement (OPC) and white Portland cement (WPC) pastes were measured during the first 28 days of hydration at room temperature. Saturation indices (SI) with respect to various solid phases known to occur in cement pastes were calculated from a thermodynamic analysis of the elemental concentrations, resulting in good agreement between the two pastes. In agreement with other published work, gypsum was saturated during the first several hours of hydration and then undersaturated thereafter, while portlandite was modestly supersaturated after the first few hours. High levels of supersaturation with respect to ettringite and calcium monosulfoaluminate were calculated, particularly prior to the consumption of gypsum at around 10 h. Results are consistent with published thermodynamic studies that show calcium monosulfoaluminate is metastable with respect to ettringite under normal hydration conditions. Three different ion activity product (IAP) equations for C-S-H were applied to the data. From 10 h onward, each of the IAP values declined gradually over time and the values for the OPC and WPC pastes were in close agreement. The same IAP equations were applied to experimental data from the pure CaO-SiO₂-H₂O system, resulting in good agreement between the cement paste pore solutions and the equilibrium between portlandite and the upper, or metastable, C-S-H solubility curve.     

The effect of two types of C-S-H on the elasticity of cement-based materials: Results from nanoindentation and micromechanical modeling

It has long been recognized, in cement chemistry, that two types of calcium-silicate-hydrate (C-S-H) exist in cement-based materials, but less is known about how the two types of C-S-H affect the mechanical properties. By means of nanoindentation tests on nondegraded and calcium leached cement paste, the paper confirms the existence of two types of C-S-H, and investigates the distinct role played by the two phases on the elastic properties of cement-based materials. It is found that (1) high-density C-S-H are mechanically less affected by calcium leaching than low density C-S-H, and (2) the volume fractions occupied by the two phases in the C-S-H matrix are not affected by calcium leaching. The nanoindentation results also provide quantitative evidence, suggesting that the elastic properties of the C-S-H phase are intrinsic material properties that do not depend on mix proportions of cement-based materials. The material properties and volume fractions are used in a novel two-step homogenization model, that predicts the macroscopic elastic properties of cement pastes with high accuracy. Combined with advanced physical chemistry models that allow, for a given w/c ratio, determination of the volume fractions of the two types of C-S-H, the model can be applied to any cement paste, with or without Portlandite, Clinker, and so on. In particular, from an application of the model to decalcified cement pastes, it is shown that that the decalcification of the C-S-H phase is the primary source of the macroscopic elastic modulus degradation, that dominates over the effect of the dissolution of Portlandite in cement-based material systems.     

Variation in the Composition of C-S-H Gel in Portland Cement Pastes Cured at Various Temperatures

Variation in the composition of C-S-H gel, the main hydration product of portland cement, cured at various temperatures, was studied using scanning electron microscopy with energy dispersive X-ray spectroscopy. Samples of two cement pastes were cured isothermally under water at 10°, 30°, and 60°C for one year. For the inner-product C-S-H gel of both cement pastes, increased curing temperature decreased the Ca/Si and Al/Ca ratios, but increased the S/Ca ratio. The Al/S and (Al + Fe)/S ratios decreased with increased curing temperature. Sulfur, probably in the form of sulfate ions, could be sorbed by the C-S-H gel at higher temperatures.     

Surface carbonation of synthetic C-S-H samples: A comparison between fresh and aged C-S-H using X-ray photoelectron spectroscopy

This paper presents a continuation of studies into silicate anion structure using X-ray photoelectron spectroscopy (XPS). A series of C-S-H samples have been prepared mechanochemically, and then stored under ambient conditions for six months. Storage led to surface carbonation, the extent of which was dependent upon the calcium/silicon ratio of the fresh sample. Carbonation arose through decalcification of the C-S-H, leading to increased silicate polymerisation. The surfaces of the most calcium-rich phases (C/S = 1.33 and 1.50) underwent complete decalcification to yield silica (possibly containing some silanol groups) and calcium carbonate. Carbonation, and hence changes in silicate anion structure, was minimal for the C-S-H phases with C/S = 0.67 and 0.75.     

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.     

Nanostructure of Calcium Silicate Hydrate Gels in Cement Paste

High-resolution electron microscopy study of calcium silicate hydrate (C-S-H) gels in ordinary portland cement (OPC) and a slag/OPC blend has been performed. Nanocrystalline regions on the scale of ∼5 nm or less in C-S-H are found in both cement pastes, and they are formed after a curing time as brief as 7 d. A change in the d -spacing of the nanocrystalline regions with time is observed for the first time, which is believed to correspond to the development of C-S-H with time. The nanoheterogeneous nature of C-S-H is demonstrated and correlated to the strong Ca:Si ratio fluctuations that are observed.     

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.     

Composition and microstructure of 20-year-old ordinary Portland cement-ground granulated blast-furnace slag blends containing 0 to 100% slag

The morphology of outer-product (Op) C-S-H in 20-year-old slag-cement pastes appeared in most blends to be finer than at younger ages. The Ca/Si and Ca/(Si + Al) ratios of the Op C-S-H decreased with increasing slag content, and the Al/Si ratio increased. The Ca/Si ratio of C-S-H in the slag-containing pastes was lower at 20 years than at 14 months and the amount of Ca(OH)₂ was reduced indicating that additional slag must have reacted. The mean aluminosilicate chain length of the C-S-H was very long in all the samples and would be expected to have increased with age. The TEM-EDX and NMR data are consistent with nanostructural models for C-S-H. The Mg/Al ratio of the Mg-Al layered double hydroxide phase (LDH) was lower at 20 years than at 14 months in all cases except for the neat slag paste; aluminium hydroxide-based structure might be interstratified with those of the Mg-Al LDH.     

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.     

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。