共查询到20条相似文献,搜索用时 15 毫秒
1.
In the context of waste confinement and, more specifically, waste from the nuclear industry, concrete is used both as a confinement and as a building material. Its exposure to high temperatures makes its geochemical behavior difficult to predict over large periods of time. The present work aims to elucidate the solubility constants, as a function of temperature, for the phases of the system CaO-SiO2-H2O. For the nanocrystalline phases, the present work investigates the existence of compounds of fixed composition, possibly in a metastable state. The question of whether the nanocrystalline C-S-H phases correspond to a series of phases of discrete composition or a solid solution is discussed and compared to the possible influence of impurities in the solid phases.For the crystalline phases, having established that the currently available values of thermodynamic properties were not consistent, we show that their refinement leads to a better agreement with the literature data. From the refined thermodynamic properties of crystalline C-S-H, a polyhedral decomposition model is developed. It enables to estimate the enthalpy of formation and the heat capacity of nanocrystalline C-S-H phases. Finally, verification shows that such phases remain unstable compared to the crystalline phases, at room or higher temperatures. A comparison, based on reaction enthalpies derived from experimental data indicates that predicted values for nanocrystalline C-S-H are in close agreement with experimental data. By estimating the properties of okenite and truscottite with the model developed in this study, we have been able to complete the CaO-SiO2-H2O phase diagram with a reasonable agreement with the literature. The case of jaffeite remains open to discussion. Finally, for the hydrate C2SH,α, the model predicts a transition with hillebrandite at 159 °C, in contradiction with the hypothesis of C2SH,α metastability. 相似文献
2.
Scanning electron microscopy (SEM) microanalyses of the calcium-silicate-hydrate (C-S-H) gel in Portland cement pastes rarely represent single phases. Essential experimental requirements are summarised and new procedures for interpreting the data are described. These include, notably, plots of Si/Ca against other atom ratios, 3D plots to allow three such ratios to be correlated and solution of linear simultaneous equations to test and quantify hypotheses regarding the phases contributing to individual microanalyses. Application of these methods to the C-S-H gel of a 1-day-old mortar identified a phase with Al/Ca=0.67 and S/Ca=0.33, which we consider to be a highly substituted ettringite of probable composition C6A2S?2H34 or {Ca6[Al(OH)6]2·24H2O}(SO4)2[Al(OH)4]2. If this is true for Portland cements in general, it might explain observed discrepancies between observed and calculated aluminate concentrations in the pore solution. The C-S-H gel of a similar mortar aged 600 days contained unsubstituted ettringite and an AFm phase with S/Ca=0.125. 相似文献
3.
Backscattered electron (BSE) images of heat-cured concretes show alite grains surrounded by inner C-S-H gel of two distinct grey levels (referred to as two-tone inner C-S-H gel). The lighter rim forms at elevated temperature whereas the darker rim develops during subsequent exposure to moisture at 20 °C. This microstructural feature can potentially be used as an indicator to assess the curing history of a concrete. However, microstructural examinations of room-temperature concretes containing silica fume or which have been exposed to severe conditions (external sulfate, carbonation) also show distinct rims of two-tone inner C-S-H gel.The chemical compositions of the rims were determined by EDX microanalysis in the scanning electron microscope (SEM). Our results show that for heat-cured samples, the different grey levels of the two-tone inner C-S-H are caused by relative differences in microporosity and water content and not by ones in chemical composition. However, in silica-fume blended concrete, sulfate attacked or carbonated specimens the different grey levels of the two-tone inner C-S-H gel were associated with significant differences in chemical composition. This difference allows two-tone inner C-S-H gel arising from heat curing to be distinguished from that arising from these other causes. 相似文献
4.
Traditional pozzolanic mortars such as those from Rhodes, Greece, or Hagia Sophia, Turkey, revealed the presence of a calcium-silicate-hydrate (C-S-H) binding phase. This phase, which is similar to that found in ordinary Portland cement (OPC), is produced under the pozzolanic reaction of slaked lime with fine reactive siliceous sources at temperatures <100 °C. The traditional siliceous sources were replaced by fumed silica or tetraethyl orthosilicate (TEOS). A microstructural analysis revealed an enhanced reaction rate but similar morphologies of the resultant C-S-H phases, confirming that the reaction-limiting factor is the dissolution of the siliceous sources. 相似文献
5.
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. 相似文献
6.
Hamlin M. Jennings Jeffrey J. Thomas Georgios Constantinides 《Cement and Concrete Research》2007,37(3):329-336
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. 相似文献
7.
A multiscale micromechanics-hydration model for the early-age elastic properties of cement-based materials 总被引:3,自引:0,他引:3
The E-modulus of early age cement-based materials, and more importantly, its evolution in time, is one of the most critical material-to-structural design parameters affecting the likelihood of early-age concrete cracking. This paper addresses the problem by means of a multistep micromechanics approach that starts at the nanolevel of the C-S-H matrix, where two types of C-S-H develop in the course of hydration. For the purpose of homogenization, the volume fractions of the different phases are required, which are determined by means of an advanced kinetics model of the four main hydration reactions of ordinary portland cement (OPC). The proposed model predicts with high accuracy the aging elasticity of cement-based materials, with a minimum intrinsic material properties (same for all cement-based materials), and 11 mix-design specific model parameters that can be easily obtained from the cement and concrete suppliers. By way of application, it is shown that the model provides a quantitative means to determine (1) the solid percolation threshold from micromechanics theory, (2) the effect of inclusions on the elastic stiffening curve, and (3) the development of the Poisson's ratio at early ages. The model also suggests the existence of a critical water-to-cement ratio below which the solid phase percolates at the onset of hydration. The development of Poisson's ratio at early ages is found to be characterized by a water-dominated material response as long as the water phase is continuous, and then by a solid-dominated material response beyond the solid percolation threshold. These model-based results are consistent with experimental values for cement paste, mortar, and concrete found in the open literature. 相似文献
8.
The role of Al in C-S-H: NMR, XRD, and compositional results for precipitated samples 总被引:2,自引:0,他引:2
X-ray diffraction, compositional analysis, and 29Si and 27Al MAS NMR spectroscopy of Al-substituted tobermorite-type C-S-H made by precipitation from solution provide significant new insight into the structural mechanisms of Al-substitution in this important and complicated phase. Al occurs in 4-, 5-, and 6-coordination (Al[4], Al[5], and Al[6]) and plays multiple structural roles. Al[4] occurs on the bridging tetrahedra of the drierkette Al-silicate chains, and Al[5] and Al[6] occur in the interlayer and perhaps on particle surfaces. Al does not enter either the central Ca-O sheet or the pairing tetrahedra of the tobermorite-type layers. Al[4] occurs on three types of bridging sites, Q3 sites that bridge across the interlayer; Q2 sites that are charge balanced by interlayer Ca+2, Na+, or H+; and Q2 sites that are most likely charge balanced by interlayer or surface Al[5] and Al[6] through Al[4]-O-Al[5,6] linkages. Although the data presented here are for relatively well-crystallized tobermorite-type C-S-H with C/S ratios ≤ 1.2, comparable spectral features for hydrated white cement pastes in previously published papers[30], [31] and [32] [M.D. Andersen, H.J. Jakobsen, J. Skibsted, Incorporation of aluminum in the calcium silicate hydrate (C-S-H) of hydrated Portland cements: a high-field 27Al and 29Si MAS NMR investigation Inorg. Chem. 42 (2003) 2280-2287; M.D. Andersen, H.J. Jakobsen, J. Skibsted, Characterization of white Portland cement hydration and the C-S-H structure in the presence of sodium aliminate by 27Al and 29Si MAS NMR spectroscopy, Cem. Concr. Res. 43 (2004) 857-868; M.D. Andersen, H. J. Jakobsen, J. Skibsted, A new aluminum-hydrate phase in hydrated Portland cements characterized by 27Al and 29Si MAS NMR spectroscopy, Cem. Concr. Res., submitted for publication.] indicate the presence of similar structural environments in the C-S-H of such pastes, and by implication OPC pastes. 相似文献
9.
Refinements to colloid model of C-S-H in cement: CM-II 总被引:5,自引:0,他引:5
Hamlin M. Jennings 《Cement and Concrete Research》2008,38(3):275-289
10.
Influence of inclusion shapes on the effective linear elastic properties of hardened cement pastes 总被引:1,自引:0,他引:1
In most micromechanical models applied to cement pastes, particulate phases are modeled as spheres. However, experimental observations clearly show that certain of them are far from being spherical. The present work focuses on the effects of particle phase shapes on the effective isotropic linear elastic moduli of hardened cement pastes (HCP). An attempt to develop a more realistic micromechanical model is proposed by using spheroidal inclusions and including a novel morphological parameter. The latter is identified on the basis of experimental result issue for example from microtomographic images of Portland cement grains. With the help of the proposed model, the validity range of spherical particulate approximations is examined for both sound and leached pastes. 相似文献
11.
Carbonation of CH and C-S-H in composite cement pastes containing high amounts of BFS 总被引:2,自引:0,他引:2
Paulo H.R. Borges Juliana O. Costa Cyril J. Lynsdale 《Cement and Concrete Research》2010,40(2):284-292
3:1 BFS:OPC, 9:1 BFS:OPC and 9:1 alkali activated BFS:OPC pastes cured at 20 °C and 60 °C for 90 days were submitted to accelerated carbonation under 5% CO2, 60% relative humidity and 25 ± 5 °C for 21 days. TGA/DTG was used to quantify the amounts of carbonates formed from calcium hydroxide (CH) and calcium silicate hydrate (C-S-H), based on the CH and carbonate contents before and after carbonation. Apparent dry density, apparent porosity and gas permeability were measured before and after accelerated carbonation testing, and the phenolphthalein method used to determine the accelerated carbonation rate. The results showed that samples cured at elevated temperature, i.e. 60 °C, were initially less porous and, therefore, had decreased levels of both total carbonation and C-S-H carbonation. In addition, the carbonation of C-S-H was significantly higher in pastes that contained less CH before carbonation. In the activated 9:1 BFS:OPC, the carbonation of C-S-H was extensive, despite a lower carbonation rate than the analogous non-activated system. In the particular case of activated 9:1 BFS:OPC, a shift in the DTG decarbonation pattern was observed and XRD showed that aragonite was present as one of the calcium carbonate polymorphs. 相似文献
12.
Modelling and simulations of the chemo-mechanical behaviour of leached cement-based materials: Interactions between damage and leaching 总被引:1,自引:0,他引:1
The assessment of the durability of cement-based materials, which could be employed in underground structures for nuclear waste disposal, requires accounting for deterioration factors, such as chemical attacks and damage, and for the interactions between these phenomena. The objective of the present paper consists in investigating the long-term behaviour of cementitious materials by simulating their response to chemical and mechanical solicitations. In a companion paper (Stora et al., submitted to Cem. Concr. Res. 2008), the implementation of a multi-scale homogenization model into an integration platform has allowed for evaluating the evolution of the mineral composition, diffusive and elastic properties inside a concrete material subjected to leaching. To complete this previous work, an orthotropic micromechanical damage model is presently developed and incorporated in this numerical platform to estimate the mechanical and diffusive properties of damaged cement-based materials. Simulations of the chemo-mechanical behaviour of leached cementitious materials are performed with the tool thus obtained and compared with available experiments. The numerical results are insightful about the interactions between damage and chemical deteriorations. 相似文献
13.
In this study, high-calcium fly ash (HCFA) and silica fume (SF) were used as mineral admixtures. The effect of these admixtures on the microstructure of cement paste was investigated using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The reaction of HCFA and SF with portlandite, which occurs in Portland cement (PC), forms a new calcium-silicate-hydrate (C-S-H) gel. 相似文献
14.
I.G. Richardson 《Cement and Concrete Research》2004,34(9):1733-1777
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. 相似文献
15.
The role of small-angle X-ray and neutron scattering (SAXS and SANS) in the characterization of cement is briefly reviewed. The unique information obtainable from SANS analysis of C-S-H gel in hydrating cement is compared with that obtainable by other neutron methods. Implications for the nature of C-S-H gel, as detected by SANS, are considered in relation to current models. Finally, the application of the SANS method to cement paste is demonstrated by analyzing the effects of calcium chloride acceleration and sucrose retardation on the resulting hydrated microstructure. 相似文献
16.
The structure and stoichiometry of C-S-H 总被引:1,自引:0,他引:1
André Nonat 《Cement and Concrete Research》2004,34(9):1521-1528
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. 相似文献
17.
Siavash Ghabezloo 《Cement and Concrete Research》2011,(8):920-922
The effect of the variations of clinker composition on the poroelastic properties of class G oil-well cement pastes is studied using a multiscale homogenization model. The model has been calibrated in a previous work based on the results of a laboratory study. Various compositions of class G cements from literature are used in a hydration model to evaluate the volume fractions of the microstructure constituents of hardened cement paste. The poroelastic parameters such as drained bulk modulus, Biot coefficient, and Skempton coefficient are evaluated using the homogenization model. The results show that the variations in chemical composition of class G cements have no important effect on the variations of the poroelastic properties. 相似文献
18.
Upscaling quasi-brittle strength of cement paste and mortar: A multi-scale engineering mechanics model 总被引:1,自引:0,他引:1
It is well known from experiments that the uniaxial compressive strength of cementitious materials depends linearly on the degree of hydration, once a critical hydration degree has been surpassed. It is less known about the microstructural material characteristics which drive this dependence, nor about the nature of the hydration degree–strength relationship before the aforementioned critical hydration degree is reached. In order to elucidate the latter issues, we here present a micromechanical explanation for the hydration degree–strength relationships of cement pastes and mortars covering a large range of compositions: Therefore, we envision, at a scale of fifteen to twenty microns, a hydrate foam (comprising spherical water and air phases, as well as needle-shaped hydrate phases oriented isotropically in all space directions), which, at a higher scale of several hundred microns, acts as a contiguous matrix in which cement grains are embedded as spherical clinker inclusions. Mortar is represented as a contiguous cement paste matrix with spherical sand grain inclusions. Failure of the most unfavorably stressed hydrate phase is associated with overall (quasi-brittle) failure of cement paste or mortar. After careful experimental validation, our modeling approach strongly suggests that it is the mixture- and hydration degree-dependent load transfer of overall, material sample-related, uniaxial compressive stress states down to deviatoric stress peaks within the hydrate phases triggering local failure, which determines the first nonlinear, and then linear dependence of quasi-brittle strength of cementitious materials on the degree of hydration. 相似文献
19.
The effects of adding sugar to cement paste on hydration and microstructure were observed. While 1% sugar delayed hydration as expected, the delay period was shortened by increased curing temperature. When samples containing sugar began to react, hydration progressed very quickly and the degree of hydration soon surpassed that of control samples. Sugar addition increased the surface area and altered the pore size distribution, as measured by nitrogen, of cement pastes. Results indicate that sugar not only alters the rate of cement paste hydration, but the microstructure of calcium-silicate-hydrate (C-S-H) as well. 相似文献
20.
Critical aspects of nano-indentation technique in application to hardened cement paste 总被引:2,自引:0,他引:2
Several open questions related to the experimental protocol and processing of data acquired by the nano-indentation (NI) technique are investigated. The volume fractions of mechanically different phases obtained from statistical NI (SNI) analysis are shown to be different from those obtained by back-scattered electron (BSE) image analysis and X-ray diffraction (XRD) method on the same paste. Judging from transmission electron microscope (TEM) images, the representative volume element of low-density calcium-silicate hydrates (C–S–H) can be considered to be around 500 nm, whereas for high-density C–S–H it is about 100 nm. This raises the question how the appropriate penetration depth for NI experiments should be selected. Changing the maximum load from 1 mN to 5 mN, the effect of penetration depth on the experimental results is studied. As an alternative to the SNI method, a “manual” indentation method is proposed, which combines information from BSE and atomic-force microscopy (AFM), coupled to the NI machine. The AFM allows to precisely indent a high-density C–S–H rim around unhydrated clinkers in cement paste. Yet the results from that technique still show a big scatter. 相似文献