The effects of carbonation of mechanochemically prepared C-S-H samples under ambient conditions for upto 6 months have been investigated by Raman spectroscopy and X-ray diffraction. The type and extent of carbonation are strongly dependent on the initial CaO/SiO 2 (C/S) ratio of the samples. Amorphous calcium carbonate hydrate is formed within minutes upon exposure to air. It crystallizes, over time, to give primarily vaterite at C/S ! 0.67 and aragonite at C/Sr0.50. Calcite was not observed as a primary carbonation product within the time frame investigated. Decalcification upon storage also initiates silicate polymerization. The dimeric silicate units seen in the calcium-rich phases polymerize rapidly to yield Q 2 silicate moieties. After 6 months, broad bands are seen in most spectra, ascribed to poorly ordered silica. C-S-H phases with C/S ratios of 0.75 and 0.67 are the most resistant to carbonation, and even after 6 months of storage, Q 2 silicate units still dominate their structures. The ability of Raman spectroscopy to probe the short-range order of poorly crystalline materials is ideal for investigations of C-S-H structure. Additionally, the technique's sensitivity toward the various calcium carbonate polymorphs illuminates the sequence of carbonation and decalcification processes during aging of C-S-H. Of particular importance is the identification of amorphous calcium carbonate as the first carbonation product. Additionally, the formation of aragonite as a carbonation product is related to the presence of SiO 2 gel in the aged samples.G. Scherer-contributing editor
The Raman spectra of a series of mechanochemically prepared calcium silicate hydrate samples of type C-S-H(I) with C/S ratios ranging from 0.2 to 1.5 reveal changes in structure with changes in the C/S ratio. These support the model of Stade and Wieker based entirely on the tobermorite structure. The main characteristic feature of the spectra is the Si-O-Si bending vibration at about 670 cm À1 . Comparisons with bending frequencies of some known crystalline phases composed of single silicate chains led to an estimation of the mean Si-O-Si angles in the C-S-H(I) phases to be B1401. Finite silicate chains (Q 2 ) dominate the structures of the samples at C/S ratios 0.2-1.0, the spectra showing characteristic bands from 1010 to 1020 cm À1 . When the samples are measured in air, the spectra exhibit carbonate bands arising from surface carbonation. The n 1 [CO 3 ] bands obscure the characteristic Raman scattering of silicate units near 1080 cm À1 , which is clearly evident in the fresh samples analyzed in closed capillaries. At C/S41.00, dimers (Q 1 ) are the main building unit of the silicate anionic structure, with a characteristic band at 889 cm À1 . At C/S ratios 1.33 and 1.50, portlandite (Ca(OH) 2 ) is also observed.G. Scherer-contributing editor
A molecular scale and microstructural description of the hydrate phases resulting from the hydration of Portland cement or blends of Portland cement with supplementary cementitious materials is essential for improving and controlling the physical and chemical properties of cement-based materials. The main hydrates are characterised by the absence of long-range order, preventing detailed structural studies by diffraction techniques. This paper illustrates and reviews recent advances in hydrate characterisation by transmission electron microscopy, solidstate nuclear magnetic resonance, and Raman spectroscopy. These techniques are suitable for characterisation of complex mixtures including crystalline as well as amorphous phases and provide important information about the composition and structure on the nano-and microscale.
Synchrotron‐based X‐ray diffraction has been used to analyze a series of mechanochemically prepared calcium silicate hydrate (C–S–H) phases with aimed Ca/Si ratios from 1/5 to 3/2. Fumed silica and CaO were used as starting materials. All samples contain 3‐dimensionally ordered C–S–H phases. Pure C–S–H phases are present in samples with Ca/Si ratios from 2/3 to 6/5. The samples with C/S ratios 1/5 and 1/2 contain unreacted silica, while those with C/S ratios 4/3 and 3/2 contain portlandite as minor component. A new approach has been used to follow structural changes with C/S ratio, involving assignment of an orthorhombic space group (I2mm) to the C–S–H phase followed by refinement of the unit cell parameters by the whole powder pattern decomposition (WPPD) method. The results reveal a discontinuity in the c parameter at C/S=5/6–1/1, indicating that at least two different structural types separated by a miscibility gap are needed to describe C–S–H, there being two ordered end members with C/S ratios of 2/3 and 5/4, respectively. Nevertheless the structure of C–S–H phases within this interval may be well described by the defect‐tobermorite model. At C/S=2/3 it consists of tobermorite slabs linked via H‐bonds without interlayer Ca. At this C/S ratio, the layer thickness is 13.2 Å. Increasing the C/S ratio leads to little change in the layer thickness, but increased disorder due to competitive omission of bridging tetrahedra and incorporation of Ca in the interlayer in samples with 2/3
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TakedownIf you consider content in White Rose Research Online to be in breach of UK law, please notify us by emailing eprints@whiterose.ac.uk including the URL of the record and the reason for the withdrawal request. Abstract: The effects on composite cements of the aluminium content of slag plus that of additional sulphate, has been investigated. Samples containing cement or composites with 40% replacement by one of 2 different slags, differing in aluminium contents, were prepared. A further blended sample was prepared with additional anhydrite replacing 3%w/w of binder. Slag blended mortars showed comparable strengths to the neat cement system at later ages. Adding slag changed the hydration kinetics of the clinker phases. The addition of sulphate had no effect on slag reactivity but increased that of alite. Slags richer in aluminium resulted in greater incorporation of aluminium into C-S-H and encouraged the presence of hemicarbonate over monocarbonate. The Ca/Si ratios of the C-S-H formed were comparable between the two blends, being marginally lower than that of the neat system. The addition of anhydrite resulted in the adsorption of sulphate onto the C-S-H, plus stabilisation of ettringite. Corresponding Author 8 9
The Role of the Alumina Content of Slag, plus the Presence of AdditionalAbstract 10 The effects on composite cements of the aluminium content of slag plus that of additional sulphate, 11 has been investigated. Samples containing cement or composites with 40% replacement by one of 2 12 different slags, differing in aluminium contents, were prepared. A further blended sample was 13 prepared with additional anhydrite replacing 3%w/w of binder. Slag blended mortars showed 14 comparable strengths to the neat cement system at later ages. Adding slag changed the hydration 15 kinetics of the clinker phases. The addition of sulphate had no effect on slag reactivity but increased 16 that of alite. Slags richer in aluminium resulted in greater incorporation of aluminium into C-S-H and 17 encouraged the presence of hemicarbonate over monocarbonate.
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