Hydration and carbonation of monoclinic C2S and C3S studied by Raman spectroscopy

We present a micro‐Raman study on the hydration and carbonation of the main silicate phases of Portland cement, i.e. monoclinic dicalcium silicate (C₂S) and monoclinic tricalcium silicate (C₃S). We investigate the reaction products and the loss of crystallinity induced by hydration on these two compounds. In the CO₂‐contaminated pastes we find that calcite, aragonite, and vaterite are inhomogeneously formed. We study sample cross sections to evaluate the maximum depth at which CaCO₃ is formed. We find that carbonation is limited to the first 500–1000 µm from the surface in the C₃S pastes, while in C₂S pastes CaCO₃ is formed well beyond this depth. Our results show the great potential of Raman spectroscopy in the study of the chemistry of cements. Copyright © 2006 John Wiley & Sons, Ltd.     

Raman spectroscopic investigations of natural jennite from Maroldsweisach,Bavaria, Germany

A full‐range pattern (100–3700 cm⁻¹) analysis of natural jennite was performed for the first time by Raman spectroscopy, applying a polarized laser at a wavelength of 532 nm. A prominent structural feature of jennite is the preferred orientation of Si‐tetrahedron and Ca‐octahedron chains parallel [010]. The latter ones are additionally coupled to H₂O molecules and OH groups. This arrangement leads to a strong dependence on orientation for the intensity ratios of mainly three different regions in the Raman spectra: 180–210, 950–1050 and 3100–3650 cm⁻¹. These sections can be assigned to Ca–O lattice vibrations, Q² Si–tetrahedron stretching and O–H vibrations of H₂O molecules and Ca–OH structures, respectively. Copyright © 2015 John Wiley & Sons, Ltd.     

Carbonation of polymeric organolithium compounds: Effects of chain end structure

The carbonation of the adduct of poly(styryl)lithium with 1,1-diphenylethylene with gaseous carbon dioxide in benzene proceeds in high yield (>99%) compared to the inefficient functionalizations for poly(styryl)lithium (66%), poly(isoprenyl)lithium (59%), and polybutadienyl)lithium (27%). The quantitative carboxylation of poly(isoprenyl)lithium and poly(butadienyl)lithium requires the presence of larger amounts of Lewis bases such as THF ([THF]/[Li] = 300) or TMEDA ([TMEDA]/[Li] = 46) compared to poly(styryl)lithium in which a ratio of [TMEDA]/[Li] = 12 is effective. © 1992 John Wiley & Sons, Inc.     

Hypothetical transformation of Ca(OH)<Subscript>2</Subscript> into CaCO<Subscript>3</Subscript> in solid-state reactions of portland cement

Summary Previous study of the hydration and ageing products of two cement pastes created the basis for the postulate of the course of solid-state reactions between the portlandite Ca(OH)₂ and the CO₂ from air in the hydrated and air dry cement. XRD basal spacing d(001) of portlandite exceeded the nominal value and increased with ageing, with the wetting and drying procedure and with carbonate content of the paste, indicating that a part of OH^- ions was gradually substituted by CO₃^2- ions, which are about twice bigger. IR spectroscopy showed a considerable content of portlandite, of CO₃^2- of water and silicates. Also HCO₃^- H₂O and CO₂ in cavities between hexagonal rings and hexagonal hydrates were indicated. By MS (mass spectrometry) in vacuum the evaporation of sorbed water was detected at 100-120°C, of gel water at 350°C of portlandite water at 400°C and of high temperature water between 500 and 700°C, simultaneously with CO₂ escape. Slightly higher peak temperatures were found by the TG test either in air or in argon. From these results and from geometric considerations it is postulated that the solid-state reactions take place on ageing of the cement paste and on its heating: hexagonal portlanditecalcium carbonate hydroxy hydratecalcium carbonate hydratehexagonal vaterite and/or orthorhombic aragoniterhombohedral calcite The analysis of the standard files of the calcium carbonate hydroxy hydrates supports this postulate and indicates a gradual transformation.     

Large time behavior of a solution of carbon dioxide transport model in concrete carbonation process

In [7] we show the global existence and uniqueness of a solution of carbon dioxide transport model in concrete carbonation process. This model is governed by a parabolic-type equation which has a non-local term depending on the unknown function itself. In this paper, we show the large time behavior of that solution.     

XPS investigation of the composition of the external surface of concrete after demoulding,cleaning and carbonation

X‐ray photoelectron spectroscopy (XPS) coupled with ion beam etching allows the measurements of concentrations gradients at the external surface of concrete. The chemical modifications, caused by the moulding and cleaning operations and due to carbonation, are efficiently investigated. Based on the detection of specific elements (such as chlorine, carbon and silicon), the presence of formworks residues is established on the concrete surface. Similarly, aliphatic (C –(C,H) and carbonaceous (C –O) residues of the demoulding agent can be detected. The concentration gradients show the presence of moulding residues is mainly superficial and decreases rapidly according to the depth. However, certain of these contaminants (and especially polydimethylsiloxane residues) could alter the wetting of aqueous‐based coatings. The sandblasting process can partially remove the moulding residues, but the decontamination remains incomplete in spite of the high increase of the roughness of the samples. On the contrary, the concentrations in aliphatic and carbonaceous residues increase after cleaning with solvents, which can be trapped in the pores of concrete to contaminate the surface. The carbonation process is also investigated by XPS. The concentration gradient of the carbonate component of the C 1 s peak shows a front of carbonation progressing as a function of the time after demoulding. Copyright © 2012 John Wiley & Sons, Ltd.     

碳化作用下不同氯盐掺量水泥浆体的微结构研究

通过加速碳化试验方法, 研究了碳化与氯盐复合作用下水泥浆体的微观结构, 分析了氯盐掺量对水泥基材料的抗碳化性能的影响. 同时, 利用X射线衍射分析了碳化前后样品的物相组成、水化产物类型和微观结构特征. 结果表明, 碳化养护更有利于浆体裂缝的愈合, 但碳化后大孔占比增加; 碳化作用下掺加氯盐会减缓水泥浆碳化速度; 碳化后产生单硫型水化硫铝酸钙和碳酸盐类物质, 钙矾石消失, 浆体的孔隙总体积减少, 孔隙结构得到了细化.     

环境催化中的陶瓷材料:应用与可能性(英文)

Environmental catalysis has been steadily growing because of the advances in its scientific and engineering aspects,as well as due to the new environmental challenges in the industrial era.The development of new catalysts and materials is essential for new technologies for various environmental applications.Ceramics play important roles in various environmental applications including the identification,monitoring,and quantification of pollutants and their control.Ceramics have important applications as sensors and photocatalysts,and they are extensively used as catalyst carriers and supports.Many ceramics are being explored as catalysts for pollution control applications.Their low cost,thermal and chemical stability,and capability of being tailored make them especially attractive for pollution control applications.Although a wide variety of materials have been developed as catalyst supports,this area is still of interest with new or modified catalyst supports being frequently reported.It is of equal importance to develop new or modified processes for the loading of catalysts on specific supports.Applications like chemical looping combustion(CLC) and other catalytic combustion processes are raising the demands to a new scale.We have been working on the development of both new and modified support materials,including mesoporous materials without structural order for possible applications in CLC and other catalytic reactions.Successful attempts have been made in the modification of conventional γ-Al2O3 and improved synthesis processes for supporting perovskite type catalysts.Our research on environmental catalysis applications of ceramic materials and processes are also briefly discussed.     

Precipitation and characterization of hollow calcite nanoparticles

A method for preparation of significant amount of hollow rhombohedral calcite nanoparticles, based on carbonation of calcium hydroxide suspension, is described. The mineralogical and morphological analyses of the precipitate confirmed the existence of exclusively stable polymorphic modification, calcite, with the mean particle size of about 100 nm and the diameter of the holes observed at the surfaces that are about 50 nm. The analysis of carbonation kinetics pointed out to a complex mechanism of hollow particles formation at high initial supersaturation, that assumed nucleation of amorphous precursor calcium carbonate phase and its solution mediated transformation into nanosized crystalline calcite. The holes obtained at the calcite surfaces are most probably the imprints remained after the dissolution of amorphous calcium carbonate particles.     

Crystal Chemistry of 1:1 Molecular Complexes of Carbamate Salts Formed by Slow Aerial Carbonation of Amines

Abstract  Amines do have rare tendency to undergo aerial carbonation to form carbamic acid. Four different 1:1 molecular complex of carbamate salts reported herein obtained by the aerial carbonation of cyclic amines. X-ray crystal structures show a systematic change in the molecular structure did bring some gradual supramolecular change from one structural motif to another. Index Abstract  Amines do have rare tendency to undergo aerial carbonation to form carbamic acid. Four different 1:1 molecular complexes of carbamate salts reported herein obtained by the aerial carbonation of cyclic amines. X-ray crystal structures show a systematic change in the molecular structure did bring some gradual supramolecular change from one structural motif to another.