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Title: Calcium silicate hydrates investigated by solid-state high resolution {sup 1}H and {sup 29}Si nuclear magnetic resonance

Abstract

This work focuses on phases formed during cement hydration under high pressure and temperature: portlandite Ca(OH){sub 2} (CH); hillebrandite Ca{sub 2}(SiO{sub 3})(OH){sub 2} ({beta}-dicalcium silicate hydrate); calcium silicate hydrate (C-S-H); jaffeite Ca{sub 6}(Si{sub 2}O{sub 7})(OH){sub 6} (tricalcium silicate hydrate); {alpha}-C{sub 2}SH Ca{sub 2}(SiO{sub 3})(OH){sub 2} ({alpha}-dicalcium silicate hydrate); xonotlite Ca{sub 6}(Si{sub 6}O{sub 17})(OH){sub 2} and kilchoanite Ca{sub 6}(SiO{sub 4})(Si{sub 3}O{sub 10}). Portlandite and hillebrandite were synthesized and characterised by high resolution solid-state {sup 1}H and {sup 29}Si Nuclear Magnetic Resonance. In addition, information from the literature concerning the last five phases was gathered. In certain cases, a schematic 3D-structure could be determined. These data allow identification of the other phases present in a mixture. Their morphology was also observed by Scanning Electron Microscopy.

Authors:
 [1];  [2];  [3];  [4];  [5]
  1. Laboratoire de Physique et Mecanique des Milieux Heterogenes, Ecole Superieure de Physique et Chimie Industrielles, 75231 Paris Cedex 05 (France). E-mail: meducin@cnrs-orleans.fr
  2. Laboratoire de Physique Quantique, ESPCI (France)
  3. Laboratoire de Physico-Chimie des polymeres et des milieux disperses, ESPCI (France)
  4. Laboratoire CECM-CNRS, 15, rue Georges Urbain, 94407 Vitry sur Seine (France)
  5. Laboratoire de Physique et Mecanique des Milieux Heterogenes, Ecole Superieure de Physique et Chimie Industrielles, 75231 Paris Cedex 05 (France)
Publication Date:
OSTI Identifier:
20995379
Resource Type:
Journal Article
Resource Relation:
Journal Name: Cement and Concrete Research; Journal Volume: 37; Journal Issue: 5; Other Information: DOI: 10.1016/j.cemconres.2007.01.011; PII: S0008-8846(07)00025-7; Copyright (c) 2007 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; CALCIUM SILICATES; CEMENTS; HYDRATES; HYDRATION; MORPHOLOGY; NUCLEAR MAGNETIC RESONANCE; RESOLUTION; SCANNING ELECTRON MICROSCOPY; SPECTROSCOPY; X-RAY DIFFRACTION

Citation Formats

Meducin, Fabienne, Bresson, Bruno, Lequeux, Nicolas, Noirfontaine, Marie-Noelle de, and Zanni, Helene. Calcium silicate hydrates investigated by solid-state high resolution {sup 1}H and {sup 29}Si nuclear magnetic resonance. United States: N. p., 2007. Web. doi:10.1016/j.cemconres.2007.01.011.
Meducin, Fabienne, Bresson, Bruno, Lequeux, Nicolas, Noirfontaine, Marie-Noelle de, & Zanni, Helene. Calcium silicate hydrates investigated by solid-state high resolution {sup 1}H and {sup 29}Si nuclear magnetic resonance. United States. doi:10.1016/j.cemconres.2007.01.011.
Meducin, Fabienne, Bresson, Bruno, Lequeux, Nicolas, Noirfontaine, Marie-Noelle de, and Zanni, Helene. Tue . "Calcium silicate hydrates investigated by solid-state high resolution {sup 1}H and {sup 29}Si nuclear magnetic resonance". United States. doi:10.1016/j.cemconres.2007.01.011.
@article{osti_20995379,
title = {Calcium silicate hydrates investigated by solid-state high resolution {sup 1}H and {sup 29}Si nuclear magnetic resonance},
author = {Meducin, Fabienne and Bresson, Bruno and Lequeux, Nicolas and Noirfontaine, Marie-Noelle de and Zanni, Helene},
abstractNote = {This work focuses on phases formed during cement hydration under high pressure and temperature: portlandite Ca(OH){sub 2} (CH); hillebrandite Ca{sub 2}(SiO{sub 3})(OH){sub 2} ({beta}-dicalcium silicate hydrate); calcium silicate hydrate (C-S-H); jaffeite Ca{sub 6}(Si{sub 2}O{sub 7})(OH){sub 6} (tricalcium silicate hydrate); {alpha}-C{sub 2}SH Ca{sub 2}(SiO{sub 3})(OH){sub 2} ({alpha}-dicalcium silicate hydrate); xonotlite Ca{sub 6}(Si{sub 6}O{sub 17})(OH){sub 2} and kilchoanite Ca{sub 6}(SiO{sub 4})(Si{sub 3}O{sub 10}). Portlandite and hillebrandite were synthesized and characterised by high resolution solid-state {sup 1}H and {sup 29}Si Nuclear Magnetic Resonance. In addition, information from the literature concerning the last five phases was gathered. In certain cases, a schematic 3D-structure could be determined. These data allow identification of the other phases present in a mixture. Their morphology was also observed by Scanning Electron Microscopy.},
doi = {10.1016/j.cemconres.2007.01.011},
journal = {Cement and Concrete Research},
number = 5,
volume = 37,
place = {United States},
year = {Tue May 15 00:00:00 EDT 2007},
month = {Tue May 15 00:00:00 EDT 2007}
}
  • In cement-based materials heavy metals contents are rarely larger than a few hundred parts per million. Sorption isotherms of Zn(II) and Pb(II) carried out on nonhydrated (C{sub 3}S) and hydrated (C-S-H) calcium silicate show t hat lead and zinc have different affinities for calcium silicate in a concentration range lower than the saturation concentration values of PbO and calcium zinc hydroxide. Lead has a much higher affinity than zinc for both nonhydrated and hydrated calcium silicate. Furthermore, the different retention sites of zinc and lead in hydrated calcium silicate have been investigated by {sup 29}Si nuclear magnetic resonance (NMR) spectroscopy.more » A spectral line analysis clearly shows that structural retention mechanisms are involved for both ions. Indeed, the additional lines at {minus}85.6 or {minus}85.9 ppm that appear in the NMR spectra have been attributed to Q{sub 1Me} sites involving Si-O-Pb and Si-O-Zn bonds, respectively.« less
  • The potential of 2D {sup 29}Si high-resolution solid-state NMR spectroscopy to establish three-dimensional Si/O/Si lattice connectivities in zeolites has been investigated using a {sup 29}Si-enriched sample of zeolite ZSM-39. Spin-diffusion measurements reveal the correct connectivities for the (known) structure, but further work on other systems will be needed to establish the reliability of these measurements due to possible contributions from non-distance-dependent factors. {sup 29}Si COSY experiments also yield the correct connectivities and are unambiguous in this regard as they depend only on scalar (through-bond) couplings and thus greatly extend the potential of high-resolution solid-state NMR in the investigation of latticemore » structures.« less
  • Partially deuterated Ca{sub 3}Al{sub 2}(SiO{sub 4}){sub y}(OH){sub 12-4y}-Al(OH){sub 3} mixtures, prepared by hydration of Ca{sub 3}Al{sub 2}O{sub 6} (C{sub 3}A), Ca{sub 12}Al{sub 14}O{sub 33} (C{sub 12}A{sub 7}) and CaAl{sub 2}O{sub 4} (CA) phases in the presence of silica fume, have been characterized by {sup 29}Si and {sup 27}Al magic-angle spinning-nuclear magnetic resonance (MAS-NMR) spectroscopies. NMR spectroscopy was used to characterize anhydrous and fully hydrated samples. In hydrated compounds, Ca{sub 3}Al{sub 2}(OH){sub 12} and Al(OH){sub 3} phases were detected. From the quantitative analysis of {sup 27}Al NMR signals, the Al(OH){sub 3}/Ca{sub 3}Al{sub 2}(OH){sub 12} ratio was deduced. The incorporation of Simore » into the katoite structure, Ca{sub 3}Al{sub 2}(SiO{sub 4}){sub 3-x}(OH){sub 4x}, was followed by {sup 27}Al and {sup 29}Si NMR spectroscopies. Si/OH ratios were determined from the quantitative analysis of {sup 27}Al MAS-NMR components associated with Al(OH){sub 6} and Al(OSi)(OH){sub 5} environments. The {sup 29}Si NMR spectroscopy was also used to quantify the unreacted silica and amorphous calcium aluminosilicate hydrates formed, C-S-H and C-A-S-H for short. From {sup 29}Si NMR spectra, the amount of Si incorporated into different phases was estimated. Si and Al concentrations, deduced by NMR, transmission electron microscopy, energy dispersive spectrometry, and Rietveld analysis of both X-ray and neutron data, indicate that only a part of available Si is incorporated in katoite structures. - Graphical abstract: Transmission electron micrograph of CaAl{sub 2}O{sub 4}-microsilica mixture hydrated at 90 deg. C for 31 days showing a cubic Ca{sub 3}Al{sub 2.0{+-}}{sub 0.2}(SiO{sub 4}){sub 0.9{+-}}{sub 0.2}(OH){sub 1.8} crystal surrounded by unreacted amorphous silica spheres.« less
  • Olivine-(Mg,Fe){sub 2}SiO{sub 4}-has been the subject of frequent investigation in the earth sciences because of its simple structure and rapid dissolution kinetics. Several studies have observed a preferential release of the divalent cation with respect to silicon during weathering under acidic conditions, which has been correlated to the formation of a silicon-rich leached layer. While leached layer formation has been inferred through the changing solution chemistry, a thorough spectroscopic investigation of olivine reacted under acidic conditions has not been conducted. The pure magnesium end member of the olivine series (forsterite-Mg2SiO4) was chosen for detailed investigations in this study because paramagneticmore » iron hinders NMR investigations by providing an extra mode of relaxation for neighboring nuclei, causing lineshapes to become significantly broadened and unobservable in the NMR spectrum. For reacting forsterite, spectroscopic interrogations using nuclear magnetic resonance (NMR) can elucidate the changing magnesium coordination and bonding environment. In this study, we combine analysis of the changing solution chemistry with advanced NMR techniques ({sup 29}Si MAS, {sup 1}H-{sup 29}Si CP MAS, {sup 25}Mg QCPMG, and {sup 1}H-{sup 25}Mg CP QCPMG NMR) to probe leached layer formation and secondary phase precipitation during the dissolution of forsterite at 150 C.« less
  • Olivine-(Mg,Fe){sub 2}SiO{sub 4}-has been the subject of frequent investigation in the earth sciences because of its simple structure and rapid dissolution kinetics. Several studies have observed a preferential release of the divalent cation with respect to silicon during weathering under acidic conditions, which has been correlated to the formation of a silicon-rich leached layer. While leached layer formation has been inferred through the changing solution chemistry, a thorough spectroscopic investigation of olivine reacted under acidic conditions has not been conducted. The pure magnesium end member of the olivine series (forsterite-Mg{sub 2}SiO{sub 4}) was chosen for detailed investigations in this studymore » because paramagnetic iron hinders NMR investigations by providing an extra mode of relaxation for neighboring nuclei, causing lineshapes to become significantly broadened and unobservable in the NMR spectrum. For reacting forsterite, spectroscopic interrogations using nuclear magnetic resonance (NMR) can elucidate the changing magnesium coordination and bonding environment. In this study, we combine analysis of the changing solution chemistry with advanced NMR techniques ({sup 29}Si MAS, {sup 1}H-{sup 29}Si CP MAS, {sup 25}Mg QCPMG, and {sup 1}H-{sup 25}Mg CP QCPMG NMR) to probe leached layer formation and secondary phase precipitation during the dissolution of forsterite at 150 C.« less