The calcium silicate hydrate (C-S-H) phase resulting from hydration of a white Portland cement (wPc) in water and in a 0.3 M NaAlO(2) solution has been investigated at 14 and 11 hydration times, respectively, ranging from 6 h to 1 year by (27)Al and (29)Si MAS NMR spectroscopy. (27)Al MAS NMR spectra recorded at 7.05, 9.39, 14.09, and 21.15 T have allowed a determination of the (27)Al isotropic chemical shift (delta(iso)) and quadrupolar product parameter (P(Q) = C(Q)) for tetrahedrally coordinated Al incorporated in the C-S-H phase and for a pentacoordinated Al site. The latter site may originate from Al(3+) substituting for Ca(2+) ions situated in the interlayers of the C-S-H structure. The spectral region for octahedrally coordinated Al displays resonances from ettringite, monosulfate, and a third aluminate hydrate phase (delta(iso) = 5.0 ppm and P(Q) = 1.20 MHz). The latter phase is tentatively ascribed to a less-crystalline aluminate gel or calcium aluminate hydrate. The tetrahedral Al incorporated in the C-S-H phase has been quantitatively determined from (27)Al MAS spectra at 14.09 T and indirectly observed quantitatively in (29)Si MAS NMR spectra by the Q(2)(1Al) resonance at -81.0 ppm. A linear correlation is observed between the (29)Si MAS NMR intensity for the Q(2)(1Al) resonance and the quantity of Al incorporated in the C-S-H phase from (27)Al MAS NMR for the different samples of hydrated wPc. This correlation supports the assignment of the resonance at delta(iso)((29)Si) = -81.0 ppm to a Q(2)(1Al) site in the C-S-H phase and the assignment of the (27)Al resonance at delta(iso)((27)Al) = 74.6 ppm, characterized by P(Q)((27)Al) = 4.5 MHz, to tetrahedrally coordinated Al in the C-S-H. Finally, it is shown that hydration of wPc in a NaAlO(2) solution results in a C-S-H phase with a longer mean chain length of SiO(4) tetrahedra and an increased quantity of Al incorporated in the chain structure as compared to the C-S-H phase resulting from hydration of wPc in water.
The incorporation of aluminum in the calcium–silicate–hydrate (C–S–H) phases formed by hydration of three different white Portland cements has been investigated by 29Si MAS NMR. The principal difference between the three cements is their bulk Al2O3 contents and quantities of alkali (Na+ and K+) ions. 29Si MAS NMR allows indirect detection of tetrahedral Al incorporated in the silicate chains of the C–S–H structure by the resonance from Q2(1Al) sites. Analysis of the relative 29Si NMR intensities for this site, following the hydration for the three cements from 0.5 d to 30 weeks, clearly reveals that the alkali ions promote the incorporation of Al in the bridging sites of the dreierketten structure of SiO4 tetrahedra in the C–S–H phase. The increased incorporation of Al in the C–S–H phase with increasing alkali content in the anhydrous cement is in accord with a proposed substitution mechanism where the charge deficit, obtained by the replacement of Si4+ by Al3+ ions in the bridging sites, is balanced by adsorption/binding of alkali ions in the interlayer region most likely in the near vicinity of the AlO4 tetrahedra. This result is further supported by similar 29Si MAS NMR experiments performed for the white Portland cements hydrated in 0.30M NaOH and NaAlO2 solutions.
The first application of variable-temperature 27Al MAS NMR spectroscopy to the satellite transitions in the
characterization of a structural phase transition is presented by an investigation of Friedels salt (Ca2Al(OH)6Cl·2H2O) over the temperature range from −121 to 109 °C. Accurate values for the 27Al quadrupole coupling
parameters (C
Q and ηQ) and the isotropic chemical shifts are obtained from either the manifold of spinning
sidebands for the satellite transitions or the line shape observed for the central transition. These data demonstrate
that the quadrupole coupling parameters clearly reflect the structural α−β phase transition for Friedels salt
at about 34 °C, whereas the isotropic chemical shift is invariant over the studied temperature range. The
variations in C
Q and ηQ with temperature show a parabolic decrease in C
Q and an increase in ηQ with increasing
temperature for the α form of Friedels salt, while only a small linear decrease in C
Q with increasing temperature
and a temperature-independent value for ηQ are observed for the β form. The nonlinear variations of C
Q and
ηQ with temperature for the α form and their relationships with changes in the structural parameters associated
with thermal expansion of the unit cell are discussed. Finally, the abrupt changes in C
Q and ηQ at the temperature
for the phase transition are investigated by point-monopole calculations of the 27Al electric-field gradient
tensor, which strongly suggest that hydrogen bonding plays an important role in the structural changes that
occur during the phase transition.
This study demonstrates a strong interaction between triacylglycerol (TAG) composition and effects of shear rate on the microstructure and texture of fats. Cocoa butter alternatives with similar saturated fat content, but different major TAGs (PPO-, PSO-, SSO-, POP- and SOS-rich blends) were evaluated. Results show how shear can create a harder texture in fat blends based on symmetric monounsaturated TAGs (up to ∼200%), primarily due to reduction in crystal size, whereas shear has little effect on hardness of asymmetric monounsaturated TAGs. Such differences could not be ascribed to differences in the degree of supercooling, but was found to be a consequence of differences in the crystallisation behaviour of different TAGs. The fractal dimension was evaluated by dimensional detrended fluctuation analysis and Fourier transformation of microscopy images. However, the concept of fractal patterns was found to be insufficient to describe microstructural changes of fat blends with high solid fat content.
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