Probing chemical disorder in glasses using silicon-29 NMR spectral editing

Hiet, J.; Deschamps, Michaël; Pellerin, Nadia; Fayon, Franck; Massiot, Dominique

doi:10.1039/b906399d

Cited by 49 publications

(61 citation statements)

References 63 publications

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“…Future use of recent methodologies using scalar or recoupled dipolar interactions for counting the number of neighbouring spins around a given atom will undoubtedly contribute to address this general issue for disordered systems. [63,64] Especially for strongly overlapping lines which is predominantly the case for 29 Si NMR spectra in glasses such techniques have been demonstrated to be successful for discriminating between the contribution of each Q (4) (nSi) species. Such a work is in progress and is presented elsewhere.…”

Section: Figure 2 (A) Theoretical (Md-gipaw) 29 Si Isotropic Chemicamentioning

confidence: 97%

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Contribution of first-principles calculations to multinuclear NMR analysis of borosilicate glasses

et al. 2010

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Boron-11 and silicon-29 NMR spectra of xSiO(2)-(1-x)B(2)O(3) glasses (x=0.40, 0.80 and 0.83) have been calculated using a combination of molecular dynamics (MD) simulations with density functional theory (DFT) calculations of NMR parameters. Structure models of 200 atoms have been generated using classical force fields and subsequently relaxed at the PBE-GGAlevel of DFT theory. The gauge including projector augmented wave (GIPAW) method is then employed for computing the shielding and electric field gradient tensors for each silicon and boron atom. Silicon-29 MAS and boron-11 MQMAS NMR spectra of two glasses (x=0.40 and 0.80) have been acquired and theoretical spectra are found to well agree with the experimental data. For boron-11, the NMR parameter distributions have been analysed using a Kernel density estimation (KDE) approach which is shown to highlight its main features. Accordingly, a new analytical model that incorporates the observed correlations between the NMR parameters is introduced. It significantly improves the fit of the (11)B MQMAS spectra and yields, therefore, more reliable NMR parameter distributions. A new analytical model for a quantitative description of the dependence of the silicon-29 and boron-11 isotropic chemical shift upon the bond angles is proposed, which incorporates possibly the effect of SiO(2)-B(2)O(3) intermixing. Combining all the above procedures, we show how distributions of Si-O-T and B-O-T (T=Si, B) bond angles can be estimated from the distribution of isotropic chemical shift of silicon-29 and boron-11, respectively.

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Section: Figure 2 (A) Theoretical (Md-gipaw) 29 Si Isotropic Chemicamentioning

confidence: 97%

“…Natural extensions of the present analysis are based on 29 Si/ 11 B heteronuclear experiments [63,64] in order to accurately integrate the effect of the surrounding (Si-O-Si and Si-O-B linkages for 29 Si e.g.) and using more sophisticated models such as in…”

Section: S167mentioning

confidence: 99%

Contribution of first-principles calculations to multinuclear NMR analysis of borosilicate glasses

et al. 2010

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“…From a general stand point, in aluminosilicate glasses, substitution of Al for Si atom as a second neighbour in the close vicinity to a Si atom (i.e. substitution of Si-O-Si to Si-O-Al in tetrahedral configuration) induces a shift in 29 Si peak of at least +5 ppm (Engelhardt et al, 1985;Schmidt et al, 2000;Hiet et al, 2009;Le Losq et al, 2014). Therefore, a Q 3 (1Al) would have a 29 Si δ iso around − 85.0 ppm.…”

Section: Si Mas Nmrmentioning

confidence: 98%

A NMR and molecular dynamics study of CO2-bearing basaltic melts and glasses

2015

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International audienceThe presence of volatile, especially carbon dioxide (CO2), in silicate liquids is considered as a key parameter to magmatic degassing and eruptive processes. Unfortunately, due to experimental difficulties, our current knowledge on the CO2 effect on silicate melt structure is weak and relies on the observation of ex-situ recovered CO2-bearing glasses.In the present work, we confront the results obtained from NMR spectroscopic observations of glass synthesised at pressure between 0.5 and 3.0 GPa and theoretical investigations from first-principles molecular dynamics (FPMD) simulations conducted at 5.0 and 8.0 GPa on high temperature melt for a simplified basaltic composition.The results obtained on the aluminosilicate framework (molar fraction of silicon species and Al average coordination number) suggest that both ex-situ and in-situ results compare adequately. The results are in agreement with our current knowledge on the change in aluminosilicate melt/glass structure with changing intensive conditions. Increasing pressure from 0.5 to 8.0 GPa induces 1) an increase in the average Al coordination number from 4.1 to almost 5.0 and 2) an increase in the degree of polymerisation with NBO/Si changing from 1.30 to 0.80.The presence of CO2 does not seem to induce a dramatic change on both the average Al coordination number and the NBO/Si. FPMD simulations performed with 0 and 20 wt.% CO2 at 8.0 GPa result in a change from 4.84 to 4.96 for the average Al coordination number and in a change from 0.87 to 0.80 for the NBO/Si value, respectively.On the contrary, there is a lack of consistency in between the CO2 speciation obtained from NMR spectroscopy and from FPMD simulations. Whereas the analysis of glasses does not reveal the presence of CO2mol species, the FPMD simulation results suggests the existence of a small proportion of CO2mol. Further work with in-situ experimental approach is therefore required to explain the observed lack of consistency between the CO2 speciation in glass and in high temperature melt with basaltic composition

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“…45 Sc, 69,71 Ga, 63,65 Cu, 93 Nb, 113,115 In, 139 La) where the effective quadrupolar broadening factor (taking into account both (i) the 'raw' second-order quadrupolar broadening factor, determined by the magnetic and quadrupolar moments along with the spin, and (ii) the local electron density 'magnification' of the external EFG as estimated by the Sternheimer antishielding factor. The effective quadrupole broadening factor is then estimated by multiplying factors (i) and (ii) (defined in Table 2 of [5])) for these nuclei is in the range ~25-250 and compares to 0.6 for 11 B and 3.6 for 27 Al.…”

Section: Half-integer Spin High-quadrupolar Nucleimentioning

confidence: 99%

“…In aluminosilicate glasses the ability to distinguish and fit 29 Si MAS NMR spectra where several different, but poorly resolved Q 4 (mAl) species are present is extremely important to constrain the Si,Al distribution. Sequences that can use the coupling, such as 4Q filtered INADEQUATE can pick up the number of differing neighbours (in a 100% 29 Si labelled system) by sequentially increasing the mixing time and this information can be used to constrain the fits of the 1D spectrum [115]. (Fig.…”

Section: Connectivity and Ordering In Glassesmentioning

confidence: 99%

Recent technique developments and applications of solid state NMR in characterising inorganic materials

Hanna

Smith

2010

Solid State Nuclear Magnetic Resonance

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A broad overview is given of some key recent developments in solid state NMR techniques that have driven enhanced applications to inorganic materials science. Reference is made to advances in hardware, pulse sequences and associated computational methods (e.g. first principles calculations, spectral simulation), along with their combination to provide more information about solid phases. The resulting methodology has allowed more nuclei to be observed and more structural information to be extracted. Cross referencing between experimental parameters and their calculation from the structure has seen an added dimension to NMR as a characterisation probe of materials. Emphasis is placed on the progress made in the last decade especially from those nuclei that were little studied previously. The general points about technique development and the increased range of nuclei observed are illustrated through a range of specific exemplars from inorganic materials science.

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Probing chemical disorder in glasses using silicon-29 NMR spectral editing

Cited by 49 publications

References 63 publications

Contribution of first-principles calculations to multinuclear NMR analysis of borosilicate glasses

Contribution of first-principles calculations to multinuclear NMR analysis of borosilicate glasses

A NMR and molecular dynamics study of CO2-bearing basaltic melts and glasses

Recent technique developments and applications of solid state NMR in characterising inorganic materials

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