Silicon-29 echo train coherence lifetimes and geminal 2J-couplings in network modified silicate glasses

• Published in: Journal of magnetic resonance (1997) Vol. 333; p. 107097
• Main Authors: Jardón-Álvarez, Daniel, Bovee, Mark O., Grandinetti, Philip J.
• Format: Journal Article
• Language: English
• Published: Elsevier Inc 01.12.2021
• Subjects: 29Si solid state NMR; Homogeneous broadening mechanisms; J couplings; Silicate glasses; Transverse relaxation; Homogeneous broadening mechanisms; Transverse relaxation; 29Si solid state NMR; Silicate glasses; J couplings
• ISSN: 1090-7807; 1096-0856
• DOI: 10.1016/j.jmr.2021.107097

[Display omitted] •Residual dipolar couplings to alkali determine Si-29 coherence lifetimes in silicates.•Residual couplings to alkali make Si-29 lifetimes sensitive probes of structure.•Si-29 coherence lifetimes increase linearly with MAS speed and pi-pulse rate.•Distribution of Si-29 J couplings across Si-O-Si linkages obtained with PIETA.•J coupling distribution widths sensitive to silicate network disorder. The natural abundance 29Si echo-train coherence lifetimes in network-modified silicate glasses were examined under static and magic-angle spinning (MAS) conditions. The nuclear magnetic properties of modifier cations were found to play a major role in determining 29Si coherence lifetimes, leading to differences as large as three orders of magnitude. In compositions with abundant NMR active nuclei, such as alkali silicates, the 29Si coherence lifetimes are dominated by coherent dephasing due to residual heteronuclear dipolar couplings, whereas in compositions dilute in NMR active nuclei, such as alkaline earth silicates, the 29Si coherence lifetimes are dominated by incoherent dephasing due to paramagnetic impurities. Expressing the inverse of the coherence lifetime as a residual full width at half maximum (FWHM), we found that increasing rates of both MAS and a π-pulse train are effective in removing the residual 29Si heteronuclear broadenings, with a near-linear relationship between FWHM and MAS rotor period and π-pulse spacing. Based on these results, we conclude that accurate 29Si J coupling measurements will be the most challenging in lithium silicate glasses due to strong homonuclear dipolar couplings among 7Li nuclei, requiring MAS speeds up to 100 kHz, and be the least challenging in the alkaline earth silicate glasses. At a modest MAS speed of 14kHz, distributions of geminal J couplings across Si-O-Si linkages were measured in alkali and alkaline earth silicate glasses giving mean values of 4.2Hz and 5.1Hz in 0.4 CaO·0.6 SiO2 and 0.33 Ba2O·0.67 SiO2 glasses, respectively, and 5.2Hz and 5.3Hz in 0.33 Na2O·0.67 SiO2 and 0.33 K2O·0.67 SiO2 glasses, respectively. We also observe greater variance in the J distributions of alkaline earth silicate glasses consistent with greater structural disorder due to increased modifier cation potential, i.e., the charge-to-radius ratio, Z/r of the cation.