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

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.