IR and NMR Analyses of Hardening and Maturation of Glass-ionomer Cement

It has been reported that the silicate phase as well as the cross-linking of the polycarboxylic acid by aluminum and calcium ions played an important role in the hardening of glass-ionomer cement. The objective of this study was to investigate the structural change during hardening of the cements by means of infrared (IR) spectroscopy and solid-state nuclear magnetic resonance (NMR) spectroscopy and to confirm the role of the silica phase in the hardening of the cement. For that purpose, we measured the change in compressive strength of an experimental glass-ionomer cement, two commercial glass-ionomer cements, and a polycarboxylate cement and carried out 29Si and 27Al NMR analyses of the cement samples after the strength measurement. In the IR spectra during hardening, a characteristic band of the silicate network around 1000 cm-1 shifted toward high frequency with time. The spectrum after hardening was similar to that for a hydrated amorphous silica structure. The 27Al NMR analysis showed that Al3+ ion was tetrahedrally coordinated by oxygen in the original glass, but a part of the Al3+ ion was octahedrally coordinated after hardening to form Al polyacrylate gel. The chemical shift of Si in the 29Si NMR spectra also changed during hardening. The variation in the chemical shift reflected the structural change in the silicate network. The initial increase in compressive strength of the cement was mainly caused by polycarboxylate gel formation. However, it was concluded that the reconstruction of the silicate network contributed to the increase in strength with time during the period after the gelation by cross-linking was completed.