Author(s)

Gomaa El-Damrawi^1*, Amal Behairy²

¹Physics Department, Faculty of Science, Mansoura University, Mansoura, Egypt.
²The High Institute of Engineering and Technology, New Damietta, Damietta, Egypt.

Silicate glasses and glass ceramics in the system CeO₂-PbO-SiO₂ have been studied as a function of the structure factors R and K. The latter two factors are defined as: R = (CeO₂ + PbO)/SiO₂ and K = (SiO₂/CeO₂) molar ratios. In this glass, PbO is fixed at 50 mol% and CeO₂ increases at the expense of SiO₂. NMR investigations have revealed that increasing R which is accompanied with decreasing K leads to reasonable decrease in the shielding of silicon atoms. The chemical shift (δ) showed an increasing behavior due to increasing non-bridging oxygen atoms (NBO) in silicate network. It is evidenced that NBO in cerium free glass is much lower than that of glasses containing CeO₂. Increasing R is clearly leading to higher chemical shift and higher NBO. This reflects that CeO₂ has an effective structural role, since it would be consumed in all cases as an intermediate oxide. The main portions from CeO₂ and PbO inter as glass modifiers which are consumed to form NBO atoms. A limited portion of CeO₂ acts as glass former which consumed to form tetrahedral cerium containing NBO due to modification by PbO as a modifier oxide. Increasing R = [(CeO₂ + PbO)/SiO₂] from 1 to 2.34 leads to a frequent increase of NBO in the average glass network. FTIR spectroscopy of the glasses showed a clear shift of the main absorbance peak toward the low wavenumber with increasing R which confirms the increasing silicate units containing NBO atoms. XRD of the investigated materials revealed the presence of some nanostructures from cerium silicate crystalline phases. Formation of separated phases containing micro clusters is found to depend on NBO concentration, since NBO can facilitate process of phase separation. Majority of modifier are consumed to form NBO in the glass network and the rest are aggregated or separated to form silicate phase riches with cerium cations. In such case, some of silicon atoms are electrically compensated with both Pb and Ce cations.

Cerium in Glasses, Crystalline Clusters, NMR Feature, Glass Ceramics

El-Damrawi, G. and Behairy, A. (2018) Structural Role of Cerium Oxide in Lead Silicate Glasses and Glass Ceramics. Journal of Minerals and Materials Characterization and Engineering, 6, 438-447. doi: 10.4236/jmmce.2018.63031.