Influence of lanthanum on borosilicate glass structure: A multinuclear MAS and MQMAS NMR investigation

The physical and chemical properties of silicate glasses containing rare-earth elements (REEs), either as dopants or at higher concentrations, are sensitive to the REE structural and chemical environment. An unambiguous role of REEs in the glass structure still remains difficult to define because many configurations may exist and are strongly composition-dependent. The structural configuration of lanthanum and its interactions with sodium and calcium are examined here in borosilicate glasses. The impact of lanthanum and calcium substituted for sodium on the boron speciation is investigated by 11B MAS NMR. The resulting 29Si MAS NMR spectra and their interpretations are discussed. A quantitative approach of 17O MQMAS NMR data with the reconstruction of 17O NMR parameter distributions provides an overview of lanthanum distribution and its interactions with the other cations in the vitreous network. No clustering of lanthanum atoms is observed; they are uniformly distributed in the glass structure, surrounded by about 6 non-bridging oxygen atoms and mixed with sodium and calcium atoms to the detriment of the number of BO4 groups. These data provide a better understanding of the addition of rare earths in the glass and of the conditions favorable to their uniform distribution in soda-lime borosilicate glass matrices.