Structural investigation and thermal properties of Al2O3-PbO-B2O3 glasses

Two series of aluminum lead borate glasses, (Al2O3)(y)(PbO)(35-y)(B2O3)(65) and (Al2O3)(y)(PbO)(70-y)(B2O3)(30), were prepared and effect of PbO -> Al(2)O(3 )substitution on their structure and thermal properties was studied. The semi- quantitative analysis of the Raman spectroscopy data was used to structural interpretation of glass transition behavior in the Al2O3-doped lead borate glasses. The mechanisms of structural reorganization of glassy network under PbO -> Al(2)O(3)substitution were found to differ for the studied series although Al3+ions are incorporated in the glass network, mainly, in form of AlO4 units in the both cases. The formation of AlO4 tetrahedra is accompanied by transformation of various isolated borate anions into finite-sized metaborate chains as well as the conversion of four-fold coordinated [B & Oslash;O-3]species with one non-bridging oxygen atom into fully polymerized [B & Oslash;(4)]tetrahedra in the (Al2O3)(y)(PbO)(70-y)(B2O3)(30 )glasses. In the series of glasses with high concentration of B2O3, B-[4] -> B-[3] transformation including the shift of [B & Oslash;(4)]<-> B & Oslash;O-2 equilibrium toward the right side is the main process of structural reorganization caused by PbO -> Al(2)O(3 )substitution. In this case, the change in the network connectivity is determined by competition between increasing the amount of Al-O-B bonds against the background of decreasing the amount of B-O-B bonds between borate structural species. In the B-poor series, the glass transition temperature increased with Al(2)O(3 )from 280 to 360 C-degrees, and the crystallization peak onset occurs at 340 and 380 C-degrees for the glasses with the 0 and 3 mol.% Al(2)O(3 )contents, respectively (higher aluminum oxide contents already prevent crystallization). In the B-rich series, T(g )increases with the Al(2)O(3 )content from 430 to 490 C-degrees, and the crystallization occurs at 560 C-degrees only for the Al2O3-free glass. The structural relaxation behavior in the glass transition rage was described in terms of the Tool-Narayanaswamy-Moynihan model. The activation energy for the relaxation movements was found to be non-monotonous in case of both compositional series.