Mid-IR and far-IR investigation of AgI-doped silver diborate glasses

The structures of {ital x}AgI+(1{minus}{ital x})Ag{sub 2}O{center_dot}2B{sub 2}O{sub 3} glasses, where 0.2{le}{ital x}{le}0.6, have been investigated using mid- and far-infrared spectroscopy. The mid-IR spectra revealed that in those glasses prepared using AgNO{sub 3} as the starting material for Ag{sub 2}O, the BO{sub 4}{sup {minus}}/BO{sub 3} ratio is constant with increasing amounts of AgI as would be expected form the proposed behavior of AgI in these glasses. However, a survey of the literature revealed those glasses prepared from pure Ag{sub 2}O show a strong linear dependence of the BO{sub 4}{sup {minus}}/BO{sub 3} ratio on AgI content. Most probably, in those glasses prepared with Ag{sub 2}O the Ag{sub 2}O/B{sub 2}O{sub 3} ratio changes with AgI content due to the decomposition of Ag{sub 2}O during melting. This different behavior is associated with AgNO{sub 3} decomposing to Ag{sub 2}O with heating followed by incorporation into the glassy network. For Ag{sub 2}O used directly, it is proposed that it decomposes to Ag metal and O{sub 2}(gas) with heating before it can be incorporated into the borate network. This latter behavior decreases with increasing AgI in the batch composition because AgI lowers the liquidus temperature of the melt considerably. The far-IR analysis of the AgI-doped silvermore » diborate glasses suggests that there are three coordination environments for the Ag{sup +} ions; one with iodide anions and the other two with oxygen ions. It is proposed that the separate oxygen coordination environments for the Ag{sup +} ions arise from one with bridging oxygens of BO{sub 4}{sup {minus}} units, and the other with nonbridging oxygens on BO{sub 3}{sup {minus}} units. Furthermore, it is proposed that the Ag{sup +} ions in the iodide-ion environments progressively agglomerate into disordered regions of AgI, but do not form structures similar to {alpha}-AgI. (Abstract Truncated)« less