Lead borate glass is the best radiation shielding glass when lead is in high concentration. However, it has low transparency after radiation exposure. Radiation decreases transparency due to chemical and physical changes in the glass matrix, such as creating or healing defects in the glass network. The addition of rare earth elements like cerium and dysprosium oxides to lead borate glasses can improve their transparency and durability as radiation shielding barriers. The newly manufactured glasses’ optical absorption, structural, and radiation shielding properties were measured. The optical characteristics of the generated samples were examined to determine the effect of the cerium/dysprosium ratio on the structural alterations, specifically in the presence of bridging oxygen (BO) and non-bridging oxygen (NBO). Incorporating Ce3+ results in peaks at 195 nm for borate units, 225 nm for Ce3+, and a broadened peak at 393 nm due to overlapping peaks for Ce3+ and Ce4+ in the UV region. By adding Dy, multiple peaks are observed at 825, 902, 1095, 1275, and 1684 nm, corresponding to the transition from 6H15/2 ground state to 6F5/2, 6F7/2, 6F9/2, 6F11/2, and 6H11/2. The samples were also tested before and after exposure to gamma irradiation from a 60Co source at a dose of 75 kGy to assess their stability against radiation. The energy gap value during irradiation shows decreased non-bridging oxygen. The energy gap difference before and after irradiation for the M4 sample shows higher NBO to BO conversion, reducing radiation damage and improving structural stability. Furthermore, X-ray photoelectron spectroscopy was utilized to get insight into the coordination chemistry of the created glass samples. The half-value layer (HVL), radiation protection efficiency (RPE), neutron removal cross-section (FRNCS), mean free path (MFP), mass attenuation coefficients (MAC), and effective atomic numbers (Zef) of the glassy structure were calculated theoretically to assess its radiation shielding qualities. The linear attenuation coefficient order for the prepared samples was M1 > M2 > M3 > M4. The FRNCS values were 0.090, 0.083, 0.081, and 0.079 cm−1 for samples M1, M2, M3, and M4, respectively.
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