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A new Bi-rich part of Bi 2 O 3 -PbO phase diagram was determined using differential thermal analysis and X-ray powder diffraction techniques. Four solid solutions, α-Bi 2 O 3 , γ-Bi 2 O 3 , δ-Bi 2 O 3 and β ss -Bi 8 Pb 5 O 17 , can be distinguished below 37.5 mol % of PbO and one compound, β 2 -Bi 8 Pb 5 O 17 . Two of them, δ-Bi 2 O 3 and β ss -Bi 8 Pb 5 O 17 are high-temperature phases. The large field of γ-Bi 2 O 3 stability was implemented making the crucial difference comparing to phasedoi:10.2298/jsc170711111d fatcat:qnu4eo2e5bb5nfjvnxr2rz2i3m