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A new experiment shows that tungstate fluorophosphate glass compositions with high WO3 concentration were prepared in the ternary system (80−0.8x)NaPO3–(20−0.2x)BaF2–xWO3 with x = 40,50 and 60 mol%. Transparency decreases as WO3 concentration increases but can be improved by addition of oxidizing systems such as CeO2 or Sb2O3/NaNO3. Characterizations by thermal analysis  point out that an increase in the amount of WO3 results in a higher glass transition temperature. In addition, such compositions are very stable against devitrification since samples containing 40% and 50% of WO3 do not even exhibit the expected crystallization event. In these samples, the stability against crystallization decreases with the WO3 content and vitreous sample containing 60% of WO3 exhibits an endothermic event around 620 °C due to crystallization of monoclinic WO3 phase. In these glasses, it was shown that the nucleation stage can be induced by thermal-treatment when external nucleating agents such as Ti or Sb are used. Finally, gold-doped samples exhibit a higher crystallization tendency and monoclinic WO3 phase can be grown in such glasses.