Heat capacity measurements and XPS studies on uranium-lanthanum mixed oxides

Research highlights: → Heat capacity measurements were carried out on (U1-yLay)O2±x (y = 0.2, 0.4, 0.6, and 0.8) using differential scanning calorimeter (DSC) in the temperature range 298-800 K. → Enthalpy increment measurements were carried out on the above solid solution using high temperature drop calorimetry in the temperature range 800-1800 K. → Chemical states of U and La in the solid solutions of mixed oxides were determined using X-ray photoelectron spectroscopy (XPS). → The anomalous increase in the heat capacity is attributed to certain thermal excitation process namely Frenkel pair defect of oxygen. → From the XPS investigation, it is observed that the O/M ratio at the surface is higher than that to the bulk. → In uranium rich mixed oxide samples, the surface O/M is greater than 2 whereas that in La rich mixed oxides, it is less than 2, though the bulk O/M in all the samples are less than 2. - Abstract: Heat capacity measurements were carried out on (U1-yLay)O2±x (y = 0.2, 0.4, 0.6, and 0.8) using differential scanning calorimeter (DSC) in the temperature range 298-800 K. Enthalpy increment measurements were carried out on the above solid solutions using high temperature drop calorimetry in the temperature range 800-1800 K. Chemical states of U and La in the solid solutions of mixed oxides were determined using X-ray photoelectron spectroscopy (XPS). Oxygen to metal ratios of (U1-yLay)O2±x were estimated from the ratios of different chemical states of U present in the sample. Anomalous increase in the heat capacity is observed for (U1-yLay)O2±x (y = 0.4, 0.6 and 0.8) with onset temperatures in the range of 1000-1200 K. The anomalous increase in the heat capacity is attributed to certain thermal excitation process, namely, Frenkel pair defect of oxygen. The heat capacity value of (U1-yLay)O2±x (y = 0.2, 0.4, 0.6, and 0.8) at 298 K are 65.3, 64.1, 57.7, 51.9 J K-1 mol-1, respectively. From the XPS investigations, it was observed that the O/M ratios at the surface are higher than that in the bulk. In uranium rich mixed oxide samples, the surface O/M ratios are greater than 2 whereas that in La rich mixed oxides, they are less than 2, though the bulk O/M in all the samples are less than 2.