The thermal decomposition process of air-aged La203 in argon atmosphere was studied using nonisothermal TG-DSC. X-ray diffraction and TG-DSC analysis showed that the aged powder was composed of La(OH)3 with small amounts of oxycarbonate. The decomposition process of air-aged La2O3 involves the two-step decomposition of La(OH)3 and the decomposition of oxycarbonate. The kinetic analysis of the two-step decomposition of La(OH)3 was carried out using Coats-Redfern and isoconversion (Ozawa) methods. The kinetics of the two-step decomposition can be described in terms of the nucleation and growth model A (m=1.5, m is the model parameter) and A (m=2.5), respectively. The apparent activation energy for the first step is 136-144 (Coats-Redfern) and 137-164 kJ/mol (isoconversion). The apparent activation energy for the second step is 191-194 (Coats-Redfern) and 186-213 kJ/mol (isoconversion).
Pr(Ga1-xCox)0.9Mg0.1O3-δ (x=0, 0.1, 0.2, 0.3) was synthesized using solid-state reaction technique to study the effects of Co doping on their structure and properties. Room and high temperature XRD, DSC and electrical conductivity measurement with D.C. four-probe technique were adopted in the study. The results indicated its orthorhombic-distorted perovskite structure at room temperature. PrGa0.9Mg0.1O3-δ maintained its orthorhombic-distorted structure between 298 and 1173 K. For Pr(Ga0.7Co0.3)0.9Mg0.1O3-δ, such structure existed below 873 K. From 873 to 1173 K, it possessed tetragonal structure. The transformation from orthorhombic to tetragonal structure at 873 K was of second order. The intrinsic volume thermal expansion of tetragonal structured Pr(Ga0.7Co0.3)0.9Mg0.1O3-δ Was about 50% higher than those of PrGa0.9Mg0.1O3-δ. The electrical conductivity increased with Co content. The activation energies of conduction for Pr(Ga1-xCox)0.9Mg0.1O3-δ are in range from 0.197 to 0.246 eV, much lower than 1.543 eV for PrGaO3.