TY - JOUR
T1 - Rare-earth perovskites along the CaTiO3-Na0.5La0.5TiO3 join
T2 - Phase transitions, formation enthalpies, and implications for loparite minerals
AU - Feng, Dawei
AU - Shivaramaiah, Radha
AU - Navrotsky, Alexandra
N1 - Publisher Copyright:
© 2016 by Walter de Gruyter Berlin/Boston 2016.
PY - 2016/9/1
Y1 - 2016/9/1
N2 - The mineral loparite is the principal ore of the light rare earth elements (LREE) with solid solution compositions in the quaternary system perovskite-lueshite-tausonite-loparite (CaTiO3-NaNbO3-SrTiO3-Na0.5Ln0.5TiO3) (Ln = La, Ce, Pr, Nd). In this study, perovskite solid solutions Ca1-2xNaxLaxTiO3 (0 ≤ x ≤ 0.50) along the perovskite-loparite join were synthesized using solid-state sintering methods. XRD analysis indicates that as the Na+La content increases, the structure changes from orthorhombic to tetragonal. The enthalpies of formation at 298 K from the constituent oxides (ΔH°f, ox) and from the elements (ΔH°f,el) have been determined using high-temperature oxide melt solution calorimetry in molten 3Na2O.4MoO3 at 973 K. Enthalpy of formation from oxides ΔH°f,ox becomes more exothermic with increasing Na+La content, suggesting a stabilization effect of the substitution Ca2+ → 0.5Na+ + 0.5La3+. The observed trend of increasing thermodynamic stability with decreasing structural distortion is in agreement with that seen in many other ABO3 perovskites. The thermodynamic stability of perovskite solid solutions Ca1-2xNaxLaxTiO3 (0 ≤ x ≤ 0.50) along the CaTiO3-Na0.5La0.5TiO3 join provides insights into the natural occurrence of loparite minerals (La, Na, Sr, Ca)(Ti, Nb, Ta, Fe3+)O3.
AB - The mineral loparite is the principal ore of the light rare earth elements (LREE) with solid solution compositions in the quaternary system perovskite-lueshite-tausonite-loparite (CaTiO3-NaNbO3-SrTiO3-Na0.5Ln0.5TiO3) (Ln = La, Ce, Pr, Nd). In this study, perovskite solid solutions Ca1-2xNaxLaxTiO3 (0 ≤ x ≤ 0.50) along the perovskite-loparite join were synthesized using solid-state sintering methods. XRD analysis indicates that as the Na+La content increases, the structure changes from orthorhombic to tetragonal. The enthalpies of formation at 298 K from the constituent oxides (ΔH°f, ox) and from the elements (ΔH°f,el) have been determined using high-temperature oxide melt solution calorimetry in molten 3Na2O.4MoO3 at 973 K. Enthalpy of formation from oxides ΔH°f,ox becomes more exothermic with increasing Na+La content, suggesting a stabilization effect of the substitution Ca2+ → 0.5Na+ + 0.5La3+. The observed trend of increasing thermodynamic stability with decreasing structural distortion is in agreement with that seen in many other ABO3 perovskites. The thermodynamic stability of perovskite solid solutions Ca1-2xNaxLaxTiO3 (0 ≤ x ≤ 0.50) along the CaTiO3-Na0.5La0.5TiO3 join provides insights into the natural occurrence of loparite minerals (La, Na, Sr, Ca)(Ti, Nb, Ta, Fe3+)O3.
KW - Rare earth perovskites
KW - calorimetry
KW - enthalpy of formation
KW - loparite
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U2 - 10.2138/am-2016-5740
DO - 10.2138/am-2016-5740
M3 - Article
AN - SCOPUS:84989245455
SN - 0003-004X
VL - 101
SP - 2051
EP - 2056
JO - American Mineralogist
JF - American Mineralogist
IS - 9
ER -