Impact of rare earth ion size on the phase evolution of MoO3-containing aluminoborosilicate glass-ceramics

Transition metal and rare earth (RE) elements are important fission products present in used nuclear fuel, which in high concentrations tend to precipitate crystalline phases in vitreous nuclear waste forms. Two phases of particular interest are powellite (CaMoO4) and oxyapatite (Ca2RE8(SiO4)6O2). The glass compositional dependencies controlling crystallization of these phases on cooling from the melt are poorly understood. In the present study, the effect of rare earth identity and modifier cation field strength on powellite and apatite crystallization were studied in a model MoO3-containing alkali/alkaline-earth aluminoborosilicate glass with focus on (1) influence of rare earth cation size (for RE3+: Ce, La, Nd, Sm, Er, Yb) and (2) influence of non-framework cations (RE3+, Mo6+, Na+, Ca2+). Quenched glasses and glass-ceramics (obtained by slow cooling) were characterized by X-ray diffraction (XRD), Raman spectroscopy, X-ray absorption spectroscopy (XAS), and electron probe microanalysis (EPMA). All samples were X-ray amorphous upon quenching, except the Ce-containing composition which crystallized ceria (CeO2), and the sample devoid of any rare earth cations which crystallized powellite. On heat treatment, powellite and oxyapatite crystallized in the majority of the samples, with the former crystallizing in the volume and the latter on the surface. The EPMA results confirmed a small concentration of boron in the oxyapatite crystal structure. RE cations were incorporated in the glass, as well as in powellite, oxyapatite, and in the case of Yb3+, keiviite (Yb2Si2O7). Raman spectroscopy showed that the primary vibration band for molybdate MoO42−in the glasses was strongly affected by the ionic field strength of the modifying cations (alkali, alkaline earth, and RE), suggesting their proximity to the MoO42−ions in the glass, though the Mo–O bond length and coordination according to XAS suggested little local change

Effect of microstructure on the stability of retained austenite in transformation-induced-plasticity steels

Two Fe-0.2C-1.55Mn-1.5Si (in wt pet) steels, with and without the addition of 0.039Nb (in wt pet), were studied using laboratory rolling-mill simulations of controlled thermomechanical processing. The microstructures of all samples were characterized by optical metallography, X-ray diffraction (XRD), and transmission electron microscopy (TEM). The microstructural behavior of phases under applied strain was studied using a heat-tinting technique. Despite the similarity in the microstructures of the two steels (equal amounts of polygonal ferrite, carbide-free bainite, and retained austenite), the mechanical properties were different. The mechanical properties of these transformation-induced-plasticity (TRIP) steels depended not only on the individual behavior of all these phases, but also on the interaction between the phases during deformation. The polygonal ferrite and bainite of the C-Mn-Si steel contributed to the elongation more than these phases in the C-Mn-Si-Nb-steel. The stability of retained austenite depends on its location within the microstructure, the morphology of the bainite, and its interaction with other phases during straining. Granular bainite was the bainite morphology that provided the optimum stability of the retained austenite.<br /