ABSTRACT
Laves phase alloys possess unique thermal and electrical conduction properties, yet the factors governing phase stability in these systems remain an open question. The influence of phonons in particular has been broadly overlooked. Here, we investigate the UCo2x Ni2(1-x) chemical space using density functional theory, which offers a unique opportunity to explore the factors influencing Laves phase stability as all three primary Laves phases (C14, C15, C36) can be stabilized by changing the ratio of Co to Ni. Calculations of the thermodynamic and dynamical stability of pure UCo2 and UNi2 in each of three primary Laves phases confirm the stability of experimentally known Laves phases for UNi2 and UCo2. A decrease in bonding strength is identified in UNi2 compared to UCo2, aligned with redshifts observed in the UNi2 phonon density of states and a decoupling of the U and Ni vibrational modes. Phonon calculations of C14 UCo2 reveal dynamical instabilities. Efforts to remove the unstable mode at the Γ point in UCo2 via atomic displacements break the symmetry of the C14 phase, revealing a lower energy P2/c structure. Vibrational contributions to the free energy were calculated and did not change the thermodynamically stable Laves phase below 1000 K. The temperature-dependent free energies of single phase UCo2 and UNi2 were used to interpolate the relative stability of ternary UCo2x Ni2(1-x) in each of the three Laves phases at varying temperatures and stoichiometries. The ternary C36 phase is only predicted to be thermodynamically stable over a narrow stoichiometric range below 600 K.
ABSTRACT
Alumina is a structural ceramic that finds many uses in a broad range of applications. It is widely employed in the aerospace and biomedical sectors due to its stability at high temperatures and in harsh chemical environments. Here, we show that magnetism can be induced at alumina surfaces by doping with 3d transition metals. We analyze the electronic structure, spin magnetic moments, and spin density of [Formula: see text]-Al[Formula: see text]O[Formula: see text] as a function of both dopant species (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu) and depth using first principles calculations. Our results show that all dopants, with the exception of Sc, produce magnetic moments that are concentrated to the surface of alumina with varying degrees of delocalization. It is seen that all of the dopants are at least meta-stable on the surface and must overcome an energy barrier of 0.19-1.14 eV in order to diffuse from the surface into the bulk. As a result of judiciously doping with select 3d transition metals the surface of alumina can be made magnetic. This could lead to novel applications in data storage, catalysis, and biomedical engineering through an added surface functionality.
ABSTRACT
Judicious doping of normally diamagnetic alumina (Al2O3) could lead to bulk magnetism that would enable the usage of cutting edge technology, such as magnetoforming, to create advanced systems that take advantage of the high chemical and physical resilience of alumina. This study builds upon initial results (Nykwest et al 2018 J. Phys.: Condens. Matter 30 395801) which have shown that alumina doped with magnetic elements such as Fe and Ni should exhibit heightened magnetic activity. Here we expand the analysis to several additional transition metals that are otherwise non-magnetic (Sc, Ti, V, Mn, and Co) and use density functional theory to understand the origin of the spin delocalization, as well as to predict the structural, electronic, energetic, and magnetic properties of doped [Formula: see text]-alumina. The results indicate that adding small concentrations of such elements to [Formula: see text]-alumina may increase magnetic activity by generating coordination environments with magnetic moments. Our findings show conclusively that significant spin delocalization can only occur when there are unpaired electrons in the transition metal e g states.
ABSTRACT
A doped non-diamagnetic alumina (Al2O3) would enable the usage of cutting edge technology, such as magnetoforming, to create advanced systems that take advantage of the high chemical and physical resilience of alumina. This study elucidates the magnetic properties of Cr, Fe, Ni, and Cu doped α- and Ï-alumina. Density functional theory was used to predict the structural, electronic, and magnetic properties of doped alumina, as well as its stability. The results indicate that the dopant species and coordination environment are the most important factors in determining the spin density distribution and net magnetic moment, which will strongly direct the ability of the doped alumina to couple with an external field. Similar coordination environments in different phases produce similar spin densities and magnetic moments, indicating that the results presented in this work may be generalizable to the other five or more phases of alumina not studied here.
