Engineering topics

Putti, Marina

Publications and source records attributed to Putti, Marina.

3 records

DOE OSTI2023

Mechanochemical Synthesis of Sustainable Ternary and Quaternary Nanostructured Cu2SnS3, Cu2ZnSnS4, and Cu2ZnSnSe4 Chalcogenides for Thermoelectric Applications

Copper-based chalcogenides have emerged as promising thermoelectric materials due to their high thermoelectric performance, tunable transport properties, earth abundance and low toxicity. We have presented an overview of experimental results and first-principal calculations investigating the thermoelectric properties of various polymorphs of Cu2SnS3 (CTS), Cu2ZnSnS4 (CZTS), and Cu2ZnSnSe4 (CZTSe) synthesized by high-energy reactive mechanical alloying (ball milling). Of particular interest are the disordered polymorphs of these materials, which exhibit phonon-glass–electron-crystal behavior—a decoupling of electron and phonon transport properties. The interplay of cationic disorder and nanostructuring leads to ultra-low thermal conductivities while enhancing electronic transport. These beneficial transport properties are the consequence of a plethora of features, including trap states, anharmonicity, rattling, and conductive surface states, both topologically trivial and non-trivial. Based on experimental results and computational methods, this report aims to elucidate the details of the electronic and lattice transport properties, thereby confirming that the higher thermoelectric (TE) performance of disordered polymorphs is essentially due to their complex crystallographic structures. In addition, we have presented synchrotron X-ray diffraction (SR-XRD) measurements and ab initio molecular dynamics (AIMD) simulations of the root-mean-square displacement (RMSD) in these materials, confirming anharmonicity and bond inhomogeneity for disordered polymorphs.

36 MATERIALS SCIENCE↗

DOE OSTI2016

Gd 3 Ni 2 and Gd 3 Co x Ni 2-x : magnetism and unexpected Co/Ni crystallographic ordering

The crystal structure, composition and physical properties of Gd 3 Ni 2 , which was earlier reported to exist in the Gd–Ni system without any details of its structure and properties, have been determined. This rare earth binary compound is a high-temperature phase: it forms via a peritectic reaction at 988 K (715 °C) and decomposes below ≈923 K (650 °C). The compound can be retained at room temperature as a metastable phase by quenching after high temperature annealing. Gd 3 Ni 2 crystallizes in the monoclinic Dy 3 Ni 2 structure type [mS20, C2/m (No. 12), Z = 4; with lattice parameters a = 13.418(3) Å, b = 3.720(1) Å, c = 9.640(2) Å, β = 106.250(3)°]. Ni can be substituted by Co up to 50% (i.e. up to and including Gd 3 CoNi) with no change in the structural prototype; the substitution of Co for Ni stabilizes the R 3 Co x Ni 2-x phases down to room temperature. The crystal structure, magnetic properties and magnetocaloric effect (MCE) have been investigated for both Gd 3 Ni 2 and the related Gd 3 Co x Ni 2-x solid solution alloys (0 ≤ x ≤ 1). The crystal structure of the Gd 3 CoNi is a ternary ordered derivative of the monoclinic Dy 3 Ni 2 -type, where Co fully occupies only one of the two 4i Wyckoff sites available for the transition metal. To the best of our knowledge, this is the first example of an intermetallic phase showing ordered site occupations by the chemically quite similar elements Co and Ni. All compounds show long range ferromagnetic ordering, with T C progressively increasing from 147 K (for Gd 3 Ni 2 ) to 176 K (for Gd 3 CoNi) as a cubic function of the Co content. Evidence of Co contributing to the magnetic interactions in these compounds has been found. First-principles total energy calculations predicted the ordered occupation of Co and Ni at the crystallographic sites of Gd3CoNi, which was later confirmed by single crystal X-ray diffraction. The increased conduction electronic state (3d) exchange splitting at the Fermi level supports the experimentally observed enhanced Curie temperature in Gd 3 CoNi compared to Gd 3 Ni 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2012

Focus on superconductivity in Fe-based systems

The past four years of incredibly intense research into Fe-based superconductors have brought about many unexpected surprises. Our understanding of their behavior and physical properties is constantly evolving. Unlike any other superconductors, those containing iron span diverse groups of materials: pnictides, chalcogenides, intermetallics and oxides. Some major properties of the materials are quite similar, yet each group has its own distinct features. Significant effort has been put into identifying new superconducting compositions, modifying the existing ones with new dopants and treatments, and producing single crystals, thin films, wires and polycrystalline bulk material. A wide array of experimental techniques was applied to study Fe-based superconductors and the result is a tremendous amount of data collected over a period of less than four years. Theoretical debates are still lively, and there is an ongoing search for possible universalities and commonalities with other unconventional superconductors, like high-Tc cuprates or heavy fermion materials. The three-dimensional electronic structures of Fe-based superconductors, as well as their extreme sensitivity to disorder, present serious challenges for both theoretical analysis and the interpretation of experiments. However, some key properties emerge from multiple studies. Unconventional, multiband superconductivity originating from an electronic mechanism has found both experimental and theoretical support. There has been great progress in the understanding of various anisotropies of superconducting gap structures, including the possibility of gap nodes even if the gap symmetry is s-wave. Similar to high-Tc cuprates, the superconducting phase has a dome-like shape on T-doping or T-pressure phase diagrams. The anisotropy of the superconducting gap evolves with doping and is likely to become stronger at the dome';s edge. In many Fe-based superconductors there is a range where superconductivity coexists and competes with long-range magnetic order, and magnetic fluctuations are considered by some to be of the utmost importance for the pairing mechanism. Others argue that orbital fluctuations, possibly in combination with phonons, are crucial for the pairing. Fe-based superconductors show extremely large upper critical fields and relatively low electronic anisotropy, which are crucial aspects for power applications. The expectations are high, though it remains unclear what maximal current densities can be supported by a properly designed bulk material with optimal pinning centers. This focus issue of Superconductor Science and Technology is a snapshot of some of the recent progress in materials preparation, experiments and theory. It includes articles on the search for new Fe-based superconductors and on the search for superconductivity at extreme conditions. Particular attention is devoted to: the effects of chemical substitutions; the development of thin films; the introduction of artificial defects to increase critical current density; and a general analysis of vortex physics. The articles on fundamental aspects of superconductivity include: the discussion of various experimental problems; an in-depth analysis of the nodal and nodeless pairing states; the discussion of the pairing mechanism; and the effects of pair-breaking due to disorder. Also discussed are nematic correlations and the coexistence of magnetism and superconductivity. The papers collected in this issue present a detailed review of the accomplishments of the last four years of research into Fe-based superconductors, up to and including last-minute developments. We hope that this combination will make this special section of Superconductor Science and Technology both interesting and useful to a broad spectrum of physicists and materials scientists.

36 MATERIALS SCIENCE↗