Mechanical properties of superionic ceramics based on (Cu1–xAgx)7GeSe5I solid solutions

Cu1–xAgx)7GeSe5I-based ceramics were prepared by pressing and sintering from the micro- and nanopowders. The ceramic samples were investigated using microstructural analysis. The microhardness was measured applying the indentation method with use of the Vickers pyramid. It has been shown that the microhardness of (Cu1–xAgx)7GeSe5I-based ceramics decreases with copper content decrease at Cu+→Ag+cationic substitution. The compositional dependences and size effects of microhardness inherent to (Cu1–xAgx)7GeSe5I-based ceramics have been analyzed. The size effects of microindentation have been interpreted within the framework of the gradient theory of plasticity.

Valence band structure and charge distribution in the layered lanthanide-doped CuCr0.99Ln0.01S2 (Ln = La, Ce) solid solutions

The comprehensive study of the electronic density distribution of CuCr0.99Ln0.01S2 (Ln = La, Ce) solid solutions was carried out using both X-ray photoelectron and emission spectroscopy. It was found that cationic substitution of chromium with lanthanum or cerium atoms does not significantly affect the atomic charges of the matrix elements (Cu, Cr, S) in the lanthanide-doped solid solutions. The copper atoms in the composition of CuCrS2-matrix and the lanthanide-doped solid solutions were found to be in the monovalent state. The chromium and lanthanide atoms were found to be in the trivalent state. This fact indicates the isovalent cationic substitution character. The sulfur atoms were found to be in the divalent state. The near-surface layers contain the additional oxidation forms of sulfur (S0, S4+, S6+) and copper (Cu2+) atoms. The detailed analysis of the valence band structure using DFT calculations has shown that partial DOS distribution character of the matrix elements is preserved after the cationic substitution. The experimental valence band spectra structure of CuCrS2-matrix and CuCr0.99Ln0.01S2 is determined by the occupied copper d-states contribution. The contribution of the lanthanide states in the valence band structure is lower in comparison with those for the matrix elements. The major contribution of the lanthanide states was found to be mainly localized near the conduction band bottom.

Cationic Substitutions in Sphalerite from the Porgera Mine, Papua New Guinea

ABSTRACT Laser ablation-inductively coupled plasma-mass spectrometry was used to traverse hydrothermal vein sphalerite from different ore-forming stages of the Porgera Au-Ag mine, Papua New Guinea. Elements were measured in situ over the growth of crystals to investigate the greatly varying concentrations of cations in sphalerite and their positions in the lattice. Traverse profiles for 16 elements were obtained and aligned to transmitted light images where possible. Each sample contained an array of elements, with many displaying orders of magnitude concentration differences. Results show the simultaneous incorporation of Cu and Sn in sphalerite, as well as Cu and Ag, In and Sn, As and Sb, Fe and Mn, and Cu and Ga. The relation [4Zn2+ ↔ 2Cu+ + Sn2+ + Sn4+] is proposed to explain the 1:1 Cu–Sn correlation. Further relations can be seen, including a Ga “ceiling” or Cu “floor”, where Ga incorporation becomes dependent on Cu concentrations. Furthermore, silver was also observed to correlate with Au, Mn, Ni, Pb, and Bi. Meta-stable solid solutions between pairs such as Cu, Ag; Fe, Mn; As, Sb; and In, Sn are also suggested. Each of these pairs are neighbors on the periodic table of elements, which suggests that simple solid solution can occur, and positive correlations for all four solid solutions were found in one sample alone. While the concept of charge-specific solid solutions in sphalerite has been discussed in the literature with reference to monovalent cations, the results presented herein also indicate solid solutions of higher oxidation states, containing many cations. Furthermore, while cations in charge-specific solid solutions have been proposed to compete for lattice sites in sphalerite, simultaneous in situ coupled concentrations at Porgera suggest otherwise. Cationic substitution equations displaying decimal ratios of each element in solid solution can then provide a novel method to distinguish between solid solution concentrations in different samples. For example, displaying 1:1 ratios of Cu–Ag and Sb–As: [2Zn2+ ↔ (Cu+0.5, Ag+0.5) + (As3+0.5, Sb3+0.5)], or for a 100:1 Fe–Mn ratio: [Zn2+ ↔ (Fe2+0.99, Mn2+0.01)].

Intrinsic and extrinsic defects build a novel mechanoluminescent phosphor Na2MgGeO4:Mn2+

Intrinsic oxygen vacancy and cationic substitution defects construct a novel mechanoluminescent material.