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We previously reported that Zr substitution improves the chemical stability of Ba3Y4O9 and nominally 20 mol% Zr-substituted Ba3Y4O9 is an oxide-ion conductor at intermediate temperatures (500–700 °C). However, the influence of Zr substitution on the structural properties of Ba3Y4O9 was poorly understood. This paper aims to comprehensively understand the crystal structure of Ba3Y4O9 with Zr substitution by powder X-ray diffraction (XRD), extended X-ray absorption fine structure (EXAFS) measurements, and first-principles calculations. From the results, firstly we found that the hexagonal unit cell of Ba3Y4O9 reported in the database should be revised as doubled along the c-axis in terms of the periodicity of oxide-ion positions. The revised unit cell of Ba3Y4O9 consists of 18 layers of BaO3 and 24 layers of Y which periodically stack along the c-axis. In this work, we focused on the cationic lattice and noticed that the periodical stacking of Ba and Y layers comprises a similar sequence to that in the body-centered cubic (BCC) structure. There are two regions in the Ba3Y4O9 structure: one is a hetero-stacking region of Ba and Y layers (Ba–Y–Ba–Y–Ba) and the other is a homo-stacking region (Ba–Y–Y–Ba). It is noteworthy that the former region is similar to a cubic perovskite. In Zr-substituted Ba3Y4O9, Zr ions preferentially substitute for Y ions in the hetero-stacking region, and therefore the local environment of Zr ions in Ba3Y4O9 is quite similar to that in BaZrO3. Besides, the Zr substitution for Y in Ba3Y4O9 increases the fraction of the cubic-perovskite-like region in the stacking sequences. The structural change in the long-range order strongly affects the other material properties such as chemical stability and the ionic-conduction mechanism. Our adopted description of perovskite-related compounds based on the stacking sequence of the BCC structure should help in understanding the complex structure and developing new perovskite-related materials. [ABSTRACT FROM AUTHOR]

Transition metal-based two-dimensional nanomaterials with competing magnetic states are at the cutting edge of spintronic and low-power memory devices. In this paper, we present a Fe-rich NbFe1+xTe3 layered telluride (x ≈ 0.5), which shows an interplay of spin-glass and antiferromagnetic states below the Néel temperature of 179 K. The compound has a layered crystal structure, where the NbFeTe3 layers are terminated by the Te atoms and van der Waals gaps. Bulk single crystals grown by chemical vapor transport reactions possess the (1¯01) cleavage plane suitable for the exfoliation of two-dimensional nanomaterials. Combination of high-resolution transmission electron microscopy and powder X-ray diffraction reveals the zigzag ladders of Fe atoms inside the structural layers, as well as complementary zigzag chains of the partially occupied Fe positions in the interstitial region. Fe atoms carry large effective magnetic moment of 4.85(3)μB per atom in the paramagnetic state yielding intriguing magnetic properties of NbFe1+xTe3. They include frozen spin-glass state at low temperatures and spin-flop transition in high magnetic fields indicating promising flexibility of the magnetic system and its potential control by magnetic field or gate tuning in the spintronic devices and heterostructures. [ABSTRACT FROM AUTHOR]

Saponification, resulting from pigment–binder interactions, is one of the most endangering phenomena affecting the appearance and stability of painted works of art. The crystallization of metal carboxylates (soaps) in paint layers is recently assumed as the most critical point for the development of undesirable changes induced by saponification, however, the factors triggering it are not fully understood. The red pigment cinnabar (HgS) has been suspected of contributing to saponification, however, the paucity of reliable reference structural data limited the experimental research of its effect at the molecular level. Within this study we synthesized mercury(II) carboxylates of the formula Hg(C16)x(C18)2−x (x = 0.0; 0.2; 0.5; 0.8; 1.0; 1.2; 1.5; 1.8; 2.0) where C16 and C18 are hexadecanoate (palmitate) and octadecanoate (stearate), respectively, and characterize them by combination of X-ray powder diffraction (XRPD) and 13C and 199Hg solid state NMR (ssNMR). For a more detailed interpretation of their structural and thermal behavior, Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) were used. The crystal structure of the studied mercury carboxylates was described on the basis of complementary ssNMR and XRPD measurements, Rietveld refinement and DFT calculations. All the subjected compounds crystallize in a monoclinic lattice of the C2/c symmetry. Mercury atoms are arranged in a slightly distorted square antiprismatic geometry and are monodentatically bonded to carboxylate anions. The structural disorder at the aliphatic end of the stearic acid chains was detected in the mixed carboxylates. Within the paper, the structural (dis)similarity with the corresponding lead carboxylates is discussed. The synthesized and characterized mercury carboxylates were applied to describe neo-formed mercury soaps in a model experiment simulating an egg-based paint system. [ABSTRACT FROM AUTHOR]

In this paper, we have studied the effect on the structural, magnetic and magnetocaloric properties of La and Sr-deficiencies in the La0.67Sr0.33MnO3 compound. Rietveld refinement of the X-ray powder diffraction patterns confirms that all of the compounds have crystallized into a rhombohedral crystal symmetry with an R3̅c space group. X-ray photoelectron spectroscopy measurements revealed that the parent compound has a mixed valance of Mn3+/Mn4+, whereas Mn2+/Mn3+/Mn4+ mixed valency is found in the case of both La and Sr-deficient compounds. The La0.67Sr0.33MnO3 compound shows a magnetic transition temperature of 365 K, while the La and Sr-deficient compounds exhibit transition temperatures of 367 K and 355 K, respectively. Among the studied compounds, the Sr-deficient compound shows the highest magnetic entropy change (ΔSM) of 5.08 J kg−1 K−1 at 352 K for a 50 kOe field with a relative cooling power (RCP) of 142 J kg−1 and an adiabatic temperature change of 3.48 K, while the parent and La-deficient compounds exhibit a −ΔSM of 4.78 J kg−1 K−1 at 364 K and of 4.12 J kg−1 K−1 at 364 K, respectively. The temperature dependence of the electrical resistivity with and without applied magnetic fields reveals that the La-deficient compound has one order and the Sr-deficient compound has two orders of suppression in the electrical resistivity. Thus, the Sr-deficient compound shows promising behaviour for reduction of the magnetic transition temperature towards room temperature, along with an increase in the ΔSM values, and enhancement in the electrical conductivity. Therefore, it could be possible to tune the transition temperature towards room temperature without compromising the magnetic entropy change in order to develop materials for magnetic refrigeration applications. [ABSTRACT FROM AUTHOR]