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The influence of kinematics of deformation on polycrystalline halite dynamic recrystallization: Full-field simulation of simple shear versus pure shear

Rock salt, composed mainly of halite, flows viscoplastically over a wide range of geological conditions, strongly impacting the dynamic evolution of sedimentary basins and orogens. Understanding how dislocation creep, which involves dislocation glide, intracrystalline recovery and dynamic recrystallization, influences the microstructure and rheology of halite under various deformation kinematics and temperatures is crucial for enhancing knowledge of salt flow dynamics. Here, this study employs a full-field numerical simulation method to compare the viscoplastic deformation of polycrystalline halite under simple shear and pure shear conditions up to a natural strain of ε = 1.5 at temperatures ranging from 100 °C to 300 °C. The results are presented in terms of crystallographic preferred orientation (CPO), grain shape preferred orientation (SPO), subgrain boundary direction, grain size and strain rate distribution. The results indicate that the crystallographic anisotropy of individual halite crystals is transferred to the polycrystalline scale, resulting in strain localization, particularly in simple shear simulations. The kinematics of deformation affect the evolution and distribution of high strain-rate bands, determining the direction of intragranular substructures and the morphology of strain-induced grain boundaries, with minimal impact on grain size. The intensity of grain boundary migration increases with temperature, significantly influencing grain morphology and size, thereby obscuring strain localization, while having little effect on CPOs. At low strain (ε < 1.0), CPOs relative to both the maximum shortening direction and the grain SPO are similar regardless of the deformation kinematics. At high strain (ε > 1.0), simple shear CPOs exhibit three stronger {100} maxima with a monoclinic symmetry relative to the grain SPO compared to the six {100} maxima with an orthotropic symmetry relative to the grain SPO generated under pure shear. Therefore, microstructures and CPOs can serve as indicators of the strain path in polycrystalline halite under various conditions, aiding in determining the shear sense and elucidating the deformation kinematics of salt structures.

58 GEOSCIENCES↗

Synthesis of Li{sub 2}PtH{sub 6} using high pressure: Completion of the homologous series A{sub 2}PtH{sub 6} (A=alkali metal)

Li{sub 2}PtH{sub 6}, the missing member of the complex transition metal hydride series A{sub 2}PtH{sub 6} (A=alkali metal), was prepared by reacting mixtures of LiH and Pt in the presence of BH{sub 3}NH{sub 3} as hydrogen source at pressures above 8 GPa. According to powder X-ray diffraction analysis, Li{sub 2}PtH{sub 6} is isostructural to its heavier homologues and crystallizes in the cubic K{sub 2}PtCl{sub 6} structure (space group Fm3-bar m, a=6.7681(3), Z=4). However, PtH{sub 6}{sup 2-} octahedral complexes in Li{sub 2}PtH{sub 6} approach each other closely and its structure may likewise be regarded as a defective perovskite structure where half of the octahedrally coordinated atoms (cations) are missing. The IR spectrum of Li{sub 2}PtH{sub 6} reveals the Pt-H T{sub 1u} stretch and bend at 1840 and 889 cm{sup -1}, respectively. - Graphical abstract: Li{sub 2}PtH{sub 6}, the missing start member of the complex metal hydride series A{sub 2}PtH{sub 6} (A=alkali metal) has been prepared by high pressure hydrogenation. In contrast to the heavier homologues, PtH{sub 6}{sup 2-} octahedral units in Li{sub 2}PtH{sub 6} are not well separated and H atoms form a substructure closely corresponding to that of O atoms in cubic perovskite.

36 MATERIALS SCIENCE↗

Unprecedented solid-state chemical reaction-from (C{sub 3}N{sub 2}H{sub 5}){sub 3}SbBr{sub 6}.H{sub 2}Oto(C{sub 3}N{sub 2}H{sub 5}){sub 5}Sb{sub 2}Br{sub 11}. From centrosymmetric to non-centrosymmetric crystal structure

Tris(imidazolium) hexabromoantimonate(III) hydrate, (C{sub 3}N{sub 2}H{sub 5}){sub 3}SbBr{sub 6}.H{sub 2}O, (abbreviated as TIBA) has been synthesized and characterized by X-ray (at 295, 225, 160, and 110 K), differential scanning calorimetry, dilatometry, and dielectric spectroscopy. At room temperature (phase I), the structure consists of discrete SbB{sub 6}{sup -} anions, disordered imidazolium cations, and water molecules forming a 3D array of hydrogen bonds. Below room temperature, TIBA was found to undergo isostructural discontinuous phase transition at 212/221 K (cooling-heating) (P2{sub 1}/c{r_reversible}P2{sub 1}/c). The phase transition mechanism is characterized by two contributions: an order-disorder (cationic substructure) and a displacive (water molecules) one. At high temperatures, the TIBA crystal was found to undergo an unprecedented in situ solid-state chemical reaction: (1)2(C{sub 3}N{sub 2}H{sub 5}){sub 3}SbBr{sub 6}.H{sub 2}O{sub (S)}{yields}(C{sub 3}N{sub 2}H{sub 5}){sub 5}Sb{sub 2}Br{sub 11(S)}+(C{sub 3}N{sub 2}H{sub 5})Br{sub (S)}+2H{sub 2}O This chemical transformation leads to multiphase crystallites dominated by an amorphous phase of (C{sub 3}N{sub 2}H{sub 5}){sub 5}Sb{sub 2}Br{sub 11}. The creation of ferroelectric crystallites - (C{sub 3}N{sub 2}H{sub 5}){sub 5}Sb{sub 2}Br{sub 11} - in an 'annealed' sample of (C{sub 3}N{sub 2}H{sub 5}){sub 3}SbBr{sub 6}.H{sub 2}O was confirmed by X-ray diffraction phase analysis, dielectric spectroscopy, and pyroelectric measurements. The dielectric response of the electric permittivity and the critical slowing down of the process observed near 140 K in the 'annealed' sample of TIBA are treated as a 'fingerprint' of a neat (C{sub 3}N{sub 2}H{sub 5}){sub 5}Sb{sub 2}Br{sub 11} ferroelectric. -- Graphical Abstract: Chemical reaction taking place in (C{sub 3}N{sub 2}H{sub 5}){sub 3}SbBr{sub 6}.H{sub 2}O at 328 K. Display Omitted

36 MATERIALS SCIENCE↗

Effects of partial anion substitution on the thermoelectric properties of silver(I) chalcogenide halides in the system Ag{sub 5}Q{sub 2}X with Q=Te, Se and S and X=Br and Cl

A selection of mixed conducting silver chalcogenide halides of the general formula Ag{sub 5}Q{sub 2}X with Q=sulfur, selenium and tellurium and X=chlorine and bromine has been investigated due to their thermoelectric properties. Recently, the ternary counterpart Ag{sub 5}Te{sub 2}Cl showed a defined d{sup 10}-d{sup 10} interaction in the disordered cation substructure at elevated temperatures where Ag{sub 5}Te{sub 2}Cl is present in its high temperature {alpha}-phase. A significant drop of the thermal diffusivity has been observed during the {beta}-{alpha} phase transition reducing the values from 0.12 close to 0.08 mm{sup 2} s{sup -1}. At the same transition the thermopower reacts on the increasing silver mobility and jumps towards less negative values. Thermal conductivities, thermopower and thermal diffusivity of selected compounds with various grades of anion substitution in Ag{sub 5}Q{sub 2}X were determined around the silver-order/disorder {beta}-{alpha} phase transition. A formation of attractive interactions could be observed for selenium substituted phases while no effect was detected for bromide and sulfide samples. Depending on the grade and type of substitution the thermopower changes significantly at and after the {beta}-{alpha} phase transition. Thermal conductivities are low reaching values around 0.2-0.3 W m{sup -1} K{sup -1} at 299 K. Partial anion exchange can substantially tune the thermoelectric properties in Ag{sub 5}Q{sub 2}X phases. -- Graphical abstract: A structure section of the {alpha}-Ag{sub 5}Te{sub 2}Cl structure type and the thermopower evolution of Ag{sub 5}Te{sub 2}Cl{sub 0.4}Br{sub 0.6} undergoing a silver ion order/disorder phase transition. Display Omitted Research highlights: > We report on thermoelectric properties of silver(I) chalcogenide halides. > We examine thermopower, thermal diffusivity and thermal behavior. > Silver mobility, phase transitions and order/disorder phenomena are discussed. > Partial anion exchange can tune thermoelectric properties significantly.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Double perovskite Sr{sub 2}FeMoO{sub 6-x}N{sub x} (x=0.3, 1.0) oxynitrides with anionic ordering

Two new oxynitride double perovskites of composition Sr{sub 2}FeMoO{sub 6-x}N{sub x} (x=0.3, 1.0) have been synthesized by annealing precursor powders obtained by citrate techniques in flowing ammonia at 750 Degree-Sign C and 650 Degree-Sign C, respectively. The polycrystalline samples have been characterized by chemical analysis, x-ray and neutron diffraction (NPD), Moessbauer spectroscopy and magnetic measurements. They exhibit a tetragonal structure with a=5.5959(1) A, c=7.9024(2) A, V=247.46(2) A{sup 3} for Sr{sub 2}FeMoO{sub 5.7}N{sub 0.3}; and a=5.6202(2) A, c=7.9102(4) A, V=249.85(2) A{sup 3} for Sr{sub 2}FeMoO{sub 5}N; space group I4/m, Z=2. The nitridation process seems to extraordinarily improve the long-range Fe/Mo ordering, achieving 95% at moderate temperatures of 750 Degree-Sign C. The analysis of high resolution NPD data, based on the contrast existing between the scattering lengths of O and N, shows that both atoms are located at (O,N)2 anion substructure corresponding to the basal ab plane of the perovskite structure, whereas the O1 site is fully occupied by oxygen atoms. The evolution of the Left-Pointing-Angle-Bracket Fe-O Right-Pointing-Angle-Bracket and Left-Pointing-Angle-Bracket Mo-O Right-Pointing-Angle-Bracket distances suggests a shift towards a configuration close to Fe{sup 4+}(3d{sup 4}, S=2):Mo{sup 5+}(4d{sup 1}, S=1/2). The magnetic susceptibility shows a ferrimagnetic transition with a reduced saturation magnetization compared to Sr{sub 2}FeMoO{sub 6}, due to the different nature of the magnetic double exchange interactions through Fe-N-Mo-N-Fe paths in contrast to the stronger Fe-O-Mo-O-Fe interactions. Also, the effect observed by low-temperature NPD seems to reduce the ordered Fe moments and enhance the Mo moments, in agreement with the evolution of the oxidation states, thus decreasing the saturation magnetization. - Graphical Abstract: We have synthesized and studied the new oxinitride double perovskites Sr{sub 2}FeMoO{sub 6-x}N{sub x}. They present anionic ordering between O and N. The nitridation process improves the long-range Fe/Mo ordering. They show a ferrimagnetic transition with a reduced saturation magnetization compared to Sr{sub 2}FeMoO{sub 6}, due to the different nature of the double exchange interactions through Fe-N-Mo-N-Fe in contrast to Fe-O-Mo-O-Fe. We suggest a shift towards a configuration Fe{sup 4+}(3d{sup 4}, S=2):Mo{sup 5+}(4d{sup 1}, S=1/2). Highlights: Black-Right-Pointing-Pointer Synthesis and study of the new oxinitride double perovskites Sr{sub 2}FeMoO{sub 6-x}N{sub x} (x=0.3, 1.0). Black-Right-Pointing-Pointer Compounds present anionic ordering between O and N. Black-Right-Pointing-Pointer Nitridation process extraordinarily improves the long-range Fe/Mo ordering. Black-Right-Pointing-Pointer We suggest a shift towards a configuration Fe{sup 4+}(3d{sup 4}, S=2):Mo{sup 5+}(4d{sup 1}, S=1/2).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electronic structure and chemical bonding of {alpha}- and {beta}-CeIr{sub 2}Si{sub 2} intermediate valence compounds

The dimorphism of the intermediate valence ternary cerium silicide CeIr{sub 2}Si{sub 2} in the ThCr{sub 2}Si{sub 2} ({alpha}) and CaBe{sub 2}Ge{sub 2} ({beta}) modifications is addressed in the framework of the density functional theory. The geometry optimization is in good agreement with the experiment and the subsequent establishment of the energy-volume equation of state (EOS) indicates a stabilization of the {beta}-type relative to the {alpha}-type concomitant with the trend of the cerium valence, changing to tetravalent in {beta}-CeIr{sub 2}Si{sub 2}. This is equally shown from the site projected DOS and from the large increase of the electronic contribution to the specific heat. The chemical bonding indicates the strongest bonding interactions within the Ir-Si substructure in both varieties. Stabilization of {beta}-CeIr{sub 2}Si{sub 2} with almost tetravalent cerium is in good agreement with Th{sup IV}Ir{sub 2}Si{sub 2} which exclusively crystallizes in the CaBe{sub 2}Ge{sub 2} type. The EOS behavior of different RIr{sub 2}Si{sub 2} (R=Th, Ce, La) is comparatively discussed. - Graphical abstract: The crystal structures of {alpha}- and {beta}-CeIr{sub 2}Si{sub 2}. Relevant interatomic distances (A), the three-dimensional [Ir{sub 2}Si{sub 2}] networks and the crystallographically independent iridium and silicon sites are indicated. Highlights: Black-Right-Pointing-Pointer Energy stabilization of (HT) {beta}-CeIr{sub 2}Si{sub 2} versus (LT) {alpha}-CeIr{sub 2}Si{sub 2} from DFT methods. Black-Right-Pointing-Pointer Concomitant with the change of Ce valence to tetravalent (HT)-enhanced specific heat. Black-Right-Pointing-Pointer Equations of states for La, Ce and Th members with CeIr{sub 2}Si{sub 2} resembling tetravalent-Th. Black-Right-Pointing-Pointer Chemical bonding shows changes on the {l_brace}Ir{sub 2}Si{sub 2}{r_brace} intralayer and Ce{sup IV}-Ir bonds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ce{sub 2}AgYb{sub 5/3}Se{sub 6}, La{sub 2}CuErTe{sub 5}, and Ce{sub 2}CuTmTe{sub 5}: Three new quaternary interlanthanide chalcogenides

Three new ordered quaternary interlanthanide chalcogenides, Ce{sub 2}AgYb{sub 5/3}Se{sub 6}, La{sub 2}CuErTe{sub 5}, and Ce{sub 2}CuTmTe{sub 5}, have been prepared by direct reaction of the elements in molten NaBr at 900 Degree-Sign C. Each compound forms a new structure-type. The Ce{sub 2}AgYb{sub 5/3}Se{sub 6} structure consists of {infinity}{sup 2}{l_brace} [AgYb{sub 5/6}Se{sub 6}]{sup 6-}{r_brace} layers intercalated by Ce{sup 3+} cations. These layers are composed of {infinity}{sup 1}{l_brace} [Yb{sub 5/3}Se{sub 6}]{sup 7-}{r_brace} quadruplet ribbons of [YbSe{sub 6}]{sup 9-} octahedra and infinite {infinity}{sup 1}{l_brace} [AgSe{sub 6}]{sup 11-}{r_brace} double chains of [AgSe{sub 5}]{sup 9-}. The La{sub 2}CuErTe{sub 5} structure is made of one-dimensional {infinity}{sup 1}{l_brace} [CuErTe{sub 5}]{sup 6-}{r_brace} ribbons separated by La{sup 3+} cations. These ribbons are formed by cis-edge sharing {infinity}{sup 1}{l_brace} [CuTe{sub 2}]{sup 3-}{r_brace} tetrahedral chains and trans-edge sharing {infinity}{sup 1}{l_brace} [ErTe{sub 4}]{sup 5-}{r_brace} chains. While La{sub 2}CuErTe{sub 5} crystallizes in the orthorhombic space group Pnma, Ce{sub 2}CuTmTe{sub 5} crystallizes in the monoclinic space group C2/m. The latter crystal structure is assembled from {infinity}{sup 2}{l_brace} [CuTmTe{sub 5}]{sup 6-}{r_brace} layers intercalated by Ce{sup 3+} cations. These layers consist of single {infinity}{sup 1}{l_brace} [TmTe{sub 4}]{sup 5-}{r_brace} chains connected to each other through dimers or pseudo-double chains. - Graphical abstract: [CuTe{sub 4}]{sup 7-} tetrahedra sharing cis-edges to yield chains in the La{sub 2}CuErTe{sub 5}. Highlights: Black-Right-Pointing-Pointer New ordered interlanthanide tellurides. Black-Right-Pointing-Pointer New quaternary chalcogenides. Black-Right-Pointing-Pointer Low-dimensional lanthanide chalcogenide substructures. Black-Right-Pointing-Pointer Flux synthesis of new chalcogenides.

36 MATERIALS SCIENCE↗

Complex long-range magnetic ordering in the Mn-bearing dugganite Pb{sub 3}TeMn{sub 3}P{sub 2}O{sub 14}

Spin liquids, multiferroics, and doubly-chiral helical structures are just some of the exotic magnetic states found in the langasite compounds. A subclass of the langasite group, the Te{sup 6+}-containing dugganites, has also shown exotic magnetism including magnetoelectric coupling, coexisting complex long-ranged ordered structures, and low-field induced magnetic transitions. Here, we present the first detailed structural study of Pb{sub 3}TeMn{sub 3}P{sub 2}O{sub 14} as well as the first neutron scattering measurements. This material undergoes long-range magnetic ordering, similar to the multiferroic Ba{sub 3}NbFe{sub 3}Si{sub 2}O{sub 14}, at T{sub N}=6.6 K, which is consistent with previous magnetization measurements. However unlike any other langasite or dugganite studied to date, we present evidence of a large, pseudohexagonal incommensurate supercell that alters the nuclear and magnetic structures away from the langasite ideal. - Graphical abstract: Two geometrically frustrated cationic substructures of the langasites and dugganites have profound effects on the magnetism of these compounds. In Pb{sub 3}TeMn{sub 3}P{sub 2}O{sub 14}, Mn{sup 2+} (S=5/2) isolated trinuclear units are shown in yellow, while the red distorted kagomé network is nonmagnetic. (For interpretation of the references to color the reader is referred to the web version of this article.) Highlights: • Polycrystalline Pb{sub 3}TeMn{sub 3}P{sub 2}O{sub 14} was prepared. • Found evidence of a large, pseudohexagonal supercell that is incommensurate with the subcell. • Long-range antiferromagnetic ordering is observed below T{sub N}=6.6 K similar to Ba{sub 3}NbFe{sub 3}Si{sub 2}O{sub 14}. • Broken symmetry probably causes magnetic peak splitting in this system.

36 MATERIALS SCIENCE↗

Structure and magnetic properties of the REAuBi{sub 2} (RE=La–Nd, Sm) phases

We present the crystal structures and basic magnetic properties of the REAuBi{sub 2} (RE=La–Nd, Sm) compounds. This isostructural family crystallizes in the tetragonal P4/nmm (no. 129) HfCuSi{sub 2}-type, as determined by single crystal X-ray diffraction. Three distinct substructures are present: an RE layer, a tetrahedral AuBi layer, and a Bi square net layer. Electronic structure calculations indicate that these compounds display bands which cross the Fermi level, derived from both the Bi square net and the covalent AuBi layer. The small size of LaAuBi{sub 2} crystals precluded detailed physical property measurements, whereas large single crystals could be grown for all other phases investigated here. Single crystal measurements of CeAuBi{sub 2}, PrAuBi{sub 2}, and NdAuBi{sub 2} show overall antiferromagnetic ordering and decreasing magnetic anisotropy with decreasing rare earth size. SmAuBi{sub 2} also shows signatures of magnetic ordering. - Graphical abstract: The crystal structures and basic electronic and magnetic properties of the five REAuBi{sub 2} (RE=La–Nd, Sm) phases are presented. These tetragonal structures have alternating layers of AuBi{sub 4} tetrahedra and a Bi square net balanced by RE cations. Measurements performed on single crystals show strong magnetic anisotropy for CeAuBi{sub 2} and PrAuBi{sub 2} and weak anisotropy for NdAuBi{sub 2}. SmAuBi{sub 2} is weakly magnetic. - Highlights: • We present the structures and basic properties of single crystals of the new, tetragonal REAuBi{sub 2} (RE=La–Nd, Sm) phases. • CeAuBi{sub 2}, PrAuBi{sub 2}, NdAuBi{sub 2}, and SmAuBi{sub 2} order magnetically. • CeAuBi{sub 2} and PrAuBi{sub 2} display magnetic anisotropy. • CeAuBi{sub 2} appears analogous to CeAuSb{sub 2} and may be worthy of further study as a potential system for quantum criticality.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

TEM study of the (SbS){sub 1+δ}(NbS{sub 2}){sub n}, (n=1, 2, 3; δ~1.14, 1.20) misfit layer phases

In the Sb–Nb–S system four new misfit layer phases have been found and carefully investigated via Transmission Electron Microscopy (TEM). Their structures are of composite modulated structure type with stoichiometries that can be formulated as (SbS){sub 1+δ}(NbS{sub 2}){sub n}; for n=1, δ~1.14 and 1.19; for n=2, δ~1.18 and for n=3, δ~1.19. Selected Area Electron Diffraction (SAED) patterns show an almost commensurate fit between the pseudo-tetragonal (SbS) and the pseudo-orthohexagonal (NbS{sub 2}){sub n} subcells along the misfit direction a, with 3(SbS)≈5(NbS{sub 2}), being b the same for both sub-lattices and c the stacking direction. For n=1, a commensurate phase with 4a{sub SbS}=7a{sub NbS2} has also been observed. In addition to the characteristic misfit and associated modulation of the two sub-structures, a second modulation is also present which appears to be primarily associated with the (SbS) sub-structure of both the n=1 and n=2 phases. High Resolution Transmission Electron Microscopy (HRTEM) images show ordered stacking sequences between the (SbS) and (NbS{sub 2}){sub n} lamellae for each of the four phases, however, disordered intergrowths were also occasionally found. Most of the crystals showed different kinds of twinning defects on quite a fine scale. Many crystals showed curled up edges. In some cases the lamellar crystals were entirely folded giving rise to similar diffraction patterns as found for cylindrical crystals. - Graphical abstract: Idealized structure models of the first three members of the homologous series (SbS){sub 1+δ}(NbS{sub 2}){sub n}. - Highlights: • Transmission Electron Microscopy study of misfit layer sulfides (SbS){sub 1+δ}(NbS{sub 2}){sub n}. • The structures consist of a (SbS) layer interleaved between n (NbS{sub 2}) layers. • Two different members n=1, one n=2 and one n=3 have been studied. • Twinning, intergrowths and different modulations in the (SbS) substructure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis and characterization of new fluoride-containing manganese vanadates A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} (A=Rb, Cs) and Mn{sub 2}VO{sub 4}F

Large single crystals of A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} (A=Rb, Cs) and Mn{sub 2}VO{sub 4}F were grown using a high-temperature (~600 °C) hydrothermal technique. Single crystal X-ray diffraction and powder X-ray diffraction were utilized to characterize the structures, which both possess MnO{sub 4}F{sub 2} building blocks. The A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} series crystallizes as a new structure type in space group Pbcn (No. 60), Z=4 (Rb{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2}: a=7.4389(17) Å, b=11.574(3) Å, c=10.914(2) Å; Cs{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2}: a=7.5615(15) Å, b=11.745(2) Å, c=11.127(2) Å). The structure is composed of zigzag chains of edge-sharing MnO{sub 4}F{sub 2} units running along the a-axis, and interconnected through V{sub 2}O{sub 7} pyrovanadate groups. Temperature dependent magnetic susceptibility measurements on this interesting one-dimensional structural feature based on Mn{sup 2+} indicated that Cs{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} is antiferromagnetic with a Neél temperature, T{sub N}=~3 K and a Weiss constant, θ, of −11.7(1) K. Raman and infrared spectra were also analyzed to identify the fundamental V–O vibrational modes in Cs{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2}. Mn{sub 2}(VO{sub 4})F crystalizes in the monoclinic space group of C2/c (no. 15), Z=8 with unit cell parameters of a=13.559(2) Å, b=6.8036(7) Å, c=10.1408(13) Å and β=116.16(3)°. The structure is associated with those of triplite and wagnerite. Dynamic fluorine disorder gives rise to complex alternating chains of five-and six-coordinate Mn{sup 2+}. These interpenetrating chains are additionally connected through isolated VO{sub 4} tetrahedra to form the condensed structure. - Graphical abstract: New vanadate fluorides A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} (A=Rb, Cs) and Mn{sub 2}(VO{sub 4})F have been synthesized hydrothermally. Upon cooling, the one-dimensional Mn(II) substructure results in antiferromagnetic ordering. Display Omitted - Highlights: • Single crystals of A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2}, (A=Rb, Cs) and Mn{sub 2}VO{sub 4}F were grown hydrothermally. • The use of fluoride mineralizers in the synthesis led to the formation of new compounds without OH{sup −} groups. • The structure of A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} features zigzag chains of MnO{sub 4}F{sub 2} units. • Cs{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} exhibits antiferromagnetic ordering with a Neel temperature of ~3 K. • Mn{sub 2}VO{sub 4}F possesses a condensed framework structure with disordered fluorine atoms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanoscale interlayer defects in iron arsenides

Using a local real-space microscopy probe, we investigate evidence of nanoscale interlayer defects along the c-crystallographic direction in BaFe 2 As 2 (‘122’) based iron-arsenide superconductors. We find ordered 122 atomic arrangements within the ab -plane, and within regions of ~10 to 20 nm size perpendicular to this plane. While the FeAs substructure is very rigid, Ba ions are relatively weakly bound and can be displaced from the 122, forming stacking faults resulting in the physical separation of the 122 between adjacent ordered domains. The evidence for interlayer defects between the FeAs superconducting planes gives perspective on the minimal connection between interlayer chemical disorder and high-temperature superconductivity. Specifically, the Cooper pairs may be finding a way around such localized interlayer defects through a percolative path of the ordered layered 122 lattice that may not affect T c .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis, structure and magnetic properties of Ba 3 M 2 Ge 4 O 14 (M = Mn and Fe): Quasi-one-dimensional zigzag chain compounds

A series of trivalent transition metal germanates with a general formula of A 3 M 2 Ge 4 O 14 ( A = Sr, Ba, M = Mn and Fe) was synthesized using a high-temperature (580 °C) hydrothermal technique. Compound I , Ba 3 Mn 2 Ge 4 O 14 , is a new structure type that is characterized by one-dimensional Mn–O–Mn chains made from edge-sharing highly distorted Mn 3+ O 6 units, and exhibits antiferromagnetic behavior below 15 K with field induced metamagnetic transitions. The A 3 Fe 2 Ge 4 O 14 ( A = Sr and Ba, II and III, respectively) series belongs to the well-known langasite structure type, crystallizing in space group P 321. In A 3 Fe 2 Ge 4 O 14 , there is one octahedral Fe 3+ site and one mixed-occupancy Fe 3+ /Ge 4+ site that form the one-dimensional substructure. The magnetic susceptibility data of Ba 3 Fe 2 Ge 4 O 14 reveals a much simpler magnetic structure with an antiferromagnetic transition near 5.5 K. The Jahn-Teller distortion of Mn 3+ appears to be influential in the phase formation, leading to significantly different structures for these Mn 3+ and Fe 3+ compounds with similar chemical formulas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A small-box approach to the local crystal structure of Y 3 NbO 7

The local crystal structure of Y 3 NbO 7 was probed using neutron total scattering. Five different structural models were fit to the experimental pair distribution function of this material up to 15 Å. Fits of defect fluorite (Fm$\overline{3}$m), pyrochlore (Fd$\overline{3}$m), and orthorhombic C weberite models (C222 1 ) were attempted based on prior structural investigations of Y 3 NbO 7 and related fluorite-based materials. Orthorhombic P weberite (P222 1 ) and monoclinic weberite models (P112 1 ) were derived via symmetry reduction of the orthorhombic C weberite structure. All models except monoclinic weberite failed to reproduce the experimental pair distribution function. Misfits were clearly visible for peaks arising from atom pairs within the first coordination shell (defect fluorite and pyrochlore) and beyond (orthorhombic C and P weberite). By contrast, monoclinic weberite (γ ≈ 91.8°) provided an excellent fit, with no major misfits observed. This unit cell features distorted YO 8 dodecahedra, YO 7 monocapped octahedra, and NbO 6 octahedra as building blocks. Comparison between the topologies of the cationic and anionic substructures in monoclinic weberite and its parent orthorhombic C structure revealed displacements of the metal atoms along the [100] direction and a less compact spatial distribution of oxygen atoms along the a axis. In conclusion, the monoclinic weberite model presented herein may serve as a starting point to revisit structural modeling of fluorite-based materials with challenging local structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microstructure and mechanical properties of spray-deposited Mg-12.55Al-3.33Zn-0.58Ca-1Nd alloy

A Mg-Al-Zn-Ca-Nd magnesium alloy was prepared by spray forming technology, and the spray-deposited alloy was subsequently hot-extruded with a reduction rate of 16:1 at 623 K. The mechanical properties of the extruded alloy were investigated, and the result shows that the spray-formed Mg alloy offers superior tensile strength with poor ductility. The morphologies, fracture characteristic and chemical compositions of the extruded alloy were then explored by scanning electron microscopy with energy dispersive spectrometer. Furthermore, microstructure of the extruded alloy was examined by X-ray diffractometry and transmission electron microscopy. The results indicate that the microstructure of the spray-deposited magnesium alloy consists of {alpha}-Mg and Al{sub 2}Ca phases, and the Al{sub 2}Ca compound is distributed along the grain boundaries of the primary {alpha}-Mg. Moreover, twin substructure is found to exist in microstructure of the Al{sub 2}Ca phase, rare earth Nd in the Al{sub 2}Ca phase in the form of solid solution.

36 MATERIALS SCIENCE↗

Nanostructured cobalt powders synthesised by polyol process and consolidated by Spark Plasma Sintering: Microstructure and mechanical properties

Bulk nanostructured cobalt was processed using a bottom-up strategy. Nanostructured particle agglomerates of about 50 and 240 nm in diameter were synthesised using a polyol route and subsequently consolidated by Spark Plasma Sintering (SPS). The microstructure of the starting powders and of the processed bulk samples was studied and characterised by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The XRD patterns of the as-prepared powders showed predominantly a face centred cubic (fcc) crystalline phase, whereas both fcc and hexagonal close packed (hcp) phases were found within the consolidated samples. A sample with the highest relative mass density (94.5%) was obtained from the small powder particles. TEM observations revealed a lamellar substructure with a high density of nanotwins and stacking faults in every grain in the sample with the highest density. Brillouin light scattering (BLS) and quasistatic compression tests were used to investigate the mechanical properties of the consolidated samples. The two techniques yielded Young modulus values of 168 GPa and 130 GPa, respectively, in the sample with the highest density. This sample also exhibited a yield stress higher than 1 GPa after the compression test, which is mainly attributed to the lamellar-like structure occurring in almost every grain of the polycrystalline aggregate. - Highlights: Black-Right-Pointing-Pointer Cobalt nanoparticles produced by the polyol process present mainly the fcc metastable phase. Black-Right-Pointing-Pointer Bulk nanostructured cobalt is obtained from the nano-particles by Spark Plasma Sintering consolidation. Black-Right-Pointing-Pointer Nanotwins and stacking faults are present in every grain of the more dense sample. Black-Right-Pointing-Pointer Yield strength and plastic domain may be varied depending on the nanoparticle size and the porosity of the consolidated material.

36 MATERIALS SCIENCE↗

Microstructure and micro-Raman studies of nitridation and structure transition of gallium oxide nanowires

Here we present a detailed study on nitridation and structure transition in monoclinic gallium oxide ({beta}-Ga{sub 2}O{sub 3}) nanowires grown on Si substrates with chemical vapor phase epitaxy. The nanowires were systematically nitridated at different temperatures. Their morphologies and microstructures were precisely characterized using field-emission scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and confocal micro-Raman spectroscopy. It is found that heat treatment of Ga{sub 2}O{sub 3} nanowires in the gas of ammonia results in rich substructures including the Ga{sub 2}O{sub 3} phase, the crystalline GaN phase, and other meta structures. The identification of these structures helps to understand some interesting phenomena observed in nanostructures, such as the microstructural origin of the unknown Raman lines in GaN nanowires. - Highlights: Black-Right-Pointing-Pointer Nitridation and structure transition of Ga{sub 2}O{sub 3} significantly depend on temperature. Black-Right-Pointing-Pointer G-N bonds form at lower temperatures but the Ga{sub 2}O{sub 3} lattice is still dominant. Black-Right-Pointing-Pointer Amorphous GaN coexists with crystalline Ga{sub 2}O{sub 3} at higher temperatures. Black-Right-Pointing-Pointer Crystalline GaN with distinct morphology is obtained at much higher temperatures.

36 MATERIALS SCIENCE↗

Microstructure and mechanical properties of bulk highly faulted fcc/hcp nanostructured cobalt microstructures

Nanostructured cobalt powders with an average particle size of 50 nm were synthesized using a polyol method and subsequently consolidated by spark plasma sintering (SPS). SPS experiments performed at 650 °C with sintering times ranging from 5 to 45 min under a pressure of 100 MPa, yielded to dense bulk nanostructured cobalt (relative density greater than 97%). X-ray diffraction patterns of the as-prepared powders showed only a face centered cubic (fcc) crystalline phase, whereas the consolidated samples exhibited a mixture of both fcc and hexagonal close packed (hcp) phases. Transmission electron microscopy observations revealed a lamellar substructure with a high density of nanotwins and stacking faults in every grain of the sintered samples. Room temperature compression tests, carried out at a strain rate of 10{sup −3} s{sup −1}, yielded to highest strain to fracture values of up to 5% for sample of holding time of 15 min, which exhibited a yield strength of 1440 MPa, an ultimate strength as high as 1740 MPa and a Young's modulus of 205 GPa. The modulus of elasticity obtained from the nanoindentation tests, ranges from 181 to 218 GPa. The lowest modulus value of 181 GPa was obtained for the sample with the highest sintering time (45 min), which could be related to mass density loss as a consequence of trapped gases releasing. - Highlights: • Co nanopowder (50 nm) was prepared by reduction in polyol medium. • SPS was used to process bulk nanostructured Co specimens. • Microstructures were made of intricate fcc/hcp, along with nanotwins and SFs. • High strengths and moderate compressive ductility were obtained. • Deformation mechanisms related to complex interplay of different length scales.

36 MATERIALS SCIENCE↗