Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “crystallization”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,693 records · Page 94

Velocity dependent dislocation drag from phonon wind and crystal geometry

The mobility of dislocations is an important factor in understanding material strength. Dislocations experience a drag due to their interaction with the crystal structure, the dominating contribution at high stress and temperature being the scattering off phonons due to phonon wind. Yet, the velocity dependence of this effect has eluded a good theoretical understanding. In a previous work, dislocation drag from phonon wind as a function of velocity was computed from first principles in the isotropic limit, in part for simplicity, but also arguing that macroscopically, a polycrystalline metal looks isotropic. However, since the single crystal grains are typically a few microns up to a millimeter in size, dislocations travel in single crystals and cross boundaries, but never actually see an isotropic material. In this work we therefore highlight the effect of crystal anisotropy on dislocation drag by accounting for the crystal and slip plane geometries. In particular, we keep the phonon spectrum isotropic for simplicity, but dislocations are modeled according to the crystal symmetry (bcc, fcc, hcp, etc.). We then compare to the earlier purely isotropic results, as well as to experimental data and MD simulations where they are available.

36 MATERIALS SCIENCE↗

Molten salt flux synthesis and crystal structure of a new open-framework uranyl phosphate Cs{sub 3}(UO{sub 2}){sub 2}(PO{sub 4})O{sub 2}: Spectroscopic characterization and cationic mobility studies

The reaction of triuranyl diphosphate tetrahydrate precursor (UO{sub 2}){sub 3}(PO{sub 4}){sub 2}(H{sub 2}O){sub 4} with a CsI flux at 750 °C yields a yellow single crystals of new compound Cs{sub 3}(UO{sub 2}){sub 2}(PO{sub 4})O{sub 2}. The crystal structure (monoclinic, space group C2/c, a=13.6261 (13) Å, b=8.1081(8) Å, c=12.3983(12) Å, β=114.61(12)°, V=1245.41(20) Å{sup 3} with Z=4) has been solved using direct methods and Fourier difference techniques. A full-matrix least-squares refinement on the basis of F{sup 2} yielded R1=0.028 and wR2=0.071 for 79 parameters and 1352 independent reflections with I≥2σ(I) collected on a BRUKER AXS diffractometer with MoKα radiation and a charge-coupled device detector. The crystal structure is built by two independent uranium atoms in square bipyramidal coordination, connected by two opposite corners to form infinite chains {sup 1}{sub ∞}[UO{sub 5}] and by one phosphorus atom in a tetrahedral environment PO{sub 4}. The two last entities {sup 1}{sub ∞}[UO{sub 5}] and PO{sub 4} are linked by sharing corners to form a three-dimensional structure presenting different types of channels occupied by Cs{sup +} alkaline cations. Their mobility within the tunnels were studied between 280 and 800 °C and compared with other tunneled uranyl minerals. The infrared spectrum shows a good agreement with the values inferred from the single crystal structure analysis of uranyl phosphate compound. - Graphical abstract: Arrhenius plot of the electrical conductivity of tunneled compounds Cs{sub 3}U{sub 2}PO{sub 10} and CsU{sub 2}Nb{sub 2}O{sub 11.5}. Highlights: ► The reaction of (UO{sub 2}){sub 3}(PO{sub 4}){sub 2}(H{sub 2}O){sub 4} in excess of molten CsI leads to single-crystals of new tunneled compound Cs{sub 3}(UO{sub 2}){sub 2}(PO{sub 4})O{sub 2}. ► Ionic conductivity measurements and crystal structure analysis indicate a strong connection of the Cs{sup +} cations to the tunnels. ► A low symmetry in Cs{sub 3}(UO{sub 2}){sub 2}(PO{sub 4})O{sub 2} is the cause of IR activation and splitting of the bands in the IR spectrum.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural properties of mixed (NH{sub 4}){sub 2−x}Rb{sub x}ZnCl{sub 4} (x=0, 1, and 2) crystals studied by {sup 1}H and {sup 87}Rb nuclear magnetic resonance

The structures of mixed (NH{sub 4}){sub 2−x}Rb{sub x}ZnCl{sub 4} (x=0, 1, and 2) single crystals were determined by x-ray diffraction. In addition, the nuclear magnetic resonance (NMR) spectra and spin–lattice relaxation times of the {sup 1}H and {sup 87}Rb nuclei in the three crystals were determined using NMR spectroscopy. We analyzed the crystallographic structures of these crystals by considering the occupation probabilities (NH{sub 4} or Rb) of the two cationic sites. Our NMR results confirm that there are two crystallographically inequivalent NH{sub 4} sites, NH{sub 4}(1) and NH{sub 4}(2), in (NH{sub 4}){sub 2}ZnCl{sub 4}, and two crystallographically inequivalent Rb sites, Rb(1) and Rb(2), in Rb{sub 2}ZnCl{sub 4}. However, only one NH{sub 4} site and two Rb sites were observed in NH{sub 4}RbZnCl{sub 4}. The NH{sub 4} and Rb occupation rates of each of the two available sites, A{sub 1} and A{sub 2}, were determined from the NMR signals. - Graphical abstract: The structures of mixed (NH{sub 4}){sub 2−x}Rb{sub x}ZnCl{sub 4} (x=0, 1, and 2) single crystals were determined by x-ray diffraction. In addition, the nuclear magnetic resonance (NMR) spectra and spin–lattice relaxation times of the {sup 1}H and {sup 87}Rb nuclei in the three crystals were determined using NMR spectroscopy. Highlights: ► Mixed (NH{sub 4}){sub 2−x}Rb{sub x}ZnCl{sub 4} (x=0, 1, and 2) crystals. ► The crystallographic structures by occupation probabilities. ► The NH{sub 4} and Rb occupation rates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Crystal and electronic structures of the new quaternary RCr₃Si₂C (R=Y, Gd–Tm, Lu, U) compounds

Nine new quaternary intermetallic RCr₃Si₂C (R=Y, Gd–Tm, Lu, U) compounds have been synthesized and characterized by both powder and single-crystal X-ray diffraction. These compounds crystallize in the hexagonal system with space group P6/mmm and lattice parameters a~9 Å and c~4 Å. Single-crystal X-ray diffraction refinement evidences a new type-structure closely related to the YCo₃Ga₂-type. Electronic structure properties and crystal stability of real YCr₃Si₂C against hypothetical YCr₃Si₂ are discussed in view of the Korringa–Kohn–Rostoker calculations, accounting for models with different atomic occupancy on selected sites as well as emphasizing the role of carbon in stabilization of YCr₃Si₂C compound. Highlights: • Crystal structure determination of the new intermetallic YCr₃Si₂C compound. • New type-structure closely related to the YCo₃Ga₂-type. • Theoretical study of the structural stability by electronic structure calculations. • Crystal structure characterization of the entire RCr₃Si₂C series.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis, crystal and electronic structures and magnetic properties of Li{sub 2}SnMo{sub 3}O{sub 8}: A novel reduced molybdenum oxide containing Mo{sub 3}O{sub 13} cluster units

Powder samples and single crystals of the quaternary oxide Li{sub 2}SnMo{sub 3}O{sub 8} were obtained by solid state reaction. The structure was determined by single-crystal X-ray diffraction. Li{sub 2}SnMo{sub 3}O{sub 8} crystallizes in the hexagonal space group P6{sub 3}mc with unit-cell parameters a=5.7720 (2) Å, c=10.3941 (3) Å and Z=2. Full-matrix least-squares refinement on F{sup 2} using 930 independent reflections for 31 refinable parameters results in R{sub 1}=0.0354 and wR{sub 2}=0.0643. The crystal structure consists of distorted hexagonal-close-packed oxygen layers with stacking sequence abac along [0 0 1] and that are held together by alternating lithium-tin and molybdenum layers. The Li{sup +} and Sn{sup 4+} ions occupy, respectively, tetrahedral and octahedral sites in the ratio 2:1. The Mo atoms occupy octahedral sites and form strongly bonded triangular clusters involving three MoO{sub 6} octahedra that are each shared along two edges, constituting a Mo{sub 3}O{sub 13} unit. Magnetic susceptibility measurements are in agreement with a spin-pairing of the eight d electrons per Mo{sub 3} cluster. The electronic structure of Li{sub 2}SnMo{sub 3}O{sub 8} is analyzed using periodic density functional calculations. - Graphical abstract: We present here the synthesis, the crystal and electronic structures, and the magnetic properties of the new quaternary compound containing Mo{sub 3}O{sub 13} units, Li{sub 2}SnMo{sub 3}O{sub 8}. - Highlights: • The new quaternary reduced molybdenum oxide containing Mo{sub 3} clusters, Li{sub 2}SnMo{sub 3}O{sub 8}, was synthesized by solid state reaction. • Eight electrons per Mo{sub 3} cluster. • Single-crystal X-ray study. • Magnetic susceptibility measurements. • Periodic density functional calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Syntheses, crystal structures, and optical properties of Pb{sub 6}B{sub 3}O{sub 10}X (X=F, Cl, Br)

A series of lead-containing halogen oxyborates, Pb{sub 6}B{sub 3}O{sub 10}X (X=F, Cl, Br), have been grown by high-temperature solution method and their crystal structures were determined by single-crystal X-ray diffraction. They are isostructural and crystallize in the space group Pbcm of the orthorhombic crystal system. The crystal structures are dominated by one-dimensional {sub ∞}[(Pb{sub 4}O)(BO{sub 3}){sub 3}] “Zig-Zag”-chains, while the remaining Pb atoms and X (X=F, Cl, Br) atoms are filled to balance the charge. Compared with the previously reported compound Pb{sub 4}O(BO{sub 3}){sub 2} (the molecular formula Pb{sub 4}O(BO{sub 3}){sub 2} can be regarded as Pb{sub 6}B{sub 3}O{sub 10.5}) with the space group Aba2, the structures of Pb{sub 6}B{sub 3}O{sub 10}X (X=F, Cl, Br) are completely different from that of Pb{sub 4}O(BO{sub 3}){sub 2}. IR spectroscopy, UV–vis-NIR diffuse reflectance spectroscopy, thermal analysis, and theoretical calculations were also performed on the reported materials. Highlights: • A new family of lead-containing halogen oxyborates, Pb{sub 6}B{sub 3}O{sub 10}X (X=F, Cl, Br), have been grown by high-temperature solution method. • Owing to the introduction of X atoms into Pb{sub 4}O(BO{sub 3}){sub 2}, the structures of Pb{sub 6}B{sub 3}O{sub 10}X are completely different. • The crystal structures are dominated by one-dimensional {sub ∞}[(Pb{sub 4}O)(BO{sub 3}){sub 3}] “Zig-Zag”-chains.

36 MATERIALS SCIENCE↗

Crystal structure, magnetism and transport properties of Ce{sub 3}Ni{sub 25.75}Ru{sub 3.16}Al{sub 4.1}B{sub 10}

Single crystals of Ce{sub 3}Ni{sub 25.75}Ru{sub 3.16}Al{sub 4.1}B{sub 10} were obtained from a process in which a polycrystalline sample of CeRu{sub 2}Al{sub 2}B was annealed in an excess of a Ni–In flux. The initial phase, CeRu{sub 2}Al{sub 2}B, does not recrystallize, instead, crystals of a new phase, Ce{sub 3}Ni{sub 25.75}Ru{sub 3.16}Al{sub 4.1}B{sub 10}, could be isolated once the flux was removed. The title compound crystallizes in the tetragonal space group P4/nmm (No. 129) with a=1139.02(8), c=801.68(6) pm (c/a=0.70) in the Nd{sub 3}Ni{sub 29}Si{sub 4}B{sub 10} structure type. Electrical resistivity measurements reveal metallic behavior with a minimum of 700 µΩ cm and a small residual resistivity ratio of RRR=1.4 indicating a large amount of disorder scattering. The cerium atoms are either in the 4+ or an intermediate valence state with a valence fluctuation temperature far above room temperature. - Graphical abstract: Single crystals of Ce{sub 3}Ni{sub 25.75}Ru{sub 3.16}A{sub l4.1}B{sub 10} were obtained using a process in which a polycrystalline sample of CeRu{sub 2}Al{sub 2}B was annealed in an excess of a Ni–In flux. Electrical resistivity measurements reveal metallic behavior with a minimum of 700 μΩ cm and a small residual resistivity ratio of RRR=1.4 indicating a large amount of disorder scattering. The cerium atoms are either in the 4+ or an intermediate valence state with a valence fluctuation temperature far above room temperature. Display Omitted - Highlights: • Flux synthesis of high quality single crystals of Ce{sub 3}Ni{sub 25.75}Ru{sub 3.16}Al{sub 4.1}B{sub 10} is presented along with the crystal structure, magnetic and transport properties. • The compound is isostructural to Nd{sub 3}Ni{sub 29}Si{sub 4}B{sub 10} but is first of this structure type showing mixed occupancies of d-elements. • This is an intermetallic phase with Ce in either the 4+ or an intermediate valence state. • The fact that this structure with mixed occupied transition metal sites exists suggests that more compounds of this type should be accessible and the physical properties tuned.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis, crystal structure and magnetic properties of Li{sub 2}InMo{sub 3}O{sub 8}: A novel reduced molybdenum oxide containing magnetic Mo{sub 3} clusters

Powder samples and single crystals of Li{sub 2}InMo{sub 3}O{sub 8} were obtained by solid state reaction. The structure was determined by single-crystal X-ray diffraction (771 independent reflections for 33 refinable, R1=0.0158 and wR2=0.0354). Li{sub 2}InMo{sub 3}O{sub 8} is isomorphous with Li{sub 2}SnMo{sub 3}O{sub 8} and crystallizes in the hexagonal space group P6{sub 3}mc with unit-cell parameters a=5.7931(2) Å, c=10.4681(4) Å and Z=2. The crystal structure consists of distorted hexagonal-close-packed oxygen layers with stacking sequence abac along [0 0 1] and that are held together by alternating lithium–indium and molybdenum layers. The Li{sup +} and In{sup 3+} ions occupy, respectively, tetrahedral and octahedral sites in the ratio 2:1. The Mo atoms occupy octahedral sites and form strongly bonded triangular clusters involving three MoO{sub 6} octahedra that are each shared along two edges, constituting a Mo{sub 3}O{sub 13} unit. The variations of the Mo–Mo and Mo–O bond lengths according to the number of electrons per Mo{sub 3} cluster are discussed. The trivalent oxidation state of the indium leads to one unpaired electron per Mo{sub 3} and thus gives rise to a paramagnetic spin behavior with an effective magnetic moment of 1.5 μ{sub B} per Mo{sub 3} cluster. The magnetic susceptibility vs. temperature curve also shows a maximum at 25 K arising probably from an antiferromagnetic ordering between the Mo{sub 3} clusters. - Graphical abstract: We present here the synthesis, the crystal structure, and the magnetic properties of the new quaternary compound Li{sub 2}InMo{sub 3}O{sub 8} containing magnetic Mo{sub 3}O{sub 13} units with one unpaired electron. - Highlights: • The new quaternary reduced molybdenum oxide containing Mo{sub 3} clusters, Li{sub 2}InMo{sub 3}O{sub 8}, was synthesized by solid state reaction. • Single-crystal X-ray study. • One unpaired electron per Mo{sub 3} cluster leading to a paramagnetic spin behavior with an effective magnetic moment of 1.5 μ{sub B} per Mo{sub 3} cluster. • Magnetic susceptibility measurements show a maximum at 25 K arising probably from an antiferromagnetic ordering between the Mo{sub 3} clusters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Crystal structure and magnetic properties of titanium-based CuTi{sub 2−x}M{sub x}S{sub 4} and CuCr{sub 2−x}Ti{sub x}Se{sub 4} chalcospinels

CuTi{sub 2−x}M{sub x}S{sub 4} (M=Fe, Mn, Co; x=0.3, 0.5) and CuCr{sub 2−x}Ti{sub x}Se{sub 4} (x=0.3, 0.5, 0.7) chalcospinels were synthesized by conventional solid-state reactions. Their crystal structures were determined by single-crystal X-ray diffraction. All of the phases crystallized in cubic spinel-type structures (space group, Fd3{sup ¯}m). For all of the chalcospinel compounds, the edge-length distortion parameter (ELD) indicated that the most distorted polyhedron was Q[(Ti,M){sub 3}Cu], which displayed an ∼8% distortion from an ideal tetrahedron structure (Q=S or Se). The Mn-based thiospinel CuMn{sub 0.3}Ti{sub 1.7}S{sub 4} is paramagnetic, whereas the Fe-based thiospinels (CuTi{sub 2−x}Fe{sub x}S{sub 4}; x=0.3 and 0.7) are strongly antiferromagnetic due to their spin-glass states. The magnetic susceptibility measurements indicated ferromagnetic behavior for the selenospinels (CuCr{sub 2−x}Ti{sub x}Se{sub 4}; x=0.3, 0.5 and 0.7). - Graphical abstract: View along [1 0 0] of CuCr{sub 2−x}Ti{sub x}Se{sub 4} crystal structure showing tetrahedral and octahedral units. To the right, experimental X-ray powder diffraction pattern of CuCr{sub 1.7}Ti{sub 0.3}Se{sub 4} (top) in compared (in a like-mirror representation) to a simulated X-ray pattern from single-crystal data (bottom). - Highlights: • Chalcogenides belong to the family of compounds spinel-type. • Resolved single crystals of the solid solutions have space group Fd-3m. • The distortion of the tetrahedral and octahedral volume were calculated. • These solid solutions shows a ferromagnetic or spin-glass behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis, crystal structure, and electrical and magnetic properties of BaMo{sub 6}Te{sub 6}: A novel reduced molybdenum telluride containing infinite chains of trans-face shared Mo{sub 6} octahedra

Powder samples and single crystals of the new ternary compound BaMo{sub 6}Te{sub 6} were obtained by solid state reaction. The structure was determined by single-crystal X-ray diffraction. BaMo{sub 6}Te{sub 6} crystallizes in the hexagonal space group P6{sub 3}/m (No. 176) with unit-cell parameters a=9.3941(2) Å, c=4.5848(1) Å and Z=1. Full-matrix least-squares refinement on F{sup 2} using 452 independent reflections for 17 refinable parameters resulted in R1=0.0208 and wR2=0.0539. The structure consists of one-dimensional infinite chains of trans-face shared Mo{sub 6} octahedra capped by Se atoms. These chains that are running along the c axis are separated from each other by nine-coordinate Ba atoms. Resistivity measurements on a single crystal indicated that the BaMo{sub 6}Te{sub 6} compound is metallic down to 160 K and semiconductor below. Magnetic susceptibility measurements showed that BaMo{sub 6}Te{sub 6} is weakly diamagnetic with no anomaly at the metal–semiconductor transition. - Graphical abstract: We present here the synthesis, the crystal structure, and the electrical and magnetic properties of the new compound BaMo{sub 6}Te{sub 6} containing infinite chains of trans-face shared Mo{sub 6} octahedra. - Highlights: • BaMo{sub 6}Te{sub 6} contains infinite chains of trans-face-sharing Mo{sub 6} octahedra |Mo{sub 6/2}|{sub ∞}{sup 1}. • Synthesis by solid state reaction. • Single-crystal X-ray study. • Continuous metal–nonmetal transition. • Anderson localization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis and crystal structure of Ba{sub 26}B{sub 12}Si{sub 5}N{sub 27} containing [Si{sub 2}] dumbbells

Black, metallic luster, platelet single crystals of Ba{sub 26}B{sub 12}Si{sub 5}N{sub 27} were grown on a BN crucible wall by slowly cooling from 900 °C to 27 °C. X-ray diffraction analysis revealed that Ba{sub 26}B{sub 12}Si{sub 5}N{sub 27} crystallizes in an orthorhombic cell (a=17.6942(4) Å, b=34.1437(6) Å, c=10.0410(2) Å; space group Fdd2). Isolated nitridoborate anionic groups [BN{sub 2}]{sup 3–}, dumbbell-type Zintl polyanions [Si{sub 2}]{sup 2.8–}, and nitride anions N{sup 3–} are included in the structure. The structural formula is represented as (Ba{sup 2+}){sub 26}([BN{sub 2}]{sup 3–}){sub 12}[([Si{sub 2}]{sup 2.8–}){sub 1.25}(N{sup 3–}){sub 2×0.75}]{sub 2}. The [Si{sub 2}]{sup 2.8–} dumbbell with a Si–Si length of 2.177(5) Å has a bond order of 2.6, which is close to the triple bond of Si. - Graphical abstract: Single crystals of Ba{sub 26}B{sub 12}Si{sub 5}N{sub 27} grown by slow cooling from 900 °C have an orthorhombic crystal structure with space group Fdd2, containing nitridoborate anionic groups [BN{sub 2}]{sup 3–}, dumbbell-type Zintl polyanions [Si{sub 2}]{sup 2.8–}, and nitride anions N{sup 3–}. - Highlights: • A novel compound, Ba{sub 26}B{sub 12}Si{sub 5}N{sub 27}, was synthesized by slow cooling from 900 °C. • Single crystal X-ray diffraction clarified a new crystal structure. • Anionic groups [BN{sub 2}]{sup 3–} and dumbbell-type Zintl polyanions [Si{sub 2}]{sup 2.8–} are contained. • The [Si{sub 2}]{sup 2.8–} dumbbell has a bond order of 2.6, which is close to the triple bond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ce{sub 11}Ge{sub 3.73(2)}In{sub 6.27}: Solid-state synthesis, crystal structure and site-preference

A novel intermetallic compound of Ce{sub 11}Ge{sub 3.73(2)}In{sub 6.27} has been synthesized through the high-temperature solid-state reaction using Nb-ampoules. A batch of well grown block-/short bar-shaped single-crystals has been obtained, and the crystal structure of the title compound has been characterized by single-crystal X-ray diffraction analyses. Ce{sub 11}Ge{sub 3.73(2)}In{sub 6.27} adopts the Ho{sub 11}Ge{sub 10}-type structure belonging to the tetragonal space group I4/mmm (Z=4, Pearson symbol tI84) with nine crystallographically unique atomic positions in the asymmetric unit. The lattice parameters are a=12.0163(1) Å and c=16.5396(2) Å. The overall crystal structure can simply be depicted as an assembly of three different types of co-facial cationic polyhedra centered by anions, which is further enclosed by the three-dimensional (3-D) cage-like anionic framework. The extra amount of In is observed in one of three isolated anionic sites resulting in introducing the Ge/In-mixed site at the Wyckoff 4e site. This unique site-preference of In substitution for Ge at the 4e site has been enlightened via the atomic size-aspect which was fully supported and rationalized by the site- and bond-energies analyses using tight-binding linear muffin-tin orbital (TB-LMTO) calculations. Energy-dispersive X-ray spectroscopy (EDS), density of states (DOS), crystal orbital Hamilton population (COHP), and electron localization function (ELF) analyses for the title compound are also presented. Magnetic susceptibility measurement proves that an antiferromagnetic ordering of Ce atoms at a low temperature with a paramagnetic Curie temperature of −23.2 K. - Graphical abstract: Reported is experimental and theoretical investigations for Ce{sub 11}Ge{sub 3.73(2)}In{sub 6.27}, which is the first reported example having the extra amounts of In substitution for Ge at one of three “isolated” anionic sites in the Ho{sub 11}Ge{sub 10}-type phase. The observed In site-preference toward the particular anionic site was rationalized via the atomic size-aspect supported by comprehensive analyses for the site-energies including the Wyckoff 4e and 8j sites. - Highlights: • Block or short-bar shaped single-crystals of Ce{sub 11}Ge{sub 3.73(2)}In{sub 6.27} were synthesized. • The first example of having the In/Ge mixture at the “isolated” anionic site. • The site-preference of In was rationalized by the site- and bond-energies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis, crystal and electronic structure of the quaternary sulfides Ln{sub 2}CuMS{sub 5} (Ln=La, Ce; M=Sb, Bi)

The series of quaternary sulfides with general formula Ln{sub 2}CuMS{sub 5} (Ln=La, Ce; M=Sb, Bi) have been synthesized by solid-state reactions. Three representative members have been structurally characterized by single-crystal X-ray diffraction. La{sub 2}CuSbS{sub 5} crystallizes in a new structure type (space group Ima2 (no. 46), Z=4, a=13.401(2) Å, b=7.592(1) Å, c=7.598(1) Å, V=773.1(3) Å{sup 3}). The bismuth analogs of composition La{sub 2}CuBiS{sub 5} and Ce{sub 2}CuBiS{sub 5} crystallize with the La{sub 2}CuInSe{sub 5} structure type (space group Pnma (no. 62), Z=4). Lattice parameters for La{sub 2}CuBiS{sub 5}: a=11.9213(5) Å, b=3.9967(2) Å, c=17.0537(8) Å, V=812.56(7) Å{sup 3}; lattice parameters for Ce{sub 2}CuBiS{sub 5}: a=11.9179(15) Å, b=3.9596(5) Å, c=16.955(2) Å, V=800.13(17) Å{sup 3}). The similarities and the differences between the two structures are discussed. Electronic structure calculations for La{sub 2}CuSbS{sub 5} and La{sub 2}CuBiS{sub 5} are also presented; they suggest semiconducting behavior with energy gaps exceeding 1.7 eV. - Graphical abstract: La{sub 2}CuSbS{sub 5} crystallizes in a new structure type (space group Ima2 (no. 46). Its bismuth analog La{sub 2}CuBiS{sub 5} crystallizes in the La{sub 2}CuInSe{sub 5} structure type (space group Pnma (no. 62)). Z=4, a=11.9213(5) Å, b=3.9967(2) Å, c=17.0536(10) Å, V=813.53(10) Å{sup 3}). The structures are based on rare-earth metal atoms coordinated by S atoms in a trigonal-prismatic and/or square-antiprismatic fashion, Cu-centered tetrahedra, and pnictogen atoms in pyramidal or distorted octahedral coordination. - Highlights: • Ln{sub 2}CuSbS{sub 5} are complex quarternary phases crystallizing in their own structure type. • Ln{sub 2}CuSbS{sub 5} and Ce{sub 2}CuBiS{sub 5} are new compound in the respective ternary phase diagrams. • Ln{sub 2}CuSbS{sub 5} on one side, and Ln{sub 2}CuBiS{sub 5} on the other are not isotypic.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis, crystal structure, electrical properties, and sodium transport pathways of the new arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6}

A new sodium cobalt (II) arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6} has been synthesized by a solid-state reaction and its crystal structure determined from single crystal X-ray diffraction data. It crystallizes in the monoclinic system, space group C2/m, with a=10.7098(9) Å, b=14.7837(9) Å, c=6.6845(7) Å, and β=105.545(9)°. The structure is described as a three-dimensional framework built up of corner-edge sharing CoO{sub 6}, CoO{sub 4} and AsO{sub 4} polyhedra, with interconnecting channels along [100] in which the Na{sup +} cations are located. The densest ceramics with relative density of 94% was obtained by ball milling and optimization of sintering temperature, and its microstructure characterized by scanning electron microscopy. The electrical properties of the ceramics were studied over a temperature interval from 280 °C to 560 °C using the complex impedance spectroscopy over the range of 13 MHz–5 Hz. The ionic bulk conductivity value of the sample at 360 °C is 2.51 10{sup −5} S cm{sup −1} and the measured activation energy is Ea=1 eV. The sodium migration pathways in the crystal structure were investigated computationally using the bond valence site energy (BVSE) model and classical molecular dynamics (MD) simulations. - Graphical abstract: Correlation between crystal structure, microstructure and ionic conductivity . Display Omitted - Highlights: • A new arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6} was prepared by solid state reaction. • Its crystal structure was determined by powder X-ray diffraction. • Na{sup +} ionic conductivity was probed by complex impedance spectroscopy. • Na{sup +} conduction pathways were modeled by bond-valence method and molecular dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Flux crystal growth, structure, magnetic and optical properties of a family of alkali uranium(IV) phosphates

A family of alkali uranium(IV) phosphates, AU 2 (PO 4 ) 3 (A = Li – Cs), was synthesized as single crystals by the reaction of US 2 and (NH 4 ) 2 HPO 4 in the respective ACl (A = Li – Cs) flux contained in a sealed fused-silica tube at 850 °C, and as phase pure powders from a similar reaction using UF 4 as the uranium source. AU 2 (PO 4 ) 3 (A = Li – Rb) crystallize in the NaTh 2 (PO 4 ) 3 (NTP) structure type with monoclinic space group C2/c and consist of a 3D structure that features a framework composed of edge- and corner-sharing polyhedra. The cesium analogue, CsU 2 (PO 4 ) 3 , crystallizes in a different structure with space group P2 1 /n that is related to the NaZr 2 (PO 4 ) 3 (NZP) structure type and consists of a framework composed of corner-sharing polyhedra. Two new alkali uranium phosphates, Li 2 U(PO 4 ) 2 and Cs 4 U 4 (P 2 O 7 ) 5 , were also grown as single crystals at 700 °C. Li 2 U(PO 4 ) 2 was isolated in approximately 30% yield based on uranium. Li 2 U(PO 4 ) 2 crystallizes in space group P2 1 /c exhibiting a layered structure while Cs 4 U 4 (P 2 O 7 ) 5 , crystallizes in space group P2 1 /n in a new structure type featuring a 3D framework. Finally, the magnetic susceptibilities and the field dependent magnetizations were measured for AU 2 (PO 4 ) 3 (A = Li, Na, K and Cs); all compounds exhibited negative Weiss temperatures with no obvious antiferromagnetic transition. Optical properties were measured by UV–vis and IR spectroscopy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Extrinsic and intrinsic properties in metal–insulator transition of hydrothermally prepared vanadium dioxide crystals

The clear insulator (monoclinic-VO{sub 2}) to metal (rutile-VO{sub 2}) transition (IMT) was observed in electrical conductivity and differential scanning calorimeter (DSC) measurements at around 340 K, which is IMT temperature (T{sub H}), in the hydrothermally prepared VO{sub 2} crystals. The occurrence of metal to insulator transition (MIT) temperature (T{sub C}) was observed below 333 K during the first resistance measurement cycle in the most of cases. The sudden jump of the electrical resistance at IMT and MIT points was amplified several times than that of the first cycle during the repeated successive thermal cycles (heating and cooling across the IMT and MIT temperatures). T{sub C} and T{sub H} shifted to higher temperature by the repeated successive thermal cycles. This shift and the amplified jump might be related to the mechanical stress between the VO{sub 2} crystals, i.e. extrinsic properties. However, the starting point of MIT, T{sub CS} = ∼ 336 K, and the starting point of IMT, T{sub HS} = ∼ 338 K, kept almost constant during the repeated thermal cycles (< 10 times). These two temperatures may be related to the intrinsic properties of the VO{sub 2}: the phase transitions initiated at these temperatures regardless of the number of the repeated thermal cycles. The neat surface of the VO{sub 2} crystals was severely damaged and the average size of particles reduced from 110 nm to 70–90 nm after extensively repeated thermal cycles (> 70 times). The damaged surface and the smaller particles, which would be originated from the mechanical stress caused by crystal volume change during the first order transition of the VO{sub 2}, would weaken the electrical conduction path (loosen grain boundaries) between the VO{sub 2} single crystals and would result in the amplified jump at the following MIT. This report may boost the study for the improved stability and lifetime of the VO{sub 2} based electronic devices. - Highlights: • The sharp phase transition in cluster of VO{sub 2} crystals depends on repeated thermal cycles. • Two intrinsic and two extrinsic temperatures are observed during the phase transition. • The mechanical stress change and surface damage may cause the extrinsic properties in transport measurement.

36 MATERIALS SCIENCE↗

Investigation and characterization of ZnO single crystal microtubes

Morphological, structural, and optical characterization of microwave synthesized ZnO single crystal microtubes were investigated in this work. The structure and morphology of the ZnO microtubes are characterized using X-ray diffraction (XRD), single crystal diffraction (SCD), field emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDX), and transmission electron microscopy (TEM). The results reveal that the as-synthesized ZnO microtube has a highly regular hexagonal cross section and smooth surfaces with an average length of 650–700 μm, an average outer diameter of 50 μm and wall thickness of 1–3 μm, possessing a single crystal wurtzite hexagonal structure. Optical properties of ZnO single crystal microtubes were investigated by photoluminescence (PL) and ultraviolet-visible (UV-vis) absorption techniques. Room-temperature PL spectrum of the microtube reveal a strong UV emission peak at around 375.89 nm and broad and a weak visible emission with a main peak identified at 577 nm, which was assigned to the nearest band-edge emission and the deep-level emission, respectively. The band gap energy of ZnO microtube was found to be 3.27 eV. - Highlights: • ZnO microtube length of 650–700 μm, diameter of 50 μm, wall thickness of 1–3 μm • ZnO microtube possesses a single crystal wurtzite hexagonal structure. • The crystal system is hexahedral oriented along a-axis with indices of (100). • A strong and sharp UV emission at 375.89 nm (3.29 eV) • One prominent absorption band around 378.88 nm (3.27 eV)

36 MATERIALS SCIENCE↗

Formation of Fe2Al5-xZnx intermetallic crystals at the Fe-Zn interface in hot-dip galvanizing

Highlights: • Interstitial-free steels were galvanized in Zn baths containing 0.14-0.28 wt% Al. • The Fe-Al layer formed in a 0.14 wt% Al bath is composed of equiaxed Fe{sub 2}Al{sub 5-x}Zn{sub x} crystals without preferred orientations. • The layers formed in baths containing 0.18 wt% Al or more are composed of orientated domains. • Each domain contains 4-12 Fe{sub 2}Al{sub 5-x}Zn{sub x} crystal variants of specific orientations. • A layer of a single variant crystal can grow epitaxially on the α-Fe grains as the Al content reaches 0.28 wt%. - Abstract: The formation of Fe{sub 2}Al{sub 5-x}Zn{sub x} inhibition layer at the Fe-Zn interface has been characterized by scanning electron microscopy/electron backscatter diffraction and transmission electron microscopy for interstitial-free steels galvanized in Zn baths containing 0.14–0.28 wt% Al. The inhibition layer formed in the 0.14 wt% Al bath is composed of fine, equiaxed Fe{sub 2}Al{sub 5-x}Zn{sub x} crystals without preferred orientations. The inhibition layers formed in the baths containing 0.18 wt% Al or more are composed of orientated domains and each domain contains 4–12 Fe{sub 2}Al{sub 5-x}Zn{sub x} crystal variants of specific orientations. All the variants follow the same Fe{sub 2}Al{sub 5-x}Zn{sub x}/Fe orientation relationship of [110]{sub Fe2Al5-xZnx}//[1 1-bar 1]{sub Fe} and (001){sub Fe2Al5-xZnx}//(110){sub Fe}. Therefore, each domain is formed on a single α-Fe grain and the number of variants in the domain is determined by the orientation of the α-Fe grain. The fraction of the area of epitaxial growth increases with increasing Al content in bath. When the Al content reaches 0.28 wt%, a layer of a single variant (SV) crystal can grow epitaxially on the α-Fe grains having orientations distributed from <110> to <113> parallel to the normal direction of the sheet surface. The formation of a dense SV inhibition layer is the major reason for the drastic reductions in both the Al-pickup rate and the inhibition layer thickness at high Al content baths.

36 MATERIALS SCIENCE↗