Structural study of amorphous In2O3 film by grazing incidence X-ray scattering (GIXS) with synchrotron radiation

Grazing incidence X-ray scattering (GIXS) using synchrotron radiation is a very useful method for structural analysis of amorphous films. We investigated the structure of amorphous In₂O₃ film utilizing GIXS at BL19B2 in SPring-8. Radial distribution function (RDF) was obtained from the measurement data. Structural models were constructed by molecular dynamics (MD) and reverse Monte-Carlo (RMC) simulations, and the calculated RDFs from the simulations were compared with that observed. It was found that the average oxygen coordination number around In ions was almost 6 and the average length 2.12 Å, which was smaller by about 3% than that of 2.18 Å in crystalline In₂O₃. It was concluded that the atomic arrangement of the amorphous In₂O₃ was characterized by the increase in the number and the boarder angle of distribution of corner-sharing In-O-In bond compared with crystalline In₂O₃.     

Bioactivity and mineralization of hydroxyapatite with bioglass as sintering aid and bioceramics with Na3Ca6(PO4)5 and Ca5(PO4)2SiO4 in a silicate matrix

Hydroxyapatite and Bioglass^®-45S5 were sintered together creating new ceramic compositions that yielded increased apatite deposition and osteoblast differentiation and proliferation in vitro compared to hydroxyapatite. The sintered products characterized by X-ray diffraction, revealed hydroxyapatite as the main phase when small quantities (1, 2.5 and 5 wt.%) of bioglass was added. Bioglass behaved as a sintering aid with β-TCP (Ca₃(PO₄)₂) being the minor phase. The amount of β-TCP increased with the amount of bioglass added. In compositions with larger additions of bioglass (10 and 25 wt.%), new phases with compositions of calcium phosphate silicate (Ca₅(PO₄)₂SiO₄) and sodium calcium phosphate (Na₃Ca₆(PO₄)₅) were formed respectively within amorphous silicate matrices. In vitro cell culture studies of the ceramic compositions were examined using bone marrow stromal cell (BMSC). Cell proliferation and differentiation of bone marrow stromal cells into osteoblasts were determined by Pico Green DNA assays and alkaline phosphatase (ALP) activity, respectively. All hydroxyapatite–bioglass co-sintered ceramics exhibited larger cell proliferation compared to pure hydroxyapatite samples. After 6 days in cell culture, the ceramic with Ca₅(PO₄)₃SiO₄ in a silicate matrix formed by reacting hydroxyapatite with 10 wt.% bioglass exhibited the maximum proliferation of the BMSC's. The ALP activity was found to be largest in the ceramic with Na₃Ca₆(PO₄)₅ embedded in a silicate matrix synthesized by reacting hydroxyapatite with 25 wt.% bioglass.     

Frequency dependent electrical conductivity and dielectric relaxation behavior in amorphous (90V2O5–10Bi2O3) oxide semiconductors doped with SrTiO3

We report on the experimental results of frequency dependent a.c. conductivity and dielectric constant of SrTiO₃ doped 90V₂O₅–10Bi₂O₃ semiconducting oxide glasses for wide ranges of frequency (500–10⁴ Hz) and temperature (80–400 K). These glasses show very large dielectric constants (10²–10⁴) compared with that of the pure base glass (≈10²) without SrTiO₃ and exhibit Debye-type dielectric relaxation behavior. The increase in dielectric constant is considered to be due to the formation of microcrystals of SrTiO₃ and TiO₂ in the glass matrix. These glasses are n-type semiconductors as observed from the measurements of the thermoelectric power. Unlike many vanadate glasses, Long's overlapping large polaron tunnelling (OLPT) model is found to be most appropriate for fitting the experimental conductivity data, while for the undoped V₂O₅–Bi₂O₃ glasses, correlated barrier hopping conduction mechanism is valid. This is due to the change of glass network structure caused by doping base glass with SrTiO₃. The power law behavior (σ_ac=A(ω^s) with s<1) is, however, followed by both the doped and undoped glassy systems. The model parameters calculated are reasonable and consistent with the change of concentrations (x).     

钛酸丁酯有机相乙酐沉淀前驱物制备纳米晶体二氧化钛

钛酸丁酯和乙酐在低于100℃非水状态下生成非晶钛氧有机化合物，经焙烧得到纳米二氧化钛晶体。差热分析表明，表面吸附物和键合有机基团在314－389℃之间发生氧化和分解而除去，389－405℃之间无定形粉体转化为锐钛矿型晶体；热重分析中，表面物理吸附物失重10．60％，键合有机基团失重46．55％。制备的纳米二氧化钛为球形粒子，粒径为10－30nm。     

Structural features of AgCaCdMg2(PO4)3 and AgCd2Mg2(PO4)3, two new compounds with the alluaudite-type structure, and their catalytic activity in butan-2-ol conversion

AgCaCdMg₂(PO₄)₃ and AgCd₂Mg₂(PO₄)₃, two new compounds with the alluaudite-type structure, were synthesized by a solid state reaction in air at 750 °C. The X-ray powder diffraction pattern of AgCaCdMg₂(PO₄)₃ indicates the presence of small amounts of (Ca, Mg)₃(PO₄)₂ with the whitlockite structure, as impurity, whereas AgCd₂Mg₂(PO₄)₃ is constituted by pure alluaudite. The Rietveld refinements of the X-ray powder diffraction patterns indicate an ordered cationic distribution for AgCd₂Mg₂(PO₄)₃, with Ag on A(2)′, Cd on A(1) and M(1), and Mg on M(2), whereas a disordered distribution of Cd and Ca between the A(1) and M(1) sites is observed for AgCaCdMg₂(PO₄)₃. The catalytic properties of these compounds has been measured in reaction of butan-2-ol dehydrogenation. In the absence of oxygen, both samples exhibit poor dehydrogenation activity. All samples displayed no dehydration activity. Introduction of oxygen into the feed changed totally the catalytic behavior of the catalysts. The production of methyl ethyl ketone increases with time on stream and the reaction temperature. AgCaCdMg₂(PO₄)₃ is more efficient than AgCd₂Mg₂(PO₄)₃.     

Analysis of oxyanion (BO33?, CO32?, SO42?, PO43?, SeO44-) substitution in Y123 compounds studied by X-ray photoelectron spectroscopy

XPS core level spectra of Y123 compounds doped by C, B, S, P, and Se elements are presented. It is found that the C1s, E1s, S2p, P2p, and Se3d binding energies of doped compounds are close to those of CaCO₃, FeBO₃, CuSO₄, NaH₂,PO₄, and SeO₂, reference compounds. It is concluded that these impurity elements form oxyanion groups in Y123 compounds.     

Excitons in organic-inorganic hybrid compounds (CnH2n + 1NH3)2PbBr4 (n = 4, 5, 7 and 12)

Thin films of microcrystalline (C_nH_2n + 1NH₃)₂PbBr₄ (n = 4, 5, 7 and 12) have been prepared by a modified spin-coating method, and the effect of the number of carbon atoms of the alkyl chain length (n) on optical properties has been investigated. Absorption spectra reveal that (C_nH_2n + 1NH₃)₂PbBr₄ films show stable excitons with a binding energy of a few hundred meV. The excitonic structure of (C_nH_2n + 1NH₃)₂PbBr₄ varies with the number of carbon atoms. The lowest-energy exciton splits into a few fine-structure levels at low temperature. (C_nH_2n + 1NH₃)₂PbBr₄ films (n = 5, 7 and 12) show not only singlet excitons but also triplet excitons at low temperature, while (C₄H₉NH₃)₂PbBr₄ films show only singlet excitons. The intersystem crossing from excited singlet state to triplet state plays an important role in the relaxation process of excitons.     

Elaborately Designed Hierarchical Heterostructures Consisting of Carbon‐Coated TiO2(B) Nanosheets Decorated with Fe3O4 Nanoparticles for Remarkable Synergy in High‐Rate Lithium Storage

The capacity and conductivity deficiencies of TiO₂(B) are addressed simultaneously through a smart morphological and compositional design. Elaborately designed hierarchical heterostructures are reported, consisting of carbon‐coated TiO₂(B) nanosheets decorated with Fe₃O₄ nanoparticles, based on a facile self‐assembly strategy. The novel hierarchical heterostructures exhibit a remarkable synergy by bridging the intriguing functionalities of TiO₂(B) nanosheets (high safety and durability), Fe₃O₄ nanoparticles (high theoretical capacity), and carbon coatings (high conductivity), which results in significantly improved cycle and rate performances. A startlingly high reversible capacity of 763 mA h g⁻¹ is delivered at 500 mA g⁻¹ after 200 charging−discharging cycles. Even when the current density is as high as 10 000 mA g⁻¹, the reversible capacity is still up to 498 mA h g⁻¹. This smart morphological and compositional design opens up new opportunities for developing novel, multifunctional hierarchical heterostructures as promising anode materials for next‐generation, high‐power lithium‐ion batteries.     

Phase transitions and ionic mobility in hydrogen zirconium phosphates with the NASICON structure, H1±XZr2−XMX(PO4)3·H2O, M = Nb, Y

Phase transitions and the mobility of proton-containing groups in hydrogen zirconium phosphate HZr₂(PO₄)₃·nH₂O with the NASICON structure were studied by X-ray powder diffraction, ¹H, ³¹P NMR, IR spectroscopy and TG analysis. Heating HZr₂(PO₄)₃·H₂O above 420 K results in dehydration and in a rhombohedral-triclinic phase transition. Continued heating to about 490 K results in the thermal activation of cation disordering and phase transition of HZr₂(PO₄)₃ from triclinic to rhombohedral phase. Parameter “a” of HZr₂(PO₄)₃ lattice decreases during the heating. It is shown that oxonium ions in HZr₂(PO₄)₃·H₂O are characterized by high rotation and translation mobility. Rotation mobility of oxonium ions can be increased by the substitution of zirconium by yttrium or niobium.