(A19N7)[In4]2 (A = Ca,Sr) and (Ca4N)[In2]: Synthesis,Crystal Structures,Physical Properties,and Chemical Bonding

Single phase powders of (A₁₉N₇)[In₄]₂ (A = Ca, Sr) and (Ca₄N)[In₂] were prepared by reaction of melt beads of the metallic components with nitrogen. The crystal structure of (Ca₁₉N₇)[In₄]₂ was refined based on neutron and X‐ray powder diffraction data. The crystal structure of (Sr₁₉N₇)[In₄]₂ was solved from the X‐ray powder pattern. The structure refinements in combination with results from chemical analyses ascertain the compositions. The compounds (A₁₉N₇)[In₄]₂ (A = Ca, Sr) are isotypes of (Ca₁₉N₇)[Ag₄]₂; (Ca₁₉N₇)[In₄]₂ is probably identical to the earlier reported (Ca_18.5N₇)[In₄]₂. The crystal structure of the isotypes (A₁₉N₇)[In₄]₂ (A = Ca, Sr; cubic, , Ca: a = 1471.65(3) pm; Sr: a = 1561.0(1) pm) contains isolated [In₄] tetrahedra embedded in a framework of edge‐ and vertex‐sharing (A₆N) octahedra. Six of these octahedra are condensed by edge‐sharing around one central A²⁺ ion to form “superoctahedra” (A₁₉N₆) which are connected three‐dimensionally via further octahedra by corner‐sharing. The crystal structure of (Ca₄N)[In₂] (tetragonal, I4₁/amd, a = 491.14(4) pm, c = 2907.7(3) pm) consists of alternating layers of perovskite type slabs of vertex‐sharing octahedra (Ca₂Ca_4/2N) and parallel arranged infinite zigzag chains equation/tex2gif-stack-1.gif[In₂]. In the sense of Zintl‐type counting the compounds (A²⁺)₁₉(N^3?)₇[(In^2.125?)₄]₂ present an electron excess, (Ca²⁺)₄(N^3?)[(In^2.5?)₂] is electron deficient. Metallic properties are supported by electrical resistivity and magnetic susceptibility measurements. The analysis of the electronic structures gives evidence for the existence of homoatomic interactions In–In and significant heteroatomic metal–metal interactions Ca–In which favor the deviations of the title compounds from the (8 – N) rule.     

Interplay of Electronic Structure and Bulk Properties in 2D and 3D Ternary Carbonitrides from First Principles

The changes in electronic structure and hardness as inferred from the bulk modulus are investigated for model structures of ternary compounds XC₃N₃ (X = B, Al, P, As, Ga) within the framework of density functional theory (DFT). The optimisations of the proposed two‐ (2D) and three‐dimensional (3D) structures and the calculations of the bulk moduli are performed by a pseudo potential method. The electronic structures are calculated with the augmented sphere wave method (ASW). The obtained hardness for 2D BC₃N₃ system (B₀ ～ 220 GPa) points to a magnitude close to that of graphitic C₃N₄. For heavier X atoms it decreases rapidly. This is equally observed for the 3D systems examined in the β‐C₃N₄ structure for which B₀(β‐BC₃N₃) amounts to ～330 GPa. Within the magnitude of the well known hard material cubic BN, the BC₃N₃ phases can be predicted as candidates for ultra hard materials. The electronic effect induced by the chemical nature of the X substitutional was examined according to its position in the periodic table i.e. X_III or X_V. Both, band structures and the electron localisation function (ELF) were used for this analysis. The ELF plots show a decreasing covalency with heavier X‐atoms. Potential applications of the devised systems are proposed such as dopings with atoms (Li, rare gas) and molecules (N₂).     

橡胶接枝苯乙烯本体共聚合全程动力学研究(Ⅰ)--接枝行为

橡胶接枝苯乙烯本体聚合的研究目前主要集中于预聚阶段接枝动力学和聚合条件对相转变的影响[1]. 对于后聚阶段, 即相转变后的接枝行为, 尤其是接枝率与橡胶相内包容物的关系、接枝率与高转化率聚合动力学的关系, 接枝率与橡胶相结构的关系等则研究很少. 这些因素对最终聚合物的性能起着至关重要的作用, 因此, 研究橡胶接枝苯乙烯本体聚合相转变以后接枝率的变化, 并找出橡胶相形态演绎过程的规律很有意义.     

Effects of various donor: acceptor blend ratios on photophysical properties in non-fullerene organic bulk heterojunctions

In this work, the donor:acceptor ratio effected photophysical properties of non-fullerene organic solar cells are comparatively investigated. Effective transportation of the photo-generated charge carriers can be obtained with the PDBD-T:ITIC ratio variation. There is no significant energy loss variation exists in the process of changing the D:A ratio.     

Inverse Perovskites (Eu3O)E with E = Sn,In – Preparation,Crystal Structures and Physical Properties

The cubic inverse Perovskites (Eu₃O)In and (Eu₃O)Sn were prepared from the metals and Eu₂O₃ or SnO₂, respectively. For (Eu₃O)In the crystal structure analysis was performed on single crystal X‐ray diffraction data (space group , a = 512.79(3) pm, Z = 1, R_gt(F) = 0.022, wR(F²) = 0.044). The data indicated full occupancy on all sites and a fully ordered structure. According to magnetic susceptibility measurements and X‐ray absorption spectroscopic data at the Eu L_III edge both compounds contain europium in the 4f⁷ (Eu²⁺) electronic state. (Eu₃O)In orders ferromagnetically at 185(5) K, (Eu₃O)Sn shows antiferromagnetic order at 31.4(2) K. Both compounds behave as metallic conductors in electrical resistivity measurements. However, (Eu₃O)In may be classified a metal, while (Eu₃O)Sn is more likely a heavily doped degenerated semiconductor or semimetal according to the absolute values of the resistivity.     

Preparation and Superconductivity of a Series of Bi2CaSr2-XBaxCu2O8+δ

By means of the addition of Ba into the Bi-Ca-Sr-Cu-O 2122 system, a series of Bi₂CaSr_2-xBa_xCu₂O_8+δ (0 ≤ × ≤ 2) quinary metal oxides were prepared by the citrate route and by the conventional powder reaction method. The samples prepared by the former method have better properties than the latter. It was found that 5 was not equal to zero for all of them and that it increased with decreasing Tc. Two phases were indentified in the oxides containing all five metal elements. One is the Bi-Ca-Sr-Cu-O 2122 phase, the other is a new insulating phase which probably contains Bi-Ca-Ba-Cu-O with undetermined stoichiometry. Superconductivity was found in those samples for which × ≤ 1.50 with their Tc onsets between 93–78 K by resistivity measurements. Superconductivity decreased monotonically with increasing x. However, residual resistance was found in those samples for which 1.00 ≤ × ≤ 1.50, The Meissner effect appears in the samples where × ≤ 1.00 with Tc onsets between 88–80 K. For x = 1.75 and 2.00, the samples were semiconductors with resistivities of 6.66 × 10² and 6.96 × 10³ Ω cm at 290 K, and activation energies of 0.109, and 0.298 eV, respectively.     

Optical and Electrical Properties of Polymerizing Plasmas and Their Correlation with DLC Film Properties

Diamond-like carbon (DLC) films were grown from radiofrequency plasmas of acetylene-argon mixtures, at different excitation powers, P. The effects of this parameter on the plasma potential, electron density, electron temperature, and plasma activity were investigated using a Langmuir probe. The mean electron temperature increased from about 0.5 to about 7.0 eV while the mean electron density decreased from about 1.2 × 10⁹ to about 0.2 × 10⁹ cm^–3 as P was increased from 25 to 150 W. Both the plasma potential and the plasma activity were found to increase with increasing P. Through actinometric optical emission spectrometry, the relative concentrations of CH, [CH], and H, [H], in the discharge were mapped as a function of the applied power. A rise in [H] and a fall in [CH] with increasing P were observed and are discussed in relation to the plasma characteristics and the subimplantation model. The optical properties of the films were calculated from ultraviolet-visible spectroscopic data; the surface resistivity was measured by the two-point probe method. The optical gap, E _G, and the surface resistivity, _s, fall with increasing P. E _G and _s are in the ranges of about 2.0–1.3 eV and 10¹⁴–10¹⁶ /, respectively. The plasma power also influences the film self-bias, V _b, via a linear dependence, and the effect of V _b on ion bombardment during growth is addressed together with variation in the relative densities of sp² and sp³ bonds in the films as determined by Raman spectroscopy.     

Single-walled carbon nanotube (SWNT)-carboxymethylcellulose (CMC) dispersions in aqueous solution and electronic transport properties when dried as thin film conductors

Obtaining uniformly dispersed SWNT within an aqueous mixture for subsequent use as a dried coating in electronic biosensors is a challenge. The objective of this study is to relate SWNT dispersion conditions to resultant dried film properties. Aqueous solutions of SWNT dispersed with CMC (a dispersing agent with unique properties compatible with biomolecules) at different SWNT:CMC weight ratios and at different sonication conditions were studied. Solution particle size distribution data was obtained using dynamic light scattering. Differently formulated/processed SWNT/CMC solutions were used to form dry thin, conductive films. The resistance of each film was measured and its resistivity calculated. Response Surface Methodology (RSM) design of experiments (DOE) analysis was used as the tool to fit the data to establish a model and identify trends for the parameters studied. Profilometry was used to examine film surface uniformity. 3D optical microscopy was used to investigate film morphology and determine film thickness, and to relate these data back to solution dispersion conditions and dried film resistances. The lowest dried film resistivity (0.012 ohm-cm) was obtained at the highest levels of parameters studied in the DOE. Smaller solution particle size resulted in lower dried film surface roughness and better film uniformity.     

Gas Storage in Single-Walled Carbon Nanotubes

Abstract

X-ray diffraction (XRD) and electrical resistance measurement on single-walled carbon nan-otube (SWNT) samples prepared by the arc-discharge method are reported. The XRD profile of heat-treated sample indicated that air (oxygen, and/or nitrogen and/or water) can be condensed inside the SWNTs. We also found that the electrical resistance of SWNT soot is significantly affected by exposing to the oxygen gas and humid air.     

One-step measurements of powder resistivity as a function of relative humidity and its effect on charging

A new one-step technique to measure the effect of ambient humidity on powder resistivity has been previously presented. In this article, we provide more experimental data obtained with five different powders. One-step measurements and traditional multi-step measurements were performed. Also, additional measurements were performed using standard resistivity cell. Results were compared and it could be concluded that the new technique provided meaningful results although significant hysteresis was observed during humidification and drying cycles. Finally, charging of the powder was also measured and it was noticed that it decreases with decreasing resistivity and increasing humidity.