Theoretical study on Fe-Al clusters: geometric structure, bonding law and electronic structures

Structures of the small Fe-Al clusters with different atom proportion are calculated using the B3LYP method in density functional theory (DFT). Calculated results show that the Al atoms lose electrons easily while the Fe atoms capture electrons easily. The most stable geometry is the bonding between Fe and Fe atoms and between Fe and Al atoms with the largest possibility, and the cluster stability law with the same atom proportion accords with the change of the highest occupied molecular orbital (HOMO) energy and the entropy of cluster system. Moreover, the electronic structure study of the ground-state Fe3Al and Fe2CrAl clusters shows that the substitution of Cr atom for the Fe atom located at the next neighboring site of Al atom reduces localized electrons not only between Al atom and the next neighboring Cr atom, but also between Al atom and the nearest neighboring Fe atom. Although the substitution increases the plasticity and the magnetism of intermetallic compound, the stability of the system slightly decreases. Our theoretical results agree well with the experimental results.     

Analysis of the carbon source for diamond crystal growth

The lattice constants of diamond and graphite at high pressure and high temperature （HPHT） were calculated on the basis of linear expansion coefficient and elastic constant. According to the empirical electron theory of solids and molecules （EET）, the valence electron structures （VESs） of diamond, graphite crystal and their common planes were calculated. The relationship between diamond and graphite structure was analyzed based on the boundary condition of the improved Thomas-Fermi-Dirac theory by Cheng （TFDC）. It was found that the electron densities of common planes in graphite were not continuous with those of planes in diamond at the first order of approximation. The results show that during the course of diamond single crystal growth at HPHT with metal catalyst, the carbon sources forming diamond structure do not come from the graphite structure directly. The diamond growth mechanism was discussed from the viewpoint of valence electron structure.     

Liquid structure of pure iron by X-ray diffraction

The liquid structure of pure iron at 1540, 1560 and 1580℃ was studied by X-ray diffraction. The results show that near the melting point there is a medium-range order structure that fades away with the increasing temperature. The average nearest distance of atoms is almost independent of the melts temperature, but the average coordination number, the atom cluster size and the atom number in an atom cluster all decrease with the increasing temperature of the melt. Near the melting point there area lot of atom clusters in the pure iron melt. The atom cluster of pure iron has the body-centered cubic lattices, which are kept from the solid state. And the body-centered cubic lattices connect into network by occupying a same edge. The atoms in the surrounding of the atom clusters are arranged disorderly.     

New crystal structure of molecular complex 1-piperidine carboxylate-piperidinium-H<Subscript>2</Subscript>O studied by X-ray single crystal diffraction

Piperidine absorbs CO2 and H2O in air to form a molecular complex： piperidium-l-piperidinecarboxylate-H2O. The structure of the complex was characterized by X-ray single crystal diffraction. The crystal structure was determined to be triclinic, space group P1^-with a=0.648 6（8） nm, b=0.809 200） nm, c= 1.357 1（16） nm, a=96.96706）°, β =102.506（15）°,γ=104.202 05）°, Z=2. The complex is stabilized via five hydrogen bonds between the three components, N-O electrostatic interaction and O-O interaction （electron transfer） betweenl-piperidinecarboxylate and H2O. Due to electron transference of carbamate ion, the oxygen atom in water molecule is strongly negatively charged and the O-H bond is considerably shorter than that of the free molecule of water. The formation of the molecular complex is a reversible process and will decompose upon heating. The mechanism of formation and stabilization is further investigated herein.     

Preparation and performance of LiNi0. 8Co0.2O2 cathode material based on Co-substituted α-Ni（OH）2 precursor

Co-substituted α-Ni（OH）2 was synthesized by a novel microwave homogeneous precipitation method in the presence of urea. LiNi0.8Co0.2O2 cathode material was synthesized by calcining Co-substituted α-Ni（OH）2 precursor and LiOH·H2O at 900℃for 10 h in flowing oxygen. XRD, FTIR, FESEM and electrochemical tests were used to study the physical and the electrochemical performances of the materials. The results show that the prepared LiNi0.8Co0.2O2 compound has a good layered hexagonal structure. Moreover, the LiNi0.8Co0.2O2cathode material demonstrates stable cyclability with a high initial specific discharge capacity of 183.9 mAh/g. The good electrochemical performance could be attributed to the uniform distribution of Ni^2＋ and Co^2＋ ions in the crystal structure and a minimal cation mixing in LiNi0.8Co0.2O2 host structure.     

Effects of electric pulse on microstructure of Al-Si alloy in liquid and solid states

In order to investigate the change in liquid microstructure of Al-Si alloy treated by electric pulse (EP), X-ray diffraction tests with liquid Al-Si alloy and ZL109 alloy treated or not by EP were carried out. The results show that the number of Al-Si atomic clusters decreases and that of Al-Al and Si-Si atomic clusters increases for the treated samples. The tests with ZL109 alloy indicate that a large amount of primary crystal Si appears in the solidified microstructure after treated by EP. It is found that EP canchange the microstructure of liquid metal by affecting the probability of electrons appearing in different atoms (Al and Si) in the liquid metal.The combining force of different atoms decreases relatively, and that of the same atoms increases, which is the main reason of reducing the atomic cluster with different atoms (Al-Si) and increasing the atomic cluster with the same atoms (Al-Al, Si-Si). The increasing of the atomic cluster with the same atom cluster resulted in the increasing of Si activity and the higher point of eutectics in the phase diagram. It makes a lot of primary silicon appeared in ZL109 alloy.     

Preparation and performance of LiNi_(0.8)Co_(0.2)O_2 cathode material based on Co-substituted α–Ni(OH)_2 precursor

Co-substituted α-Ni(OH)2 was synthesized by a novel microwave homogeneous precipitation method in the presence of urea. LiNi0.8Co0.2O2 cathode material was synthesized by calcining Co-substituted α-Ni(OH)2 precursor and LiOH·H2O at 900℃ for 10 h in flowing oxygen. XRD, FTIR, FESEM and electro- chemical tests were used to study the physical and the electrochemical performances of the materials. The results show that the prepared LiNi0.8Co0.2O2 compound has a good layered hexagonal structure. Moreover, the LiNi0.8Co0.2O2 cathode material demonstrates stable cyclability with a high initial specific discharge capacity of 183.9 mAh/g. The good electrochemical performance could be attributed to the uniform distribution of Ni2 and Co2 ions in the crystal structure and a minimal cation mixing in LiNi0.8Co0.2O2 host structure.     

Combined effect of pre-aging and Ag/Cu addition on the natural aging and bake hardening in Al-Mg-Si alloys

The combined effect of pre-aging and Ag/Cu addition on natural aging and bake hardening in Al-Mg-Si alloys were studied by Vickers microhardness measurement, tensile test, atom probe tomography and transmission electron microscopy. The results showed that Ag and/or Cu addition could further enhance the positive effect of pre-aging on bake hardening for Al-Mg-Si alloys. Although the pre-aged alloys with individual Ag/Cu addition had higher paint bake hardness, the hardness in T4 P temper was relatively high due to effectively forming of Cluster(2) during pre-aging. While the pre-aged Ag-Cu-added alloy had low T4 P temper hardness and higher bake hardening response. The strong interaction energies between Ag/Cu atoms and Mg atoms were responsible for the facilitated clustering and precipitation processes. After paint bake treatment, most of Ag atoms accumulated preferentially at β″/α-Al matrix interface, while Cu atoms entered into the interior of β″resulting in disordered structure within the precipitate.     

First-principle study of interaction of H2 and H2O molecules with (ZnO)n(n=3?6) ring clusters

A density functional calculation was performed to investigate the impact of hydrogen and water molecules on zinc oxide clusters (ZnO)n=3–6 ··· X, where X=H2 and H2O. The calculated binding energies were corrected for the basis set superposition error (BSSE). The structural parameters and chemical hardness were calculated for the complexes of zinc oxide clusters and guest molecules. The strength values of the interaction between the clusters and the guest molecules were analyzed based on the topological properties of atoms in molecules (AIM) theory of Bade r. The stereo electronic interact ions inside the ZnO clusters were analyzed in detail using the natural bond orbital (NBO) analysis.     

Synthesis and formation mechanism of micro/nano flower-like MgCO3·5H2O

Micro/nano magnesium carbonate pentahydrate（MgCO3 ·5H2 O） with flower-like morphology was synthesized using magnesite as a substrate and potassium dihydrogen phosphate as an additive. The synthesized samples were characterized by scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetry and differential scanning calorimetry. The influence of pyrolysis time on crystal morphology was explored. The formation mechanism was investigated on the basis of the characterized results and the crystal structure of MgCO3 ·5H2 O. The results showed that the flower-like MgCO3 ·5H2 O was 1.5-3.0 μm in length and 100-500 nm in diameter and was successfully obtained with a pyrolysis time of 30 min. The formation mechanism of flower-like MgCO3 ·5H2 O is suggested to be the selective adsorption of potassium dihydrogen phosphate on the surface. The process of flower-like crystal growth is as follows： amorphous nanoparticles formation, acicular and rod monocrystal formation, flower-like monocrystal formation, and flower-like polymers（MgCO3 ·5H2 O） crystallization. In the MgCO3 ·5H2 O crystal, the magnesium ion presents two different octahedral coordinations corresponding to2 26 Mg（H O）＋and2 2 2 4 23 [Mg（H O）（CO） ]--, and the chemical formula of the crystal is2 2 6 2 4 23 Mg（H O） Mg（H O）（CO）2.     

Community structure of β-Proteobacterial ammonia-oxidizing bacteria in prawn farm sediment

To examine the community structure of β-Proteobacterial ammonia-oxidizing bacteria （AOB） in prawn farm sediment, the 16S rRNA gene library was constructed with β-Proteobacterial AOB-specific primers. The library was screened by PCR-restriction fragment length polymorphism （RFLP） analysis and clones with unique RFLP patterns were sequenced. Two groups of β-Proteobacterial AOB, the Nitrosomonas and the Nitrosospira, were detected. The Nitrosomonas occupied an absolute dominant position, accounting for more than 90% of total clones in the clone library, while the Nitrosospira accounting for 5.48%. Nitrosomonas-affiliated clones were grouped into the Nitrosomonas marina and the Nitrosomonas sp. Nm143 clusters, and Nitrosospira-affiliated clones were grouped into the Nitrosospira cluster 1. No other clusters of β-Proteobacterial AOB were found. The results enriched our knowledge of AOB diversity in the prawn farm sediment and provided important foundational data for further functional studies of these microbes in mariculture environments.     

Synthesis and crystal structure of tetranuclear zinc benzoate

A tetranuclear zinc benzoate Zr4O(C6H5CO2)6 was synthesized and characterized by X-ray single crystal determination. It crystallizes in cubic, space group Ia-3d. Its crystal cell is very large, α=4.10063(18)nm, V=68.953(5)nm^3 and Z=48. The structure is composed of discrete Zr4O(C6H5CO2)6 molecules. In each molecule, four zinc atoms are held together by a central oxygen atom, which results in the formation of a regular tetrahedron. All benzoate ligands coordinate to zinc atoms in a bidentate bridging mode. Each zinc atom is in a slightly distorted tetrahedral geometry, coordinated by three benzoate oxygen atoms and the central oxygen atom. The intermolecular interactions result in the formation of a three-dimensional supramolecular framework, with non-intersecting parallel channels.     

NMR and FT-IR analysis of new molecular complex 1-piperidine-carboxylate-piperidinium-H2O

Piperidine absorbs CO2 and H2O contents in air to form a molecular complex： piperidium-1-piperidinecarboxylate-H2O. The structure of the complex was characterized by FT-IR and NMR. The complex is stabilized via five hydrogen bonds between the three components, N…O electrostatic interaction and O…O interaction （electron transfer） betweenl-piperidinecarboxylate and H2O. Through electron transfer from the carbamate ion, the oxygen atom in water molecule is strongly negatively charged and the O-H bond is considerably shorter than that of free water molecule. The formation of the molecular complex is a reversible process and will decompose upon heating. The mechanism of formation and stabilization is further investigated herein.     

Refinement of the crystal structure for a new mineral──antimonselite

The crystal structure of a new mineral of the stibnite group, Sb-2Se-3, has been determined. The cell constants, obtained by least-squares calculation from direct θ -value's measurements on the diffractometer are: a =1.158 8(5), b =1.174 4(4), c =0.395 5(2) nm; orthorhombic; V =0.538 23 nm+3; Z =4. The space group is Pbnm. X-ray single crystal data, using Mo K α radiation, were measured on a RIGAKU RASA-5RP automated diffractometer and refined to a final R index of 0.048 1. Sb-2Se-3 is isostructural with Sb-2S-3 and Bi-2S-3. Each Sb(1) atom is six-coordinated by 3 Se(1), 1 Se(2) and 2 Se(3) atoms at distances 0.266 0-0.323 6 nm. Each Sb(2) atom is seven-coordinated by 2 Se(1), 2 Se(2) and 3 Se(3) atoms at distances of 0.258 1- 0.346 7 nm. The crystal structure consists of chains parallel to c or needle axis. The strongest bonds (shortest separations) are within the chains. Many important physical properties of antimonselite (optical, ferroelectric, etc.) are related to its crystal structure.     

Direct numerical simulation of hydrogen turbulent lifted jet flame in a vitiated coflow

The direct numerical simulation (DNS) method with 16 steps detailed chemical kinetics was applied to a lifted turbulent jet flame with H2/N2 fuel issuing into a wide hot coflow of lean combustion products,at temperature of 1045 K and low oxygen concentrations. The chemical reactions were handled by the library function of CHEMKIN which was called by the main program in every time step. Parallel com-putational technology based on message passing interface method (MPI) was used in the simulation. All the cases were run by 12 CPUs on a high performance computer system. Faver-averaged DNS re-sults were obtained by long time averaging the transient profile and compared with the experimental data. The roll-up and evolution of the vortices in jet flame were well captured. The vortices in the same rotating direction attracted each other and those in different rotating directions repulsed each other. Through complex interactions between vortices,the original symmetrical vortex structure could be converted into nonsymmetrical and more complex structures by combination,distortion and splitting of the vortices. The transient profiles of H,OH and H2O mass fraction at 5.76 ms showed the flame structure in jet flame,especially the autoignition regions clearly. The lift-off height was about 9 d―11 d,in agreement with the experimental observation. At the corner point of the flame sheet indicated by OH and H profiles,the combustion was always enhanced by the flame curvature and extended resident time. The profiles of turbulence intensities show that the flames were diffused from the original two outside flame sheets into the core. The DNS results can be considered in developing more accurate and more universal turbulence models.     

Effect of bilayer number on the photoluminescent property of TPE-based self-assembled film

Tetraphenylethylene (TPE) derivatives have been proved to be typical aggregation-induced emission (AIE) luminogens when they were aggregated in the free three-dimensional space. In order to reveal the effect of the dimensional degree on AIE property of TPEs, we utilized tetra(4-hydroxyphenyl)ethylene (TPE-4OH) and 1,4-benzenediamine diazonium salt (BD) to fabricate the ultrathin films (TPE-4OH/BD LBL SA film) through layer-by-layer self-assembled technique. The interaction between TPE-4OH and BD in the films was converted from electrostatic force and hydrogen-bond to covalent bonds through photodecomposition of diazonium groups under UV irradiation. Fluorescence emission spectroscopy, UV-Vis absorption spectroscopy and atomic force microscope were carried out to evaluate the relationship between bilayer number and photoluminescence of the TPE-based self-assembled films. The experimental results showed that the TPE-based film with three bilayers only displayed AIE character, whereas the fluorescence of the film became randomly changed if the bilayer number was above three. It is supposed that the fluorescence property of the TPE-4OH/BD LBL SA film with limited molecular length in z-axis and infinite aggregation space in x-and y-axis is dominated by two competitive effects, one is the partial restriction of intramolecular rotation through short inter-molecular interactions in cross-linked structure of TPE-4OH/BD, and the other is deactivation of its excited state through unrestricted intramolecular rotations or π-π interactions.     

Coating for Nano Super Soil-repellency of Cashmere Fabric

The nano-size metal oxide was prepared by the single-disperse technique on liquid phase, and formed sol dusters, its uniform film was covered on the surface of cashmere fibers by coating, and it had good oil repellency and water repellency. The results of IR（infrared） Spectrometer analysis revealed： The nano material combines through the strong bonds with the surface of cashmere fibers by the live groups. These analyses by SEM techniques showed that the nano material was distributed on the fiber surface even, and the nano material formed the strong peak of the regular crystal phase structure using the X-Ray Diffractometry （XRD） to analysis the fabric. The optimum techniques were selected by a series of experiments, coated cashmere fabric not only has preserved original properties of softness and comfort, but also has good properties of Bi-repellency function. Therefore, the technique will have potential appfication in engineers.     

Boron isotopic fractionation during incorporation of boron into Mg（OH）2

Experiments of boron incorporated into Mg（OH）2 from magnesium-free synthetic seawater were carried out at various pH values, in order to investigate the adsorption species and the variation of isotopic fractionation of boron on Mg（OH）2. The results showed that the incorporation of boron into Mg（OH）2 was very rapid and reached the equilibrium after 4 h. The [B]s and the partition coefficient Kd between Mg（OH）2 and final solution decreased with the increasing pH. The maximum values of [B]s and Kd were much higher than that of boron adsorbed on metal oxide or clay minerals, indicating that the incorporation capability of boron into Mg（OH）2 was very strong. When the adsorption reached the equilibrium, the δ 11Bfsw was lower than δ 11Bisw. The boron isotopic fractionation αs-fsw was between 1.0186 and 1.0220 with an average of 1.0203. All these indicated that 11B incorporated into Mg（OH）2 preferentially due to B（OH）3 incorporation into Mg（OH）2 preferentially. The deposition reaction of B（OH）3 with Mg（OH）2 was the direct reason for B（OH）3 incorporation into Mg（OH）2. During the boron incorporation into Mg（OH）2, the isotopic fractionation characteristic of boron was decided by the simultaneous existence of adsorption of boron on Mg（OH）2 and the deposition reaction of H3BO3 with Mg（OH）2. Different from the fact that only B（OH）4-species incorporated into bio-carbonate, B（OH）3 and B（OH）4 incorporated into Mg（OH）2 simultaneously, and B（OH）3 incorporated into it preferentially. The lower pH is, the more incorporated fraction of B（OH）3 will be. Mg（OH）2 exists widely in madrepore, which influences the quantitative correspondence of the boron isotopic composition δ 11Bcarb of corals on the pH of the seawater badly, and brings serious uncertainty to the δ 11Bcarb as the indicator of the ancient seawater pH.     

A piezoelectric spectroelectrochemical study on the structural interconversion for poly（o-phenylenediamine） between its ladder structure with phenazine units and polyaniline-like chains

The combination of reflectance UV-Vis spectroelectrochemistry with electrochemical quartz crystal microbalance （EQCM） and separate reflectance FTIR characterization were used to investigate the structural interconversion for poly（o.phenylenediamine） （PoPD） between its ladder structure with phenazine units and polyaniline-like linear chains. The poly（o-phenylenediamine） films potentiostatically （0.8 V vs. SCE） grew on Au electrodes from 0.20 mol·L^-1 H2SO4 （PoPD1） or 0.40 mol·L^-1 NaOH （PoPD2） aqueous solution containing 0.20 mol·L^-1 Na2SO4 ＋ 0.10 mol·L^-1 o-phenylenediamine. By considering the mass of deposited PoPD2 film obtained from the EQCM data and the charge consumed under the current peak at ca. 0.6 V vs. SCE for oxidation of -NH2 groups in as-prepared PoPD2 during potential cycling in 0.10 mol·L^-1 aqueous H2SO4, the molar percentage of the polyaniline-like chains was estimated to be 19% （relative to total phenylenediamine units）, being in agreement with the result obtained from a formaldehydecombination experiment through the aminocarbonyl reaction. After 40-cycle potential sweeps between 0.2 and 0.8 V vs. SCE the polyaniline-like chains in PoPD2 could be completely converted via intramolecular cyclization into the ladder structure with phenazine units. However, PoPD1 was found to be perfectly composed of the ladder structure with phenazine units, and after 40-cycle potential sweeps between -0.4 and 0.1 V vs. SCE only 2.5% in molar percentage of PoPD＇s ladder structure could be converted into polyani line-like chains, suggesting that the ladder structure with phenazine units is thermodynamically more stable due to its possessing higher conjugation.