密度泛函理论方法研究稀土-过渡金属化合物的磁性和自旋密度图

Magnetic coupling constants J for the complete structures of rare earth\|transition metal compounds:LGdCu(NO\-3)\-3·Me\-2CO(1,Gd(Ⅲ)Cu(Ⅱ)) and [Ce(C\-4H\-7ON)\-4(H\-2O)\-3][Cr(CN)\-6]·2H\-2O(2, Ce(Ⅲ)Cr(Ⅲ)) have been calculated by the combination of the broken\|symmetry approach with the spin project method under the DFT framework.The J value for 1 is a small number in absolute value -2 4cm -1 for calculation,3 5cm -1 for experimental measurement.The spin density distributions are in detail discussed on the basis of Mulliken population analysis,taking into account the coexistence of spin delocalization and spin polarization mechanisms.For 1,the spin distribution in the ground state may be understood as a result of the competition between two mechanisms:a spin delocalization from Cu(Ⅱ) and a spin polarization of Gd(Ⅲ),and the former is dominant.In the case of 2,both transition metal Cr(Ⅲ) and rare earth Ce(Ⅲ) display a spin polarization effect on the surrounding atoms,where a counteraction of the opposite polarization effects leads a low spin density on the bridging ligand C1N1.In the ground state of 2,the stronger polarization effect of Cr(Ⅲ) even causes the positive spin density on the adjacent bridging atom N1.     

二[(R-R'-环己烯基)-甲基取代茂]二氯钛和锆化合物的核磁共振和红外光谱研究

The NMR and FT\|IR Spectra of ten (ηC 6H\-9CRR′ Cp)\-2MCl\-2 (M=Ti,Zr) were measured.The constructions of the compounds were identified by 1H NMR and 13 C NMR spectra.All complexes are bonded by M\|Cp through center of Cp.The vibration modes were reasonably assigned,absorption of ν s M\|Cp (A\-1) (M=Ti and Zr) vibration all appear in 310?cm -1 or so,while ν as M\|Cp (B) appear around 410?cm -1 and 360?cm -1 for Ti and Zr respectively.The influence of the center metal atoms and the substituents upon the NMR and FT\|IR spectra were discussed.     

The Influence of Transmutation Conditions on the Adulteration Performance of Nano—scale Nickel Hydroxide

Spherical Nano-scale nickel hydroxide was prepared through precipitaition transmutation method by controlling the transmutation conditions in this paper.The measurement results of XRD and TEM indicate that the crystallization of the nano-Scale nickel hydroxide is β-style and its shape is spherical with a diameter of 40-70 nanometer.The adulteration experiment shows that the adulteration ratio of nono-scale Ni(OH)2 in common spherical micrometer-scale Ni(OH)2 exists a optimal value(1:9) And at this point,the utilization ratio of Ni(OH)2 in electrodes can be raised by 10%,and the nono-Scale nickel hydroxide with sphericity shape shows a better adulteration performance than that with needle shapge.     

CeO2 thin films grown on biaxially textured nickel (001)

CeO\-2 films have been grown on biaxially textured Ni substrates at various temperatures. The results show that CeO\-2 films without IBAD are dominated by (111) orientation from room temperature to 800℃ while the preferential orientation of CeO\-2 films with IBAD is (001) at lower deposition temperature and (111) at deposition temperature higher than 450℃. CeO\-2 films with better in_plane texture and out_of_plane orientation can be grown at 360℃ with 240 eV ion energy and 200 μA/cm\+2 ion current density.     

Thermoelectric properties of p-type (Bi0.15Sb0.85)2Te3-PbTe graded thermoelectric materials with different barriers

The p-type (Bi_0.15Sb_0.85)₂Te₃ and PbTe are typical thermoelectric materials used for low and middle temperature range and functional graded materials (FGM) is an inevitable way to widen the working temperature range. Here two segments graded thermoelectric materials (GTM) consisting of (Bi_0.15Sb_0.85)₂Te₃, PbTe and different barriers were fabricated by the common hot pressure method. Metals Fe, Mg and Ni were used as barriers between the two segments. The diffusion of different barriers between the barriers and bases were analyzed by electron microprobe analysis (EMA). The phase and crystal structures were determined by X-ray diffraction analysis (XRD). The thermoelectric properties were measured at 303 K along the direction parallel to the pressing direction. The results show that the compositional diffusion occurs when there is no barrier at the interface of the two segments, and the diffusion of Pb is most obvious; as the barrier material, the diffusion of metals Fe, Mg and Ni between different bases is not very obvious, and the thermoelectric properties of GTM is much better than that of the original segment.     

Microstructure and electrolysis behavior of self-healing Cu-Ni-Fe composite inert anodes for aluminum electrowinning

The microstructure evolution and electrolysis behavior of(Cu_(52)Ni_(30)Fe_(18))–x Ni Fe_2O_4(x=40wt%,50wt%,60wt%,and 70wt%)composite inert anodes for aluminum electrowinning were studied.Ni Fe_2O_4 was synthesized by solid-state reaction at 950°C.The dense anode blocks were prepared by ball-milling followed by sintering under a N_2 atmosphere.The phase evolution of the anodes after sintering was determined by scanning electron microscopy and energy-dispersive X-ray spectroscopy.The results indicate that a substitution reaction between Fe in the alloy phase and Ni in the oxide phase occurs during the sintering process.The samples were also examined as inert anodes for aluminum electrowinning in the low-temperature KF–NaF–AlF_3 molten electrolyte for 24 h.The cell voltage during electrolysis and the corrosion scale on the anodes were analyzed.The results confirm that the scale has a self-repairing function because of the synergistic reaction between the alloy phase with Fe added and the oxide phase.The estimated wear rate of the(Cu_(52)Ni_(30)Fe_(18))–50Ni Fe_2O_4 composite anode is 2.02 cm·a~(-1).     

Julia sets of the random iteration systems and its subsystems

Suppose that P=(p\-1, p\-2, ..., p\-M)\% is a probability vector with p\-i>0 and Y={1, 2, ..., M}. Let (Y, 2\+Y, μ) be a probability space with μ(i)=p\-i, i=1, 2, ..., M, and (∑\-M, B, m)= Π \+∞\-0(Y, 2\+U, μ). It is shown that for any a \%(0≤a ≤1) \%, there exists a set U∈B such that m(U)=a and the Julia set associated with U is equal to the Julia set associated with ∑\-M\%. Moreover repelling fixed points with respect to U are dense in the Julia set associated with U.     

Co-oxidation of arsenic(Ⅲ) and iron(Ⅱ) ions by pressurized oxygen in acidic solutions

The co-oxidation of As(Ⅲ) and Fe(Ⅱ) in acidic solutions by pressured oxygen was studied under an oxygen pressure between 0.5 and2.0 MPa at a temperature of 150℃. It was confirmed that without Fe(Ⅱ) ions, As(Ⅲ) ions in the solutions are virtually non-oxidizable by pressured oxygen even at a temperature as high as 200℃ and an oxygen pressure up to 2.0 MPa. Fe(Ⅱ) ions in the solutions did have a catalysis effect on the oxidation of As(Ⅲ), possibly attributable to the production of such strong oxidants as hydroxyl free radicals(OH·) and Fe(IV) in the oxidation process of Fe(Ⅱ). The effects of such factors as the initial molar ratio of Fe(Ⅱ)/As(Ⅲ), initial pH value of the solution, oxygen pressure, and the addition of radical scavengers on the oxidation efficiencies of As(Ⅲ) and Fe(Ⅱ) were studied. It was found that the oxidation of As(Ⅲ) was limited in the co-oxidation process due to the accumulation of the As(Ⅲ) oxidation product, As(V), in the solutions.     

Optical properties of NdxGd1−xAl3(BO3)4 crystal

The optical properties of Nd x Gd 1-x Al\-3(BO\-3)\-4 (NGAB) crystal are reported. The refractive index of it were mesured by V_prism method. The absorption spectra and the flourescence specra of NGAB were also obtained. The optical parameters of NGAB were calculated following J_O theory, the three optical parameters are Ω 2 =1 805×10 -20 , Ω 4=1 85×10 -20 , Ω 6=3 793×10 -20 (RMS=1 4×10 -7 ) and β c( 4F 3/2 → 4I 11/2 ) is about 0 53.     

Synthesis,Characteristics and Applications of Fibrous Composites with Immobilized Nanomolecular Layers of Ferrocyanides and Phosphates of Some d-Elements

1 Results The general principle of the synthesis of fibrous inorganic ion-exchanging composites, containing the combination of polymer analogous conversion reactions of the fibres and cycles of ion-molecular layering is advanced. Synthesis of thin nanomolecular layers of the acid Ti(Ⅳ) and Zr(Ⅳ) phosphates on surface of the cotton fibres and Cu(Ⅱ) and Fe(Ⅲ) ferrocyanides-on polyacrylonitrile fibres was performed on the basis of this principle. By the method of X-ray analysis it was stated that the formed pellicular inorganic layers have a crystalline structure. The synthesis of thin layers of Cu(Ⅱ) and Fe(Ⅲ) hexacyanoferrates (Ⅱ) was performed by the method of the chemosorption layering on a matrix which represented the derivatives of polyacrylonitrile fibres containing HO-N=C·-NH2 groups with the degree of substitution of CN-groups about 50%. According to the data from the X-ray studying of the synthesized pellicular hexacyanoferrates, their composition is described by the formulas KxCu(2-x)[Fe(CN)6]·4H2O and KxFe(4-x)[Fe(CN)6]3 (compounds Ⅰand Ⅱ respectively). By the methods of IR-spectroscopy, formation of heteroatomic cycles by polyacrylonitrile derivatives (with participation of strong H-bonds) was shown. They were capable to disintegrate under the effect ofthe ions of d-metals. It is suggested that strong adhesion of the layers withthe matrix is caused by formation of linkage between [Fe(CN)6]4-ions and the ions in chelates' composition through CN-bridges. The equilibrium ion-exchange capacity on the Rubidium, Cesium and Thallium ions linearly depends on the layer's thickness, which is determined by the number of layering cycles (n) and is equal to 1.0 mmol·g-1 when n=8. Theion-exchange property testing of the synthesized compositions on the basis of the acid Ti(Ⅳ) and Zr(Ⅳ) phosphates was carried out by sorption from water solutions of the strontium and caesium-137 ions, on the basis of the Cu(Ⅱ) and Fe(Ⅲ) ferrocyanides-stable and radioactive caesium isotopes. There is a linear dependency of ion-exchange capacity on the amount of the cycles layering in case the acid Ti(Ⅳ)and Zr(Ⅳ) phosphates is observed. Moreover, the equality of the ionite ion-exchange capacity both on ion strontium, and on ion caesium is observed under fourfold cycle layering. S-figurative nature of such dependence was stated for ferrocyanides. It is shown that the process of the ion exchange proceeding in two stages. The full ion-exchange capacity of ionites on the basis of the acid Ti(Ⅳ) and Zr(Ⅳ) phosphates reaches 2.0 mmol-equ/g, but on the basis Cu(Ⅱ) and Fe(Ⅲ) ferrocyanides-1.0 mmol-equ/g. Ion-exchange equilibrium on synthesized ionites is reachedapproximately 30 times faster, than on corresponding powdery crystalline phosphates and ferrocyanides. Conclusion about prospect of the synthesized material usage in ion-exchange technology, including for extraction of radionuclides is made.     

Nerve growth factor activity of several immunal related serine proteases

Rabbit was immuned by the previously purified protein with high nerve growth factor (NGF) bioactivity (NGF_like protease) from \%Agkistrodon halys Pallas\% and the antisera were collected. The polyclonal antibodies were tentatively purified and then used as ligands of an affinity column. The \%A.h.Pallas\% crude venom was fractionated by this affinity column and then by Mono Q on fast protein liquid chromatography (FPLC). As a result, fraction Ⅱ and fraction Ⅲ were purified respectively, whose N_terminal amino acid sequences show high homology with the serine proteases in snake venoms, as well as the previous NGF_like protease. However, they possessed different levels of NGF bioactivity. The NGF activity of the previous NGF_like protease is equivalent to that of NGF, while the activity of fraction Ⅱ seems relatively low in contrast to fraction Ⅲ which had no NGF activity.     

Fabrication of SrFe_(12-x)Ni_xO_(19) nanoparticles and investigation on their structural,magnetic and dielectric properties

Sr Fe12-xNixO19 nanoparticles(x = 0–1) were synthesized by a combustion sol–gel method. Their structure, dielectric and magnetic properties were investigated by X-ray diffraction(XRD), scanning electron microscopy(SEM), an LCR metry, and vibrating sample magnetometry(VSM).The results reveal that all samples of Ni doped compounds(Sr Fe12-xNixO19) with x 0.2 are single phase. It appears that the Fe3+ ions are substituted by Ni2+ ions on the crystallographic sites of the Sr Fe12O19 structure; however, for x ≥ 0.2, the secondary Ni phase ferrite(Ni Fe2O3) appears, which reduces the saturation magnetization and coercivity. In addition, Ni doping reduces the dielectric constant, dielectric loss, and alternating current(ac) electrical conductivity of the samples. The variation in ac conductivity(σac) with frequency shows that the electrical conductivity in these ferrites is mainly attributed to the electron hopping mechanism.Therefore; all the single-phase Ni doped samples are suitable for use in magnetic recording media and microwave devices.     

Investigation on high magnetoresistance Ni0.81Fe0.19 films grown on （Ni0.81Fe0.19）1-xCrx underlayers

We have fabricated Ni0.18Fe0.19 films with (Ni0.18Fe0.19)1-xCrx films as underlayers by dc magnetron sputtering, the results show that larger anisotropic magnetoresistance (△R/R) values of Ni0.18Fe0.19 films are observed using the underlayers with Cr concentration of -36 at.% at an optimum underlayer thickness of -4.4 nm, the maximum AMR value is 3.35%. The results of atomic force microscope (AFM) and X-ray diffraction (XRD) show that the △R/R enhancement is attributed to the formation of large average grain size and the strong(111)texture in the Ni0.18Fe0.19 films.     

Photo-induced reactions of sulfonated aluminum phthalocyanine with peptide

The photosensitized oxidation mechanism of peptide in the presence of the ClAIPcS is studied by UV-Vis spectroscopic method. It is found that the oxidation of peptide is totally quenched in 1.1 × 10-2 mol/L NaN3 solution, and the same reaction cannot proceed in the dark. K3Fe(CN)6 and L-Cys cannot quench the reaction. Therefore, the reaction mechanism is mainly Foote's type Ⅱ. This reaction process can be inferred as follows: ( i ) active oxygen can attack acylamide bond near by carbon atom; ( ii ) carboxyl group departs from peptide; (iii ) l-benzazole cycle is destroyed when reaction is continued; (iv) the peptide is completely damaged.     

Direct hydrothermal synthesis and magnetic property of titanate nanotubes doped magnetic metal ions

Pure titanate nanotubes and titanate nanotubes doped with Fe3+/Ni2+/Mn2+ ions were synthesized by the hydrothermal method. In this process,titanate nanotubes were first prepared synchronously with doping Fe3+/Ni2+/Mn2+ ions. The morphology,structure,thermal stability and magnetic property of titanate nanotubes were characterized by X-ray diffraction (XRD),transmission electron microscope (TEM),and magnetic measurement. The titanate nanotubes transformed into the anatase titania nanocrystals,and further the mixture of anatase and rutile titania along with increasing temperature. The results indicate that the titanate nanotubes doped with Fe3+/Ni2+/Mn2+ ions are paramagnetic behaviors.     

Subsolidus phase relations in the system MgO-ZnO-SiO2 at high pressure

The subsolidus phase relations were determined experimentally in the system MgO-ZnO-SiO2 at 1.0 GPa and 1 200℃, by use of the high-pressure apparatus "piston-cylinder". The results showed characteristics of the phases assemblage different from that in similar ternary systems. It is impossible to form complete Mg2SiO4-Zn2SiO4 olivine and Mg2Si2O6-Zn2Si2O6 pyroxene solid solution. This is controlled by the properties of Zn2+ with an outer layer of electron (Ar)3d10, different from others transition metal ions, like Fe2+ , Ni2+ , Co2+ .     

Extraction and separation of nickel and cobalt from saprolite laterite ore by microwave-assisted hydrothermal leaching and chemical deposition

Extraction and separation of nickel and cobalt from saprolite laterite ore were studied by using a method of microwave-assisted hydrothermal leaching and chemical deposition. The effects of leaching temperature and time on the extraction efficiencies of Ni2+ and Co2+ were investigated in detail under microwave conditions. It is shown that the extraction efficiencies of Ni2+ and Co2+ from the ore pre-roasted at 300℃ for 5 h were 89.19% and 61.89% when the leaching temperature and time were about 70℃ and 60 min, respectively. For the separation process of Ni and Co, the separation of main chemical components was performed by adjusting the pH values of sulfuric leaching solutions using a NaOH solution based on the different pH values of precipitation for metal hydroxides. The final separation efficiencies of Ni and Co were 77.29% and 65.87%, respectively. Furthermore, the separation efficiencies of Fe of 95.36% and Mg of 92.2% were also achieved at the same time.     

Methanol as a probe to investigate the relationship between the secondary electron donor Tyr<Subscript>Z</Subscript> and the substrate water molecules in active photosystem II

The secondary electron donor, TyrZ, is implicated in tuning the primary charge separation and the water oxidation in active pho-tosystem II (PSII). Two types of mechanisms have been proposed to explain the function of TyrZ. One is that TyrZ tunes the water oxidation through the direct interaction with substrate water molecules; the other is that TyrZ is located in a hydrophobic envi-ronment without interacting with H2O, and controls the water oxidation by tuning the strength of the hydrogen bond between TyrZ and His190. Here, methanol was used as a probe to study the possible relationship between TyrZ and H2O by monitoring the TyrZ oxidation and TyrZ· reduction at cryogenic temperatures with electron paramagnetic resonance spectroscopy. The oxidation of TyrZ and reduction of TyrZ· in both S2 and S0 states at 10 K were accelerated by addition of a small amount of methanol (6%). Theoretical studies indicate that Tyr oxidation becomes more difficult if it interacts directly with the methanol molecule; while the decrease of the polarity of its environment accelerates the oxidation of Tyr. Accordingly, CH3OH does not directly interact with TyrZ in active PSII, and the accelerative effect of methanol is caused by the strength increase of the hydrogen bond between TyrZ and His190, resulting from the decrease of polarity of their environment after the displacement of H2O by CH3OH inside PSII. Considering the similarity between methanol and water, the results in this study support the model in which TyrZ does not interact with H2O in active PSII.     

Hardness variations during aging process of deformed W-Ni-Fe ternary alloys with high nickel-to-iron ratios

The aging precipitation behavior of β phase in two kinds of alloys with 7/3 and 9/1 nickel-to-iron ratios during aging at 800℃ after deformation was studied. The results show that there are two different kinds of aging hardness variation mechanisms (the softening mechanism and the hardening mechanism) deciding the hardness variations of the alloys. When Ni/Fe is smaller than 8/2, there is only the softening mechanism which results from the decreasing of dislocation density and recovery or re-crystallization.And when Ni/Fe is greater than 8/2 besides the softening mechanism there is still the hardening mechanism that is induced by the precipitation of β phase.     

Influence of microstructure on the corrosion resistance of Fe–44Ni thin films

An Fe–44Ni nanocrystalline (NC) alloy thin film was prepared through electrodeposition. The relation between the microstructure and corrosion behavior of the NC film was investigated using electrochemical methods and chemical analysis approaches. The results show that the NC film is composed of a face-centered cubic phase (γ-(Fe,Ni)) and a body-centered cubic phase (α-(Fe,Ni)) when it is annealed at temperatures less than 400℃. The corrosion resistance increases with the increase in grain size, and the corresponding corrosion process is controlled by oxygen reduction. The NC films annealed at 500℃ and 600℃ do not exhibit the same pattern, although their grain sizes are considerably large. This result is attributed to the existence of an anodic phase, Fe_0.947Ni_0.054, in these films. Under this condition, the related corrosion process is synthetically controlled by anodic dissolution and depolarization.