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urnal of Shandong University(Engineering Science)Journal of Shandong University(Engineering Science)Journal of Shandong University(Engineering Science)Journal of Shandong University(Engineering Science)Journal of Shandong University(Engineering Science     

在酸性溶液中加压氧化三价砷离子和二价铁离子

The co-oxidation of As(III) and Fe(II) in acidic solutions by pressured oxygen was studied under an oxygen pressure between 0.5 and 2.0 MPa at a temperature of 150°C. 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°C 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.     

The advancement of oscillation theory of functional differential equations

The oscillation theory of functional differential equations (FDEs) is surveyed including (ⅰ) formulation of oscillation problems; (ⅱ) a brief history of the oscillation theory of FDEs; (ⅲ) main topics in the oscillation theory of FDEs; (ⅳ) open problems in the oscillation theory of FDEs.     

Mechanism of Cathode Process of B(Ⅲ) in LiF-NaF-KBF4 Melt by Electrochemical Titration Technique

The mechanism of cathode process of B(Ⅲ) at molybdenum and platinum electrodes in LiF-NaF-KBF₄ melt was studied and the transferred electron number of the reaction was calculated by means of cyclic voltammetry.The effect of adsorption of electroactive component on the electrochemical response (e.g., the voltammetric i─E curves) was analyzed and discussed. The "electrochemical spectra" for linear sweep voltammetry was used to elucidate the electrode reaction accompanied by a following transform process. The results show that the reduction of B(Ⅲ) to B(0) proceeds in reversible one step three-electron reaction and the cathode process of B(Ⅲ) is affected by product adsorbed strongly at the electrode surface. It is assumed that the reduction and deposition of B(Ⅲ) at molybdenum and platinum electrodes proceed in two kinds of mechanism: (1) B(Ⅲ)+ 3e = B_ads→ B (surface diffusion deposition mechanism) and (2) B(Ⅲ) + 3e = B (direct deposition mechanism).     

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rsity(Engineering Science)Journal of Shandong University(Engineering Science)Journal of Shandong University(Engineering Science)Journal of Shandong University(Engineering Science)Journal of Shandong University(Engineering Science)S     

Roles of chloride ion in photo-reduction/oxidation of mercury

Photo-reduction of divalent mercury(Hg(II)) in aquatic systems plays a key role in global biogeochemistry cycling of mercury(Hg) in the Earth's surface environment. The mechanisms of this process with various Clconcentrations([Cl-]) under different pH values and irradiation wavelength ranges are still unclear. In this work,photo-reduction and photo-oxidation experiments of Hg with different [Cl-] and pH values under various light conditions were conducted. The results show that photoreduction rate constants of Hg(II) decrease with the increasing of [Cl-] in neutral solution under full light spectrum. Photo-reduction rate constants of Hg(II) with Cl-is highly dependent on Hg(II) species, which is determined by [Cl-] and pH value. Irradiation wavelength ranges have significant effects on reaction processes of photo-reduction of Hg(II) and photo-oxidation of Hg(0) in the presence of Cl-. When cut off ultraviolet(UV) radiation(280–400 nm), the reduction rate constants decrease without Cl-, and increase with higher [Cl-], and the photooxidation rates of Hg(0) decrease with or without Cl-.Except Cl-complexation stabilize the reducible Hg ions in solutions, photo-oxidation is an important reason for Cllowering photo-reduction rate of Hg(II). The results are of great importance for understanding the photo-redox characters of Hg(II) with Cl-.     

Stability of a Certain Retard Functional Differential Equation

The authors obtain some sufficient conditions for the stability of zero solutions to some types of the functional equation. x(t) +p(t)x(t) +q(t)x(t) +f (t, xt) = 0 by transformations and the Liapunov's Second method. The obtained conclusions generalize some results of Stability of Equation x (t) +p( t) x(t) + q(t)x(t) =0 and Jack Hale in his paper of Theory of Functional Differential Equations.     

Supporting Information

Figure S1 The UV-visible spectra of the HPBs of SiW 11 Cu (a),SiW 11 Ni (b),SiW 11 Co (c),and SiW 11 Zn (d).Figure S2 The visible adsorption spectra (400-800 nm) of TMSPs.(A) SiW 11 Cu (a) and HPB of SiW 11 Cu (b);(B) SiW 11 Ni (a) and HPB of SiW 11 Ni (b);(C) SiW 11 Co (a) and HPB of SiW 11 Co (b);(D) SiW 11 Zn (a) and HPB of SiW 11 Zn (b).     

The Recent Advances in Plant Protection Researches of China

There are eight examples briefly given in this paper, namely, (1) Polymyxa graminis and the cereal viruses it transmits; (2) the geographical types and facultative migration of cotton bollworm as well as the safety of Bt transgenic cotton; (3) development of crop near-isogenic lines with resistance to diseases; (4) molecular-biological researches induced resistance of rice by infection of blast fungus;(5) to use cytological and molecular-biological techniques for breeding wheat varieties resistant to barley yellow dwarf virus; (6) mass rearing and field releasing of Microplitis mediator for cotton bollworm control; (7) identification and recombination of insecticidal crystal genes of Bacillus thuringiensis; and (8) interplanting of diverse resistance rice varieties for sustainable control of blast disease; which reflect the general situation of recent advances in plant protection researches of China.     

Modulation of active Cr(III) complexes by bath preparation to adjust Cr(III) electrodeposition

The preparation process of the Cr(III) bath was studied based on a perspective of accelerating the formation of active Cr(III) complexes. The results of ultraviolet-visible absorption spectroscopy (UV-Vis) and electrodeposition showed that active Cr(III) complexes in the bath prepared at room temperature in several days were rare for depositing chromium. The increase of heating temperature, time, and pH value during the bath preparation promoted the formation of active Cr(III) complexes. The chromium deposition rate increased with the concentration of active Cr(III) complexes increasing. Increasing the heating temperature from 60 to 96℃, the chromium deposition rate increased from 0.40 to 0.71 μm/min. When the concentration of active Cr(III) complexes increased, the grain size of Cr coatings increased, and the carbon content of the coating decreased. It is deduced that Cr(H₂O)₄(OH)L2+ (L is an organic ligand, and its valence is omitted) is a primary active Cr(III) complex.     

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.     

Synthesis of aluminum nitride in a coke-calcium reduction bed using nitrogen in air

An experimental study on the heating of a mixture of aluminum and lithium hydroxide (LiOH) powders in a reductive bed under air atmosphere is reported. The formation of aluminum nitride (AlN) during this process was the focus of this study. The formation of AlN was achieved using LiOH as an additive and heating the sample in a resistance furnace in a specially designed double crucible within a bed of a mixture of coke and filamentous calcium. The temperature range of the reaction was between 700°C and 1100°C. The optimum tem-perature of 1100°C and the optimum LiOH amount (5wt%) required to achieve maximum yield were determined by powder X-ray diffrac-tion (XRD) analysis. Scanning electron microscopy (SEM) micrographs clearly indicated the transformation of grain structures from rods (700°C) to cauliflower shapes (1100°C).     

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 forme...     

Resistance to chemical attack of bittern-resisting cement in high-bittern environment

A new kind of bittern-resisting cement (BRC) was introduced. This material is based on the ternary cementitious system of clinker containing C₄A3 S phase, high-activity ground granulated blast-furnace slag (GGBFS) and fly ash (FA). The hydration process and the hydrated products of BRC were studied by means of XRD, TG-DTA and SEM, and the resistance to chemical attack of BRC in high-bittern environment was also examined. The corrosion experiment in seven kinds of brines proved that BRC exhibits an excellent resistance to chemical attack of bittern. The corrosion resistance factors were calculated and all of them were greater than 0.96. It showed that BRC totally controls the cement-based material corrosion in brines from four aspects: (1) making full use of the dominant complementation effect of mineral materials; (2) diminishing the hydrated products easy to be attacked; (3) improving the microstructure of hardened cement mortar; (4) degrading the chemical attack of bittern.     

One-step disposal of Cr (Ⅵ)-bearing wastewater by natural pyrrhotite

Cr(Ⅵ)-bearing wastewater can be treated by natural pyrrhotite which is used for reductant to reduce Cr(Ⅵ) and precipitant to precipitate Cr(Ⅲ) simultaneously. The disposal products can be divided into three parts in the beakers,namely supernatant in the upper part,the yellowish colloidal precipitates in the middle part and the pyrrhotite in the lower part. The content of total Cr=Cr(Ⅵ)+Cr(Ⅲ) in the supernatant liquid is 0.06 mg/L,which is lower than 1.5 mg/L of the discharge standard of China and near to 0.05 mg/L of the standard of potable water. This one-step disposal composing of both reduction and precipitation which is traditionally divided into two independent steps called reducing technology and precipitating technology respectively. The new method is of obvious economic advantage and favourable to decreasing surplus mud derived from adding Ca(OH)2 to precipitate Cr(Ⅲ) traditionally so as to avoid recontamination. In fact,sodium sulfite (Na2SO3) used in disposal of Cr(Ⅵ) was traditionally produced from natural mineral of pyrrhotite (FeS). One molecule of FeS is 4 times more than that of Na2SO3 from a view point of rational use of mineral resources. Therefore the prospective of application of the one-step disposal of Cr(Ⅵ) method is full of promise.     

Binding of vanadium compounds perturbs conformation and aggregation state of insulin

The interactions between zinc-free insulin and vanadium compounds, NaVO3, VO(acac)2 and VO(ma)2, have been investigated by fluorescence spectroscopy, circular dichroism (CD) and Fourier-transformed infrared (FT-IR) spectroscopy. The results showed that binding of vanadium compounds produced a static quenching of the intrinsic fluorescence of insulin. The apparent association constants were determined to be (0.17±0.01)×104 L*mol-1 for NaVO3, (2.8±0.2)×104 L*mol-1 for VO(acac)2, and (4.0±0.1)×104 L*mol-1 for VO(ma)2, respectively. The light scattering intensity of insulin decreased upon incubation with the vanadium compounds, suggesting the disaggregation of insulin. The attenuation of the band at 273 nm of insulin CD spectra also supported the disaggregation of insulin observed above. A new band at 1650～1653 cm-1 appeared in the FT-IR spectra of insulin upon incubation with the vanadium compounds, indicating the formation of an α-helix structure at B (9-19) motif. This α-helix structure suggests a structural change of insulin from an extended conformation (T state) to a helical conformation (R state), which is essential for binding of insulin to its receptor. In conclusion, binding of vanadium compounds results in conformational changes and disaggregation of insulin. These changes might account for the enhancement of binding affinity for insulin to its receptor in the presence of vanadium compounds.     

Influence of flow control devices on metallurgical effects in a large-capacity tundish

The influence of flow control devices on metallurgical effects in a large-capacity tundish has been studied carefully with elements tracing, sampling and theoretical prospecting. The results from the studies are (1) in the continuous casting of clean steel, bad control of tundish operation may deteriorate the cleanliness of steel; (2) the cleanliness of steel is deteriorated mainly at the unsteady state; (3) large amount of macro inclusions come from the top slag and the refractory of tundish; (4) installing dam and weir can improve the cleanliness of steel and lighten the influence of steel fluctuation; and (5) the result of theoretical calculation suggests that the inclusions larger than the critical size of 92.6 μm can be floated out from the tundish bath completely.     

Tunable tribological properties in water-based lubrication of water-soluble fullerene derivatives via varying terminal groups

In this paper,three kinds of water-soluble fullerene derivatives were synthesized via electrophilic addition reaction and cycloaddition reaction,respectively.The chemical composition characterizations of these derivatives indicated the successful preparation of C60(OH)x,C60(C(COOH)2)x and C60(OH)x(NHCH2COOH)y fullerene derivatives.The aggregation and morphology characterizations showed that the three kinds of derivatives had an ideal spherical aggregating structures and excellent dispersibility in water,especially C60(OH)x and C60(C(COOH)2) x.The lubrication performance of the fullerene derivatives acted as lubricant additives were investigated at different concentrations in the range of 0-1 wt%.The results indicated that the addition of polyhydroxyl and carboxylic derivatives could improve the lubrication properties,which led to the reduction of wear to about 40% at most.It is attributed that the optimized substitutions of fullerene molecules may be of benefit to their distribution properties and lubricating behaviors in water based lubrication.     

Electrooxidation of Mn(Ⅱ) on Pb-Sb-As Electrode in Sulfuric Acid

The electrooxidation of Mn(Ⅱ) on Pb-Sb-As alloy electrode in sulfuric acid has been investigated.In order to make the two steps of indirect electrosynthesis of benzaldehyde carried out in the same sulfuric acid concentration and also obtain high current efficiency of Mn(Ⅱ) to Mn(Ⅲ) and high yield of Mn(Ⅲ) oxidizing toluene to benzaldehyde in the mean time,the electrooxidation of Mn(Ⅱ) in 60% H2SO4 has been studied.Experimental results show that high current efficiency of Mn(Ⅲ) (about 75%) is obtained in 60%H2SO4 at 60℃.The reason affecting the current efficiency of Mn(Ⅲ) is discussed,and it is the coordination of sulfuric acid concentration and electrolytic temperature.The law is found that it is suitable for electrolysis at low temperature when sulfuric acid concentration is low and at high temperature when sulfuric acid concentration is high.