Investigation of the deterioration of passive films in H2S-containing solutions

The effect of H2S on the corrosion behavior of 316L stainless steel was investigated using electrochemical methods by changing the gas condition from CO2 to H2S and then back to CO2. The presence of H2S showed an acceleration effect on the corrosion of 316L stain-less steel in comparison with CO2. The acceleration effect remained even after the complete removal of H2S by CO2, indicating that the pas-sive film was irreversibly damaged. X-ray photoelectron spectroscopy (XPS) analysis indicated that the passive film was composed of Cr2O3, Fe2O3, and FeS2 after being immersed in H2S-containing solutions. The semiconducting property of the passive film was then investigated by using the Mott–Schottky approach. The presence of sulfides resulted in higher acceptor and donor densities and thus was responsible for the deterioration of passive films.     

Investigation of the deterioration of passive films in H_2S-containing solutions

The effect of H_2S on the corrosion behavior of 316 L stainless steel was investigated using electrochemical methods by changing the gas condition from CO_2 to H_2S and then back to CO_2. The presence of H_2S showed an acceleration effect on the corrosion of 316 L stainless steel in comparison with CO_2. The acceleration effect remained even after the complete removal of H_2S by CO_2, indicating that the passive film was irreversibly damaged. X-ray photoelectron spectroscopy(XPS) analysis indicated that the passive film was composed of Cr_2O_3, Fe_2O_3, and FeS_2 after being immersed in H_2S-containing solutions. The semiconducting property of the passive film was then investigated by using the Mott–Schottky approach. The presence of sulfides resulted in higher acceptor and donor densities and thus was responsible for the deterioration of passive films.     

Intense laser induced field ionization of C<Subscript>2</Subscript>H<Subscript>2</Subscript>, C<Subscript>2</Subscript>H<Subscript>4</Subscript>, and C<Subscript>2</Subscript>H<Subscript>6</Subscript>

Using HOMO Field Ionization Model, the tunneling probabilities and the theoretical threshold intensities of the field ionizations of acetylene, ethylene, and ethane in intense laser field are calculated. C2H2, C2H4, and C2H6 were irradiated by 800 nm, 100 fs laser pulses with the intensity range of 10^13-10^14 W/cm^2. A TOF-mass spectrometer was coupled to the laser system and used to experimentally investigate the field ionization of these molecules. The experimental ionization threshold intensities are obtained. The calculating results of the three molecules agree well with the experimental results, indicating that HOMO Field Ionization Model is valid for the ionization of polyatomic molecules in intense laser field.     

Fabrication of porous alumina templates with a large-scale tunable interpore distance in a H<Subscript>2</Subscript>C<Subscript>2</Subscript>O<Subscript>4</Subscript>-C<Subscript>2</Subscript>H<Subscript>5</Subscript>OH-H<Subscript>2</Subscript>O solution

Highly ordered porous alumina templates with a large-scale tunable interpore distance （100-445 nm） have been successfully fabricated under an electric field of 40-180 V by modifying oxalic acid solution with adequate alcohol. The results under our experimental conditions show that the phenomena of burning and breakdown during the high-field anodization process can be avoided by adding a proper amount of alcohol to the oxalic acid solution. An excellent linear relationship between interpore distance and anodization voltage is obtained under 40-170 V, and the maximum anodization voltage that could be used to avoid burning and breakdown is 180 V.     

Comparative analysis of the dissolution kinetics of galena in binary solutions of HCl/FeCl<Subscript>3</Subscript> and HCl/H<Subscript>2</Subscript>O<Subscript>2</Subscript>

A comparative study of the dissolution kinetics of galena ore in binary solutions of FeCl₃/HCl and H₂O₂/HCl has been undertaken. The dissolution kinetics of the galena was found to depend on leachant concentration, reaction temperature, stirring speed, solid-to-liquid ratio, and particle diameter. The dissolution rate of galena ore increases with the increase of leachant concentration, reaction temperature, and stirring speed, while it decreases with the increase of solid-to-liquid ratio and particle diameter. The activation energy (E _a) of 26.5 kJ/mol was obtained for galena ore dissolution in 0.3 M FeCl₃/8.06 M HCl, and it suggests the surface diffusion model for the leaching reaction, while the E _a value of 40.6 kJ/mol was obtained for its dissolution in 8.06 M H₂O₂/8.06 M HCl, which suggests the surface chemical reaction model for the leaching reaction. Furthermore, the linear relationship between rate constants and the reciprocal of particle radius supports the fact that dissolution is controlled by the surface reaction in the two cases. Finally, the rate of reaction based on the reaction-controlled process has been described by a semiempirical mathematical model. The Arrhenius and reaction constants of 11.023 s⁻¹, 1.25×10⁴ and 3.65×10² s⁻¹, 8.02×10⁶ were calculated for the 0.3 M FeCl₃/8.06 M HCl and 8.06 M H₂O₂/8.06 M HCl binary solutions, respectively.     

Synthesis, Characterization and Calorimetry of Ni（C4H8N2O3）2Cl2

A coordination complex was synthesized from NiCl2 and dipeptide glycylglycine（GG）. It was characterized by element analysis, NMR and TG methods, and then was determined to be Ni（C4HsN2O3）2Cl2. Using an isoperibolic reaction calorimeter, the standard molar enthalpy of formation of Ni（GG）2Cl2（solid） has been determined to be -（1 674.66±2.02） kJ · mol^-1 at 298.15 K.     

Investigation of the cross-reaction mechanism of C<Subscript>6</Subscript>H<Subscript>5</Subscript>F-HNO<Subscript>2</Subscript> aqueous solution irradiated at 355 nm by transient absorbance spectrum technique

The transient absorption spectrum technique was employed to investigate the cross-reaction mechanism of C6H5F-HNO2 aqueous solution irradiated at 355 nm. The characteristic and the kinetic parameters of transient species were also detected. Hydroxyl radical derived from the photolysis of HNO2 was added to monofluorobenzene with a second-order rate constant of （5.83±0.17）×10^9 L·mol^-1·s^-1 to form an adduct, C6H5F…OH, which was able to react with HNO2 as the main reaction pathway with a rate constant of （8.3±0.1）×10^7 L·mol^-1·s^-1. The C6F6…OH adduct can also be decayed by elimination of H2O to yield monofluorophenyl radical C6H4F-. By GC-MS technique, the final products were identified to be monofluorophenol, nitro-monofluorobenzene, nitro-monofluorophenol and para-fluorobiphenyl.     

Immobilization of hemoglobin on platinum nanoparticles-modified glassy carbon electrode for H<Subscript>2</Subscript>O<Subscript>2</Subscript> sensing

This work described an amperometric hydrogen peroxide (H2O2) biosensor based on immobilization of hemoglobin (Hb) on a glassy carbon (GC) electrode modified by platinum nanoparticles, which was prepared by an in situ chemical reductive growth method. The electrochemical impedance measurements confirmed that the Hb was immobilized on the platinum nanoparticles-modified glassy carbon surface and has a synergistic effect with platinum nanoparti-cles in improving the catalytic reduction of H2O2. The Hb immobili...     

Effect of CO<Subscript>2</Subscript> and H<Subscript>2</Subscript>O on gasification dissolution and deep reaction of coke

To more comprehensively analyze the effect of CO₂ and H₂O on the gasification dissolution reaction and deep reaction of coke, the reactions of coke with CO₂ and H₂O using high temperature gas-solid reaction apparatus over the range of 950-1250℃ were studied, and the thermodynamic and kinetic analyses were also performed. The results show that the average reaction rate of coke with H₂O is about 1.3-6.5 times that with CO₂ in the experimental temperature range. At the same temperature, the endothermic effect of coke with H₂O is less than that with CO₂. As the pressure increases, the gasification dissolution reaction of coke shifts to the high-temperature zone. The use of hydrogen-rich fuels is conducive to decreasing the energy consumed inside the blast furnace, and a corresponding high-pressure operation will help to suppress the gasification dissolution reaction of coke and reduce its deterioration. The interfacial chemical reaction is the main rate-limiting step over the experimental temperature range. The activation energies of the reaction of coke with CO₂ and H₂O are 169.23 kJ·mol-1 and 87.13 kJ·mol-1, respectively. Additionally, water vapor is more likely to diffuse into the coke interior at a lower temperature and thus aggravates the deterioration of coke in the middle upper part of blast furnace.     

Preparation and radar-absorbing properties of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/TiO<Subscript>2</Subscript>/Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>/Yb<Subscript>2</Subscript>O<Subscript>3</Subscript> composite powder

Al₂O₃/TiO₂/Fe₂O₃/Yb₂O₃ composite powder was synthesized via the sol-gel method. The structure, morphology, and radar-absorption properties of the composite powder were characterized by transmission electron microscopy, X-ray diffraction analysis and RF impedance analysis. The results show that two types of particles exist in the composite powder. One is irregular flakes (100-200 nm) and the other is spherical Al₂O₃ particles (smaller than 80 nm). Electromagnetic wave attenuation is mostly achieved by dielectric loss. The maximum value of the dissipation factor reaches 0.76 (at 15.68 GHz) in the frequency range of 2-18 GHz. The electromagnetic absorption of waves covers 2-18 GHz with the matching thicknesses of 1.5-4.5 mm. The absorption peak shifts to the lower-frequency area with increasing matching thickness. The effective absorption band covers the frequency range of 2.16-9.76 GHz, and the maximum absorption peak reaches -20.18 dB with a matching thickness of 3.5 mm at a frequency of 3.52 GHz.     

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.     

Investigation of solvatochromism and aggregation behavior of C_(60)(C_4H_(10)N~+)I~- in binary solvent mixtures

Solvatochromism was observed in some solutions of C60 or C70, which was thought to arise from the formation of fullerene clusters[1—6]. This special type of solvato- chromism has aroused much interest because it has some potential applications in material science and sensor tech- nology. On the other hand, C60 or C70 can be made soluble in water by connecting it to various functional groups[7—20]. Those functionalized fullerenes not only have been found a number of important applicati…     

Studies of several systems with air electrode electro-synthesizing H<Subscript>2</Subscript>O<Subscript>2</Subscript> on the spot for degrading aniline in aqueous

A gas diffusion electrode (air electrode) with a high current efficiency of electro-synthesizing H₂O₂ using O₂ in air was prepared. The several systems with air electrode as cathode of electro-synthesizing H₂O₂ on the reaction spot for degrading aniline in aqueous—electro-Fenton system, photo-excitation electro-H₂O₂ system and photo-electro-Fenton system, were developed. The rates of decomposition of H₂O₂ and mineralization of aniline were experimentally measured respectively under different conditions, and the results indicated there has an excellent parallel relation between decomposition rate of H₂O₂ and mineralization rate of aniline. Especially, photo-electro-Fenton system, where H₂O₂ is decomposed the fastest, is the best system of oxidizing and degrading organic toxicants. Compared photo-electro-Fenton system with photo-Fenton system, important role is revealed in the interface of air electrode. In this paper, the mineralization mechanism of aniline in the photo-electro-Fenton system was also discussed. Foundation item: Supported by the National Natural Science Foundation of China (200710026) and Foundation of Environmental Sciences Academy of Jiangsu Province. Biography: Cao xiao-yu (1979-), male, Master candidate, research direction: Electrochemistry     

Electrodeposition and characterization of thermoelectric Bi<Subscript>2</Subscript>Se<Subscript>3</Subscript> thin films

Bi₂Se₃ thin films were electrochemically deposited on Ti and indium tin oxide-coated glass substrates, respectively, at room temperature, using Bi(NO₃)₃·5H₂O and SeO₂ as starting materials in diluted HNO₃ solution. A conventional three-electrode cell was used with a platinum sheet as a counter electrode, and a saturated calomel electrode was used as a reference electrode. The films were annealed in argon atmosphere. The influence of cold isostatic pressing before annealing on the microstructure and thermoelectric properties of the films was investigated. X-ray diffraction analysis indicates that the film grown on the indium tin oxide-coated glass substrate is pure rhombohedral Bi₂Se₃, and the film grown on the Ti substrate consists of both rhombohedral and orthorhombic Bi₂Se₃.     

Synthesis and characterization of wormhole-like mesoporous Ce0.6Zr0.35Y0.05O2 solid solutions

Nanoparticles of Ce0.6Zr0.35Y0.05O2 (CZY) solid solution have been prepared by the CTAB (hexadecyl-trimethyl ammonium bromide), CTAB-EG (ethylene glycol) templating, and CTAB-EG-NaCl (in which the pores of the precursor synthesized by the CTAB-EG method is filled by a certain amount of NaCl) method, respectively. The physical properties of these materials were characterized by means of tech-niques such as X-ray diffraction (XRD), high resolution scanning electron microscopy (HRSEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), and N2 adsorp-tion-desorption measurements. The CZY samples synthesized by the above three methods display wormhole-like mesoporous morphology and cubic crystal structures. The materials are narrow in pore size distribution (averaged pore diameter = 5.3―7.1 nm), high in surface areas (95―119 m2/g), and large in pore volumes (0.16―0.18 cm3/g). It has been demonstrated that the introduction of NaCl is capable of retaining the pore structures of solid nanomaterials at high-temperature calcination.     

Dissolution of Al<Subscript>2</Subscript>TiO<Subscript>5</Subscript> inclusions in CaO-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> slags at 1823 K

Al-Ti-O inclusions always clog submerged nozzles in Ti-bearing Al-killed steel. A typical synthesized Al₂TiO₅ inclusion was immersed in a CaO-SiO₂-Al₂O₃ molten slag for different durations at 1823 K. The Al₂TiO₅ dissolution paths and mechanism were revealed by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). Decreased amounts of Ti and Al and increased amounts of Si and Ca at the dissolution boundary prove that inclusion dissolution and slag penetration simultaneously occur. SiO₂ diffuses or penetrates the inclusion more quickly than CaO, as indicated by the w(CaO)/w(SiO₂) value in the reaction region. A liquid product (containing 0.7–1.2 w(CaO)/w(SiO₂), 15wt%–20wt% Al₂O₃, and 5wt%–15wt% TiO₂) forms on the inclusion surface when Al₂TiO₅ is dissolved in the slag. Al₂TiO₅ initially dissolves faster than the diffusion rate of the liquid product toward the bulk slag. With increasing reaction time, the boundary reaches its largest distance, the Al₂TiO₅ dissolution rate equals the liquid product diffusion rate, and the dissolution process remains stable until the inclusion is completely dissolved.     

Giant magneto-optical faraday effect of nanometer Fe-In<Subscript>2</Subscript>O<Subscript>3</Subscript> granular films

The giant magneto-optical Faraday effect of nanometer ferromagnetic metal-semiconductor matrix Fe-ln2O3 granular films prepared by the radio frequency sputtering are studied. The result shows that the Faraday rotation angle θF value of the granular film samples with Fe volume fraction x = 35% is of the order of 10^5（°）/cm at room temperature. Temperature dependence of the Faraday rotation angle θF of Fe0.35（In2O3）0.65 granular films shows that θF value below 10 K increases rapidly with the decrease of the temperature, and when T= 4.2 K, θF value is 106（°）/cm. Through the study of the dependence of low field susceptibility on temperature and the hysteresis loops at different temperatures, it has been found that when the temperature decreases to a critical point Tp = 10 K, the transformation of state from ferro-agnetic to spin-glass-like occurs in Fe0.35（In2O3）0.65 granular films. The remarkable increase of the Faraday rotation angle θF value of Fe0.35（In2O3）0.65 granular films below 10 K seems to arise from the sp-d exchange interaction of the granular film samples in the spin-glass-like state.     

Electro-deoxidation of V<Subscript>2</Subscript>O<Subscript>3</Subscript> in molten CaCl<Subscript>2</Subscript>-NaCl-CaO

The electro-deoxidation of V₂O₃ precursors was studied. Experiments were carried out with a two-terminal electrochemical cell, which was comprised of a molten electrolyte of CaCl₂ and NaCl with additions of CaO, a cathode of compact V₂O₃, and a graphite anode under the potential of 3.0 V at 1173 K. The phase constitution and composition as well as the morphology of the samples were studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM). 3 g of V₂O₃ could be converted to vanadium metal powder within the processing time of 8 h. The kinetic pathway was investigated by analyzing the product phase in samples prepared at different reduction stages. CaO added in the reduction path of V₂O₃ formed the intermediate product CaV₂O₄.     

Influence of post-annealing on the properties of Ta-doped In<Subscript>2</Subscript>O<Subscript>3</Subscript> transparent conductive films

Ta-doped In₂O₃ transparent conductive oxide films were deposited on glass substrates using radio-frequency (RF) sputtering at 300°C. The influence of post-annealing on the structural, morphologic, electrical and optical properties of the films was investigated using X-ray diffraction, field emission scanning electron microscopy, Hall measurements and optical transmission spectroscopy. The obtained films were polycrystalline with a cubic structure and were preferentially oriented in the (222) crystallographic direction. The lowest resistivity, 5.1×10⁻⁴ Ω cm, was obtained in the film annealed at 500°C, which is half of that of the un-annealed film (9.9×10⁻⁴ Ω cm). The average optical transmittance of the films was over 90%. The optical bandgap was found to decrease with increasing annealing temperature.     

Chemical quenching and inhibition of positronium in Cr<Subscript>2</Subscript>O<Subscript>3</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts

The pore structure of Cr2O3/Al2O3 catalysts and the surface chemical properties of these pores were characterized by positron lifetime and coincidence Doppler broadening (CDB) measurements. Four lifetime components could be resolved from the positron lifetime spectrum, with two long lifetime components and two short lifetime components. The two long lifetimes τ4 and τ3 are attributed to ortho-positronium (o-Ps) annihilation in large pores and microvoids, respectively. With increasing Cr2O3 content, both τ4 and its intensity I4 show sharp decrease, while τ3 and its intensity I3 keep nearly unchanged. The Doppler broadening S parameters also show sharp decrease with increasing Cr2O3 content. Detailed analysis of the CDB spectrum reveals that the parapositronium (p-Ps) intensity also decreases with increasing Cr2O3 content. This indicates that the change of o-Ps lifetime τ4 is due to the chemical quenching by Cr2O3 but not spin-conversion of positronium. The decrease of o-Ps intensity I4 indicates that Cr2O3 also inhibits positronium formation.