应用扫描电化学显微镜研究水/1,2-二氯乙烷界面上离子诱导的电子转移反应

应用扫描电化学显微镜和微电极技术研究了水 / 1,2 二氯乙烷界面上的反向电子转移反应 .分别以K4 Fe(CN) 6和 7,7,8,8 四氰代二甲基苯醌 (TCNQ)作为水相和有机相的电活性物质 ,通过选择合理的共同离子 (TPAs+与TBA+)来控制界面电位差 ,实现了这一在热力学上通常不可能实现的反向电子转移反应 .利用扫描电化学显微镜给出的正负反馈信息 ,研究了界面电位差驱动的液 /液界面上的电子转移反应 ,并进一步得到了在不同的共同离子浓度比时 ,此异相界面反应速率常数kf 为 1 3× 10 -31 8× 10 -2 cm/s(共同离子为TBA+)和 2 5× 10 -32 8× 10 -2 cm/s(共同离子为TPAs+) .验证了此反应速率常数kf 是由界面电位差所决定的 .在此实验条件下 ,此反应速率常数kf 与界面电位差的关系遵守Butler Volmer公式 .

Development of advanced electron tomography in materials science based on TEM and STEM

The recent developments of electron tomography（ET） based on transmission electron microscopy（TEM） and scanning transmission electron microscopy（STEM） in the field of materials science were introduced. The various types of ET based on TEM as well as STEM were described in detail, which included bright-field（BF）-TEM tomography, dark-field（DF）-TEM tomography, weak-beam dark-field（WBDF）-TEM tomography, annular dark-field（ADF）-TEM tomography, energy-filtered transmission electron microscopy（EFTEM） tomography, high-angle annular dark-field（HAADF）-STEM tomography, ADF-STEM tomography, incoherent bright field（IBF）-STEM tomography, electron energy loss spectroscopy（EELS）-STEM tomography and X-ray energy dispersive spectrometry（XEDS）-STEM tomography, and so on. The optimized tilt series such as dual-axis tilt tomography, on-axis tilt tomography, conical tilt tomography and equally-sloped tomography（EST） were reported. The advanced reconstruction algorithms, such as discrete algebraic reconstruction technique（DART）, compressed sensing（CS） algorithm and EST were overviewed. At last, the development tendency of ET in materials science was presented.

On Cuticular Compressions of Glyptostrobus europaeus (Taxodiaceae) from Kaydagul Formation (Lower Miocene) of the Central Kazakhstan$V. L. Komarov Botanical Institute! Russian Academy of Sciences,St Petersburg 19737

Numerous leaf compressions of Glyptostrobus europaeus (Brongn.) Ung. (Taxodiaceae) are found in Aquitanian (Lower Miocene) lignified clay localities Bolattam and Akzhar in the Southern Turgay, on the right bank of the Dulygaly-Zhilanshik river (Central Kazakhstan). The finely preserved lignified compression remains of leafy shoots make micro-morphological investigation feasible. Comparative studies of the epidermal features both living G. pensilis C. Koch and a new finding of G. europaeus from Early Miocene of Kazakhstan and illustrate their certain difference. The cuticular organization and epidermal features of fossil leaves, which have been compared with these of 'the nearest living relative', G. pensilis, were studied by scanning electron microscopy (SEM) and light microscopy (LM). The fossil leaves of G. europaeus from Kazakhstan are distinguished by stronger, than in living species, G. pensilis, developed 'micro-papillae' ('Kristallucken'), visible in SEM as ring-like structures left on the outer surface of cuticle in both nonstomatal and stomatal zones.

Characteristics and geological genesis of pyrites in coal of Huainan

Using optical microscope and scanning electron microscopy （SEM）, revealed the content of pyrite and the microscopic or sub-microscopic occurrence features of pyrite in coal of Huainan. The samples of this study are from four different mines in Huainan coal field. The results show that, in general, the coal of Huainan is low sulfur coal, but the con- tent of pyrite in Guqiao mine is relatively higher. The occurrence types of pyrite in coal mainly include： strawberry ball pyrites, massive pyrites, tuberculoid pyrite and pyrite filling in cracks or joints. After analysis based on three indicating facies parameters IAA, IS and/R, the reason for the higher level of pyrite component is that the deoxidization of swamp wa- ter is stronger, salinity is greater and the hydrodynamic is bad. The strawberry ball pyrites found in Guqiao mostly formed in the syngenesis stage. The spherical raspberry pyrites symbiotic with clay minerals was formed due to the reaction of H2S with Fe in the grid of silicate crystal.

Corrosion behaviors and mechanism of electroless Ni-Cu-P/n-TiN composite coating

In the present investigation, electroless Ni-Cu-P/n-TiN composite coating was prepared using alkaline citrate-based bath. X-ray diffraction （XRD）, scanning electron microscopy（SEM）, energy-dispersive spectroscopy（EDS）, electrochemical measurements, weight loss tests and Raman spectrometer were used to character the properties of the coating. As the Cu content increased from 7.3 wt% to 24.8 wt%, the corrosion current density of the Ni-Cu-P/n-TiN coating decreased from 10.80 to 4.34 ~tA. And the inclusion of Cu in NiP alloy resulted in refinement and less porosity in microstructure. The addition of TiN resulted in a slight decline in anti-corrosion property of the coating. As the mass loss test showed, Ni-24.8%Cu-P exhibited perfect corrosion resistance. Studies by Raman spectroscopy on coatings proved that Cu（II）3（PO4）（OH）3, Cu（OH）2 and CuO were examined while no compound of nickel was found, and Cu exhibited preferred corrosion in saline solution, providing cathodic protection to Ni alloy.

Electrochemical performances of LiFePO_4/C composites prepared by molten salt method

LiFePO4/C composites were synthesized by a molten salt (MS) method using the mixture of LiCl,LiOH and NaCl.The prepared LiFePO4/C composites are characterized by X-ray diffractometry (XRD),field emission scanning electron microscopy (FESEM) and charge-discharge test.XRD patterns indicate that LiFePO4 prepared in the temperature range of 550-700 ℃ crystallizes well in an olivine-type structure.Through FESEM images,the sphere-like and homogeneous particles of 0.2 μm can be observed.The charge-discharge test shows that the materials prepared at 600 ℃ for 12 h have good electrochemical performance.At the rates of 0.2C (34 mA/g) and 0.5C,the discharge capacities are 144.6 and 122.3 mA·h/g,respectively,together with good cycle performances.

Separation of chalcopyrite and pyrite from a copper tailing by ammonium humate

Copper tailings constitute a large proportion of mine wastes. Some of the copper tailings can be recycled to recover valuable minerals. In this paper, a copper tailing was studied through the chemical analysis method, Xray diffraction and scanning electron microscope-energy dispersive spectrum. It turned out that chalcopyrite(Cu) and pyrite(S) were the main recoverable minerals in the tailing. In order to separate chalcopyrite from pyrite in low pulp pH, ammonium humate(AH) was singled out as the effective regulator. The depression mechanism of AH on the flotation of pyrite was proved by FTIR spectrum and XPS spectrum, demonstrating that there was a chemical adsorption between AH and pyrite. By Response Surface Methodology(RSM), the interaction between AH, pulp pH and iso-butyl ethionine(Z200) was discussed. It was illustrated that the optimal dosage of AH was 1678 g·t^(-1) involving both the recovery of Cu and S. The point prediction by RSM and the closed-circuit flotation displayed that the qualified Cu concentrate and S concentrate could be obtained from the copper tailing.The study indicated that AH was a promising pyrite depressor in the low pulp pH from copper tailings.

Corrosion Process Detection of Tinplate in Deaerated Functional Beverage by EIS

The corrosion process of tinplate in deaerated functional beverage was investigated by using electrochemical impedance spectroscopy (EIS) combined with scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) techniques. The results reveal that the uncoated tinplate shows a poor corrosion resistance and the corrosion type is detinning. During the initial stage of immersion, EIS spectrum consisted of two capacitance arcs with obvious time-constant dispersion effect, which was attributed to the two-dimensional and three-dimensional inhomogeneous distribution of the electrode surface. With the increase of immersion time, the capacitance arc of high frequency shrunk and degenerated, due to the corrosion of tin coating. The pore resistance of tin coating and the charger transfer resistance of substrate, which are determined from the electrochemical equivalent circuit, can be used as the indicators of tinplate corrosion process. The decrease of the pore resistance of tin coating indicates that the corrosion degree of tin layer becomes more severe, whereas the decrease of the charger transfer resistance of substrate implies that the corrosion degree of steel substrate also becomes more severe as the immersion time prolongs.

Kinetics analysis of Ni-TiO_2 composite system during initial stages of electro-crystallization

The initial stage of Ni-TiO2 composite system electrodeposition on glassy carbon electrode from an acidic solution of nickel sulfate was investigated using cyclic voltammetry （CV）, chronoamperometry （CA） and electrochemical impedance spectroscopy （EIS）. Analysis of current density-time transients was performed using the nonlinear fitting procedure and electrochemical impedance spectroscopy was simulated by Z-view software. Besides, the surface morphology of Ni-TiO2 co-deposition at the initial stage was observed by scanning electron microscopy （SEM）. The results show that, in the case of low overpotential （-790 mV vs SCE）, the presence of TiO2 particles in the plating bath makes the nucleation relaxation time tm^x decreased clearly. Meanwhile, the electro-crystallization of Ni-TiO2 system follows a Scharifker-Hills （SH） progressive nucleation/growth mechanism. While in the case of higher overpotential, the presence of the TiO2 particles in solution makes the nucleation relaxation time tmax increased. At -850 mV （vs SCE）, the co-deposition of Ni-TiO2 system meets SH instantaneous nucleation/growth mechanism. The results of impedance spectra show that the appearance of the characteristic inductive loops represents the nucleation/growth of nickel and the presence of TiO2 particles reduces the charge transfer resistance of solution. The SEM observation confirms that TiO2 particles can be considered as favorable sites for nickel nucleating.

Carbonaceous mesophase spherule/activated carbon composite as anode materials for super lithium ion capacitors

A series of carbonaceous mesophase spherule/activated carbon composites were prepared as anode materials for super lithium ion capacitors using carbonaceous mesophase spherules as the core materials and pitch as the active carbon shell precursor.The structures of the composites were examined by scanning electron microscopy and X-ray diffractometry.The electrochemical performance was investigated in electric double layer capacitor and half-cell.The results show that,the composite exhibits good performance in both capacitor and battery with a high reversible capacity of 306.6 mA·h/g(0.2C) in the half-cell,along with a capacitance of 25.8 F/g in the capacitor when an optimum ratio of carbonaceous mesophase spherules to active carbon is adopted.The composite also shows a favorable rate performance and good cycle ability.A working model of this anode in super lithium ion capacitors was established.

Corrosion Behavior of Anodic Oxidized TiO_2 Film in Seawater

TiO2 films were formed on metallic titanium substrates by the anodic oxidation method in H2SO4 solution under the 80V D.C..Phase component and microstructure were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM).Water contact angles on titanium oxide film surface were measured under both dark and sunlight illumination conditions.Corrosion tests were carried out in seawater under different illumination conditions by electrochemistry impedance spectrum (EIS) and polarization curves.The result showed that the TiO2 film prepared by the anodic oxidation method was anatase with a uniform structure and without obvious pores or cracks on its surface.The average water contact angle of the film was 116.4? in dark, in contrast to an angle of 42.7? under the UV illumination for 2 hours, which demonstrates good hydrophobic property.The anti-corrosion behavior of the TiO2 film was declining with the extended immersion time.Under dark conditions, however, the hydrophobic TiO2 film retarded the water infiltrating into the substrate.The impedance changed slowly and the corrosion current density was 2 orders of magnitude lower than that with the film illuminated by sunlight.All of those mentioned above indicate that the TiO2 film possesses much better performance under dark condition, and it can be applied as an engineering material under dark seawater environment.

Adsorption isotherm and inhibition effect of a synthesized di-(m-Formylphenol)-1,2-cyclohexandiimine on corrosion of steel X52 in HCl solution

The potential of di-(m-Formylphenol)-1,2-cyclohexandiimine as an environmentally friendly corrosion inhibitor for steel was investigated in 1 mol/L HCl using potentiodynamic polarization, electrochemical impedance spectroscopy and chronoamperometry measurements. All electrochemical measurements suggest that this compound is an excellent corrosion inhibitor for mild steel and the inhibition efficiency increases with the increase in inhibitor concentration. The effect of temperature on the corrosion behavior of mild steel with the addition of the Schiff base was studied in the temperature range from 25 °C to 65 °C. It is found that the adsorption of this inhibitor follows the Langmuir adsorption isotherms. The value of activation energy and the thermodynamic parameters such as ΔHads, ΔSads, Kads and ΔGads were calculated by the corrosion currents at different temperatures using the adsorption isotherm. The morphology of mild steel surface in the absence and presence of inhibitor was examined by scanning electron microscopy(SEM) images.

Healing of Stoma After Magnetic Biliary-Enteric Anastomosis in Canine Peritonitis Models

Objective To assese the healing of stoma after magnetic anastomosis for the reconstruction of biliary-enteric continuity under severe inflammation. Methods Acute bile duct injury was constructed as a bile peritonitis model in mongrel dogs(n=32). Magnetic anastomosis(group A, n=16) and traditional suture anastomosis(group B, n=16) were performed to reconstruct the biliary-enteric continuity in one stage. Half of the dogs in each group were euthanized on the 30 th postoperative day, and the other half on the 90 th postoperative day to harvest the stoma region. The healing conditions of the stoma after the 2 anastomotic approaches were observed with naked eyes, under light microscope and scanning electron microscope. Results The stoma leakage rate(50% versus 0% on the 30 th postoperative day, 37.5% versus 12.5% on the 90 th postoperative day, both P<0.05) and stenosis degree(13.9%±0.3% versus 7.1%±0.3% on the 30 th postoperative day, 17.2%±0.4% versus 9.4%±0.4% on the 90 th postoperative day, both P<0.01) were significantly higher in group B than in group A. Compared with traditional manual anastomoses, the histological analysis under light and electron microscope showed a more continuous stoma with more regular epithelium proliferation and collagen arrangement, less inflammation in group A. Conclusions Magnetic anastomosis stent ensures better healing of the stoma even under the circumstance of severe inflammation.

Ethylene Polymerization Using Improved Polyethylene Catalyst

The study concerns the use of MgCl2-supported high-activity Ziegler-Natta catalysts for the polymerization of ethylene.In particular,two types of catalysts were investigated,which were N-catalyst（BRICI）and improved polyethylene catalyst.The effects of catalyst structure on kinetic behavior were examined.The distribution of active centers in these catalysts was investigated by energy dispersive analysis by X-rays（EDAX）,and morphologies of catalyst particles and polymer products were examined by scanning electron microscope（SEM）.Hydrogen response and copolymerization performance were investigated and compared with the two catalysts.The results were correlated with the kinetic behavior of the two catalysts and appropriate models for polymer particle growth were presented.The improved polyethylene catalyst showed higher activity,better hydrogen response and copolymerization performance.

Preparation of Tungsten Film and Its Tribological Properties under Boundary Lubrication Conditions

Tungsten film(W film) is deposited by using the ion beam assisted deposition(IBAD) on the 316 L substrate surface in this experiment. The micro structure and nano-hardness of the film are investigated by scanning electron microscopy(SEM) and nano-indentation tester. The tribological behavior of W film under lubrication by oil with ZDDP and MoDTC is evaluated by a SRV test machine. The tribo-film formed on the worn surfaces is investigated by X-ray photoelectron spectroscopy(XPS) to find out the tribological mechanisms between the W film and the two additional additives. The result shows that the W film lubricated by ZDDP and MoDTC-blended base oil has synergistic effects on the friction reduction property, while the anti-wear property is mainly caused by the hard surface of W film.

Corrosion behavior of 907 steel under thin electrolyte layers of artificial seawater

The corrosion behavior of 907 steel under thin electrolyte layer(TEL) has been investigated by means of cathodic polarization curve measurement, electrochemical impedance spectroscopy(EIS) and scanning electron microscopy(SEM). The results show that the cathodic diffusion current density presents the variation trend of initial increase and subsequent decrease with the decrease of TEL thickness, and the maximum deposits at 58 μm. The cotangent-hyperbolic impedance(O) is rationally first introduced to study the diffusion process of the reactants through the corrosion products layer with many permeable holes. The initial corrosion rate of 907 steel under different TEL thickness increases with the decrease of TEL thickness except that of 104 μm,whereas the corrosion rate after long time corrosion can be ranked as 104 μm﹥402 μm﹥198 μm﹥301 μm﹥bulk solution.

Stability of [BMIM]HSO_4 for using as additive during zinc electrowinning from acidic sulfate solution

The stability of ionic liquid additive 1-butyl-3-methylimidazolium hydrogen sulfate （[BMIM]HSO4） during zinc electrowinning from acidic sulfate solution was investigated by cyclic voltammetry, electrochemical impedance spectroscopy and scanning electron microscopy. Compared with the traditional industrial additives, gelatine and gum arabic, [BMIM]HSO4 has more excellent chemical and thermal stabilities. The inhibition effects of gelatine and gum arabic on the zinc electrocrystallization are observed to markedly weaken due to their part degradation after 12 h longtime successive electrolysis and high temperature （90 ℃） treatments. In contrast, the activity of [BMIM]HSO4 is practically unaffected after 24 h longtime successive electrolysis and high temperature treatments. These results are corroborated with the corresponding morphological analysis of the cathodic deposits.

2,3,5-Triphenyl-2H-tetrazolium Chloride and 2,4,6-Tri（2-pyridyl）-s-triazine on the Corrosion of Mild Steel in HCl

Electrochemical measurement, quantum chemical method, and scanning electron microscopy （SEM） were performed to investigate the inhibitive effect of 2,3,5-triphenyl-2H-tetrazolium chloride （TTC） and 2,4,6-tri（2-pyridyl） -s-triazine（TPT） on the corrosion of mild steel in lmol.L^-1 HCl at room temperature. Impedance spectroscopy measurement showed that the polarization resistance increased and that double layer capacitance decreased with the increase in the inhibitive concentration, and the results of potentiodynamic polarization showed that the inhibitors suppressed both cathodic and anodic processes of steel corrosion without change in the mecha-nism. Higher the orbital density distribution strength of the lowest unoccupied molecular orbital, higher is the molecule dipole, and lower energy gap between the energy of the highest occupied molecular orbital and the energy of the lowest unoccupied molecular orbital resulted in higher inhibitory efficiency. The results of SEM analysis showed that the metal-was protected from aggressive corrosion by the addition of TTC and TPT.

Experimental study on the effects of drying methods on the stabilities of lignite

The drying processes are always applied prior to the transportation or utilization of lignite, and result in notable changes in the stabilities of lignite. In this paper, the study on the effects of nitrogen and MTE drying process on the physico-chemical properties and stabilities of Zhaotung lignite was carried out. The briquettes produced by MTE drying in this study were 150 mm in dimension, and so had a much larger particle size than nitrogen- dried samples. Nitrogen adsorption, mercury intrusion porosimetry and scanning electron microscopy all suggested that drying was accompanied by the transformation of larger pores into smaller ones. Compared to nitrogen drying, the pore structures could be stabilized by the MTE process. The soluble salts were removed during MTE drying which resulted in the decrease in ash and the concentrations of some of the major metals. The removal of water enhanced the hydrophilicity of nitrogen dried samples, but did not affect the hydrophilicity of MTE dried samples. The moisture holding capacity of MTE dried samples reduced faster than nitrogen dried samples with the decrease of residual moisture content. The moisture readsorption processes of MTE dried sam- ples were strongly inhibited due to the much larger particle size of sample produced by MTE drying than nitrogen drying. The susceptibility to spontaneous combustion, indicated by cross point temperature and self-heating tests, of nitrogen and MTE dried samples increased with the decrease of residual moisture content. The MTE dried samples are more liable to spontaneous combustion than nitrogen dried samples with the same residual moisture and particle size. However, the larger particle size of the MTE product made it more stable with respect to spontaneous combustion and also moisture readsorption.

Comparative experimental study on reactive crystallization of Ni(OH)2 in an airlift-loop reactor and a stirred reactor

The objective of this work is to study the reactive crystallization in an airlift-loop reactor （ALR） using the precipitation of Ni（OH）2 as a model reaction. The growth of Ni（OH）2 particles in an ALR and a stirred tank was quantified by scanning electronic microscope （SEM）, X-ray diffraction （XRD）, laser particle analyzer, tap densitometer and optical microscope, and the growth process of Ni（OH）2 particles is analyzed. It is found that the Ni（OH）2 particles prepared in an ALR have a better sphericity than those in a stirred tank and the growth of Ni（OH）2 particle tap density mainly depends on the size of crystallites： the bigger the size of crystallites, the bigger the tap density is. Based on these, the growth process of Ni（OH）2 particles in ALR is elaborated. Crystallites precipitated from solution aggregate to form large particles with much void. These constituting crystallites continue to grow up, that takes up the void inside particles and makes the tap densitv increase.