TR-ESR Investigation on Reaction of Vitamin C with Excited Triplet of 9,10-phenanthrenequinone in Reversed Micelle Solutions

Time-resolved electron spin resonance has been used to study quenching reactions between the antioxidant Vitamin C （VC） and the triplet excited states of 9,10-phenanthrenequinone （PAQ） in ethylene glycol-water （EG-H2O） homogeneous and inhomogeneous reversed micelle solutions. Reversed micelle solutions were used to be the models of physiological environment of biological cell and tissue. In PAQ/EG-H2O homogeneous solution, the excited triplet of PAQ （3PAQ＊） abstracts hydrogen atom from solvent EG. In PAQ/VC/EG-H2O solution, 3pAQ＊ abstracts hydrogen atom not only from solvent EG but also from VC. The quenching rate constant of 3pAQ＊ by VC is close to the diffusion-controlled value of 1.41 × 108 L/（mol.s）. In hexadecyltrimethylammonium bromide （CTAB）/EG-H2O and aerosol OT （AOT）/EG- H2O reversed micelle solutions, 3pAQ＊ and VC react around the water-oil interface of the reversed micelle. Exit of 3pAQ＊ from the lipid phase slows down the quenching reaction. For Triton X-100 （TX-100）/EG-H2O reversed micelle solution, PAQ and VC coexist inside the hydrophilic polyethylene glycol core, and the quenching rate constant of 3pAQ＊ by VC is larger than those in AOT/EG-H2O and CTAB/EG-H2O reversed micelle solutions, even a little larger than that in EG-H2O homogeneous solution. The strong emissive chemically induced dynamic electron polarization of As＇- resulted from the effective TM spin polarization transfer in hydrogen abstraction of 3pAQ＊ from VC.

Effects of calcination temperature on properties of Li_2SiO_3 for precursor of Li_2FeSiO_4

Li2SiO3 was synthesized by combination of sol-gel method and calcination at high temperature using Li2CO3, HNO3, Si（OC2H5）4 and C2H5OH as starting materials. The effects of calcination temperature and refluxing system on the composition and properties of lithium silicate were investigated. The samples were characterized by TGA/DTA, XRD, SEM and particle size analysis. Li2FeSiO4 was prepared by the solid-state reaction between Li2SiO3 and FeC2O4·2H2O. The XRD patterns show that the use of refluxing system in the sol-gel preparation can decrease the Li2Si2O5 and Li4SiO4 impurities in the Li2SiO3 sample. The calcination temperature plays an important role in the properties of the Li2SiO3 samples. The sample calcined at 700 °C has high purity of 97% Li2SiO3 and good morphology as precursor of Li2FeSiO4. It consists of primary particles with size of 1-3 μm, and the primary particle clusters form agglomerates with loose and porous appearance.

Effect of Mn-doping on performance of Li_3V_2(PO_4)_3/C cathode material for lithium ion batteries

Li3V2-2/3xMnx（PO4）3（0≤x≤0.12） powders were synthesized by sol-gel method. The effect of Mn2＋-doping on the structure and electrochemical performances of Li3V2（PO4）3/C was characterized by XRD, SEM, XPS, galvanostatic charge /discharge and electrochemical impedance spectroscopy（EIS）. The XRD study shows that a small amount of Mn2＋-doped does not alter the structure of Li3V2（PO4）3/C materials, and all Mn2＋-doped samples are of pure single phase with a monoclinic structure （space group P21/n）. The XPS analysis indicates that valences state of V and Mn are ＋3 and ＋2 in Li3V1.94Mn0.09（PO4）3/C, respectively, and the citric acid in raw materials was decomposed into carbon during calcination, and residual carbon exists in Li3V1.94Mn0.09（PO4）/C. The results of electrochemical measurements show that Mn2＋-doping can improve the cyclic stability and rate performance of these cathode materials. The Li3V1.94Mn0.09（PO4）3/C cathode material shows the best cyclic stability and rate performance. For example, at the discharge current density of 40 mA/g, after 100 cycles, the discharge capacity of Li3V1.94Mn0.09（PO4）3/C declines from initial 158.8 mA·h/g to 120.5 mA·h/g with a capacity retention of 75.9%; however, that of the Mn-undoed sample declines from 164.2 mA·h/g to 72.6 mA·h/g with a capacity retention of 44.2%. When the discharge current is increased up to 1C, the intial discharge capacity of Li3V1.94Mn0.09（PO4）3/C still reaches 146.4 mA·h/g, and the discharge capacity maintains at 107.5 mA·h/g after 100 cycles. The EIS measurement indicates that Mn2＋-doping with a appropriate amount of Mn2＋ decreases the charge transfer resistance, which is favorable for the insertion/extraction of Li＋.

Synthesis of LiMnPO_4/C composite material for lithium ion batteries by sol-gel method

The LiMnPO4/C composite material was synthesized via a sol-gel method based on the citric acid. The X-ray diffraction （XRD）, scanning electron microscopy （SEM） and electrochemical performance tests were adopted to characterize the properties of LiMnPO4/C. The XRD studies show that the pure olivine phase LiMnPO4 can be obtained at a low temperature of 500 °C. The SEM analyses illustrate that the citric acid used as the chelating reagent and carbon source can restrain the particle size of LiMnPO4/C well. The LiMnPO4/C sample synthesized at 500 °C for 10 h performs the highest initial discharge capacity of 122.6 mA-h/g, retaining 112.4 mA-h/g over 30 cycles at 0.05C rate. The citric acid based sol-gel method is favor to obtain the high electrochemical performance of LiMnPO4/C.

Analysis of Wettability and X-ray Photoelectron Spectroscopy of Wheat Straw/SPI

[Objective] The aim was to improve the adhesive bonding property of wheat straw surface to prepare wheat straw particleboard of soy protein isolate （SPI） adhesive through chemical and enzyme treatments. [Method] Evaluation and analysis were made on wettability of wheat straws in the control group and treated groups （chemical and enzyme treatments） by means of measurement of contact angle and calculation of spreading-penetration parameters （K）. In addition, we made analysis on surface elements through X-ray photoelectron spectroscopy （XPS）. [Result] The re- sults showed that K value of straw treated with sodium hydroxide, hydrogen peroxide and lipase increased by 58.0%, 48.7% and 83.2% compared to that of control group, respectively. The XPS analysis indicated that rapid decrease of silicon content and destruction of wax layer greatly contributed to wettability improvement of wheat straw surface. [Conclusion] The chemical and lipase treatments of wheat straw provided technical support for manufacture of wheat straw particle boand.

Samaria-doped Ceria Modified Ni/YSZ Anode for Direct Methane Fuel in Tubular Solid Oxide Fuel Cells by Impregnation Method

A porous NiO/yttria-stabilized zirconia was prepared by gel casting technique. anode substrate for tubular solid oxide fuel cells Nano-scale samaria-doped ceria （SDC） particles were formed onto the anode substrate to modify the anode microstructure by the impregnation of solution of Sm（NO3）3 and Ce（NO3）3. Electrochemical impedance spectroscopy, current-voltage and current-powder curves of the cells were measured using an electrochemical workstation. Scanning electron microcopy was used to observe the microstructure. The results indicate that the stability of the performance of the cell operated on humidified methane can be significantly improved by incorporating the nano-structured SDC particles, compared with the unmodified cell. This verifies that the coated SDC electrodes are very effective in suppressing catalytic carbon formation by blocking methane from approaching the Ni, which is catalytically active towards methane pyrolysis. In addition, it was found that a small amount of deposited carbon is beneficial to the performance of the anode. The cell showed a peak power density of 225 mW/cm^2 when it was fed with H2 fuel at 700 ℃, but the power density increased to 400 mW/cm^2 when the fuel was switched from hydrogen to methane at the same flow rate. Methane conversion achieved about 90%, measured by gas chromatogram with a 10.0 mL/min flow rate of fuel at 700 ℃. Although the carbon deposition was not suppressed absolutely, some deposited carbon was beneficial for performance improvement.

Water-Resistant and Stretchable Conductive Ionic Hydrogel Fibers Reinforced by Carboxymethyl Cellulose

Conductive ionic hydrogels(CIH)have been widely studied for the development of stretchable electronic devices,such as sensors,electrodes,and actuators.Most of these CIH are made into 3D or 2D shape,while 1D CIH(hydrogel fibers)is often difficult to make because of the low mechanical robustness of common CIH.Herein,we use gel spinning method to prepare a robust CIH fiber with high strength,large stretchability,and good conductivity.The robust CIH fiber is drawn from the composite gel of sodium polyacrylate(PAAS)and sodium carboxymethyl cellulose(CMC).In the composite CIH fiber,the soft PAAS presents good conductivity and stretchability,while the rigid CMC significantly enhances the strength and toughness of the PAAS/CMC fiber.To protect the conductive PAAS/CMC fiber from damage by water,a thin layer of hydrophobic polymethyl acrylate(PMA)or polybutyl acrylate(PBA)is coated on the PAAS/CMC fiber as a water-resistant and insulating cover.The obtained PAAS/CMC-PMA and PAAS/CMC-PBA CIH fibers present high tensile strength(up to 28 MPa),high tensile toughness(up to 43 MJ/m~3),and good electrical conductivity(up to 0.35 S/m),which are useful for textile-based stretchable electronic devices.

Preparation of dual-shell Si/TiO_(2)/CFs composite and its lithium storage performance

A dual-shell Si/TiO2/CFs composite was synthesized through a simple method to deal with the intrinsic drawbacks of silicon-based anode,in terms of huge volume change,unstable SEI films,and low electronic and ionic conductivity.The inner rigid TiO2 shell alleviates the huge volume expansion of the nano silicon,and the outer resilient carbon fiber,which is porous and staggered,is beneficial to the rapid transport of electrons and ions.The as-prepared Si/TiO2/CFs composite displays a superior reversible specific capacity of 583.4 mA·h/g,high rate capability and decent cycling performance.The dual-shell encapsulation method provides a guideline for other anode materials with huge volume expansion during the cycling process.

Influence of Li_3PO_4 addition on properties of lithium ion-conductive electrolyte Li_(1.3)Al_(0.3)Ti_(1.7)(PO_4)_3

The sintered Li1.3Al0.3Ti1.7（PO4）3 pellets with different mole fractions of Li3PO4 were prepared by sol-gel method.The structure,surface morphology,electrochemical window,ionic conductivity and activation energy of the sintered pellets were studied by X-ray diffraction,scan electron microscopy,cyclic voltammetry,and electrochemical impedance spectroscopy.The results show that all the sintered Li1.3Al0.3Ti1.7（PO4）3 pellets with different mole fractions of Li3PO4 have similar X-ray diffraction patterns.The sintered Li1.3Al0.3Ti1.7（PO4）3 pellet with Li3PO4 shows a lower porosity and is denser than the one without Li3PO4.The addition of Li3PO4 has a large effect on the porosity and density of the sintered Li1.3Al0.3Ti1.7（PO3）4 pellet,and little effect on its electrochemical window.Among the sintered Li1.3Al0.3Ti1.7（PO3）4 pellets with different mole fractions of Li3PO4,the one with 1% Li3PO4 shows the activation energy of 0.314 2 eV and the highest ionic conductivity of 6.15-10-4 S/cm.

Preparation of Organic/Inorganic Hybrid Polymer Emulsions with High Silicon Content and Sol-gel-derived Thin Films

A novel polymer/SiO2 hybrid emulsion(PAES)was prepared by directly mixing colloidal silica with polyacrylate emulsion(PAE)modified by a saline coupling agent.The sol-gel-derived thin films were obtained by addition of co-solvents into the PAES.The effects ofγ-methacryloxypropyltrimethoxysilane(KH-570)content and co-solvent on the properties of PAES films were investigated.Dynamic laser scattering(DLS)data indicate that the average diameter of PAES(96 nm)is slightly larger than that of PAE(89 nm).Transmission electron microscopy (TEM)photo discloses that colloidal silica particles are dispersed uniformly around polyacrylate particles and some of the colloidal silica particles are adsorbed on the surface of PAE particles.The crosslinking degree data and Fourier transform infrared(FT-IR)spectra confirm that the chemical structure of the PAES is changed to form Si-O-Si-polymer crosslinking networks during the film formation.Atomic force microscope(AFM)photos show the solvent induced sol-gel process of colloidal silica and the Si-based polymer distribution on the film surface of the dried PAES.Thermogravimetric analysis(TGA)curves demonstrate that the PAES films display much better thermal stability than PAE.

Effect of Potassium Oleate on Rheological Behavior of Cationic Guar in Aqueous Solution with Varying Temperatures

The rheology of the cationic guar （CG） solution was measured and the effects of potassium oleate （KOA） upon the rheological properties of CG solution were studied. The steady shear viscosity measurement has shown that the viscosity of CG solution increased dramatically in the presence of KOA. The viscosity enhancement of KOA upon CG solution can be approximate three orders in magnitude. The gel-like formation of CG solution is observed at the high concentration of KOA. The excess addition of KOA results in the phase separation of CG solution. The oscillatory rheological measurement has shown that the crossover modulus Gc （corresponding to either storage modulus G＇ or loss modulus G＇＇ at the frequency wc where G＇ equals G＇＇） for CG solution, decreases with the increasing the concentration of KOA in solution. On the other hand, the apparent relaxation time 7-app （=1/wc） increases with increasing the concentration of KOA in solution. Our experimental results suggest that for surfaetant such as KOA which has a stronger tendency to form micelles in solution, the cooperative hydrophobic interaction of polymer bound to surfactants is less necessary to the formation of aggregates in solution, especially at the high concentration of surfactants. In fact, with the increase of the concentration of KOA, the number of the aggregates which associate polymer together decreases whereas the intensity of these aggregates increases. The effect of temperature upon the aggregation is also significant. With the increase of temperature, the number of the aggregates increases whereas the intensity of these aggregates decreases, probably because the ionization of KOA increases at high temperature.

Investigation of Swelling and Dissolution Process of Natural Rubber in Aromatic Oil

Aromatic oil has been used to promote the properties of crumb rubber modified asphalt which is an ideal method to deal with the resource utilization of waste rubber tires and by-product of refinery. Furfural extract oil(FEO) was separated into the light fraction and the heavy fraction. Swelling and dissolution process of natural rubber sheet in these three oil samples was investigated to shed light on the interaction mechanism. Crumb rubber also interacted on FEO and asphalt respectively. Energy dispersive spectrometer(EDS), thermo-gravimetric analysis(TGA) and scanning electron microscope(SEM) were used to characterize the chemical and structural properties of processed rubber. The chemical composition of processed oils and asphalt was investigated by using the hydrocarbon group analysis(SARA) and gel permeation chromatography. The results revealed that the swelling rate and mass loss of rubber in oils were much higher than those in asphalt and rose with an increasing processing temperature. The heavy fraction of FEO had more diffusion and dissolving capability than the light fraction, whilst compatibility was observed between the heavy fraction and the light fraction. Selective absorption was not observed in the study and detachment of dissolved rubber was disseminated from the outside to the inside. The cross-linking degree of the residue rubber was unchanged with the processing time, and sulfur predominantly remained in the undissolved rubber. Dissolution of crumbed rubber in oils was attributed to devulcanization, while that in the asphalt was mainly attributed to depolymerization.

Utilization of Starch to Accelerate the Growth of Degrading Microorganisms on the Surface of Natural Rubber Latex Films

NRL （natural rubber latex） films with 0 （control） and 10 phr sago starch loading were buried in compost soil for 4 weeks. The biodegradation assessments were carried out through films WVT （water vapor transmission） and mass loss. Scanning electron microscopy was carried out to identify and monitor the properties of rubber degrading organism colonies. Results showed that incorporation of sago starch increased the formation and rates of propagation for microorganism colonies on NRL films with duration of biodegradation. The results also indicate the mechanism of sago starch granules utilization as sole source of energy for microbial growth. The behavior and characteristics of microorganisms involved in NRL films degradation also successfully discussed.

Microstructure and electrical properties of La_2 O_3-doped ZnO-based varistor thin films by sol-gel process

Microstructure and electrical properties of La2 O3-doped ZnO-Bi2 O3 thin films prepared by sol–gel process have been investigated.X-ray diffraction shows that most diffraction peaks of ZnO are equal,and the crystals of ZnO grow well.Scanning electron microscopy and atomic force microscopy results indicate that the samples have a good structure and lower surface roughness.The nonlinear V–I characteristics of the films show that La2 O3 develops the electrical properties largely and the best doped content is 0.3% lanthanum ion,with the leakage current of 0.25 mA,the threshold field of 150 V/mm and the nonlinear coefficient of 4.0 in detail.

Fast-ionic conductor Li_(2.64)(Sc_(0.9)Ti_(0.1))_(2)(PO_(4))_(3) doped PVDF-HFP hybrid gel-electrolyte for lithium ion batteries

With increasing demand on energy density of lithium-ion battery,wide electrochemical window and safety performance are the crucial request for next generation electrolyte.Gel-electrolyte as a pioneer for electrolyte solidization development aims to solve the safety and electrochemical window problems.However,low ionic conductivity and poor physical performance prohibit its further application.Herein,a fast-ionic conductor(Li_(2.64)(Sc_(0.9)Ti_(0.1))_(2)(PO_(4))_(3))(LSTP)was added into poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)base gel-electrolyte to enhance mechanical properties and ionic conductivity.Evidences reveal that LSTP was able to weaken interforce between polymer chains,which increased the ionic conductibility and decreased interface resistance during the cycling significantly.The obtained LiFePO_(4)/hybrid gel-electrolyte/Li-metal coin cell exhibited excellent rate capacity(145 mA·h/g at 1C,95 mA·h/g at 3C,28℃)which presented a potential that can be comparable with commercialized liquid electrolyte system.

Photocatalytic H_2 evolution activity of CuO/ZrO_2 composite catalyst under simulated sunlight irradiation

Zirconia-supported CuO （CuO/ZrO2） composite photocatalysts were successfully synthesized via citric acid-assisted sol-gel technique. For comparison, CuO/ZrO2 materials were also prepared by solid state reaction and co-precipitation method. The as-prepared powders were characterized by X-ray diffractometry （XRD）, transmission electron microscopy （TEM）, and thermogravimetric-differential thermal analysis （TG-DTA）. The photocatalytic activity of CuO/ZrO2 catalyst was investigated based on the H2 evolution from oxalic acid solution under simulated sunlight irradiation. The effects of molar ratio of CuO to ZrO2, preparation method, phase change with the calcination temperature and the durability on the photocatalytic activity of the photocatalyst were investigated in detail. It is found that the optimal activity of photocatalytic H2 evolution （2.41 mmol.h i.g-~） can be obtained when CuO/ZrO2 composite photocatalyst is synthesized by sol-gel technique and the mole ratio of CuO to ZrO2 is 40%. The activity of copper oxide supported on monoclinic ZrO2 calcined at higher temperature is much higher than that on tetragonal ZrO2 calcined at lower temperature, and the best calcination temperature is 900 ℃.

Characterization of Dust and Non-dust Aerosols with SEM/EDX

Total suspended particulate （TSP） samples were collected at three sites along the coast of Qingdao, China, before and during a major dust storm in March, 2002. For comparison, PM10（particulate matter with aerodynamic diameters less than 10μm） samples were collected at one of the three sites. The morphological observation and compositional analysis of bulk and individual particles were performed by using scanning electron microscopy equipped with an energy dispersive X-ray system （SEM/EDX） for the TSP and PM10 samples. The results showed that the particles of different kinds of morphology had different elemental compositions, but the particles of similar morphology did not always have the same elemental composition for non-dust samples. The morphology and composition of non-dust particles were different at different sites. The fractal and spherical particles existed mainly in the coarse fraction for non-dust samples, while in the fine mode （〈 10μm） there were floccules formed by fine particles flocking together and containing crustal elements. Compared with the non-dust particles, the dust particles were more homogeneous in terms of morphology, particle size and composition. Particles with irregular shapes and well-distributed sizes dominated in the dust samples, containing crustal elements such as Mg, A1, Si, Ca, Fe, etc. The high sulfur content indicated that homogeneous and heterogeneous reactions took place on the surfaces of the dust particles in the specific environment of Qingdao.

Synthesis and Characterization of Ethylenediamine Tetraacetic Acid Tetrasodium Salt Loaded in Microcapsules with Slow Release Properties

The microcapsules with cores of ethylenediamine tetraacetic acid tetrasodium salt(Na4-EDTA)and walls of polyurea were synthesized via an interfacial polycondensation reaction with 2,4-tolylene diisocyanate as an oil-soluble monomer and diethyl triamine as a water-soluble monomer.Various manufacturing parameters,including the amount of emulsifier,agitation speed,stirring time and ratios of the wall materials to core materials,were altered to optimize process variables during the synthesis of microcapsules,and the effects of these parameters on the characteristics of the microcapsules were examined.The structure,morphology,mean particle size and size distribution were characterized by optical microscope and scanning electron microscopy(SEM),showing that the mean diameter of optimal microspheres was approximately 6μm,and microcapsules were spherical.In vitro release of Na4-EDTA from these microcapsules was performed in distilled water.Under the optimal preparation conditions, the Na4-EDTA release profiles were biphasic with a burst release followed by a gradual release phase.After an initial burst,a continuous Na4-EDTA release was up to 5-7 days.The optimal synthesis conditions for the microcapsules with stable,good morphology and good controlled-release properties were as follows:emulsifier Span-80 10% (by mass),agitation speed 900 r·min1,stirring time 30 min,and the ratio of the wall materials to core materials 0.15.

Electron-Irradiation Induced Nanocrystallization of Pb（ll） in Silica Gels Prepared in High Magnetic Field

In a previous study, structure of silica gels prepared in a high magnetic field was investigated. While a direct application of such anisotropic silica gels is for an optical anisotropic medium possessing chemical resistance, we show here their possibility of medium in materials processing. In this direction, for example, silica hydrogels have so far been used as media of crystal growth. In this paper, as opposed to the soft-wet state, dried silica gels have been investigated. We have found that lead （II） nanocrystallites were formed induced by electron irradiation to lead （ll）-doped dried Hydrogels made from a sodium metasilicate solution doped with silica gels prepared in a high magnetic field such as B = 10 T. lead （II） acetate were prepared. The dried specimens were irradiated by electrons in a transmission electron microscope environment. Electron diffraction patterns indicated the crystallinity of lead （II） nanocrystallites depending on B. An advantage of this processing technique is that the crystallinity can be controlled through the strength of magnetic field B applied during gel preparation. Specific skills are not required to control the strength of magnetic field.