Tetrathiafulvalene esters with high redox potentials and improved solubilities for non-aqueous redox flow battery applications

The exploitation of high performance redox-active substances is critically important for the development of non-aqueous redoxflow batteries.Herein,three tetrathiofulvalene(TTF)derivatives with different substitution groups,namely TTF diethyl ester(TTFDE),TTF tetramethyl ester(TTFTM),and TTF tetraethyl ester(TTFTE),are prepared and their energy storage properties are evaluated.It has been found that the redox potential and solubility of these TTF derivatives in conventional carbonate electrolytes increases with the number of ester groups.The battery with a catholyte of 0.2 mol L^(-1) of TTFTE delivers a specific capacity of more than 10 Ah L^(-1) at the current density of 0.5 C with two discharge voltage platforms locating at as high as 3.85 and 3.60 V vs.Li/Liþ.Its capacity retention can be improved from 2.34 Ah L^(-1) to 3.60 Ah L^(-1) after 100 cycles by the use of an anion exchange membrane to block the crossover of TTF species.The excellent cycling stability of the TIF esters is supported by their well-delocalized electrons,as revealed by the density function theory calculations.Therefore,the introduction of more and larger electron-withdrawing groups is a promising strategy to simultaneously increase the redox-potential and solubility of redox-active ma-terials for non-aqueous redoxflow batteries.

Experimental study on the dispersion behavior of a microemulsion collector and its mechanism for enhancing low-rank coal flotation

As the poor dispersion of oily collectors and the inferior hydrophobicity of the mineral surface, the lowrank coal has an unsatisfactory flotation performance when using traditional collectors. In this paper, an ionic liquid microemulsion was used as a collector to enhance its floatability. Flotation test results demonstrated the microemulsion collector exhibited a superior collecting ability. A satisfactory separation performance of 78.66% combustible material recovery was obtained with the microemulsion collector consumption of 6 kg/t, which was equivalent to the flotation performance of diesel at a dosage of25 kg/t. The dispersion behavior of the microemulsion collector was investigated using the CryogenicTransmission Electron Microscopy. The interaction mechanism of the microemulsion collector on enhancing the low-rank coal flotation was elucidated through the Zeta potential and contact angle measurements, the Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy analysis.The microemulsion collector exhibited superior dispersibility, which was dispersed into positively charged oil droplets with an average size of 160.21 nm in the pulp. Furthermore, the nano-oil droplets could be more efficiently adsorbed on the low-rank coal surface through electrostatic attraction, resulting in the improvement of its hydrophobicity. Thus, the microemulsion collector shows great application potential in improving the flotation performance of low-rank coal.

Design of the reactive dyes containing large planar multi-conjugated systems and their application in non-aqueous dyeing

The development of pollution-free dyeing technology, including anhydrous dyeing and non-aqueous dyeing technologies, has always been an important way and research hot in energy conservation and emission reduction. Designing new structural dye molecules is the key to water-saving dyeing processes.Herein, three reactive dyes were designed and synthesized, which contained large planar multiconjugated systems and multi-reactive groups. The designed reactive dyes are expected to have high affinity and high fixations in non-aqueous or small bath dyeing processes. The reactive dyes were applied in the decamethylcyclopentasiloxane(DMCS) reverse micelle dyeing for cotton fabric. High exhaustion rate of 99.35%, 98.10% and 98.80%, and fixation rate of 95.15%, 96.34% and 94.40% for three dyes, R1,R2 and R3, could be respectively obtained. The dyes can be fully utilized and had excellent dyeing performance, fastness and levelling properties under the revere micelle dyeing. The cotton fabric is like an oil-water separator in the dyeing process, where the dye micelles rapidly absorb and permeate into the cotton fibers. DMCS circulates around the fabric to transfer mass and energy. After dyeing, the solvent can be separated quickly and reused. The new reactive dyes containing large planar and multi-conjugated systems have potential application in green and sustainable dyeing technology with less wastewater and higher utilization.

Interaction of Foam and Microemulsion Components in Low-Tension-Gas Flooding

Low-Tension-Foam(LTF)flooding is an emerging enhanced oil recovery technique for low-permeability carbonate reservoirs.Foam capacity is closely related to the salinity environment(or,equivalently,the phase behavior of the oil/water/surfactant system).Therefore,the interactions between microemulsion and foam components are of primary importance in the LTF process.In this study,the phase behavior of an oil/water/surfactant system under equilibrium is analyzed,firstly by assuming perfect mixing.Meanwhile,the formation kinetics of microemulsion are monitored through a novel low-field NMR technique,which is able to provide quantitative assessment on the microemulsion evolution characteristics.Then,foam stability is examined in the absence and in the presence of Winsor-Ⅰ and Winsor-Ⅲ type microemulsions.It is revealed that foam stability depends on the oil solubilization(oil swollen micelle size).A decrease in the oil swollen micelle size and micellar structure effectiveness,in conjunction with an increasing salinity,leads to lower foam stability in the presence of a Winsor-Ⅲ type microemulsion.

Analyses of non-aqueous reactive polymer insulation layer in high geothermal tunnel

The scenario of geothermal tunnel is commonly observed around the world,and increases with the new constructions in the long and deep tunnels,for example in China.Tunnel insulation is generally divided into active and passive insulation.In passive insulation,it is an effective way to set low thermal con-ductivity materials as the thermal insulation layer as the choice of insulation material mainly depends on the thermal conductivity.Polymer is a kind of material with good geothermal performance,but there are relatively few studies.In this context,the transient plane source(TPS)method was used to measure the thermal conductivity of the developed polymer.Then,the temperature field of the high geothermal tunnel insulated by the non-aqueous reactive polymer layer was simulated.With the parametric analysis results,the suggestions for the tunnel layers were proposed accordingly.It revealed that the thermal conductivity of polymer first increases and then decreases with temperature.There are two rising sec-tions(?40e10?C and 20e90?C),one flat section(10e20?C)and one descending section(>90?C).It is observed the thermal conductivity of polymer increases with increase of the density of insulation layer and the density,and the thermal conductivity decreases when exposed to high temperatures.The temperature of the surrounding rocks increases with increase of the thermal conductivity and the thickness of polymer.Finally,a more economical thickness(5 cm)was proposed.Based on the parametric study,a thermal insulation layer with thermal conductivity less than 0.045 W/(m K),thickness of 5 cm and a density less than 0.12 g/cm 3 is suggested for practice.

Performance evaluation of microemulsion acid for integrated acid fracturing in Middle Eastern carbonate reservoirs

Considering the characteristics of carbonate reservoirs in the Middle East,a low-viscosity microemulsion acid that can be prepared on site and has an appropriate retardation ability was developed.It was compared with four conventional acid systems(hydrochloric acid,gelled acid,emulsified acid and surfactant acid)through experiments of rotating disk,multistage acid fracturing and core flooding with CT scanning.The micro-etching characteristics and conductivity of fracture surfaces were clarified,and the variation of saturation field during water invasion and flowback of spent acid and the recovery of oil phase relative permeability were quantitatively evaluated.The study shows that the addition of negatively charged agent to the oil core of microemulsion acid can enhance its adsorption capacity on the limestone surface and significantly reduce the H+mass transfer rate.Moreover,the negatively charged oil core is immiscible with the Ca^(2+)salt,so that the microemulsion acid can keep an overall structure not be damaged by Ca^(2+)salt generated during reaction,with adjustable adsorption capacity and stable microemulsion structure.With high vertical permeability along the fracture walls,the microemulsion acid can penetrate into deep fracture wall to form network etching,which helps greatly improve the permeability of reservoirs around the fractures and keep a high conductivity under a high closure pressure.The spent microemulsion acid is miscible with crude oil to form microemulsion.The microemulsion,oil and water are in a nearly miscible state,with basically no water block and low flowback resistance,the flowback of spent acid and the relative permeability of oil are recovered to a high degree.

Phase behavior of TXs/toluene/water microemulsion systems for solubilization absorption of toluene

Triton Xs （TXs） surfactants/cosurfactant/water/oil （toluene） microemulsion systems for enhancing toluene solubilization were proposed and its potential was investigated for toluene removal from gas stream. The results indicated that TX-100 was superior to other TXs surfactants in removing toluene without cosurfactant. The efficiency of cosurfactants for improving toluene solubilization capacity follows the order： amine 〉 alcohol 〉 acid. According to the factor analysis, the linear cosurfactants are better than the branched ones. The effects of hydrophile-lipophile balance （HLB）, salt （NaCl） concentration and temperature on the formation of microemulsion system were also discussed. The results suggested that the optimum value of HLB was 15, the effect of NaCl concentration on the system was inconspicuous and the lower temperature enhanced the solubilization capacity. Nonionic surfactant-based microemulsions had a significant absorption enhancement for toluene, indicated by as much as 82.72% of toluene in phase composition diagram, which will have a great prospect in air pollution treatment.

A study of the mechanism of enhancing oil recovery using supercritical carbon dioxide microemulsions

Supercritical carbon dioxide （scCO2） microemulsion was formed by supercritical CO2, H20, sodium bis（2-ethylhexyl） sulfosuccinate （AOT, surfactant） and C2HsOH （co-surfactant） under pressures higher than 8 MPa at 45 ℃. The fundamental characteristics of the scCO2 microemulsion and the minimum miscibility pressure （MMP） with Daqing oil were investigated with a high-pressure falling sphere viscometer, a high-pressure interfacial tension meter, a PVT cell and a slim tube test. The mechanism of the scCO2 microemulsion for enhancing oil recovery is discussed. The results showed that the viscosity and density of the scCO2 microemulsion were higher than those of the scCO2 fluid at the same pressure and temperature. The results of interfacial tension and slim tube tests indicated that the MMP of the scCO2 microemulsion and crude oil was lower than that of the scCO2 and crude oil at 45 ℃. It is the combined action of viscosity, density and MMP which made the oil recovery efficiency of the scCO2 microemulsion higher than that of the scCO2 fluid.

Water solubility enhancements of PAHs by sodium castor oil sulfonate microemulsions

Water solubility enhancements of naphthalene(Naph), phenantherene(Phen) and pyrene(Py) in sodium castor oil sulfonate(SCOS) microemulsions were evaluated. The apparent solubilities of PAHs are linearly proportional to the concentrations of SCOS microemulsion, and the enhancement extent by SCOS solutions is greater than that by ordinary surfactants on the basis of weight solubilization ratio(WSR). The log K em values of Naph, Phen, and Py are 3 13, 4 44 and 5 01 respectively, which are about the same as the log K ow values. At 5000 mg/L of SCOS conccentration, the apparent solubilities are 8 80, 121, and 674 times as the intrinsic solubilities for Naph, Phen, and Py. The effects of inorganic ions and temperature on the solubilization of solutes are also investigated. The solubilization is improved with a moderate addition of Ca 2+ , Na +, NH + 4 and the mixture of Na +, K +, Ca 2+ , Mg 2+ and NH + 4. WSR values are enhanced by 22 0% for Naph, 23 4% for Phen, and 24 6% for Py with temperature increasing by 5℃. The results indicated that SCOS microemulsions improve the performance of the surfactant enhanced remediation(SER) of soil, by increasing solubilities of organic pollutants and reducing the level of surfactant pollution and remediation expenses.

Kinetics of the Esterification Reaction Catalyzed by Lipase in W/O Microemulsions of Alkyl Polyglucoside

A novel kinetic mechanism of esterification reaction of 1-hexanoic acid with 1-butanol, catalyzed by lipase, was studied in water-in-oil microemulsions. The microemulsions were formed by alkyl polyglucoside C10G1.54/1-butanol / cyclohexane/phosphate buffer solution. The result shows that when the ratio of mol concentration of 1-butanol to 1-hexanoic acid is about 3.0, the initial rate V0 get the maximum values. This phenomenon was explained by the modified fishlike phase diagrams.

Catalytic spectrophotometric determination of trace selenium in microemulsion after separation and enrichment by SDG

A new catalytic spectrophotometric method was developed for the determination of trace amount of Se（Ⅳ） in microemulsion medium. The method is based on the catalytic effect of traces of Se（Ⅳ） on the oxidation of 2＇,4＇-dichlorophenylfluomne （p-CPF） by potassium bromate with HNO3 as an activator in the presence of nonionic microemulsion medium. Under optimum conditions, the calibration graph is linear in the range of 0.4-15 μg·L^-1 of Se（Ⅳ） at 480 nm. The detection limit achieved is 9.86 × 10^-10μg·L^-1. Samples were dissolved and the obtained trace Se（Ⅳ） was separated and enriched by sulphydryl dextrane gel （SDG）. The method has been applied for determination of trace selenium with satisfactory results.

Studies on the Microscopic Mechanism of the Thermodynamic Stability of Pesticide Microemulsion

The cryo-fracture electron microscope was used to study the micro-structure of pesticide mi-croemulsions. The hydromechanical radius (Rh) and the distribution (fRh) of pesticide microemulsions were determined by photo-correlation spectroscopy. This study showed that the Rh was significantly greater when the ratio of surfactants to water (w/w) decreased to 20/31 from 27/26, and a bicontinuous structure was formed when the ratio dropped to 15/36. These results explained the relationship between pesticide properties and the microscopic structure, and provided a good method for studying the microscopic structure of pesticide formulations.

Physicochemical Properties and Evaluation of Microemulsion Systems for Transdermal Delivery of Meloxicam

Microemulsion systems, composed of water, isopropyl myristate （IPM）, polyoxyethylene sorbitan trioleate （Tween 85 ）, and ethanol, were investigated as transdermal drug delivery vehicles for a lipophilic model drug（ meloxicam）. The purpose of this study was to investigate the physicochemieal properties of the tested microemulsion and to find the correlation between the physicoehemical properties and the skin permeation rate of the microemulsion. Pseudo-ternary phase diagram of the investigated system at a constant surfactant/cosurfactant mass ratio （ Km = 1 ： 1 ） was constructed by titration at 20℃, and the five fommlations were selected for further research in the o/w microemulsion domains. The values of electrical conductivity and viscosity showed that the selected systems were bicontinuous or non-spherical o/w microemulsion, and the electrical conductivity and viscosity were increased with increasing the content of water. These results suggest that the optimum formulation of microemulsion, containing 0. 375 meloxicam, 5% isopropyl myristate, 25% Tween 85. 25% ethanol, and water, showed the maximum permeation rate. It had a high electrical conductivity, small droplet size, and proper viscocity.

High Solids-Content Nanosize Polymeric Microlatexes Made by Microemulsion Copolymerization at Ambient Temperature

The microemulsion copolymerizations of acrylic acid (AA),acrylamide (AM),N-methylol acrylamide (NMA),methylmethacrylate (MMA),butyl acrylate (BA) and acrylonitrile (AN) initiated by the redox initiator ammonium persulfate (APS) and N,N,N′,N′-tetramethylethylenediamine (TMEDA) at ambient temperature were investigated.With this process high solids-content (44.0 wt%) and small (less than 50 nm) particle diameter copolymer latexes were attained.The effects of surfactants,the mechanical stabilities and application properties as an environmentally friendly self-crosslinking pigment printing binder with multifunctional groups were studied.

Percutaneous absorption and brain distribution facilitation of borneol on tetramethylpyrazine in a microemulsion-based transdermal therapeutic system

In this study, we show that the percutaneous absorption and brain distribution of tetramethylpyrazine(TMP) is enhanced when combined with borneol(BN) in a microemulsionbased transdermal therapeutic system(ME-TTS). The formulation of the TMP and BN microemulsion(TEM-BN-ME) was optimized in skin permeation studies in vitro following a uniform experimental design. Male Sprague-Dawley rats were used for the in vivo pharmacokinetic and tissue distribution studies of TMP-BN-ME-TTS. In the pharmacokinetic study, the TMP-BN-ME-TTS treated rats had significantly higher( P < 0.05) C max and AUC of TMP than the TMP-ME-TTS treated rats, indicating that BN improves the rate and extent of TMP percutaneous absorption. In the tissue distribution study, the AUC of TMP in brain was significantly higher in the TMP-BN-ME-TTS group( P < 0.05), indicating that BN facilitates the distribution of TMP in brain. In summary, BN enhanced the percutaneous absorption and brain distribution of TMP in a microemulsion-based transdermal therapeutic system.

Synthesis and characterization of CePO_4 nanowires via microemulsion method at room temperature

Uniform CeVO4 nanowires with diameter of about 25 nm were synthesized by the water-in-oil microemulsion method at room temperature from cerous chloride, sodium orthophosphate, sodium chloride, cyclohexane, Triton X-100 and cetyltrimethyl ammonium bromide （CTAB）. The crystal structure and morphology of the nanowires were characterized by XRD and TEM, respectively. The UV-vis absorption was detected by UV-vis spectrophotometer techniques. The results showed that as-prepared nanowires with the hexagonal phase have obvious quantum confinement effect and semiconductor characteristics. Little sodium chloride could play a positive role on the formation of CePO4 nanowires at room temperature. The size of the nanowires can be controlled through the joining of sodium chloride. C 2009 Yi Bin Yin. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

Preparation and Characterization of CeO_2-ZrO_2 Solid Solution Ultrafine Particles Using Reversed Microemulsion

Ce0.6Zr0.4O2 solid solution ultrafine particle was prepared in the cyclohexane/water/OP-10/n-hexanol reversed microemulsion. The quasi-ternary phase diagram investigations showed that the system has narrow W/O type microemulison region, so it is the proper system to prepare Ce0.6Zr0.4O2 solid solution ultrafine particle. Some physical-chemical techniques such as TG/DTA, XRD, BET, and HRTEM are used to characterize the resultant powders. The results show that the fluorite cubic Ce0.6Zr0.4O2 solid solution is obtained at 400 ℃. The surface area is （146.7 m^2·g^-1）, which is higher than the surface area for sol-gel prepared sample （59.5m^2·g^-1）. HRTEM images indicated that the Ce0.6Zr0.4O2 solid solution ultrafine particle is well-crystallized, narrow size distribution, less agglomeration, within mean size of 5 -7 nm.

Electrochemical Oxidation of L-Cystenine in SDS/BA/H_2O Microemulsion

The electrochemical oxidation of L-cysteine in an SDS/BA/H_2O microemulsion system was studied with the methods of ultramicroelectrode cyclic voltammetry and AC impedance. The catalytic efficiency of the microemulsion on the electrochemical oxidation increases with the increase of BA or SDS content, but decreases with the increase of the water content because of the effects of BA, SDS and water on the solubilization of L-cysteine in the microemulsion. Furthermore, the catalytic efficiency of the bicontinuous structure is greater than that of an O/W microemulsion system. The results derived from both the rate constant k0 and Gibbs free energy ΔG≠ accord with those from the catalytic efficiency.

Preparation of Y_2O_3 Nanoparticles Organosol by Microemulsion Method

Y 2O 3 nanoparticles organosol coated with DBS was prepared by microemulsion method. The optimum preparative conditions of Y 2O 3 nanoparticles organosol were obtained. TEM analysis indicates that the prepared Y 2O 3 nanoparticles are spherical in shape. The size is about 5 nm. The size distribution is in the narrow range and no agglomerates are observed. Y 2O 3 nanoparticles coated with DBS are easy to dissolve in weak polar solvents.