Molecular dynamics simulation of gas diffusion in polyethylene-clay nanocomposites with different silicate layers configurations

Barrier properties of pristine polyethylene (PE) and polyethylene/montmorillonite-clay (PE/MMT) nanocomposite films with different MMT layers configurations were studied using molecular dynamics simulation within NVT ensemble. The force field parameters were optimized for bond lengths, bond angles and torsion angles of the MMT structure. A special simulation box was designed to simulate the diffusion of oxygen, nitrogen and methane, through pristine PE and PE/MMT nanocomposite films. The diffusion coefficients of these gases and the tortuosity values were calculated and analyzed. Results showed that the configuration of clay nanoparticles has strong effect on the barrier properties of the nanocomposite films. The parallel configuration for layered silicates was predicted to have a low diffusion coefficient and a high tortuosity parameter for gas diffusive molecules. The simulation could also indicate that the diffusion coefficient of oxygen is higher than those of nitrogen and methane gases in the examined systems which can be attributed to the smaller kinetic diameter of oxygen.     

氧分压对固体氧化物电解池性能的影响

High-temperature (700–900 ℃) steam electrolysis based on solid oxide electrolysis cells (SOECs) is valuable as an efficient and clean path for large-scale hydrogen production with nearly zero carbon emissions, compared with the traditional paths of steam methane reforming or coal gasification. The operation parameters, in particular the feeding gas composition and pressure, significantly affect the performance of the electrolysis cell. In this study, a computational fluid dynamics model of an SOEC is built to predict the electrochemical performance of the cell with different sweep gases on the oxygen electrode. Sweep gases with different oxygen partial pressures between 1.01 × 10³ and 1.0 × 10⁵ Pa are fed to the oxygen electrode of the cell, and the influence of the oxygen partial pressure on the chemical equilibrium and kinetic reactions of the SOECs is analyzed. It is shown that the rate of increase of the reversible potential is inversely proportional to the oxygen partial pressure. Regarding the overpotentials caused by the ohmic, activation, and concentration polarization, the results vary with the reversible potential. The Ohmic overpotential is constant under different operating conditions. The activation and concentration overpotentials at the hydrogen electrode are also steady over the entire oxygen partial pressure range. The oxygen partial pressure has the largest effect on the activation and concentration overpotentials on the oxygen electrode side, both of which decrease sharply with increasing oxygen partial pressure. Owing to the combined effects of the reversible potential and polarization overpotentials, the total electrolysis voltage is nonlinear. At low current density, the electrolysis cell shows better performance at low oxygen partial pressure, whereas the performance improves with increasing oxygen partial pressure at high current density. Thus, at low current density, the best sweep gas should be an oxygen-deficient gas such as nitrogen, CO₂, or steam. Steam is the most promising because it is easy to separate the steam from the by-product oxygen in the tail gas, provided that the oxygen electrode is humidity-tolerant. However, at high current density, it is best to use pure oxygen as the sweep gas to reduce the electric energy consumption in the steam electrolysis process. The effects of the oxygen partial pressure on the power density and coefficient of performance of the SOEC are also discussed. At low current density, the electrical power demand is constant, and the efficiency decreases with growing oxygen partial pressure, whereas at high current density, the electrical power demand drops, and the efficiency increases.     

A molecular dynamics study on permeability of gases through parylene AF8 membranes

The amorphous and crystalline poly‐p‐xylylene (parylene) AF8 membranes are constructed by a novel computational technique, that is, a combined method of NVT + NPT‐molecular dynamics (MD) and gradually reduce the size. The related permeation properties are calculated using Grand Canonical Monte Carlo (GCMC) and NVT‐MD methods. The results show that amorphous and crystalline parylene AF8 membranes have different permeation properties. Compared with amorphous parylene AF8 area, crystalline parylene AF8 membranes provide less walking paths of gases. In parylene AF8 membranes, gases walk front and back among the stable sites for holding the minimal energy. Furthermore, gases walk just along the y axis of crystalline cell, however, randomly in amorphous area. The corresponding permeability coefficients approach the experimental data. Copyright © 2011 John Wiley & Sons, Ltd.     

Design of an in-house ambient pressure AP-XPS using a bench-top X-ray source and the surface chemistry of ceria under reaction conditions

A new in-house ambient pressure XPS (AP-XPS) was designed for the study of surfaces of materials under reaction conditions and during catalysis. Unique features of this in-house AP-XPS are the use of monochromated Al Kα and integration of a minimized reaction cell, and working conditions of up to 500 °C in gases of tens of Torr. Generation of oxygen vacancies on ceria and filling them with oxygen atoms were characterized in operando.     

Mixed Conduction in Tb2O3 Doped BaCeO3

BaxCe0.8Tb0.2O3-a （x=0.98-1.03） solid electrolytes were synthesized and characterized by using X-ray diffraction （XRD）. By using AC impedance spectroscopy and gas concentration cell electromotive force （EMF） measurements, the electrical conduction behavior of the specimens was investigated in different gases during 500-1000 ℃ The influence of nonstoichiometry in the specimens with x ≠ 1 on conduction properties was studied and compared with that in the specimen with x = 1. The results show that the specimens are all of perovskite-type orthorhombic structure. In 500-1000 ℃, electronic hole conduction is dominant in dry and wet oxygen, air or nitrogen. Protonic conduction is dominant in wet hydrogen and it is about two orders of magnitude higher than that in hydrogen-free atmospheres （oxygen, air and nitrogen）. The electrical conductivity of the same specimen in water vapor-saturated oxygen, air or nitrogen is slightly higher than that in corresponding gas without water vapor. The electrical conductivities of the nonstoichiometric specimens are higher than those of the stoichiometric one.     

A new equation of state for studying the thermodynamic properties of real gases

In this study, based on the compressibility effect of gas molecules, a new three-parameter cubic equation of state (EOS) is derived. To validate this EOS, density predictions of methane, ethane, carbon dioxide and oxygen have been studied using the new EOS at the temperature of 373 K and at the pressures up to 100 MPa. The results show a good agreement with reference data and this suggests that the proposed EOS would help to improve the study of thermodynamic properties for real gases.     

Ionic liquids: Electrochemical investigation on corrosion activity of ethyl-dimethyl-propylammonium bis(trifluoromethylsulfonyl)imide at high temperature

In the present work we report on our investigation on the corrosion properties of the ethyl-dimethyl-propylammonium bis(trifluoromethylsulphonyl)imide at temperatures up to 473 K. The tests were performed both for commercially pure iron alloys and for pure copper. The electrochemical measurements showed that the metals corrosion rates can be dramatically reduced by purging the ionic liquid with inert gases to remove the dissolved oxygen.     

Cyclodextrin nanosponges as effective gas carriers

Cyclodextrin based carbonate nanosponges were synthetized starting from native ??-cylodextrin and active carbonyl compounds i.e. carbonildiimidazole. In this work they were used to form inclusion complexes with three different gases i.e. 1-methylcyclopropene, oxygen and carbon dioxide. The encapsulation of gases were proved by direct reaction to known adduct (1-methylcyclopropene), by gravimetric analysis (CO₂) and by oxymeter (Oxygen). The complexetion of oxygen or carbon dioxide could be useful for many biomedical applications. In particular the oxygen-filled nanosponges could supply oxygen to the hypoxic tissues which are present in various deseases. 1-methylcyclopropene included in ??-cyclodextrin nanosponges showed superior antiethylenic performances in long lasting cut flowers in comparison with marketed products.     

High purity oxygen production with a polymer electrolyte membrane electrolyser

Oxygen is required for treatment of patients in hospitals and at home, in industrial processes and for fuel combustion. Most commonly oxygen is produced by cryogenic or pressure swing adsorption routes. Other techniques include oxygen-ion conducting ceramic membranes, polymer membranes and chemical processes used mainly in civil aviation to reduce the condition of hypoxia at high altitudes. Water electrolysis is used mainly for the production of hydrogen with oxygen as a by-product. In order to use this system only for oxygen production, hydrogen must be utilised and disposed off safely. This, however, is not practical in many instances where there is no use for hydrogen and it poses an explosion hazard. In this paper, an electrolyser system based on polymer electrolyte membrane is described in which hydrogen produced on one side of the electrochemical cell is consumed by combining it with atmospheric oxygen, through operating the cell in a carefully configured fuel cell mode. This reduces the power consumed in the electrolysis operation by more than 35% and eliminates hydrogen in exit gases. Oxygen generated is of high quality and can be used for human consumption (portable and plug-in home care oxygen therapy devices, in hospitals, defence or aerospace requirements) and for many other industrial applications.     

Synthesis and gas permeation properties of poly(4-methyl-2-pentyne)

Poly(4-methyl-2-pentyne) [PMP] is an amorphous, glassy, di-substituted acetylene-based polymer. PMP has a low density of 0.78 g/cm³ and a high fractional free volume of 0.28. The permeabilities for helium, hydrogen, nitrogen, oxygen, carbon dioxide, methane, ethane, propane, and n-butane were determined at temperatures from 20 to 65°C and pressures from 10 to 150 psig. PMP is the most permeable purely hydrocarbon-based polymer known; its permeabilities are only exceeded by poly(1-trimethylsilyl-1-propyne) [PTMSP] and poly(1-trimethylgermyl-1-propyne) [PTMGeP]. The oxygen permeability of PMP at 25°C is 2700 × 10⁻¹⁰ cm³(STP) cm/cm² s cmHg and the nitrogen permeability is 1330 × 10⁻¹⁰ cm³(STP) cm/cm² s cmHg. The high gas permeabilities in PMP result from its very high free volume, and probably, interconnectivity of the free-volume-elements. For a glassy polymer, PMP exhibits unusual organic vapor permeation properties. Permeabilities in PMP are higher for large, condensable gases, such as n-butane, than for small, permanent gases such as helium. The permeabilities of condensable gases and permanent gases decrease as the temperature is increased. This behavior is completely unexpected for a glassy polymer and has been observed previously in only high-free-volume glassy PTMSP.     

Blowing‐out effect and temperature profile in condensed phase in flame retarding epoxy resins by phosphorus‐containing oligomeric silsesquioxane

A series of flame retardant epoxy resins (EPs) containing phosphorus‐containing oligomeric silsesquioxane are prepared, and an interesting blowing‐out effect is detected in flame retardant EPs. The temperature profiles show that blowing‐out effect slows the heat transfer from the fire to the unburned matrix; furthermore, this blowing‐out effect can even take away some heat from the surface zone by the spurting gases. The thermo gravimetric analyzer and Fourier transform infrared spectrometer result shows that the spurting gases during the blowing‐out effect have a high content of CO₂, which could reduce the combustion capability of the jetting gases. The flame retardancy of these EPs is tested by limit oxygen index and UL‐94. The incorporation of 2.5 wt% phosphorus‐containing oligomeric silsesquioxane into EP gives a remarkable blowing‐out effect, which results in a significant enhancement of limit oxygen index value and UL‐94 rating. The flame retardancy mechanism of blowing‐out effect is quite different from the traditional mechanisms. The char strength and morphology of EP composites are also investigated to explain the mechanism of the blowing‐out effect. Copyright © 2013 John Wiley & Sons, Ltd.     

Determination of oxygen in certain gases : Improved winkler method

An improved method is described for the determination of micro-amounts of oxygen gas in argon, carbon dioxide, helium, hydrogen and nitrogen by the Winkler. procedure. The technique is such that a mean standard deviation of ± 0.33 ppm oxygen with a reproducibility of ± 0.67 is obtained for gases varying in oxygen content from 1 to 30 ppm. The results are reproducible on a day-to-day basis. The reagent blank is equivalent to about 2.5 ppm with a deviation of 0.2 ppm. The method can be used for oxygen gas determination from 1 to 1.50 ppm. The accuracy of the method is ± 0.1 ppm for the lower range of oxygen concentrations.The method may also be extended to higher oxygen-containing gases, except that the oxygen determination is made by titration and smaller gas samples are used.     

Ba0.9La0.1Ce0.7Zr0.2Nd0.1O3-α陶瓷的化学稳定性和离子导电性

用高温固相反应法制备了Ba0.9La0.1Ce0.7Zr0.2Nd0.1O3-α陶瓷。粉末X-射线衍射(XRD)结果表明,该材料为单一钙钛矿型BaCeO3斜方晶结构,在高温下、CO2或水蒸气气氛中具有较高的稳定性。在500～900℃温度范围内,分别用交流阻抗谱技术和气体浓差电池方法研究了材料在不同气体气氛中的离子导电特性,并与Ba0.9Ca0.1Ce0.9Nd0.1O3-α材料的导电特性进行了比较。结果表明,在500～900℃温度范围内,干燥和湿润的氢气、氮气、空气和氧气气氛中,材料的电导率均随着温度升高和氧分压增加而增加,且材料在湿润气氛中的电导率稍高于相应的干燥气氛中的电导率(氢气气氛中则相反)。在湿润氢气中,材料的质子迁移数为1,是一个纯的质子导体;在干燥空气中,材料的氧离子迁移数为0.087～0.155,是一个氧离子与电子空穴的混合导体;在湿润空气中,材料的质子迁移数为0.001～0.004,氧离子迁移数为0.160～0.198,是一个质子、氧离子和电子空穴的混合导体。材料在干燥和湿润空气中的氧离子电导率均高于相同条件下Ba0.9Ca0.1Ce0.9Nd0.1O3-α材料的氧离子电导率。     

A study of the gas barrier properties of highly oriented polyethylene

Measurements of permeability and diffusivity have been undertaken for the gases helium and oxygen in a range of highly oriented polyethylene films. The solubilities deduced for both gases are proportional to the amorphous volume fraction, showing that the noncrystalline regions are the transport medium in all instances. The changes in diffusion coefficient are more complex. A large reduction in diffusion coefficient is observed with increasing draw ratio, and this is particularly marked in the case of the larger oxygen molecule, where significant differences are also observed for different grades of polymer and different drawing conditions. These changes in diffusion coefficient are discussed in the light of previous studies of diffusion in polymers and present knowledge of the changes in structure produced by drawing.     

Nanoscale surface chemistry over faceted substrates: structure, reactivity and nanotemplates

Faceting is a form of self-assembly at the nanometre-scale on adsorbate-covered single-crystal surfaces, occurring when an initially planar surface converts to a "hill and valley" structure, exposing new crystal faces of nanometre-scale dimensions. Planar metal surfaces that are rough on the atomic scale, such as bcc W(111), fcc Ir(210) and hcp Re(1231), are morphologically unstable when covered by monolayer films of oxygen, or by certain other gases or metals, becoming "nanotextured" when heated to temperatures above approximately 700 K. Faceting is driven by surface thermodynamics (anisotropy of surface free energy) but controlled by kinetics (diffusion, nucleation). Surfaces can spontaneously rearrange to minimize their total surface energy (by developing facets), even if this involves an increase in surface area. In this critical review, we discuss the structural and electronic properties of such surfaces, and first principles calculations are compared with experimental observations. The utility of faceted surfaces in studies of structure sensitive reactions (e.g., CO oxidation, ammonia decomposition) and as templates for growth of metallic nanostructures is explored (122 references).     

Determination of vanadium by reaction cell inductively coupled plasma mass spectrometry

Recent advances in inductively coupled plasma mass spectrometry (ICP-MS) have included the addition of interference reduction technologies, such as collision and reaction cells, to improve its detection capability for certain elements that suffer from polyatomic interferences. The principle behind reaction cell (RC)-ICP-MS is to remove a particular polyatomic interference by dissociation or formation of a different polyatomic species that no longer interferes with the analyte of interest. However, some interferences cannot be removed by commonly reported reaction gases, such as hydrogen, oxygen, or methane, necessitating using more reactive and hazardous gases, such as ammonia. The current study investigates oxygen as a reaction gas in RC-ICP-MS to specifically react with vanadium analyte ions, rather than the interferents, to produce a polyatomic analyte species and thereby provide a way to analyze for vanadium in complex environmental matrices. The technique has been tested on a series of river water, tap water, and synthetic laboratory samples, and shown to be successful in vanadium analyses in high chloride and sulfate matrices. The zinc isobaric interference on the new vanadium oxide analyte at m/z 67 is also investigated, and can be corrected by using a standard mathematical correction equation. The results of this study further increase the utility of RC-ICP-MS analytical techniques for complex environmental matrices.     

Turbulent flow technique for the estimation of oxygen diffusive permeability of membranes for the oxygenation of blood and other cell suspensions

When transport-efficient membrane modules (such as those where the liquid flows outside hollow fibre membranes) or membranes with prolonged resistance to wetting are used for the oxygenation of blood or other cell suspensions, membrane contribution to the overall oxygen transfer resistance into the liquid may become significant. Thus, estimation of membrane diffusive permeability towards relevant gases (e.g., oxygen) is important to develop new membranes and to ensure reproducible commercial membrane performance.

In this paper, we report on a turbulent flow technique for the estimation of the oxygen diffusive permeability of membranes used in outside-flow oxygenators. Water is re-circulated under turbulent flow conditions in a closed-loop from a reservoir to the shell of lab-scale membrane modules. The overall oxygen transfer to water coefficient is estimated at increasing water flow rates from the time the change of dissolved oxygen tension in the stream leaving the water reservoir occurs. Oxygen diffusive permeability is estimated as the reciprocal overall transfer resistance at infinitely high water flow rates, for negligible gas-side oxygen transport resistance. The technique was used to estimate oxygen diffusive permeability of commercial Oxyphan^® polypropylene membranes for blood oxygenation and of two laboratory polypropylene membranes, the one featuring a microporous wall structure with smaller-than-standard pore size, the other featuring an outer thin, dense layer supported by a thick spongy layer. The turbulent flow technique yields oxygen diffusive permeability estimates consistent both with membrane hydraulic permeability towards gaseous nitrogen, membrane wall structure, and with values in literature obtained using a liquid reactive with oxygen, but without the complications associated with reaction and physical transport kinetic characterisation. We conclude that the turbulent flow technique is a useful tool in the development and quality control of membranes for the oxygenation of blood and other cell suspensions.     

MECHANISM OF THE REACTION BETWEEN LUMINOL AND MOLECULAR OXYGEN

Abstract— The oxidation of luminol by molecular oxygen in dimethylsulfoxide was studied by following the intensity of emitted light. The results indicate that the reaction takes place through reversible formation of an oxygen-containing intermediate. The stability constant of this compound has been determined in IDMSO: ethanol (4:1) mixed solvent. The effects of different parameters were investigated and a quantitative relationship established between the intensity of emitted light and the concentrations of the reactants.
New methods for determining (oxygen concentrations in gases and for demonstrating cold light emission are suggested.     

Some features of the incorporation of oxygen in different oxidation states in the apatitic lattice—II On the synthesis and properties of calcium and strontium peroxiapatites

New apatites: peroxiapatites, containing in their lattices oxygen in an oxidation state — I, are found with calcium and strontium phosphate apatites. The oxygen (-I) containing groups are peroxide ions, which are associated with vacancies. Peroxiapatites are formed at high temperatures by a reaction involving O²⁻ of the oxyapatites and molecules of oxygen, provided the treatment atmosphere is sufficiently free of water. The peroxiapatite formation must be correlated with the very high reactivity of oxyapatites, which has been shown in the first part of this paper.When peroxiapatites are heated, in air, inert gases or vacuum, the peroxide ions disproportionate: molecular oxygen originating from this disproportionation reaction, is practically retained till 350°C by the lattice of strontium apatites, while it is released on formation from calcium apatites.