Characterisation of wettability in gas diffusion layer in proton exchange membrane fuel cells

This paper presents a detailed study of the wetting properties of three fuel cell gas diffusion layers (GDLs) having different morphologies and different contents of hydrophobic agent. An internal contact angle to water at temperature representative of PEM fuel cell operating conditions was directly obtained using the Washburn method with 66 ° C water as test liquid. These results show that the surface of the carbon fibres is hydrophilic under fuel cell operating conditions. Surface energy values of the GDL fibres, determined by a combination of the Washburn method and the Owens-Wendt two parameters theory, were found to be low, indicating that GDLs are wet very poorly by most liquids. About 40% of the total surface free energy values was related to a polar component allowing dipole-dipole and hydrogen bonding interactions with water. The origin of this polar character is discussed.     

The beneficial influence of ultrasound in the polymerization of epsilon-caprolactam to polyamide-6 (Nylon 6). Part I: primary experimental results

ε-caprolactam (CL) polymerization to polyamide-6 (Nylon 6) was studied at different contents of water in CL (0.01–2 wt%), with or without ε-amino-caproic acid (ACA) as an activator, applying to the mixture an initial treatment of Ultrasound (US) (17.5–20 kHz) at low temperatures (70–110 °C) and for short times (max 10 min). It was verified that polymerization at 260 °C produces a polymer having a much higher molecular weight (MW) when US is applied with respect to silent (SIL) conditions i.e. without the use of ultrasound. This constitutes a “pre-sonication effect”. The ratio (MW)_US/(MW)_SIL is inversely proportional to the initial content of water in CL. The action of US converts CL at very low temperatures (70–110 °C) and water content, in comparison with silent conditions where CL was unconverted.

Optimized conditions are studied with respect to nature and pressure of gas inside the reactor, temperature, time and frequency of US irradiation, energy consumption and nature of activator.     

Water and other tetrahedral liquids: order, anomalies and solvation

In order to understand the common features of tetrahedral liquids with water-like anomalies, the relationship between local order and anomalies has been studied using molecular dynamics simulations for three categories of such liquids: (a)?atomistic rigid-body models for water (TIP4P, TIP4P/2005, mTIP3P, SPC/E), (b)?ionic melts, BeF(2) (TRIM model) and SiO(2) (BKS potential) and (c)?Stillinger-Weber liquids parametrized to model water (mW) and silicon. Rigid-body, atomistic models for water and the Stillinger-Weber liquids show a strong correlation between tetrahedral and pair correlation order and the temperature for the onset of the density anomaly is close to the melting temperature. In contrast, the ionic melts show weaker and more variable degrees of correlation between tetrahedral and pair correlation metrics, and the onset temperature for the density anomaly is more than twice the melting temperature. In the case of water, the relationship between water-like anomalies and solvation is studied by examining the hydration of spherical solutes (Na(+), Cl(-), Ar) in water models with different temperature regimes of anomalies (SPC/E, TIP4P and mTIP3P). For both ionic and nonpolar solutes, the local structure and energy of water molecules is essentially the same as in bulk water beyond the second-neighbour shell. The local order and binding energy of water molecules are not perturbed by the presence of a hydrophobic solute. In the case of ionic solutes, the perturbation is largely localized within the first hydration shell. The binding energies for the ions are strongly dependent on the water models and clearly indicate that the geometry of the partial charge distributions, and the associated multipole moments, play an important role. However the anomalous behaviour of the water network has been found to be unimportant for polar solvation.     

Ultrasound and microwave assisted synthesis of high loading Fe-supported Fischer–Tropsch catalysts

Supported iron-based Fischer–Tropsch (FT) catalysts with high loading of active metal have been prepared using both traditional and innovative methods. In these latter the impregnation of silica support has been performed by adding a step involving an ultrasound (US) or a microwave (MW) treatment to improve the metal deposition and to increase the catalyst activity. FT results have indicated the catalysts prepared by US as the most efficient, particularly when sonication is performed in argon atmosphere. MW prepared samples have given results very similar to those obtained with the traditional method. In order to explain the different catalytic activity, all the samples have been characterized by BET, TPR, SEM, TEM, XRD and micro-Raman analyses.     

Method of bimodal photoacoustic and ultrasound microscopy for simultaneous structural and functional diagnostics of biotissues

The excitation of external electrode of focused photoacoustic (PA) detector by the backscattered laser radiation can ensure a cost-effective upgrade from single-modality PA microscopy to dual-modality PA/US imaging. In this work we approbated thermoelastic generation of probing ultrasonic pulses for bimodal photoacoustic (PA) and optically mediated Ultrasound (US) microscopy in vivo, using single optical pulse delivered from tunable laser to form both PA and US A-scans. The presented results of bimodal in vivo visualization of rat brain provide with the experimental evidence, that the proposed approach can be used for both functional and structural bioimaging simultaneously.     

液体-液体相变与反常特性

绝大多数物质的液态密度随温度降低而增大,即常见的热胀冷缩现象.但存在一类物质,如水及第四主族的硅、锗等,其液态密度在一定温度范围内随温度的升高而增大,即密度反常现象.此外,该类物质还存在动力学反常(密度越大粒子运动越快)、热力学反常(热力学量的涨落随温度降低而升高)等其他反常特性.这类材料的化学性质千差万别,但却具有相似的物理反常特性.进一步的理论研究发现部分材料具有两种液态,即高密度液态和低密度液态,两者之间存在一级相变.因此,反常特性与液体-液体相变是否有直接关联是一个值得深入研究的课题.本文主要介绍了具有液体-液体相变的一类材料及其反常特性,包括高温高压下氢的液体-液体相变及其超临界现象,镓的反常特性及其与液体-液体相变的关联等.     

Solvent Polarity and Excitation Wavelength Dependence of the Dual Fluorescence in N,N-Diethyl-4-Nitrosoaniline

Dual fluorescence in N,N-Diethyl-4-nitrosoaniline (DENA) has been studied employing absorption, excitation and emission spectroscopic techniques and computational methods. The absorption and fluorescence spectra of DENA were measured in solvents of various polarities at room temperature. The emission spectra of DENA were found to exhibit a single emission band in non polar solvent (cyclohexane) and in a highly polar solvent (acetonitrile). In the contrary, two emission bands were observed in medium polar solvents (tetrahydrofuran, 1,2-dichloroethane and dichloromethane) whereby the short (local excited; LE) and long (charge transfer; CT) emission maxima correspond to the emission maxima of the compound observed in cyclohexane and acetonitrile solutions, respectively. Moreover, the two emission bands have shown strong excitation wavelength dependence, and area normalization resulted in an iso-emissive point. The two emission maxima were in addition found to correspond to two excitation maxima in 3D fluorescence spectra. Further, two minima were obtained in potential energy surface calculation of DENA. From the experimental and computational results it was concluded that the dual fluorescence may be attributed to the presence of two different ground state structural conformers of DENA in equilibrium that are stabilized through solute-solvent interaction.     

Ultrasound and microwave assisted synthesis of dihydroxyacetophenone derivatives with or without 1,2-diazine skeleton

A thorough study concerning O-alkylation and α-bromination of dihydroxyacetophenone (DA) and N-alkylation of 1,2-diazine, under ultrasound (US) and microwave (MW) irradiation as well as under conventional thermal heating (TH) is presented. Under US and MW irradiation the yields are higher, the amount of used solvent decreases substantially, the reaction time decreases considerable (from hours or days to minutes) and the consumed energy decreases, consequently the O-alkylation, α-bromination and N-alkylation methods could be considered environmentally friendly. A selective and efficient way to either bis-O-alkylation or mono-O-alkylation of DA has been found, the relative position of the two hydroxyl groups on the phenyl moiety being compulsory. A selective and efficient way for α-bromination in heterogeneous catalysis of DA derivatives under US irradiation is presented. The N-alkylation reaction of DA under US and MW irradiation proved to be the most convenient setup procedure for these types of reactions. Overall, the use of US proved to be more efficient than MW or TH.     

Monitoring hydrate formation and dissociation in sandstone and bulk with magnetic resonance imaging

Magnetic resonance imaging (MRI) has been shown to be a very effective tool for monitoring the formation and dissociation of hydrates because of the large intensity contrast between the images of the liquid components and the solid hydrate. Tetrahydrofuran/water hydrate was used because the two liquid components are miscible and form hydrate at ambient pressure. These properties made this feasibility study proceed much faster than using methane/water, which requires high pressure to form the hydrate. The formation and dissociation was monitored first in a THF/water-saturated Berea sandstone plug and second in the bulk. In both cases it appeared that nucleation was needed to begin the formation process, i.e., the presence of surfaces in the sandstone and shaking of the bulk solution. Dissociation appeared to be dominated by the rate of thermal energy transfer. The dissociation temperature of hydrate formed in the sandstone plug was not significantly different from the dissociation temperature in bulk.     

Spatial, Spectral, and Temporal Characteristics of Stimulated Light Scattering in Water

Spatial, temporal, and spectral characteristics of stimulated light scattering (SS) in water were investigated in both nano- and picosecond ranges under different experimental conditions and compared with the analogous characteristics of stimulated light scattering in other liquids. Stimulated Raman scattering (SRS) and stimulated Brillouin scattering (SBS) of light were studied. The results obtained provide useful information on the structure of water, its purity, and additions, which can result in its pollution. The excitation conditions of stimulated light scattering (SS) in one spatial mode and with maximum pulse energy conversion were determined. It is shown that stimulated light scattering can be successfully applied to control water quality (and it can be done very fast) as well as for information processing, i.e., the amplitude–phase structure of complex light fields can be registered in water as a dynamic hologram and reconstructed in real time.     

Two simultaneous mechanisms causing glass transition temperature reductions in high molecular weight freestanding polymer films as measured by transmission ellipsometry

We study the glass transition in confined polymer films and present the first experimental evidence indicating that two separate mechanisms can act simultaneously on the film to propagate enhanced mobility from the free surface into the material. Using transmission ellipsometry, we have measured the thermal expansion of ultrathin, high molecular-weight (MW), freestanding polystyrene films over an extended temperature range. For two different MWs, we observed two distinct reduced glass transition temperatures (T(g)'s), separated by up to 60 K, within single films with thicknesses h less than 70 nm. The lower transition follows the expected MW dependent, linear T(g)(h) behavior previously seen in high MW freestanding films. We also observe a much stronger upper transition with no MW dependence that exhibits the same T(g)(h) dependence as supported and low MW freestanding polymer films.     

The radio frequency conductivity of some aliphatic alcohols at different temperatures

Activation energies for viscous flow and conductivity are computed from experimental values of RF conductivity (frequency 400 kHz) at different temperatures for eight polar liquids. It is observed that for aliphatic alcohols the activation energy for conductivity is greater than that for viscous flow. However, their ratio is slightly greater than unity and is different for different alcohols whereas for nonassociating polar liquids the ratio is almost equal to unity. The dependence of conductivity on viscosity for the liquid alcohols does not follow the Walden’s law but can be well represented by Adamczewskis relation.     

A FT-IR spectroscopic study of ultrasound effect on aqueous imidazole based ionic liquids having different counter ions

Ultrasound (US) effect on 1-butyl-3-methyl-imidazolium (BMI) ionic liquids having different counter anions, BF₄⁻, PF₆⁻ and Cl⁻ in aqueous medium was studied by FT-IR spectroscopy. Their deconvolution spectra were used to analyze the change of hydrogen bond in the absence and presence of US exposure to the ionic liquid. The FT-IR spectra were measured in different water contents without and with US at 23 kHz. These results indicated that the counter anion species in the imidazole based the ionic liquids played an important role for water solvation, when the US was exposed. The US hardly changed hydrogen bonding in the aqueous BMI–PF₆, while the BMI–BF₄ and BMI–Cl showed obvious change in their FT-IR spectra. Especially for the BMI–Cl, significant change was observed by the US exposure in the range of 2.6 wt% to 20 wt% of water contents. The results showed that the US could break the hydrogen bond in the BMI–Cl ionic liquids. In the case of BMI–BF₄, the FT-IR band at 950–1152 cm⁻¹ was significantly intensified under US exposure, due to that the US influenced BF₄⁻-water interaction. But, it was observed that the ionic liquid having PF₆⁻ was very less changed in the US system.     

Effect of different microwave-based treatments on multi-walled carbon nanotubes

Three new methods for the functionalization of multi-walled carbon nanotubes (MWCNTs) are reported using microwave (MW) energy and water as a mild chemical agent. In the first method we reported the effect of MW irradiation on a dispersion of MWCNTs in deionized water, in the second method we studied the exposing of MWCNT to microwave irradiation in the presence of steam, and in the third method we used microwave oven-generated plasma for the functionalization of MWCNTs. We also performed thermal oxidation and acid treatment as two conventional methods for oxidative functionalization of carbon nanotubes, to compare their effect with our results. Transmission electron microscopy (TEM) and Raman spectroscopy results showed that although these microwave methods introduced some defects to the carbon nanotubes, the damage was less severe than conventional treatments. X-ray photoelectron spectroscopy (XPS) measurements confirmed that the functionalization of carbon nanotubes by these methods favored hydroxyl groups, which are useful when further functionalization is required.     

离子液体Ammoeng 100与水之间相互作用的红外光谱分析

本文研究测量了Ammoeng 100与其水溶液在不同压力环境下的红外光谱,以期了解该离子液体与水之间的相互作用.结果表明,Ammoeng 100与水之间的相互作用主要来自离子液体的阴离子与水分子,且两者会根据能量稳定性而有选择性的接近;相对于阴离子,Ammoeng 100的烷基链受D_2O的扰动不大.与纯Ammoeng 100相比,在Ammoeng 100/D_2O的红外光谱中显示烷基C-H伸缩振动频率并没有太大变化,而压力小于1.0 GPa时D_2O会造成在Ammoeng 100的S=O对称伸缩振动频率红移.压力大于1.0GPa时,纯Ammoeng 100与Ammoeng 100/D_2O中的S=O对称伸缩振动频率大同小异,表明高压环境下D_2O不会对阴离子的对称伸缩振动频率造成明显影响,同时也显示离子液体在极性区的缔合结构会受到高压的扰动而有显著变化.     

A new reactor for process intensification involving the simultaneous application of adjustable ultrasound and microwave radiation

Ultrasound (US) and Microwaves (MW) are effective methods for processes intensification. Their combined use in the same reactor can lead to remarkable results. Recently there has been a resurgence of interest in this field for new synthetic applications using reactors based upon existing technologies. We describe here a new type of apparatus in which the thermal energy is continuously removed from the system making possible the use of high power and adjustable ultrasonic and microwave densities throughout the process. The installation consists of a glass reactor located in a monomode applicator which is immersed at the same time in an ultrasonic device which can be operated at different frequencies and powers. A liquid, transparent to microwaves, was used to couple ultrasonic energy to the reactor and to remove the heat generated. Comsol software was used to get information about the distribution of ultrasonic and microwave energy between the reactor liquid and the coupling fluid. The performance was assessed using the conversion of p-nitrophenol into 4-nitrocatechol as a chemical dosimeter and a transesterification.     

Detection of short-lived muonium in liquids via spin trapping

The radiolytical fate of energetic positive muons injected in liquids is investigated using transverse field μSR. Transient, near thermal muonium is detected by means of spin trapping with 2,3-dimethylbutadiene in cyclohexane, tetramethylsilane, acetonitrile, dimethylsulfoxide, dimethylformamide and chloroform, but not in dimethylthioformamide, carbontetrachloride and carbondisulfide. Two muonated free radicals are assigned to Mu adducts to C=S double bonds.     

Water dynamics in glass ionomer cements

Glass ionomer cements (GIC) are an alternative for preventive dentistry. However, these dental cements are complex systems where important motions related to the different states of the hydrogen atoms evolve in a confined porous structure. In this paper, we studied the water dynamics of two different liquids used to prepare either conventional or resin-modified glass ionomer cement. By combining thermal analysis with neutron scattering data we were able to relate the water structure in the liquids to the materials properties.     

Phase Diagrams Semicrystalline Polymer–Liquid Revisited: Isotactic Polypropylene-Dibutyl Phthalate and Other Systems

The full phase diagram of an isotactic polypropylene (i-PP)–dibutyl phthalate (DBP) mixture is for the first time constructed by an optical method and discussed within the concept of semicrystalline polymers as microheterogeneous liquids with a three-dimensional network structure. It is demonstrated that the liquidus in this and other polymer–solvent systems is not thermodynamically equivalent to the liquidus in low molecular weight (MW) mixtures. Qualitatively different thermal behavior of those two types of binary systems in the liquidus vicinity is corroborated by differential scanning calorimetry (DSC) experiments. In the former case, a liquid-solid transition resulting in the formation of polymer crystallites does not lead to separating the mixture into crystalline and amorphous phases. On cooling, the system remains macroscopically single phase until the low MW liquid can be fully dissolved in the amorphous regions of the polymer. The correct location of the corresponding borderline is crucially important for the microporous membrane formation via thermally induced phase separation (TIPS). It is also argued that the topology of a phase diagram polymer–low MW liquid does not depend on whether the polymer is amorphous or crystalline.     

Structure and oil repellency: Textiles with liquid repellency to hexane

Combining structure and liquid repellent coatings to optimise non-wettability is a well-established field. However, the area in recent years has been dominated by data on water repellency. The work here provides data on how certain plant structures can be used to develop surfaces that provide repellency towards both polar and non-polar, low surface tension fluids. Combining fluoropolymer coatings with ‘hairy’ fibres is particularly beneficial for providing liquid-repellent textiles. None of these surfaces can however be regarded as super-repellent to low surface tension liquids (i.e. with little difference in advancing and receding contact angles).