New polymer electrolyte membrane for medium-temperature fuel cell applications based on cross-linked polyimide Matrimid and hydrophobic protic ionic liquid

New hydrophobic protic ionic liquid, 2-butylaminoimidazolinium bis(trifluoromethylsulfonyl)imide (BAIM-TFSI), has been synthesized. The ionic liquid showed good thermal stability to at least 350 °C. The conductivity of BAIM-TFSI determined by electrochemical impedance method was found to be 5.6 × 10^?2 S/cm at 140 °C. Homogeneous composite films based on commercial polyimide (PI) Matrimid and BAIM-TFSI containing 30–60 wt% of ionic liquid were prepared by casting from methylene chloride solutions. Thermogravimetric analysis data indicated an excellent thermal stability of PI/BAIM-TFSI composites and thermal degradation points in the temperature range 377 °C–397 °C. The addition of ionic liquid up to 50 wt% in PI films does not lead to any significant deterioration of the tensile strength of the polymer. The dynamic mechanical analysis results indicated both an increase of storage modulus E′ of PI/BAIM-TFSI composites at room temperature and a significant E′ decrease with temperature compared with the neat polymer. The cross-linking of the PI with polyetheramine Jeffamine D-400 allowed to prepare PI/Jeffamine/BAIM-TFSI (50%) membrane with E′ value of 300 MPa at 130 °C. The ionic conductivity of this cross-linked composite membrane reached the level of 10^?2 S/cm at 130 °C, suggesting, therefore, its potential use in medium-temperature fuel cells operating in water-free conditions.     

Ideal and non-ideal behaviour of {1-butyl-1-methylpyrrolydinium bis(trifluoromethylsulfonyl)imide + γ-butyrolactone} binary mixtures

Density, electrical conductivity and viscosity of binary liquid mixtures of 1-butyl-1-methylpyrrolydinium bis(trifluoromethylsulfonyl)imide, [bmpyrr][NTf₂], with γ-butyrolactone (GBL) were measured at temperatures from (293.15 to 323.15) K and at atmospheric pressure over the whole composition range. Excess molar volumes have been calculated from the experimental densities and fitted with the Redlich–Kister polynomial equation. These values are positive over the whole range of ionic liquid mole fraction and at all temperatures. In the range between 0.55 and 0.6 [bmpyrr][NTf₂] mole fraction, an ideal behaviour of the ionic liquid mixture with molecular solvent was observed for the first time. Other volumetric properties, such as isobaric thermal expansion coefficients, partial molar volumes and partial molar volumes at infinite dilution have been also calculated, in order to obtain information about interactions between GBL and selected ionic liquid. Positive values of these properties for both components also indicate weaker interactions between GBL and IL compared to the pure components. From the viscosity results, the Angell strength parameter was calculated and found to be 3.24 indicating that [bmpyrr][NTf₂] is a “fragile” liquid. From the volumetric and transport properties obtained, formation of the [bmpyrr]⁺ micellar structures was also discussed. All the results are compared to those obtained for imidazolium-based ionic liquid with GBL.     

碳纤维自焊接骨架结构的形成及其复合材料性能研究

报道了一种将短切碳纤维(CF)自发焊接成三维网络结构的新方法.研究发现,尼龙6(PA6)与CF具有较强的相互作用,SEM照片及储能模量高温平台表明,添加少量PA6能够在PS基体中形成耐高温的CFPA6自焊接骨架结构,PA6用量越多,高温储能模量越高,自焊接骨架结构强度越大.研究证明,这种自焊接骨架结构能够大幅度提高PS/CF复合体系的热变形温度,碳纤维具有优异的导电导热性能,碳纤维骨架结构能够降低导电临界浓度,增强面内导热系数.进一步分析表明,PA6在碳纤维表面定向聚集是一个动力学过程,CF-PA6自焊接骨架强度与PA6黏附率NPA6呈线性关系;扩大PA6与PS的黏度差,延长热压时间均有利于提高NPA6,进而大幅提高网络结构强度.     

Cooperative Crystallization of Heterometallic Indium–Chromium Metal–Organic Polyhedra and Their Fast Proton Conductivity

Metal–organic polyhedra (MOPs) or frameworks (MOFs) based on Cr³⁺ are notoriously difficult to synthesize, especially as crystals large enough to be suitable for characterization of the structure or properties. It is now shown that the co‐existence of In³⁺ and Cr³⁺ induces a rapid crystal growth of large single crystals of heterometallic In‐Cr‐MOPs with the [M₈L₁₂] (M=In/Cr, L=dinegative 4,5‐imidazole‐dicarboxylate) cubane‐like structure. With a high concentration of protons from 12 carboxyl groups decorating every edge of the cube and an extensive H‐bonded network between cubes and surrounding H₂O molecules, the newly synthesized In‐Cr‐MOPs exhibit an exceptionally high proton conductivity (up to 5.8×10^?2 S cm^?1 at 22.5 °C and 98 % relative humidity, single crystal).     

Thermal Conductivity of Soils at Very Low Moisture Content and Moderate Temperatures

An analysis of soil thermal conductivity data shows that, at very low moisture content, this property first varies insignificantly and then begins to increase from a certain critical moisture content, whose value tends to depend on clay mass fraction. Two simple models evaluating the critical moisture content were developed; the first one is a fraction of the permanent wilting point; the second one is a simple linear function dependent on clay mass fraction. An insignificant variation of soil thermal conductivity is observed at 20°C, within a water pressure head ranging from 1×10³ to 1×10³m, while for higher temperatures (45–50°C) from 5000 to 100000m. Three extensions of the enhanced thermal conductivity model by Sundberg, namely SUN-1, SUN-2 and SUN-3, were proposed and tested. They produce an average root mean square error of 27%, 24% and 30%, respectively, with respect to experimental data. SUN-1and SUN-2 predictions could be further improved if better estimates of thermal conductivity at the dry state and the permanent wilting point were provided. SUN-3 is a simple model which does not require information about the PWP and critical moisture content. All SUN models have a potential for implementing the latent heat transfer component.     

Diffusion of moisture in deformable porous media. Anisotropic fibrous materials

This paper presents a study on the deformation of anisotropic fibrous porous media subjected to moistening by water in the liquid phase. The deformation of the medium is studied by applying the concept of effective stress. Given the structure of the medium, the displacement of the solid matrix is not taken into account with respect to the displacement of the liquid phase. The transport equations are derived from the model proposed by Narasimhan. The transport coefficients and the relation between the variation in apparent density and effective stress are obtained by test measurements. A numerical model has been established and applied for studying drip moistening of mineral wool samples capable or incapable of deformation.Nomenclature D mass diffusion coefficient [L²t^–1] - e void fraction - g gravity acceleration [Lt^–2] - J mass transfer density [ML^–2t^–1] - K hydraulic conductivity [Lt^–1] - K _s hydraulic conductivity of the solid phase [Lt^–1] - K ^* hydraulic conductivity of the deformable porous medium [Lt^–1] - P pressure of moistening liquid [ML^–1 t^–2] - S degree of saturation - t time [t] - V speed [Lt^–1] - X horizontal coordinate [L] - Z vertical coordinate measured from the bottom of porous medium [L] - z z-coordinate [L] Greek Letters porosity - ₁ total hydric potential [L] - _g gas density [ML^–3] - ₁ liquid density [ML^–3] - ₀ apparent density [ML^–3] - _s density of the solid phase [ML^–3] - density of the moist porous medium [ML^–3] - external load [ML^–1t^–2] - effective stress [ML^–1t^–2] - bishop's parameter - matrix potential or capillary suction [L] Indices g gas - 1 moistening liquid - p direction perpendicular to fiber planes - s solid matrix - t direction parallel to fiber planes - v pore Exponent * movement of solid particles taken into account     

A Solute Transport in Stratified Media

Two-dimensional and steady solute transport in a stratified porous formation is analysed under assumption that the effect of pore-scale dispersion is negligible. The longitudinal dispersion produced as a result of the vertical variation of hydraulic conductivity is analysed by averaging the variability of a solute flux concentration and conductivity. The evolution of the solute flux concentration is expressed with respect to the correlated variable, that is the travel (arrival) time at a fixed location and the averaging procedure is constructed to satisfy the boundary condition where the inlet concentration is a known function of time. In such a statement, a velocity-averaged solute flux concentration is described by a conventional dispersion model (CDM) with a dispersion coefficient which is a function of the arrival time. It is demonstrated that such CDM satisfies the assumption that hydraulic conductivity of the layers is gamma distributed with the parameter of distribution which is chosen to represent a reasonable value of the field scale solute dispersion. The overall behaviour of the model is illustrated by several examples of two-dimensional mass transport.     

A Lattice Boltzmann model with high Reynolds number in the presence of external forces to describe microfluidics

We present here a lattice Boltzmann model with high Reynolds number in the presence of external force fields to describe electrokinetic phenomena in microfluidics, by considering pressure as the only external force for liquid flow. Our results from a 9-bit square lattice Boltzmann model are in excellent agreement with experimental data in pressure-driven microchannel flow that could not be fully described by electrokinetic theory. The difference between the predicted and experimental Reynolds numbers from pressure gradients are well within 5%. Our results suggest that the lattice Boltzmann model described here is an effective computational tool to predict the more complex microfluidic systems that might be problematic using conventional methods.     

A Two-Equation Model for Heat Conduction in Porous Media (II: Application)

The formulism of a two-equation model for heat conduction in porous media, developed in a previous paper, is applied to the case of steady state one-dimensional heat transfer in a porous medium that is made up of geometrically similar units of similar size and of ordered spatial distribution. For this case study, the model-predicted locally volume-averaged temperature distributions for the solid and the fluid phase are compared to a numerical solution at a microscopic level, showing excellent agreement.     

Steady-State Source Flow in Heterogeneous Porous Media

The flow of fluids in heterogeneous porous media is modelled by regarding the hydraulic conductivity as a stationary random space function. The flow variables, the pressure head and velocity field are random functions as well and we are interested primarily in calculating their mean values. The latter had been intensively studied in the past for flows uniform in the average. It has been shown that the average Darcy's law, which relates the mean pressure head gradient to the mean velocity, is given by a local linear relationship. As a result, the mean head and velocity satisfy the local flow equations in a fictitious homogeneous medium of effective conductivity. However, recent analysis has shown that for nonuniform flows the effective Darcy's law is determined by a nonlocal relationship of a convolution type. Hence, the average flow equations for the mean head are expressed as a linear integro-differential operator. Due to the linearity of the problem, it is useful to derive the mean head distribution for a flow by a source of unit discharge. This distribution represents a fundamental solution of the average flow equations and is called the mean Green function G _d (x). The mean head G _d(x) is derived here at first order in the logconductivity variance for an arbitrary correlation function (x) and for any dimensionality d of the flow. It is obtained as a product of the solution G _d ⁽⁰⁾(x) for source flow in unbounded domain of the mean conductivity K _A and the correction _d (x) which depends on the medium heterogeneous structure. The correction _d is evaluated for a few cases of interest.Simple one-quadrature expressions of _d are derived for isotropic two- and three-dimensional media. The quadratures can be calculated analytically after specifying (x) and closed form expressions are derived for exponential and Gaussian correlations. The flow toward a source in a three-dimensional heterogeneous medium of axisymmetric anisotropy is studied in detail by deriving ₃ as function of the distance from the source x and of the azimuthal angle . Its dependence on x, on the particular (x) and on the anisotropy ratio is illustrated in the plane of isotropy (=0) and along the anisotropy axis ( = /2).The head factor k ^* is defined as a ratio of the head in the homogeneous medium to the mean head, k ^*=G _d ⁽⁰⁾/G _d= _d ^–1. It is shown that for isotropic conductivity and for any dimensionality of the flow the medium behaves as a one-dimensional and as an effective one close and far from the source, respectively, that is, lim _x0 k ^*(x) = K _H/K _A and lim _x k ^*(x) = K ^efu/K _A, where K _A and K _H are the arithmetic and harmonic conductivity means and K ^efu is the effective conductivity for uniform flow. For axisymmetric heterogeneity the far-distance limit depends on the direction. Thus, in the coordinate system of (x) principal directions the limit values of k ^* are obtained as . These values differ from the corresponding components of the effective conductivities tensor for uniform flow for = 0 and /2, respectively. The results of the study are applied to solving the problem of the dipole well flow. The dependence of the mean head drop between the injection and production chambers on the anisotropy of the conductivity and the distance between the chambers is analyzed.