Unified determination of relative molecular diffusivity and fluid permeability for partially saturated cement-based materials

From conductivity theory, general models for relative molecular diffusivity and fluid permeability are first derived with unknown tortuosity function and modification coefficient, which can be respectively deduced from hydraulic diffusivity and water retention curve (WRC). Based on empirical laws for hydraulic diffusivity and WRC of cement-based material, unified models for relative molecular diffusivity and fluid permeability are further formulated with only two measurable parameters. Because of practical difficulty for measuring water permeability and pure gaseous molecular diffusivity, only relative gas permeability and relative chloride diffusivity models are verified by the reported data. It is found that the predicted relative gas permeability agrees with measured values and exponential law is a little more preferable than power law for quantifying hydraulic diffusivity. Moreover, relative chloride diffusivity from the unified model also agrees well with experimental data derived via Nernst–Einstein Equation. However, the unified model doesn't capture the possibly overestimated relative chloride diffusivity from Fick's law.     

General solution of hydraulic diffusivity from sorptivity test

A general approach to solving hydraulic diffusivity from sorptivity test is established and verified in this paper. The diffusion equation governing capillary water absorption is first converted into normalized ordinary differential and integral forms via Boltzmann transformation, which are then directly solved by the method of weighted residuals. By this method, the approximate solution of Boltzmann variable is determined for any distribution law of diffusivity. The relationship between sorptivity and diffusivity is further analytically established. It's found that initial diffusivity is proportional to square of the ratio of sorptivity to the water content difference between saturated and initial states. Ignoring the water vapor diffusion leads to the underestimation of derived water content profile and diffusivity. The Boltzmann variable and diffusivity calculated by the proposed method are verified by experimental data. Finally, the relationship between coefficients of general solution for diffusion equation and shape parameter for exponential diffusivity is also derived.     

Fundamental salt and water transport properties in directly copolymerized disulfonated poly(arylene ether sulfone) random copolymers

Water and sodium chloride solubility, diffusivity and permeability in disulfonated poly(arylene ether sulfone) (BPS) copolymers were measured for both acid and salt form samples at sulfonation levels from 20 to 40 mol percent. The hydrophilicity of these materials, based on water uptake, increased significantly as sulfonation level increased. The water permeability of BPS materials in both the salt and acid forms increases more than one order of magnitude as sulfonation level increases from 20% to 40%, while NaCl permeability increases by two orders of magnitude. The water and salt diffusivity and permeability were correlated with water uptake, consistent with expectations from free volume theory. In addition, a tradeoff was observed between water/salt solubility, diffusivity, and permeability selectivity and water solubility, diffusivity and permeability, respectively. This finding suggests a water/salt permeability/selectivity tradeoff, similar to that operative in gas separation polymers, in this family of polymers.     

The permeability of Portland limestone cement concrete

The effect of limestone addition on the air permeability, water permeability, sorptivity, and porosity of limestone cement concrete has been investigated. Six Portland limestone cements (PLCs) with different limestone content (10-35% w/w) were produced by intergrinding clinker, gypsum, and limestone. A water-to-cement ratio (w/c) of 0.70-0.62—depending on the cement strength class—was used to prepare concrete of the compressive strength class C20/25 of EN 206-1. A modified commercial triaxial cell for 100-mm-diameter samples was used for the determination of the gas (N₂) and the water permeability of concretes. In addition, the sorptivity and porosity of the samples were measured, while thin sections of the concrete specimens were examined by means of optical microscopy. It is concluded that the PLC concrete indicates competitive properties with the ordinary Portland cement (OPC) concrete. Furthermore, the limestone addition has a positive effect on the water permeability and the sorptivity of concrete.     

Hydrophobic concrete using waste paper sludge ash

The feasibility of using a low-cost super hydrophobic powder as water-resisting admixture or water-repellent surface coating for concrete has been investigated. The powder was produced from paper sludge ash (PSA), a by-product from the manufacture of recycled paper. The effect of hydrophobic PSA on workability, strength and transport properties, including sorptivity, water absorption, diffusivity, permeability and electrical conductivity is reported. Samples were prepared at water/cement ratio of 0.38, cured up to 28 days and conditioned at 50 °C to constant mass prior to testing. It was found that replacing Portland cement with 12% hydrophobic PSA reduced water absorption, sorptivity and conductivity by 84%, 86% and 85% respectively, with no major detrimental effects on hydration, strength and density. When used as a surface coating, the hydrophobic PSA reduced both absorption and sorptivity by 85–99% depending on the adhesive used. Samples surface coated with hydrophobic PSA showed excellent water repelling and self-cleaning characteristics.     

PEMFC带沟槽气体扩散层内传输特性孔隙网络模拟

采用三维孔隙网络模型计算了不同沟槽参数下气体扩散层(GDL)的液态水突破压力、毛细压力分布、气体扩散率和液相相对渗透率随饱和度变化,并从孔隙尺度角度探究了沟槽的作用机制。研究结果表明:沟槽改变了GDL的毛细压力分布,提供了液态水直接传输路径并优化了GDL内氧气和液态水的分布,从而提高了氧气有效扩散率。沟槽位置对氧气传输有明显影响,对液相传输的影响取决于是否形成贯穿GDL的传输路径;沟槽加深,氧气和液态水传输性能增强,沟槽穿透GDL时传输性能达到最佳;沟槽变宽,液相传输性能增强,氧气传输性能在低饱和度范围内先增强后减弱。综合各因素,给出了氧气和液态水传输性能最优时的沟槽参数。     

The influence of moisture content on the polymer structure of polyvinyl alcohol in dispersion barrier coatings and its effect on the mass transport of oxygen

This paper presents a study of the effect of moisture on the gas permeability of polyvinyl alcohol (PVOH) and PVOH–kaolin dispersion barrier coatings. The oxygen permeability was measured at different humidity levels, and the material properties were characterized under the same conditions: polymer crystallinity, kaolin concentration, and kaolin orientation were all evaluated. The experimental results revealed that the water plasticizes the PVOH material of the coatings, and the presence of kaolin filler is unable to affect such behavior significantly. The PVOH crystallinity was affected drastically by the humidity, as water melts polymer crystallites, which is a reversible process under removal of water. The permeability data were analyzed using a thermodynamic-based model able to account for the water effect on both the solubility of the gas and the diffusivity coefficients in the polymer and composite. The results showed good agreement between the model’s predictions and the experimental data in terms of the overall permeability of the material.     

Hydraulic behavior of synthetic non-woven filter fabrics

The filtration performance of non-woven thick synthetic membranes used as filter fabrics is predicted from a proposed analytical method. The morphological analysis of many commercial fabrics has been utilized to identify internal structure parameters responsible for their hydraulic properties and also to predict the water permeability and the retention of particles in these fabrics. Experimental filtration tests were performed to gather data on the water permeability used in predicting clogging level. Also fibres' density and pore size histograms of fabrics were measured with an Image Analyser and a relationship was developed between the water permeability and the fibres' density. Finally it was found that the pore size histogram of non-woven fabrics of thickness greater than 1.5 mm could be calculated simply by measuring its water permeability and using an empirical correlation.     

Permeation properties of self-compacting concrete

Permeation properties, which include permeability, absorption, diffusivity etc., have been widely used to quantify durability characteristics of concrete. This paper presents an experimental study on permeation properties of a range of different self-compacting concrete (SCC) mixes in comparison with those of selected traditional vibrated reference (REF) concretes of the same strength grade. The SCC mixes with characteristic cube strength of 40 and 60 MPa were designed containing either additional powder as filler or containing no filler but using a viscosity agent. The results indicated that the SCC mixes had significantly lower oxygen permeability and sorptivity than the vibrated normal reference concretes of the same strength grades. The chloride diffusivity, however, appeared to be much dependent on the type of filler used; the SCC mixes containing no additional powder but using a viscosity agent were found to have considerably higher diffusivity than the reference mixes and the other SCCs.     

Effect of water on permeation,diffusion, and solution of gases in cellophane

The laminate method for studying the permeability and diffusivity of moistened cellophane to gases is described and the humidity dependence of the transport parameters for H₂, He, and Ne is presented. In the relative humidity region of about 0% to 60%, a small increase in the permeability was observed, which is caused by a comparatively small increase in the diffusivity owing to the plasticizing effect of sorbed water and a decrease in the solubility. On the other hand, an extremely large increase in the permeability observed in the relative humidity region above 60% is mainly based on the diffusion coefficient of gas enhanced by the swelling effect of sorbed water. The presence of a minimum in the solubility–relative humidity curves has been confirmed and is discussed.     

Gas barrier properties of butyl rubber/vermiculite nanocomposite coatings

Gas barrier properties of butyl rubber/vermiculite nanocomposites coatings are described here. The coating formulations consisting of a butyl rubber latex (the rubber particles are about 1 μm in diameter) to which exfoliated vermiculite was added were applied to a poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) coated Anapore ceramic disc; composites containing 0, 20 and 30 wt% of vermiculite were evaluated. The permeability of the nanocomposite coatings to various gases was measured and compared to permeation models for composites with flake-like fillers proposed by Cussler, Nielsen, Fredrickson and Bicerano, and Gusev and Lusti. The gas permeability of the nanocomposite materials was decreased remarkably by the presence of the high loadings of vermiculite. Diffusion coefficients computed from time lag data also decreased remarkably with the vermiculite content. TEM and SEM were used to observe the internal structure of the nanocomposite membranes in an effort to gain further understanding of the permeability properties. Aspect ratios ranging from 100 to 480 were predicted from the gas permeation results and the above models. TEM experiments could not provide a precise estimate of the aspect ratio but the range predicted from the models are of this order. Apparent solubility coefficients, computed by dividing the experimental permeability by the diffusivity obtained from the time lag observation, increased significantly with vermiculite content in contradiction to the theoretical prediction. Independent gas sorption isotherm experiments for CO₂ were measured and found to be larger than that in butyl rubber possibly due to adsorption on the vermiculite. While this turned out to be a very complicated system, it seems clear from these results that the transient tortuosity factor defined by the time lag is significantly larger than the steady-state tortuosity factor defined by permeability.     

Three-dimensional CFD modelling of PEM fuel cells: An investigation into the effects of water flooding

In this work, a three-dimensional PEM fuel cell model has been developed and is used to investigate the effects of water flooding on cell performance parameters. The presence of liquid water in the cathode gas diffusion layer (GDL) limits the flow of reactants to the cathode catalyst layer, thereby reducing the overall reaction rate and curtailing the maximum power that can be derived from the cell. To characterize the effects of water flooding on gas diffusion, effective diffusivity models that account for the tortuosity and relative water saturation of the porous fuel cell electrodes have been derived from percolation theory and coupled with the CFD model within a single phase flow skeleton. The governing equations of the overall three-dimensional PEM fuel cell model, which are a representative of the coupled CFD and percolation theory based effective diffusivity models, are then solved using the finite volume method. Parametric studies have been conducted to characterize the effects of GDL permeability, inlet humidity and diffusivity of the reactants on the various cell performance parameters such as concentration of reactants/products and cell current densities. It is determined that the GDL permeability has little or no effect on the current densities due to the diffusion dominated nature of the gas flow. However, through the incorporation of percolation theory based effective diffusivity model; a marked reduction in the cell performance is observed which closely resembles published experimental observations. This is a reasonable approximation for effects of water flooding which has been inherently used for further parametric studies.     

Prediction of the hydraulic diffusivity from pore size distribution of concrete

A model is presented in this work through which variation of hydraulic diffusivity of concrete with relative water content can be obtained from pore size distribution as an input. The specific water capacity and hydraulic conductivity of concrete are expressed in terms of pore size characteristics, considering laminar flow due to capillary suction through tortuous elliptic tubes, oriented equally in three orthogonal directions. Hydraulic diffusivity being the ratio of hydraulic conductivity and specific water capacity is thus expressed in terms of pore size characteristics. The input pore size distributions have been determined experimentally for normal strength concrete mixes through mercury intrusion porosimetry. Using the model the variation of hydraulic diffusivity with relative water content is determined for three cases viz. 1) ideal continuous wetting, 2) ideal continuous drying and 3) random access of pores by water. These results are then compared with an experimentally obtained variation.     

Diffusivity of water in groundnut oil and paraffi oil

The difliisivity of water in parafin oil and grortndnrit oil has been measured at 24°c using a simple difusion cell. The measured diffusivity of water in parafin oil conipares well with previous determinations. The diffusivity of water in graundnut oil at 24°c and those predicted at higher temperatures are the only experimentally based data available at present. The measurment extend the data present range of knowledge to higher molecular weight and higher viscosity solvents aid reinforce the demanand of previous investigation for more experimental data outside the range of present correlations.     

Estimating transport properties of mortars using image analysis on backscattered electron images

The pore structure of two ordinary Portland cement mortars at water-cement ratio of 0.35 and 0.70 was characterised using quantitative backscattered electron imaging. The mortars were cured and conditioned to produce a range of pore structure characteristics. Image analysis was used to characterise the pore structure in terms of simple morphological parameters such as resolvable porosity and the specific surface area. These were found to be correlated to measured transport coefficients (diffusivity, permeability and sorptivity), suggesting the feasibility of image analysis to derive valuable quantitative information describing the pore structure that can be used as input values for a transport prediction model. A simple analytical model incorporating tortuosity and constrictivity was used to predict oxygen diffusivity and a variant of the Kozeny-Carman model was used to predict oxygen permeability. The diffusion model tended to over-predict for the lower w/c ratio mortar, but the general agreement was reasonable, with 90% of the estimated values within a factor of two from the measured values. The modified Kozeny-Carman model, however, over-predicted all permeability values with an error of between half to one order of magnitude.     

不同三次风速下分解炉二相流场的数值模拟

为了优化分解炉内的气固二相流流场以提高其性能指标,基于一实际尺寸的SLC-S分解炉,分别对不同三次风速下的气固二相流场进行了数值模拟,其中对连续相、颗粒相的计算分别采用k-ε双方程湍流模型和离散相模型,对离散相与湍流之间的相互作用采用随机跟踪模型。计算所得气流场分布规律与实测值吻合较好,且颗粒相的质量浓度场分布形式与实际情况相一致。模拟结果表明:在所考察的边界条件下,当三次风速≤28 m/s时,分解炉本体压力损失较低,且物料停留时间的绝对值和料气停留时间比值皆相对很高,为适宜的三次风速范围。     

Permeability of polyimides derived from non-coplanar diamines and 4,4′-(hexafluoroisopropylidene)diphthalic anhydride

A series of polyimides including a non-coplanar moiety were synthesized in order to investigate the effect on gas permeability and selectivity. The gas permeation properties of He, H₂, O₂, N₂, CH₄ and CO₂ were measured using a constant-volume method. Only 6FDA-terphenyl consisting of laterally attached phenyl groups shows a substantial increase because its terphenyl moiety is a rigid structure with a high aspect ratio. The order of permeability increase from 6FDA-phenyl to 6FDA-terphenyl is consistent with the calculated fraction free volume and measured permittivity. It is observed that the most gain in permeability for 6FDA-terphenyl polyimide arises from the enhancement in apparent diffusion coefficient, while the permeability increase for 6FDA-biphenyl is mainly due to the increase in solubility. A relationship of diffusivity vs. gas penetrant size as well as gas solubility vs. critical temperature of gas penetrant was also investigated.     

Barrier Properties of Blends Based on Liquid Crystalline Polymers and Poly(ethylene terephthalate)

Abstract

Blends of poly(ethylene terephthalate) (PETP) and two different thermotropic liquid crystalline (LC) polymers of the Vectra-type were prepared by melt mixing. Oxygen and water vapor permeability, light transmission and welding properties were measured on compression-molded and film-blown specimens. SEM showed that the LC polymers were the disperse phase with a good phase adhesion to the PETP matrix in the majority of the compression-molded blends. The 50/50 blend based on the low melting point LC polymer showed possibly a continuous LC polymer phase. The film-blown specimens showed LC polymer spheres at low LC polymer content. Above a certain LC polymer content (10-30% LC polymer), fibrous and ellipsoidal LC polymer particles was the dominant morphological feature of the blends. Density measurements showed that the void content in the blends was low. The compression-molded blends based on the high melting point LC polymer showed permeabilities conforming to the Maxwell equation assuming low permeability (LC polymer) spheres in a high permeability (PETP) matrix. The compression-molded blends based on the low melting point Vectra showed lower permeabilities than predicted by the Maxwell equation, particularly at high LC polymer content. The film-blown blends showed extensive scattering in the permeability data. The blend with 30% low melting LC polymer exhibited a 96% lower oxygen permeability than PETP. This was due to a reduction in both oxygen diffusivity and solubility. Ellipsoidal and fibrous LC polymer particles increased the diffusional path and lowered the diffusivity. The transparency of the compression-molded samples was lost already at 1% LCP. The blends showed welding properties superior to those of PETP.     

MODELLING AND CORRELATING THE PERMEABILITY OF PULP AND PAPER

A sheet of paper is modelled as a network of cellulose fibres, either cylindrical or band-shaped. The equations for creeping flow through such structures are solved, and The calculated permeabilities are compared with measured values. Flow through some paper structures such as pulp sheets and handsheets of unbeaten sulphate pulp is adequately described by the structural model involving band-shaped fibres when a fibre aspect ratio of 3.5 is used. For newsprint sheets the measured permeability is lower than that predicted by the models when physically realistic values of the aspect ratio are taken. A total of 19 different paper grades have been characterised by measurement of the total specific surface area and The fibre orientation ratio in addition to the measurements of effective diffusivity, permeability and porosity. Permeability and effective diffusivity correlate with each other and permeability correlates with fibre orientation, so that at constant porosity, permeability decreases with increasing fibre orientation.     

Gas transmission through polymers

Little data is available on gas transmission through thick polymer samples. There is, therefore, a temptation to assume an inverse relationship between gas transmission rate and thickness and to calculate flow through thick samples using permeability data obtained on thin films. This is incorrect, as the calculation assumes steady flow, and with thick samples this state may not be reached for months or even years. Thus both diffusivity and permeability are needed to calculate the gas flow and the calculations are more complex than simple permeability calculations. Because of the long time scale, the effects of varying the thickness are difficult to demonstrate experimentally. We describe a computer simulation of the manometric method which compares the behavior of two materials with similar permeabilities but different diffusivities. Although thin samples behave identically, they differ increasingly with thickness. The pitfalls in using the gradient and time lag of the pressure curve to calculate permeability and diffusivity are also discussed.