Effect of penetrant size and shape on its transport through a thermoset adhesive: I. n-alkanes

The diffusion behaviors of a series of n-alkanes, ranging from C₆ to C₁₇, through a polyamide-type polymeric matrix have been investigated by means of mass uptake measurements. Since n-alkanes are known to display negligible interactions with the polymer matrix, this study serves to isolate the effects of penetrant size and shape on the transport process without undue interference from polymer-penetrant interactions. It is established that the diffusion of the n-alkanes through the polymer matrix studied is Fickian and proceeds via a Henry's law-type mechanism. The diffusion coefficients, D, are evaluated based on a thin-film approximation of the Fickian equation. The activation energies of diffusion, E_d, are determined from the temperature dependence of D, using the Arrhenius equation. Correlations between the Arrhenius terms, E_d and D₀, are also established which enable the prediction of diffusion coefficients for similar polymer-penetrant systems. It is also demonstrated by means of activation energy calculations and molecular simulations that the n-alkanes assume a linear geometry within the polymer matrix and diffuse along their long axes.     

Effect of initial moisture content on wick action through concrete

Wick action is the transport of water through a concrete element from a face in contact with water to a drying face. Wick action tests were conducted on concrete specimens of varying thickness and initial moisture condition over a period of 300 days. The rate of wick action was inversely proportional to thickness regardless of the specimen preparation. Initial moisture condition was found to significantly influence wick action with vacuum-saturated specimens having the highest rate followed by saturated and then dried specimens. Possible reasons are discussed.     

Anomalous penetrant transport in glassy polymers VI. Effect of temperature on transport

Transport of liquid cyclohexane through well characterised, initially glassy, crosslinked polystyrene slabs was Investigated at 20, 30, 40, and 50°C. The samples used were produced by bulk polymerization of styrene and divinyl benzene (DVB) at 90°C for 43 hr using benzoyl peroxide as an initiator. The samples tested had initial cross-linking ratios, X, between 5 and 25 × 10^?3 mol DVB/mol styrene. The initial thickness of the samples tested varied from 0.25 mm to 1.80 mm, and the aspect ratio (length to thickness ratio) was maintained above 10;1 in order to analyze the results by one-dimensional transport equations. Cyclohexane uptake was followed as a function of time along with dimensional changes in the thickness and area of the samples. The results of penetrant uptake as a function of time were analyzed using a simplified exponential expression and employing all the data points from the beginning of the experiment until the time of observation of the maximum in uptake. Good correlations were established between the penetrant uptake and the transport temperature. These results were interpreted in terms of competitive relaxational and diffusional mechanisms.     

Diffusion of organic penetrants through low density polyethylene (LDPE) films: Effect of size and shape of the penetrant molecules

The diffusion coefficient at zero penetrant concentration D₀ of dichloromethane, chloroform, carbon tetrachloride, cyclohexane, benzene, o-xylene, m-xylene, and p-xylene, and n-hexane in LDPE were measured at 25°C, using the desorption method. The D₀ values obtained in this way are correlated with the size, shape, and chemical nature of the penetrant molecules. The temperature dependence of the diffusion coefficients of toluene and n-hexane in LDPE are also reported in the limited temperature range of 25–45°C. It indicates that, in spite of a size larger than that of toluene, n-hexane has a lower activation energy of diffusion.     

Modeling of transport, chemical and electrochemical phenomena in a cathode-supported SOFC

This paper investigates the performance of a planar cathode-supported solid oxide fuel cell (SOFC) with composite electrodes using a detailed numerical model. The methane reforming reaction is included in the model and takes place mostly in the porous, thin anode at the high operating temperature of 800-1000^°C. A single computational domain comprises the fuel and air channels and the electrodes-electrolyte assembly eliminating the need for internal boundary conditions. The equations governing transport and chemical and electrochemical processes for mass, momentum, chemical and charged species and energy are solved using Star-CD augmented by subroutines written in-house. The operating cell voltage is determined by the potential difference between the cathode and the anode, whose potentials are fixed. Results of temperature, chemical species, current density and electric potential distribution for a co-flow configuration are shown and discussed. It is found that the sub-cooling effect observed in anode-supported cells is almost ameliorated, making the cathode-supported cell favorable from the viewpoint of material stability.     

Characterization and modeling of diffusion process for mass transport through the Tournemire argillites (Aveyron, France)

Argillites are one of the geological formations studied by IRSN for their confining properties for isolation of radioactive wastes. One of the main objectives is the study of water transport through rocks with very low water content and very low hydraulic conductivity by modeling of natural tracer profiles. This paper presents the protocol developed for and applied to the acquisition of data for chloride content in interstitial water of the Toarcian argillites at the Tournemire site (Southern France). This protocol is based on laboratory diffusion experiments and on modeling. Experimental data obtained during the transient and steady-state parts of diffusion experiments enable, respectively, the assessment of the diffusion coefficient and the determination of Cl concentration in pore water. Using this protocol, profiles with depth for both of these data sets have been acquired along the geological sequence. Taking into account the present knowledge of the geological and hydrogeological history of the Tournemire massif, a conceptual model granting the main role for mass transport to diffusion has been proposed. According to this conceptual model, a one-dimensional numerical model was built for simulating the mass transport of chloride through the sedimentary column, over 53 Ma. The good agreement between experimental data and calculated values for both diffusion coefficients and concentrations of chloride confirms that diffusion is likely the main process for mass transport in the massif. This model was also tested with the deuterium content of interstitial water, applying variable concentrations at the aquifer system boundaries for reflecting the thermal dependency of isotopic composition in precipitation. These simulations also reveal the likely important role of heterogeneities, such as fractures, in the variability of tracer concentrations with regards to a simple diffusion profile.     

Effect of the degree of crosslinking on penetrant transport in polystyrene

The effect of the degree of crosslinking of glassy polymers on the transport mechanism of penetrants was investigated using a series of divinyl benzene (DVB)-crosslinked polystyrenes of nominal crosslinking ratio X from 0.001 38 to 0.060 mol DVB/mol styrene. The number average molecular weight between crosslinks, $\text{M}\text{?}{}_{\mathrm{<mtext>c</mtext>}}$, was determined from equilibrium swelling experiments in cyclohexane. Dynamic swelling experiments with cyclohexane at 30°C showed that the mechanism of penetrant transport was anomalous. An overshoot in the penetrant uptake was observed, characteristic of macromolecular relaxations and of changing solubility of the cyclohexane in the continuously swelling polystyrene. Photographs of various samples during the swelling process showed that solvent crazing occurred predominantly in loosely crosslinked samples.     

Diffusion of radioactively tagged penetrants through rubbery polymers. II. Dependence on molecular length of penetrant

The diffusion of radioactively tagged n-hexadecane, n-dotriacontane, and a polybutadiene oligomer with molecular weight 1600 has been studied in 12 rubbery polymers. Diffusion coefficients were obtained from the theory for the thin smear method: for n-hexadecane and for n-dotriacontane (with one exception), in the form appropriate for a completely miscible polymer–penetrant pair, and for the oligomer in the form appropriate for slow entry of the penetrant across the penetrant–polymer interface. For the four flexible linear penetrants, n-dodecane, n-hexadecane, n-dotriacontane, and oligomer, the ratios of diffusion coefficients (or translational friction coefficients) are nearly the same in every polymer. It is concluded that these penetrants travel with similar segmentwise motions, although that is not the case with bulkier, more rigid penetrants. For the three normal paraffins, the friction coefficient is approximately proportional to molecular weight, but that for the oligomer is smaller than would be predicted on this basis.     

Comparison of Wicke-Kallenbach and Graham's diffusion cells for obtaining transport characteristics of porous solids

Counter-current gas diffusion measurements on a series of porous solids covering a broad range of pore sizes (mean pore radii between 78 nm and ) were performed in the Wicke-Kallenbach and Graham's diffusion cells. Mutual agreement of diffusion fluxes from both cells was found in the whole range of tested pore radii and inert gas systems. For pore materials with mean pore radii exceeding the experimentally unavoidable tiny total pressure gradient induces additional permeation flow which precludes the use of Graham's law for evaluation of transport parameters of the porous solids. Transport parameters together with 95% confidence regions were determined for porous materials with pore radii up to and the prevailing diffusion mechanism, intimately connected with the shape of confidence regions, was estimated.     

Effect of entrained air voids on the microstructure and mass transport properties of concrete

The effects of entrained air on microstructure and transport properties of concrete with up to 11.5% air at different w/c ratios, curing and conditioning regimes were investigated. It was found that air voids disrupt the packing of cement and increase the heterogeneity of the microstructure. The width of the affected interface is around 30 μm. Gaseous diffusivity and permeability are increased by up to a factor of 2–3 at the highest air contents. This effect is similar to that due to increasing w/c ratio from 0.35 to 0.50 when samples are conditioned at 52% r.h or 50 °C. The effect on sorptivity is less consistent, while the effect on electrical conductivity is influenced by the moisture condition of the air voids. It is estimated that every 1% increase in air content increases transport by 10% or decreases it by 4%, depending on whether the air voids act as conductors or insulators.     

A stochastic analysis of contaminant transport through a rough-surfaced fracture

A stochastic model for the calculation of flow and contaminant transport in a single fracture with variable apertures was presented. The spatially varying apertures of the fracture were generated using a geostatistical method, based on a given aperture probability density distribution and a specified spatial correlation length. Fluid flowed between two points in the fracture plane. The fluid potential at each node of the discretization mesh was computed and the steady state flow rates between all the nodes were obtained. Then the contaminant transport was calculated using a particle tracking method. The migration plumes of contaminant between the inlet and the outlet were displayed in contour plots and contaminant elution profiles were also plotted. Calculations showed that fluid flow occured predominantly in a few preferred paths. Hence, the large range of apertures in the fracture gives rise to flow channeling. Simulation results were correlated with the basic input parameters: standard deviation of a lognormal aperture distribution function and the spatial correlation length.     

Physical modeling of the electrical double layer effects on multispecies ions transport in cement-based materials

The transport of ions through cement-based materials is described at a microscopic scale with a pore modeled by two infinitely large flat plates. The theory of the electrical double layer (EDL) shows that (i) the overlapping between the diffuse layers occurring in the pore is more important as the pore diameter will be small (low than the Debye length) and the pore walls will be strongly charged, (ii) the fluxes of coions and counterions will be respectively increased and attenuated in such pores. The gel pores of cement based materials have similar characteristics. As the capillary pores of the cement based materials with low porosity are connected between them by the pores gel, the transport of ions at a macroscopic scale could be greatly influenced by the overlapping effect of the diffuse layers.     

Enhanced modeling of moisture equilibrium and transport in cementitious materials under arbitrary temperature and relative humidity history

This paper focuses on behaviors of moisture dispersed in nano‐macro scale pores under various temperature and relative humidity conditions. The authors formulated an equilibrium relationship between liquid and vapor phases and a moisture flux driven by pore pressure, vapor pressure and temperature gradients. In addition, liquid and interlayer water were measured separately by ethanol in order to reveal each temperature sensitivity in saturation‐humidity paths. Based on the experiments, a modified hysteresis model for moisture isotherm was proposed. Verifications with experimental data showed that the proposed method can simulate moisture behaviors under various temperature conditions.     

Effect of a high calcite filler addition upon microstructural, mechanical, shrinkage and transport properties of a mortar

Sands produced from limestone rock deposits in Algeria contain high proportions of fine 0/100 μm particles (named filler hereafter), which are available in large quantities. This study aims to identify the maximum filler amount which may be added to cementitious materials without performance loss. Performance is quantified here as related to varied properties, either microstructural (density, porosity, pore size distribution, capillary absorption, Klinkenberg effect), mechanical (Young's modulus, compressive and flexural strengths), or indicative of durability (intrinsic gas permeability, drying shrinkage and mass loss). To that purpose, mortars with various amounts of filler, ranging from 15 to 45% sand mass (i.e. 45 to 135% cement mass), have been formulated, tested and compared to a reference mortar. As recommended by J. Baron [J. Baron, Les additions normalisées pour le Béton, Les bétons - Bases et données pour leur formulation, Association technique - industrie des liants hydrauliques (in French), Eyrolles Ed., Paris, 1996, pp. 47-57], substitution to sand is privileged, whereby cement proportion and workability are kept constant while water need varies with increasing filler amount. Preliminary XRD analysis of filler powder shows no other minerals than calcite CaCO₃ and traces of dolomite CaMg(CO₃)₂. Results point out the existence of an optimal performance value and a high effect of filler addition. In particular, for high filler amounts, total porosity increases while bigger pore populations diminish. This is confirmed by SEM examinations of the microstructure as well as by the increase of Klinkenberg coefficient β determined from gas permeability measurements, and by capillary absorption results. Moreover, intrinsic gas permeability, compressive and flexural strengths remain remarkably high whatever the filler proportion. Drying shrinkage and mass loss are not impacted dramatically either.     

几种小分子酯类有机物对矿渣粉磨性能及矿渣水泥强度的影响

从筛余量、比表面积、粒径分布、胶砂强度、SEM分析等方面研究了几种小分子酯类有机物对矿渣粉磨和矿渣水泥强度的影响。结果表明：几种酯类物质均能降低矿渣筛余量,增加比表面积,提高3μm~32μm颗粒含量,对矿渣具有良好的助磨效果;酯类有机物分子的链长越长（对称结构除外）,官能团越多（官能团相距较远）,助磨效果越好;链长相同时,官能团数目的影响占主导地位。酯类物质的加入能使矿渣水泥水化产物Ca（OH）2成片层状紧密生长,能有效提高矿渣水泥的强度。     

The effects of diffusion mechanism and void structure on transport rates and tortuosity factors in complex porous structures

Tracer diffusion simulations within random porous structures show that tortuosity factors are independent of diffusion mechanism for all practical void fractions when an equivalent Knudsen diffusivity is correctly defined. Previous studies concluded that tortuosity factors, a geometric property of the void space as defined, increase with increasing Knudsen number, K_n, a measure of the relative number of molecule-surface and intermolecular collisions. The model porous structures in this study consist of random-loose packings of spheres overlapped to achieve a given void fraction and to accurately reflect the void space in practical porous solids. Effective diffusivities were estimated using tracer or flux-based Monte Carlo methods for Knudsen numbers of 10⁻³-10¹⁰; the two methods lead to similar diffusivities for void fractions of 0.06-0.42. Tortuosity factors estimated using the number-averaged distance between collisions, 〈l_p〉, for the characteristic void length scale increased with increasing Knudsen number, even though simulations in infinite cylinders confirmed the accuracy of the Bosanquet equation for all values of K_n. These unexpected changes in a geometric property of the void space become most apparent near the percolation void fraction (∼0.04). For example, the Knudsen tortuosity factor defined in this manner is 1.8 times larger than in the bulk regime for a solid with 0.10 void fraction. Even at high void fractions (∼0.42), the two extreme values of tortuosity factor differ by a factor of ∼1.4. These apparent effects of diffusion mechanism on tortuosities reflect the inaccurate use of number-averaged chord lengths when tracer reflections from random obstacles obey the Knudsen cosine law for diffuse reflection. A corrected length scale, first proposed by Derjaguin, leads to tortuosity factors independent of K_n for void fractions above 0.20; tortuosities differ by only 18% and 4% between Knudsen and bulk regimes even for void fractions of 0.10 and 0.15, respectively. The residual differences at void fractions below 0.10 arise from the increasingly serial nature of the remaining voids. Thus, a long-standing inconsistency between the defined geometric nature of tortuosity factors and their inexplicable dependence on diffusion mechanism is essentially resolved. In practice, these simulations allow the consistent and accurate use of tortuosity factors determined at any value of K_n for all diffusion regimes; they also prescribe, rigorously for void fractions above 0.15 and empirically for lower void fractions, the length scale relevant to diffusion in the Knudsen and transition diffusion regimes.     

Numerical simulation of hydration-driven moisture transport in bulk and interface paste in hardening concrete

In real concrete two types of cement paste can be distinguished, i.e., bulk paste and interface paste. Initially the paste in the interface zone will generally contain more water than the bulk paste and will therefore hydrate differently. Differences in relative humidity and associated differences in pore water pressure will result as well. If the interface paste and the bulk paste could hydrate individually, a situation will result where a relatively porous water-rich interfacial zone coexists with a relatively dry bulk paste. However, due to gradients in porosity, permeability, relative humidity and pore water pressure, a flow of moisture will start from the water-rich interfacial zone to the bulk paste. It will be shown how the moisture transport can be simulated numerically and how this transport phenomenon influences the overall rate of hydration of cement in concrete. Numerical results are compared with experimental data presented in literature. The relevance of modelling of this kind of transport phenomena is briefly dealt with.     

An epoxy-terminated structural adhesive. II. Curing,adhesive strength,and flammability characteristics

Curing characteristics and the curing schedule of an epoxy-terminated polymer (ETP) were investigated using diaminodiphenyl ether (DADPE), diaminodiphenyl sulfone (DADPS), diaminodiphenyl methane (DADPM), and the hardener of a commercial epoxy, two-pack Araldite (Ciba-Geigy), as curing agents. The adhesive strength of the ETP was measured by various ASTM methods like lap-shear, cohesion, and adhesion tests on metal-metal, wood-metal, wood-wood, and metal-polymer interfaces. All these results are compared with Araldite GY250, a two-pack Araldite (Ciba-Geigy). The flame retardancy of virgin ETP, ETP-Araldite GY250 blends, and various commercial-grade fire-resistant epoxies was measured. A structure flammability correlation for the ETP-Araldite GY250 blends is also reported.