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.     

Catalyst surface at a fractal of cost—a quest for optimal catalyst loading

Intuition tells us that any decrease in the catalytically active surface area should result in an equivalent decrease in the reaction yield and efficiency. Our findings counter this by showing that the active surface and hence the catalyst loading can be reduced drastically in the diffusion-limited heterogeneous reaction systems, while the conversion rate remains essentially unchanged by using fractals for spatial distribution of the catalyst load. The results of this study provide an unusual circumstance for optimal design of chemically active surfaces and can be used to drastically reduce cost of heterogeneous chemical and biological reactors, sensors, and electrodes of fuel cells. The proposed approach can be exploited to its fullest extent in chemical microsystems by utilizing the latest advances in our abilities to manipulate matter on the micro/nano scale.     

Modelling the transport of carbonic acid anions through anion-exchange membranes

Electrodiffusion of carbonate and bicarbonate anions through anion-exchange membranes (AEM) is described on the basis of the Nernst-Planck equations taking into account coupled hydrolysis reactions in the external diffusion boundary layers (DBLs) and internal pore solution. The model supposes local electroneutrality as well as chemical and thermodynamic equilibrium. The transport is considered in three layers being an anion exchange membrane and two adjoining diffusion layers. A mechanism of competitive transport of HCO₃⁻ and CO₃²⁻ anions through the membrane which takes into account Donnan exclusion of H⁺ ions is proposed. It is predicted that the pH of the depleting solution decreases and that of the concentrating solution increases during electrodialysis (ED). Eventual deviations from local electroneutrality and local chemical equilibrium are discussed.     

Estimating the electrical conductivity of cement paste pore solutions from OH, K and Na concentrations

A proposed method for estimating the electrical conductivity of cement paste pore solution at 25 °C is based on the concentrations of OH⁻, K⁺ and Na⁺. The approach uses an equation that is a function of the solution ionic strength, and requires a single coefficient for each ionic species. To test the method, the conductivity of solutions containing mixtures of potassium hydroxide and sodium hydroxide with molar ratios of 4:1, 2:1 and 1:1, and having ionic strengths varying from 0.15 to 2.00 mol/l were measured in the laboratory and compared to predicted values. The proposed equation predicts the conductivity of the solutions to within 8% over the concentration range investigated. By comparison, the dilute electrolyte assumption that conductivity is linearly proportional to concentration is in error by 36% at 1 mol/l and in error by 55% at 2 mol/l. The significance and utility of the proposed equation is discussed in the context of predicting ionic transport in cement-based systems.     

Influence of aggregates on chloride diffusion coefficient into mortar

In order to determine the influence of aggregates on chloride ion ingress, mortar specimens were cast with different aggregate size distribution and the same aggregate volume content. One side of the specimen was in contact with alkaline solution containing sodium chloride. The process of chloride ingress is due to diffusion. The effect of the interfacial transition zone (ITZ) around aggregate and of the tortuosity due to aggregates have been taken into account for interpreting the experimental data obtained. These two competing effects have been quantified by using the theory of composite materials. It appears that the diffusion coefficient varies as a function of the ITZ volume content and of the tortuosity.     

Exploring Internal Structure of Nanoporous Glasses Obtained by Leaching of Phase‐Separated Alkali Borosilicate Glasses

Mesoporous glasses – the leaching products of phase‐separated alkali borosilicate glasses – are widely used in fundamental research and practical applications. In this work, the option to control their internal mesopore structure by varying the conditions of microphase separation has been studied. Structure and transport characterization of a family of nanoporous glasses obtained under different conditions has been performed using a combination of several experimental techniques, including gas adsorption, nuclear magnetic resonance cryoporometry and diffusometry.     

Dissolution,Transport and Reaction at a DICY/DGEBA Interface

The curing of an epoxy consisting of the solid hardener dicyandiamide (DICY) and the resin diglycidyl ether of bisphenol A (DGEBA) is studied in a system consisting of a tablet of DICY embedded in liquid DGEBA. Dissolution of DICY within the liquid DGEBA in combination with the transport of dissolved DICY from the tablet border into DGEBA and the chemical reaction of both reactants is studied by scanning Brillouin microscopy and infrared spectroscopy. Scanning Brillouin microscopy demonstrates the spatial and temporal evolution of the static and dynamic hypersonic properties in the course of curing in the vicinity of the DICY tablet. Infrared spectroscopy performed on epoxy pieces extracted from the final sample at different distances from the tablet surface give information about the spatial evolution of the curing process. The results achieved by both techniques are finally combined to yield a better understanding of the curing of DICY-based epoxies, which transform upon curing from strongly heterogeneous systems towards increasingly homogeneous systems.     

New method for monitoring of adsorption column saturation and regeneration I. Demonstration of the measurement principle

A new method suitable for the on-line monitoring of adsorption column saturation/regeneration cycles was developed based on the discovery that the electrical resistance of adsorbents changes dramatically upon adsorption and returns to its original value upon desorption, and that this change can be measured reliably. The phenomenon was demonstrated on four different adsorbent/adsorbate systems, on both single particles and in a packed bed between parallel plates. The observed phenomenon was studied on the carbon/CO2 system in more detail, because of the availability of extensive literature data. It was found that the resistance change in this system correlated with the amount of CO2 adsorbed. The correlation was used to construct an adsorption isotherm based on resistance change data.     

A DYNAMIC,ADAPTIVE, LOCALLY CONSERVATIVE,AND NONCONFORMING SOLUTION STRATEGY FOR TRANSPORT PHENOMENA IN CHEMICAL ENGINEERING

A family of discontinuous Galerkin (DG) methods are formulated and applied to chemical engineering problems. They are the four primal discontinuous Galerkin schemes for space discretization: symmetric interior penalty Galerkin, Oden-Babu?ka-Baumann DG formulation, nonsymmetric interior penalty Galerkin, and incomplete interior penalty Galerkin. Numerical examples of DG to solve typical chemical engineering problems, including a diffusion-convection-reaction system in a catalytic particle, a problem of heat transfer in a fixed bed, and flow and contaminant transport simulations in porous media, are presented. This article highlights the substantial advantages of DG on adaptive mesh modification over traditional methods. In particular, we propose and investigate the dynamic mesh modification strategy for DG guided by mathematically sound a posteriori error estimators.     

Multi-Scale Analysis of Vacuum Contact Drying

The modeling of the unit operation of vacuum contact drying is approached as a multi-scale problem. At the particle assembly length scale, effective transport properties (thermal conductivity, relative gas- and liquid-phase permeability) have been determined computationally by simulations on reconstructed porous media and verified by direct measurements. A distributed-parameter model of vacuum contact drying including liquid and vapor flow and differential energy balance has been formulated and used for the calculation of drying time as function of vacuum level, temperature, vessel diameter, and batch size at the unit operation length scale. Drying curves for a model system of sodium carbonate–isopropanol have been measured experimentally and compared with the model predictions. A very good agreement has been found.