Chloride transport and the resulting corrosion of steel bars in alkali activated slag concretes

As the relative performance of alkali activated slag (AAS) concretes in comparison to Portland cement (PC) counterparts for chloride transport and resulting corrosion of steel bars is not clear, an investigation was carried out and the results are reported in this paper. The effect of alkali concentration and modulus of sodium silicate solution used in AAS was studied. Chloride transport and corrosion properties were assessed with the help of electrical resistivity, non-steady state chloride diffusivity, onset of corrosion, rate of corrosion and pore solution chemistry. It was found that: (i) although chloride content at surface was higher for the AAS concretes, they had lower chloride diffusivity than PC concrete; (ii) pore structure, ionic exchange and interaction effect of hydrates strongly influenced the chloride transport in the AAS concretes; (iii) steel corrosion resistance of the AAS concretes was comparable to that of PC concrete under intermittent chloride ponding regime, with the exception of 6% Na2O and Ms of 1.5; (iv) the corrosion behaviour of the AAS concretes was significantly influenced by ionic exchange, carbonation and sulphide concentration; (v) the increase of alkali concentration of the activator generally increased the resistance of AAS concretes to chloride transport and reduced its resulting corrosion, and a value of 1.5 was found to be an optimum modulus for the activator for improving the chloride transport and the corrosion resistance.

Assessing Initial Conditions for Chloride Transport Across Low- permeability Argillaceous Rocks, Wellenberg, Switzerland

Information about fluid evolution and solute transport in a low-permeability metamorphic rock sequence has been obtained by comparing chloride concentrations and chlorine isotope ratios of pore water, groundwater, and fluid inclusions. The similarity of d37Cl values in fluid inclusions and groundwater suggests a closed-system evolution during the metamorphic overprint, and signatures established at this time appear to form the initial conditions for chloride transport after exhumation of the rock sequence.

Modelling of chloride transport in non-saturated concrete : from microscale to macroscale

Corrosion of steel bars embedded in concrete has a great influence on structural performance and durability of reinforced concrete. Chloride penetration is considered to be a primary cause of concrete deterioration in a vast majority of structures. Therefore, modelling of chloride penetration into concrete has become an area of great interest. The present work focuses on modelling of chloride transport in concrete. The differential macroscopic equations which govern the problem were derived from the equations at the microscopic scale by comparing the porous network with a single equivalent pore whose properties are the same as the average properties of the real porous network. The resulting transport model, which accounts for diffusion, migration, advection, chloride binding and chloride precipitation, consists of three coupled differential equations. The first equation models the transport of chloride ions, while the other two model the flow of the pore water and the heat transfer. In order to calibrate the model, the material parameters to determine experimentally were identified. The differential equations were solved by means of the finite element method. The classical Galerkin method was employed for the pore solution flow and the heat transfer equations, while the streamline upwind Petrov Galerkin method was adopted for the transport equation in order to avoid spatial instabilities for advection dominated problems. The finite element codes are implemented in Matlab® . To retrieve a good understanding of the influence of each variable and parameter, a detailed sensitivity analysis of the model was carried out. In order to determine the diffusive and hygroscopic properties of the studied concretes, as well as their chloride binding capacity, an experimental analysis was performed. The model was successfully compared with experimental data obtained from an offshore oil platform located in Brazil. Moreover, apart from the main objectives, numerous results were obtained throughout this work. For instance, several diffusion coefficients and the relation between them are discussed. It is shown how the electric field set up between the ionic species depends on the gradient of the species’ concentrations. Furthermore, the capillary hysteresis effects are illustrated by a proposed model, which leads to the determination of several microstructure properties, such as the pore size distribution and the tortuosity-connectivity of the porous network. El fenómeno de corrosión del acero de refuerzo embebido en el hormigón ha tenido gran influencia en estructuras de hormigón armado, tanto en su funcionalidad estructural como en aspectos de durabilidad. La penetración de cloruros en el interior del hormigón esta considerada como el factor principal en el deterioro de la gran mayoría de estructuras. Por lo tanto, la modelización numérica de dicho fenómeno ha generado gran interés. El presente trabajo de investigación se centra en la modelización del transporte de cloruros en el interior del hormigón. Las ecuaciones diferenciales que gobiernan los fenómenos a nivel macroscópico se deducen de ecuaciones planteadas a nivel microscópico. Esto se obtiene comparando la red porosa con un poro equivalente, el cual mantiene las mismas propiedades de la red porosa real. El modelo está constituido por tres ecuaciones diferenciales acopladas que consideran el transporte de cloruros, el flujo de la solución de poro y la transferencia de calor. Con estas ecuaciones se tienen en cuenta los fenómenos de difusión, migración, advección, combinación y precipitación de cloruros. El análisis llevado a cabo en este trabajo ha definido los parámetros necesarios para calibrar el modelo. De acuerdo con ellas, se seleccionaron los ensayos experimentales a realizar. Las ecuaciones diferenciales se resolvieron mediante el método de elementos finitos. El método clásico de Galerkin se empleó para solucionar las ecuaciones de flujo de la solución de poro y de la transferencia de calor, mientras que el método streamline upwind Petrov-Galerkin se utilizó para resolver la ecuación de transporte de cloruros con la finalidad de evitar inestabilidades espaciales en problemas con advección dominante. El código de elementos finitos está implementado en Matlab® . Con el objetivo de facilitar la comprensión del grado de influencia de cada variable y parámetro, se realizó un análisis de sensibilidad detallado del modelo. Se llevó a cabo una campaña experimental sobre los hormigones estudiados, con el objeto de obtener sus propiedades difusivas, químicas e higroscópicas. El modelo se contrastó con datos experimentales obtenidos en una plataforma petrolera localizada en Brasil. Las simulaciones numéricas corroboraron los datos experimentales. Además, durante el desarrollo de la investigación se obtuvieron resultados paralelos a los planteados inicialmente. Por ejemplo, el análisis de diferentes coeficientes de difusión y la relación entre ellos. Así como también se observó que el campo eléctrico establecido entre las especies iónicas disueltas en la solución de poro depende del gradiente de concentración de las mismas. Los efectos de histéresis capilar son expresados por el modelo propuesto, el cual conduce a la determinación de una serie de propiedades microscópicas, tales como la distribución del tamaño de poro, además de la tortuosidad y conectividad de la red porosa.

Modelling of chloride transport in non-saturated concrete : from microscale to macroscale

A model for chloride transport in concrete is proposed. The model accounts for transport several transport mechanisms such as diffusion, advection, migration, etc. This work shows the chloride transport equations at the macroscopic scale in non-saturated concrete. The equations involve diffusion, migration, capillary suction, chloride combination and precipitation mechanisms. The material is assumed to be infinitely rigid, though the porosity can change under influence of chloride binding and precipitation. The involved microscopic and macroscopic properties of the materials are measured by standardized methods. The variables which must be imposed on the boundaries are temperature, relative humidity and chloride concentration. The output data of the model are the free, bound, precipitated and total chloride ion concentrations, as well as the pore solution content and the porosity. The proposed equations are solved by means of the finite element method (FEM) implemented in MATLAB (classical Galerkin formulation and the streamline upwind Petrov-Galerkin (SUPG) method to avoid spatial instabilities for advection dominated flows).

Regulation of epithelial chloride transport by tyrosine phosphorylation

Background: Chloride transport proteins are involved in a variety of human diseases and thus represent important drug targets. They are regulated in part through the amount present at the plasma membrane and tyrosine phosphorylation has been described as a novel regulator.

'PERMIT' ion migration test for measuring the chloride ion transport of concrete on site

The ingress of chlorides into concrete is predominantly by the mechanism of diffusion and the resistance of concrete to the transport of chlorides is generally represented by its coefficient of diffusion. The determination of this coefficient normally requires long test duration (many months). Therefore, rapid test methods based on the electrical migration of ions have widely been used. The current procedure of chloride ion migration tests involves placing a concrete disc between an ion source solution and a neutral solution and accelerating the transport of ions from the source solution to the neutral solution by the application of a potential difference across the concrete disc. This means that, in order to determine the chloride transport resistance of concrete cover, cores should be extracted from the structure and tested in laboratories. In an attempt to facilitate testing of the concrete cover on site, an in situ ion migration test (hereafter referred to as PERMIT ion migration test for the unique identification of the new test) was developed. The PERMIT ion migration test was validated in the lab by carrying out a comparative investigation and correlating the results with the migration coefficient from the one-dimensional chloride migration test, the effective diffusion coefficient from the normal diffusion test and the apparent diffusion coefficient determined from chloride profiles. A range of concrete mixes made with ordinary Portland cement was used for this purpose. In addition, the effects of preferential flow of ions close to the concrete surface and the proximity of reinforcement within the test area on the in situ migration coefficients were investigated. It was observed that the in situ migration index, found in one working day, correlated well with the chloride diffusion coefficients from other tests. The quality of the surface layer of the cover concrete and the location of the reinforcement within the test area were found to affect the flow of ions through the concrete during the test. Based on the data, a procedure to carry out the PERMIT ion migration test was standardised.

Chloride ingress through alkali activated slag concretes

Alkali activated slag (AAS) is a credible alternative to Portland cement (PC) based binder systems. The superior strength gain and low embodied carbon make it a potential binder for next generation concretes. However there is little known about the long term durability of AAS systems, especially the chloride transport and subsequent corrosion of reinforcing steel.
In this study, chloride transport through 12 AAS concretes with different alkali concentrations (Na2O% of mass of slag) and different modulus (Ms) of sodium silicate solution activator was investigated. A non-steady state chloride diffusion test was used for this study due to its similarity to the real exposure environment in terms of chloride transport through concrete. The results showed that the chloride concentration at the surface (Cs) of AAS concretes was higher than that for PC concrete.
However, lower non-steady state chloride diffusion coefficient (Dnssd) was obtained for the AAS concretes. The Dnssd of the AAS concretes decreased with the increase of Na2O% and Ms of 1.50 gave the lowest Dnssd. The results are encouraging and it can be concluded that AAS concrete offers a superior performance in terms of chloride transport.

Influence of compressive loading on chloride ingress through concrete

Chloride-induced corrosion of steel in concrete is one of most important durability and safety concern for reinforced concrete structures. To study chloride ingress into concrete is thus very important. However, most of the researchers focus on the studying chloride ingress through concrete samples without any loading. In reality concrete structures are subjected to different kinds of loads and therefore studying the effect of such loads on chloride transport is critical. In this work, 28 different concrete mixes were subjected to three levels of compressive load (0%, 50% and 75% of compressive failure load – f) for 24 hours. Further to unloading, these samples were subjected to non-steady state chloride diffusion test as per NT Build 443. The results were compared against the diffusion coefficient obtained for concrete samples that had no previous loading. D value for concretes subjected to 75% f showed a significant increase compared to 0% loading condition, but the increase was insignificant for 50% f. The results indicate that the influence of concrete mixes variables on D is more significant than that of loading level. Surface chloride concentration also increased with the loading level, which might be due to the increased concrete surface area caused by micro cracking.

Influence of service loading and the resulting micro-cracks on chloride resistance of concrete

Chloride-induced corrosion of steel in reinforced concrete structures is one of the main problems affecting their durability, but most previous research projects and case studies have focused on concretes without cracks or not subjected to any structural load. Although it has been recognised that structural cracks do influence the chloride transport and chloride induced corrosion in reinforced concrete structures, there is little published work on the influence of micro-cracks due to service loads on these properties. Therefore the effect of micro-cracks caused by loading on chloride transport into concrete was studied. Four different stress levels (0%, 25%, 50% and 75% of the stress at ultimate load – fu) were applied to 100 mm diameter concrete discs and chloride migration was measured using a bespoke test setup based on the NT BUILD 492 test. The effects of replacing Portland cement CEMI by ground granulated blast-furnace slag (GGBS), pulverised fuel ash (PFA) and silica fume (SF) on chloride transport in concrete under sustained loading were studied. The results have indicated that chloride migration coefficients changed little when the stress level was below 50% of the fu; however, it is desirable to keep concrete stress less than 25% fu if this is practical. The effect of removing the load on the change of chloride migration coefficient was also studied. A recovery of around 50% of the increased chloride migration coefficient was found in the case of concretes subjected to 75% of the fu when the load was removed.

Chloride Penetration Prediction in Concrete through an Empirical Model Based on Constant Flux Diffusion

An empirical model based on constant flux is presented for chloride transport through concrete in atmospherical exposure conditions. A continuous supply of chlorides is assumed as a constant mass flux at the exposed concrete surface. The model is applied to experimental chloride profiles obtained from a real marine structure, and results are compared with the classical error-function model. The proposed model shows some advantages. It yields a better predictive capacity than the classical error-function model. The previously observed chloride surface concentration increases are compatible with the proposed model. Nevertheless, the predictive capacity of the model can fail if the concrete microstructure changes with time. The model seems to be appropriate for well-maturated concretes exposed to a marine environment in atmospherical conditions.

Chloride ingress into marine exposed concrete: A comparison of empirical- and physically- based models

In establishing the reliability of performance-related design methods for concrete – which are relevant for resistance against chloride-induced corrosion - long-term experience of local materials and practices and detailed knowledge of the ambient and local micro-climate are critical. Furthermore, in the development of analytical models for performance-based design, calibration against test data representative of actual conditions in practice is required. To this end, the current study presents results from full-scale, concrete pier-stems under long-term exposure to a marine environment with work focussing on XS2 (below mid-tide level) in which the concrete is regarded as fully saturated and XS3 (tidal, splash and spray) in which the concrete is in an unsaturated condition. These exposures represent zones where concrete structures are most susceptible to ionic ingress and deterioration. Chloride profiles and chloride transport behaviour are studied using both an empirical model (erfc function) and a physical model (ClinConc). The time dependency of surface chloride concentration (Cs) and apparent diffusivity (Da) were established for the empirical model whereas, in the ClinConc model (originally based on saturated concrete), two new environmental factors were introduced for the XS3 environmental exposure zone. Although the XS3 is considered as one environmental exposure zone according to BS EN 206-1:2013, the work has highlighted that even within this zone, significant changes in chloride ingress are evident. This study aims to update the parameters of both models for predicting the long term transport behaviour of concrete subjected to environmental exposure classes XS2 and XS3.

Avoiding Overfitting in Inverse Modeling of Chloride Migration in Concrete

Inverse analysis for reactive transport of chlorides through concrete in the presence of electric field is presented. The model is solved using MATLAB’s built-in solvers “pdepe.m” and “ode15s.m”. The results from the model are compared with experimental measurements from accelerated migration test and a function representing the lack of fit is formed. This function is optimised with respect to varying amount of key parameters defining the model. Levenberg-Marquardt trust-region optimisation approach is employed. The paper presents a method by which the degree of inter-dependency between parameters and sensitivity (significance) of each parameter towards model predictions can be studied on models with or without clearly defined governing equations. Eigen value analysis of the Hessian matrix was employed to investigate and avoid over-parametrisation in inverse analysis. We investigated simultaneous fitting of parameters for diffusivity, chloride binding as defined by Freundlich isotherm (thermodynamic) and binding rate (kinetic parameter). Fitting of more than 2 parameters, simultaneously, demonstrates a high degree of parameter inter-dependency. This finding is significant as mathematical models for representing chloride transport rely on several parameters for each mode of transport (i.e., diffusivity, binding, etc.), which combined may lead to unreliable simultaneous estimation of parameters.

Numerical assessment of potential impacts of hydraulically fractured Bowland Shale on overlying aquifers

Natural gas extracted from hydraulically fractured shale formations potentially has a big impact on the global energy landscape. However, there are concerns of potential environmental impacts of hydraulic fracturing of the shale formations, particularly those related to water quality. To evaluate the potential impact of hydraulically fractured shale on overlying aquifers, we conduct realizations of numerical modeling simulations to assess fluid flow and chloride transport from a synthetic Bowland Shale over a period of 11,000 years. The synthetic fractured shale was represented by a three-dimensional discrete fracture model that was developed by using the data from a Bowland Shale gas exploration in Lancashire, UK. Chloride mass exchange between fractures and the rock matrix was fully accounted for in the model. The assessment was carried out to investigate fluid and chloride mass fluxes before, during, and after hydraulic fracturing of the Bowland Shale. Impacts of the upward fracture height and aperture, as well as hydraulic conductivity of the multilayered bedrock system, are also included this assessment. This modeling revealed that the hydraulically fractured Bowland Shale is unlikely to pose a risk to its overlying groundwater quality when the induced fracture aperture is ≤200 µm. With the fracture aperture ≥1000 µm, the upward chloride flux becomes very sensitive to the upward fracture height growth and hydraulic conductivity of the multilayered bedrock system. In the extremely unlikely event of the upward fracture growth directly connecting the shale formation to the overlying Sherwood Sandstone aquifer with the fracture aperture ≥1000 µm, the upward chloride mass flux could potentially pose risks to the overlying aquifer in 100 years. The model study also revealed that the upward mass flux is significantly intercepted by the horizontal mass flux within a high permeable layer between the Bowland Shale and its overlying aquifers, reducing further upward flux toward the overlying aquifers.

Axe et rotaxane parapluie : vers de nouveaux transporteurs transmembranaires de chlorures et de médicaments cycliques

La membrane cellulaire est principalement une bicouche phospholipidique constituant une barrière qui régule les échanges entre la cellule et son environnement. Son intérieur hydrophobe empêche le passage d’espèces hydrophiles, chargées, de grande masse moléculaire et polaires, qui sont généralement transportées par des protéines à travers la bicouche. Dans certains cas de systèmes défectueux (e.g. les canalopathies), l’équilibre des concentrations en ions à l’intérieur et à l’extérieur des cellules est perturbé et les cellules sont compromises. C’est pourquoi le développement de transporteurs transmembranaires synthétiques est nécessaire. De nombreux travaux ont été faits dans le développement de transporteurs synthétiques d’anions (particulièrement du chlorure). Dans cette thèse, nous présentons nos travaux sur un nouveau transporteur d’anion appelé axe parapluie, capable de changer de conformation dépendamment de la polarité de son environnement. Dans un premier temps, nous avons conçu le design, puis synthétisé ces axes parapluie qui montrent une importante activité en tant que transporteur de chlorures. Ces composés réunissent deux concepts : - Le parapluie, constitué d’acides biliaires amphiphiles (une face hydrophile, une face hydrophobe). La flexibilité des articulations combinée à la grande surface des acides choliques permettent d’empêcher les interactions défavorables entre les parties hydrophiles et hydrophobes, ce qui facilite l’insertion dans la bicouche. - Un site ammonium secondaire en tant que site de reconnaissance, capable de former des ponts hydrogène avec des ions chlorure. De plus, l’axe peut complexer une roue de type éther couronne pour former un pseudo-rotaxane ou rotaxane parapluie ce qui résulte en l’inhibition partielle de leurs propriétés de transport. Ceci nous mène au second objectif de cette thèse, le développement d’un nouveau moyen de transport pour les médicaments cycliques. Certains macrocycles polaires et biologiquement actifs tels que les nactines ont besoin d’atteindre leur objectif à l’intérieur de la cellule pour jouer leur rôle. La membrane cellulaire est alors un obstacle. Nous avons imaginé tirer profit de notre axe parapluie pour transporter un médicament cyclique (en tant que roue d’un rotaxane parapluie). Les assemblages des rotaxanes parapluie furent accomplis par la méthode de clipage. Le comportement de l’axe et du rotaxane parapluie fut étudié par RMN et fluorimétrie. Le mouvement du parapluie passant d’une conformation fermée à exposée dépendamment du milieu fut observé pour le rotaxane parapluie. Il en fut de même pour les interactions entre le rotaxane parapluie et des vésicules constituées de phospholipides. Finalement, la capacité du rotaxane parapluie à franchir la bicouche lipidique pour transporter la roue à l’intérieur de la vésicule fut démontrée à l’aide de liposomes contenant de la α-chymotrypsine. Cette dernière pu cliver certains liens amide de l’axe parapluie afin de relarguer la roue.