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.

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.

The Validation of a Two-Dimensional Transient Catalyst Model for Direct Injection Two-Stroke Applications

This paper describes the detailed validation of a computer model designed to simulate the transient light-off in a two-stroke oxidation catalyst. A plug flow reactor is employed to provide measurements of temperature and gas concentration at various radial and axial locations inside the catalyst. These measurements are recorded at discrete intervals during a transient light-off in which the inlet temperature is increased from ambient to 300oC at rates of up to 6oC/sec. The catalyst formulation used in the flow reactor, and its associated test procedures, are then simulated by the computer and a comparison made between experimental readings and model predictions. The design of the computer model to which this validation exercise relates is described in detail in a separate technical paper. The first section of the paper investigates the warm-up characteristics of the substrate and examines the validity of the heat transfer predictions between the wall and the gas in the absence of chemical reactions. The predictions from a typical single-component CO transient light-off test are discussed in the second section and are compared with experimental data. In particular the effect of the temperature ramp on the light-off curve and reaction zone development is examined. An analysis of the C3H6 conversion is given in the third section while the final section examines the accuracy of the light-off curves which are produced when both CO and C3H6 are present in the feed gas. The analysis shows that the heat and mass transfer calculations provided reliable predictions of the warm-up behaviour and post light-off gas concentration profiles. The self-inhibition and cross-inhibition terms in the global rate expressions were also found to be reasonably reliable although the surface reaction rates required calibration with experimental data.

Isotopic composition of tropospheric and soil N2O from successive depths of agricultural plots with contrasting crops and nitrogen amendments

Agricultural soils are the dominant contributor to increases in atmospheric nitrous oxide (N2O). Few studies have investigated the natural N and O isotopic composition of soil N2O. We collected soil gas samples using horizontal sampling tubes installed at successive depths under five contrasting agricultural crops (e.g., unamended alfalfa, fertilized cereal), and tropospheric air samples. Mean d 15N and d 18O values of soil N2O ranged from -28.0 to +8.9‰, and from +29.0 to +53.6‰. The mean d 15N and d 18O values of tropospheric N2O were +4.6 ± 0.7‰ and +48.3 ± 0.2‰, respectively. In general, d values were lowest at depth, they were negatively correlated to soil [N2O], and d 15N was positively correlated to d 18O for every treatment on all sampling dates. N2O from the different agricultural treatments had distinct d 15N and d 18O values that varied among sampling dates. Fertilized treatments had soil N2O with low d values, but the unamended alfalfa yielded N2O with the lowest d values. Diffusion was not the predominant process controlling N2O concentration profiles. Based on isotopic and concentration data, it appears that soil N2O was consumed, as it moved from deeper to shallower soil layers. To better assess the main process(es) controlling N2O within a soil profile, we propose a conceptual model that integrates data on net N2O production or consumption and isotopic data. The direct local impact of agricultural N2O on the isotopic composition of tropospheric N2O was recorded by a shift toward lower d values of locally measured tropospheric N2O on a day with very high soil N2O emissions.

Conductivity sensor technology application in steady state migration test

In this paper the current development of the steady state migration test was reviewed. Experiments were carried out for a series of concrete mixes with the steady state migration test in which conductivity sensor technology is applied. With the developed steady state migration test, conductivity in anolyte, loop current and temperature can be monitored in real time. The experimental results are conductive to understand the mechanism of chloride migration during both unsteady state and steady state. The conductivity of anolyte could be used to calculate the chloride concentration in anolyte and the theoretical correlation between them was explained. Over all, the developed steady state migration is an effective, convenient, well-defined in theory and plentiful with information method which could be used to determine the chloride diffusion coefficient of cementitious materials.

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.

Chloride induced corrosion of steel bars in alkali activated slag concretes

The studies on chloride induced corrosion of steel bars in alkali activated slag (AAS) concretes are scarcely reported in the past. In order to make this issue clearer and compare the corrosion performance of AAS with Portland cement (PC) counterpart, an investigation was carried out and the results are reported in this paper. Corrosion properties were assessed with the help of rate of corrosion, electrical resistivity and pore solution chemistry. It was found that: (i) steel corrosion resistance of the AAS concretes was comparable or in some cases even worse than that of Portland cement (PC) concrete under intermittent chloride ponding regime; (ii) the corrosion behaviour of the AAS concretes was significantly influenced by ionic exchange, carbonation and sulphide concentration; (iii) the increase of alkali concentration of the activator generally reduced chloride resulting corrosion, and a value of 1.5 was found to be an optimum modulus for the activator for improving the corrosion resistance.

Effect of Cyclic Carbonation on Chloride Ingression in GGBS Concrete

Carbonation and chloride ingress are the two main causes of corrosion in reinforced concrete structures. An investigation to monitor the ingress of chlorides and the effect of carbonation on chloride ingression during an accelerated 12 month cyclic wetting and drying exposure regime that simulates conditions in which multiple mode transport mechanisms are active was conducted on ground granulated blast furnace slag (GGBS) concrete. The penetration of chloride and carbon dioxide was evaluated using water and acid soluble chloride profiles and phenolphthalein indicator, respectively. The results indicated that when chloride and carbon dioxide ingress concomitantly the effects can be adverse. Carbonation has a detrimental effect on the binding capacity of the concrete, increasing the concentration of free (water soluble) chlorides. This contributed to greater concentration and greater penetration of chlorides and thus an increased corrosion risk.

'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.