• Corrosion Science and Technology
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• v.8 no.2
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• pp.81-88
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• 2009

Chloride induced corrosion of steel reinforcement inside concrete is a major concern for concrete structures exposed to a marine environment. It is well known that transport of chloride ions in concrete occurs mainly through ionic/molecular diffusion, as a gradient of chloride concentration in the concrete pore solution is set. In the process of chloride transport, a portion of chlorides are bound in cement matrix then to be removed in the pore solution, and thus only the rest of chlorides which are not bound (i.e. free chlorides) leads the ingress of chlorides. However, since the measurement of free/bound chloride content is much susceptible to environmental conditions, chloride profiles expressed in total chlorides are evaluated to use in many studies In this study, the capacity of chloride binding in cement matrix was monitored for 150 days and then quantified using the Langmuir isotherm to determine the portions of free chlorides and bound chlorides at given total chlorides and the redistribution of free chlorides. Then, the diffusion of chloride ion in concrete was modeled by considering the binding capacity for the prediction of chloride profiles with the redistribution. The predicted chloride profiles were compared to those obtained from conventional model. It was found that the prediction of chloride profiles obtained by the model has shown slower diffusion than those by the conventional ones. This reflects that the prediction by total chloride may overestimate the ingress of chlorides by neglecting the redistribution of free chlorides caused by the binding capacity of cement matrix. From the evaluation, it is also shown that the service life prediction using the free chloride redistribution model needs different expression for the chloride threshold level which is expressed by the total chlorides in the conventional diffusion model.

• Proceedings of the Korea Concrete Institute Conference
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• 2006.11a
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• pp.537-540
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• 2006

Over the past few decades, a considerable number of studies on the durability of concrete have been carried out extensively. A lot of improvements have been achieved especially in modeling of ionic flows. However, the majority of these researches have not dealt with the chloride binding isotherm based on the mechanism, although chloride binding capacity can significantly impact on the total service life of concrete under marine environment. The purpose of this study is to develop the model of chloride binding isotherm based on the individual mechanism. It is well known that chlorides ions in concrete can be present; free chlorides dissolved in the pore solution, chemical bound chlorides reacted with the hydration compounds of cement, and physical bound attracted to the surface of C-S-H grains. First, sub-model for water soluble chloride content is suggested as a function of pore solution and degree of saturation. Second, chemical model is suggested separately to estimate the response of binding capacity due to C-S-H and Friedel's salt. Finally, physical bound chloride content is estimated to consider a surface area of C-S-H nano-grains and the distance limited by the Van der Waals force. The new model of chloride binding isotherm suggested in this study is based on their intrinsic binding mechanisms and hydration reaction of concrete. Accordingly, it is possible to characterize chloride binding isotherm at the arbitrary stage of hydration time and arbitrary location from the surface of concrete. Comparative study with experimental data of published literature is accomplished to validity this model.

• Analytical Science and Technology
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• v.25 no.1
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• pp.33-38
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• 2012

Despite the importance of chloride binding, it is very difficult to measure the binding capacity, in particular, for the concrete body in an existing structure: in fact, the measurement procedure for chloride binding is much influenced by the environmental condition such as temperature, fineness of sample and pore water extraction techniques. The present study concerns the quantification of the binding capacity of chloride ions in concrete using the X-ray diffraction (XRD) technique. Once the binding isotherm of chlorides was determined by the Langmuir isotherm, as a function of the W/C, curing age and binder type, the generation of bound chlorides (i.e. Friedel's salt) was simultaneously ensured by the XRD technique. The amount of bound chloride was then determined by analyzing the peak intensity for the bound chlorides in the XRD curve. It was found that an increase in the curing age and a decrease in the W/C resulted in an increase in the binding capacity.

• Proceedings of the Korea Concrete Institute Conference
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• 1999.10a
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• pp.131-134
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• 1999

Microstructure modification and electrochemical properties are investigate to estimate the effects of internal chlorides on the steel corrosion in the blended cement systems. According to the test results, slag cement system showed high chloride binding capacity and low corrosion rate. The impedance data showed three distince arcs from lowest(mHz) frequency to highest (MHz) frequency due to product layer, interfacial reaction and bulk matrix. Through the microstructural investigation, fine steel-matrix interface of slag cement system was observed but rough steel-matrix interface of OPC system was observed. Friedel's salt was thought that the substantial material contributed to the chloride binding of slag cement system.

• KSCE Journal of Civil and Environmental Engineering Research
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• v.28 no.5A
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• pp.709-718
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• 2008

Developed is a chloride penetration analysis program in which changes of environmental conditions such as temperature, humidity and external chloride concentration, and the diffusion, convection and binding of chlorides are considered. In order to consider the changes of environmental conditions, analyses for temperature and moisture distribution are implemented simultaneously, and variation of diffusion coefficients due to temperature, humidity and age is also considered. By comparing the calculated total chloride contents with some experimental data, it has been confirmed that the proposed analysis program can trace measured chloride distribution well. Also, through some example analyses, the mechanism of accumulation of chlorides at near surface and acceleration of corrosion of steel reinforcement in case that the moisture distribution changes according to repeated drying and wetting cycles have been verified.

• Journal of the Korean Chemical Society
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• v.20 no.5
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• pp.406-416
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• 1976

A series of $N^1$-alkylnicotinamide chlorides, $N^1$-methyl-to $N^1$-dodecylnicotinamides inclusive were studied with rabbit muscle L-${\alpha}$-glycerophosphate dehydrogenase to investigate the possibility of reversible and irreversible inactivation of the pyridine-linked dehydrogenases by the coenzyme-competitive inhibitor derivatives. The inhibition of the enzyme by $N^1$-alkylnicotinamide chlorides was demonstrated to be reversible at the dilute concentration of the inhibitors but this reversible inhibition was found to be followed by an irreversible time-dependent inactivation measuable at high concentrations of the inhibitors. The properties of this time-dependent inactivation were discussed on the basis of the denaturation of the enzyme by the binding of small micelle-like structures formed at higher concentrations of the inhibitors.

• Computers and Concrete
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• v.17 no.1
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• pp.53-66
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• 2016

Currently, most of the investigations on chloride diffusion were based on the experiments and simulations concerning single cation type chlorides. Chloride diffusion associated with dual or multi cation types was rarely studied. In this paper, several groups of diffusion experiments are conducted using chloride solutions containing single, dual and multi cation types. A multi-ionic model is also proposed to simulate the chloride diffusion behavior in the experimental tests. The MATLAB software is used to numerically solve the nonlinear PDEs in the multi-ionic model. The experimental and simulated results show that the chloride diffusion behavior associated with different cation types is significantly different. When the single cation type chlorides are adopted, it is found that the bound rates of chloride ions combined with divalent cations are greater than those combined with monovalent cations. When the dual/multi cation type chlorides are adopted, the chloride bound rates increase with the $Ca^{2+}/Mg^{2+}$ percentage in the source solutions. This evidence indicates that the divalent cations would markedly enhance the chloride binding capacity and reduce the chloride diffusivity. Moreover, on the basis of the analysis, it is also found that the complicated cation types in source solutions are beneficial to reducing the chloride diffusivity.

• Corrosion Science and Technology
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• v.8 no.5
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• pp.171-176
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• 2009

The chloride threshold level (CTL) in mixed concrete containing, ordinary Portland cement (OPC), pulverized fuel ash (PFA) ground granulated blast furnace slag (GGBS), and silica fume (SF) is important for study on corrosion of reinforced concrete structures. The CTL is defined as a critical content of chloride at the steel depth of the steel which causes the breakdown of the passive film. The criterion of the CTL represented by total chloride content has been used due to convenience and practicality. In order to demonstrate a relationship between the CTL by total chloride content and the CTL by free chloride content, corrosion test and chloride binding capacity test were carried out. In corrosion test, Mortar specimens were cast using OPC, PFA, GGBS and SF, chlorides were admixed ranging 0.0, 0.2, 0.4, 0.8, 1.0, 1.5, 2.0, 2.5 and 3.0% by weight of binder. All specimens were cured 28 days, and then the corrosion rate was measured by the Tafel's extrapolation method. In chloride binding capacity, paste specimens were casting using OPC, PFA, GGBS and SF, chlorides were admixed ranging 0.1, 0.2, 0.3, 0.5, 1.0, 1.5, 2.0, 2.5 and 3.0% by weight of binders. At 28days, solution mixed with the powder of ground specimens was used to measure binding capacity. All specimens of both experiments were wrapped in polythene film to avoid leaching out of chloride and hydroxyl ions. As a result, the CTL by total chloride content ranged from 0.36-1.44% by weight of binders and the CTL by free chloride content ranged from 0.14-0.96%. Accordingly, the difference was ranging, from 0.22 to 0.48% by weight of binder. The order of difference for binder is OPC > 10% SF > 30% PFA > 60% GGBS.

• Proceedings of the Korea Concrete Institute Conference
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• 2005.05b
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• pp.205-208
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• 2005

The present study surveys the concrete properties-concerned factors influencing the chloride threshold level for steel corrosion in concrete, altogether with supporting experimental works, in particular, chloride binding capacity, buffering capacity, condition of steel-concrete interface and cement replacement. It concluded that the order of the dominance on CTL is such that chloride binding < buffering capacity of cement matrix < physical condition of steel-concrete interface. This is attributed to the fact that calcium hydroxide does not form a continuous layer on the steel surface and that bound chlorides are released at the stage of corrosion initiation.

• Journal of the Korea institute for structural maintenance and inspection
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• v.12 no.5
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• pp.133-142
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• 2008

This paper studies the early-aged chloride binding capacity of various blended concretes including OPC(ordinary Portland cement), PFA(pulversied fly ash), GGBFS(ground granulated blast furnace slag) and SF(silica fume) cement paste. Cement pastes with 0.4 of a free water/binder ratio were cast with chloride admixed in mixing water, which ranged from 0.1 to 3.0% by weight of cement and different replacement ratios for the PFA, GGBFS and SF were used. The content of chloride in each paste was measured using water extraction method after 7 days curing. It was found that the chloride binding capacity strongly depends on binder type, replacement ratio and total chloride content. An increase in total chloride results in a decrease in the chloride binding, because of the restriction of the binding capacity of cement matrix. For the pastes containing maximum level of PFA(30%) and GGBFS(60%) replacement in this study, the chloride binding capacity was lower than those of OPC paste, and an increase in SF resulted in decreased chloride binding, which are ascribed to a latent hydration of pozzolanic materials and a fall in the pH of the pore solution, respectively. The chloride binding capacity at 7 days shows that the order of the resistance to chloride-induced corrosion is 30%PFA > 10%SF > 60%GGBFS > OPC, when chlorides are internally intruded in concrete. In addition, it is found that the binding behaviour of all binders are well described by both the Langmuir and Freundlich isotherms.