Comparative study of methods used to estimate ionic diffusion coefficients using migration tests

Ionic diffusion coefficients are estimated rapidly using electromigration tests. In this paper, electromigration tests are accurately simulated by numerically solving the Nernst-Planck (NP) equation (coupled with the electroneutrality condition (EN)) using the finite element method. Numerical simulations are validated against experimental data obtained elsewhere [E. Samson, J. Marchand, K.A. Snyder, Calculation of ionic diffusion coefficients on the basis of migration test results, Materials and Structures/Matériaux et Constructions 36 (257) (2003) 156-165., H. Friedmann, O. Amiri, A. Aït-Mokhtar, A direct method for determining chloride diffusion coefficient by using migration test, Cement and Concrete Research 34 (11) (2004) 1967-1973.]. It is shown that migration due to the non-linear electric potential completely overwhelms diffusion due to concentration gradients. The effects of different applied voltage differences and chloride source concentrations on estimations of chloride diffusion coefficients are explored. We show that the pore fluid within concrete and mortar specimens generally differs from the curing solution, lowering the apparent diffusion coefficient, primarily due to interactions of chloride ions with other ions in the pore fluid. We show that the variation of source chloride concentration strongly affects the estimation of diffusion coefficients in non-steady-state tests; however this effect vanishes under steady-state conditions. Most importantly, a comparison of diffusion coefficients obtained from sophisticated analyses (i.e., NP-EN) and a variety of commonly used simplifying methods to estimate chloride diffusion coefficients allows us to identify those methods and experimental conditions where both approaches deliver good estimates for chloride diffusion coefficients. Finally, we demonstrate why simultaneous use and monitoring of current density and fluxes are recommended for both the non-steady and steady-state migration tests.     

氯离子扩散系数快速测试方法综述

氯离子扩散系数是评价混凝土结构抗氯离子渗透性能和使用寿命的重要指标,选择一种快速、准确的测试方法至关重要.本文以非稳态电迁移实验(Rapid Chloride Migration,RCM)为基准,与国内外常用的几种氯离子扩散系数快速测试法比较,总结每种方法的特点及适用范围,建立RCM法与其他测试方法的相关性.结果表明:...     

Influence of traversing crack on chloride diffusion into concrete

This study examined the effects of traversing cracks of concrete on chloride diffusion. Three different concretes were tested: one ordinary concrete (OC) and two high performance concretes with two different mix designs (HPC and HPCSF, with silica fume) to show the influence of the water/cement ratio and silica fume addition. Cracks with average widths ranging from 30 to 250 μm, were induced using a splitting tensile test. Chloride diffusion coefficients of concrete were evaluated using a steady-state migration test. The results showed that the diffusion coefficient of uncracked HPCSF was less than HPC and OC, but the cracking changed the material behavior in terms of chloride diffusion. The diffusion coefficient increased with the increasing crack width, and this trend was present for all three concretes. The diffusion coefficient through the crack D_cr was not dependent of material parameters and becomes constant when the crack width is higher than  80 μm, where the value obtained was the diffusion coefficient in free solution.     

Improvement of the chloride ingress resistance of OPC mortars by using spent cracking catalyst

The influence of the incorporation of spent cracking catalyst (FC3R) on the chloride ingress resistance has been evaluated. Thermogravimetric analyses have shown that the pozzolanic reaction of FC3R yields higher contents of hydrated calcium aluminates and silicoaluminates, so chloride binding capacity of mortars was highly improved. Mercury intrusion porosimetry analyses demonstrated that FC3R produces a significant reduction of capillary pore volume. As a result non-steady-state and steady-state chloride diffusion coefficients were reduced, enhancing the chloride ingress resistance of mortars incorporating FC3R. Additionally, the corrosion behaviour of steel embedded in Portland cement mortars partially substituted by spent cracking catalyst (FC3R) under chloride attack has been studied. Results showed that the incorporation of FC3R decreased the corrosion rates of steels and increased chloride thresholds for corrosion. For this reason, FC3R is an interesting pozzolanic material that can be used in reinforced concrete for civil engineering applications exposed to the action of chlorides.     

Effect of uniaxial compressive loading on gas permeability and chloride diffusion coefficient of concrete and their relationship

Knowledge of the transport properties of damaged concrete in marine environments is essential for predicting its durability. The objective of this study was to fill this gap by correlating the change in permeability and chloride diffusivity with an increasing uniaxial load on ordinary concrete (OC) and high performance concrete (HPC). Concrete cylinders were induced microcracks by mechanical uniaxial compression between 60% and 90% of the ultimate strength to get diffuse damage. The damage variable of specimens was evaluated by elastic stiffness degradation and ultrasound pulse velocity. After unloading intrinsic gas permeability was measured using a constant head permeameter, the chloride migration coefficient was evaluated by migration test in steady state conditions, with the same concrete specimen. The damage variable of specimens showed relationship with gas permeability and chloride diffusion of concrete in this experiment. A correlation was obtained between intrinsic permeability coefficient and chloride diffusion coefficient depending on the damage variable, specific for each concrete type (OC and HPC).     

Change of pore size in concrete due to electrochemical chloride extraction and possible implications for the migration of ions

Electrochemical chloride extraction (ECE) is used for the rehabilitation of chloride-contaminated concrete. Anions such as chloride and hydroxide are pushed away from the cathode (reinforcement), and cations such as sodium, potassium and calcium are attracted to the cathode. During ECE an increase of the concrete resistance can be observed. The results of a petrography study on ECE-treated concrete are presented in this paper. It also investigates the influence of pore size on ion migration using a concrete substitute model with known pore size. Findings showed that the pore size and pore size distribution of concrete are altered due to ECE. It is therefore suggested that concrete acts as active migration medium in the migration process by releasing ions into the pore solution. Moreover, small pores hinder the migration of ions, which may partially be responsible for changes in concrete resistance.     

Approximate migration coefficient of percolated interfacial transition zone by using the accelerated chloride migration test

In this study, the electrochemical technique is applied to accelerate chloride ion migration in cement-based material to estimate its migration coefficient. In order to investigate the chloride migration coefficient of percolated interfacial transition zone (ITZ) on the chloride migration coefficient of specimen, specimens with cylindrical aggregates of the same height as the specimen were cast and tested. In this study, the volume fraction of aggregate is constant and the varied lateral surface area of the aggregate cylinder was obtained by using different diameters and number of aggregate. The chloride migration coefficient of cement-based material was determined experimentally as a function of the lateral surface area of aggregate. A model obtained for the migration coefficient of cement-based material and the regression analysis are used to determine the approximate chloride migration coefficient of the percolated ITZ. Based on the experimental and regression analytical results, the approximate percolated ITZ migration coefficient is 40.6, 35.5, and 37.8 times of the altered migration coefficient of matrix mortar for the water/cement (w/c) ratio of 0.35, 0.45, and 0.55, respectively.     

The apparent and effective chloride migration coefficients obtained in migration tests

The apparent (D_app) and effective (D_eff) migration coefficients obtained in chloride migration tests are investigated in this study. The presented D_app profiles in concrete show that the apparent migration coefficient is strongly concentration-dependent. As demonstrated, the binding of chlorides during the migration tests is very low at low free-chloride concentrations and therefore the chloride penetration front progresses throughout the concrete only slightly retarded by the binding. The diffusion flux during migration tests is shown to be insignificant compared to the migration flux. The D_RCM obtained from the Rapid Chloride Migration (RCM) tests are found to be equal to the computed D_app at the locations of the chloride penetration fronts, which gives an indication that the D_RCM represents only the migration coefficient at the front. A linear correlation is found between the D_RCM obtained from the traditional RCM model and the D_eff obtained from the chloride transport model which includes non-linear chloride binding and concentrations in non-equilibrium.     

Relating rapid chloride transport parameters of concretes to microstructural features extracted from electrical impedance

The rapid chloride transport parameters such as the rapid chloride permeability (RCP) and non-steady state migration coefficient are related to the material microstructural parameters in this paper. Electrical impedance spectroscopy and associated equivalent circuit modeling are used to extract the microstructural features of the plain concrete as well as concretes modified with varying amounts of Class F fly ash or silica fume. A methodology is developed in this paper that utilizes the ratios of RCP values and the ratios of effective conductivities to pore solution conductivities of plain and modified concretes, to quantify the relative influence of pore solution conductivity and pore structure on the RCP values. The resistance attributable to the connected pores is extracted from an equivalent circuit model for the impedance spectra of concretes, which is found to relate well to the rapid chloride transport parameters as well as the microstructural parameters. Based on the experimental results and electrical circuit models, it is shown that a reduction in pore connectivity has a higher impact on the rapid chloride transport parameters than a reduction in the porosity, and reduction in pore sizes is more consequential than porosity reduction in reducing pore connectivity.     

An electrochemical method for accelerated testing of chloride diffusivity in concrete

In the present paper an electrochemical method for accelerated testing of chloride diffusivity in concrete is presented. The method is based on a theoretical relationship between chloride diffusivity and observed steady-state rate of chloride migration through the concrete. The concrentration of the chloride source solution has a significant influence on the rate of chloride migration and, therefore, a correction factor for ionic interaction in the relationship is introduced. It is shown that the relationship can be used for calculation of chloride diffusivity under various testing conditions. Some experimental results are also presented.     

New method to measure the rapid chloride migration coefficient of chloride-contaminated concrete

The apparent chloride diffusion coefficient, D_app, which is obtained by fitting chloride profiles as the result of time-consuming immersion tests can be substituted in a model on chloride ingress by the rapid chloride migration (RCM) coefficient of concrete, D_RCM, which is determined under electrically accelerated conditions. Until now, it was not possible to measure D_RCM of chloride-contaminated concrete, as already inherent chlorides interfere with the common colorimetric indicator used for penetration depth measurements. Furthermore, carbonation may also interfere with the penetration depth reading. To overcome these problems, the regular test has been modified by using iodide as penetrating ion and iodate-starch acetic acid as indicator. A strong linear relationship between the regular RCM test and the newly developed Rapid Iodide Migration (RIM) Test was found. Carbonated specimens can be tested using the RIM test without additional interference. Thus, the new method enables the quantification of the actual concrete quality sampled from existing structures during a condition assessment.     

混凝土孔结构及其分形维数与氯离子扩散性能的关系

氯离子扩散系数是研究海洋环境下混凝土结构耐久性的重要参数之一。通过开展不同水胶比混凝土的压汞试验和盐雾扩散试验,研究了混凝土内部孔隙率、孔径分布及临界孔径对氯离子扩散系数的影响规律。结合Menger海绵体模型,建立孔体积分形维数与氯离子扩散系数的关系。结果表明:孔隙率和临界孔径与无量纲化氯离子扩散系数的相关性很高,可作为反映混凝土氯离子扩散性能的重要参数;通过数学分析计算得到的孔表面分形维数分布在2.56~3.86之间,孔体积分形维数分布在2.85~2.98之间;基于压汞法和分形理论计算得到的孔体积分形维数可以作为评价氯离子扩散系数的指标,在孔径小于10 nm、10～100 nm、100～1 000 nm以及大于1 000 nm四类区间,氯离子扩散系数随孔体积分形维数的增加而下降。     

In situ leaching method for determination of chloride in concrete pore water

In the in situ leaching (ISL) method, pore water ionic content is determined in small cavities drilled in mortar/concrete specimens. Prior investigations have demonstrated the ISL applicability to obtain pH and nitrite ion concentration in concrete/mortar pore water. The application of the method is extended here to determine pore water chloride ion concentration (and pH) within practical test times in mortars and concretes prepared in the laboratory and in concrete cores extracted from a bridge deck in deicing salt service. Spatial resolution for the determination of composition profiles is also illustrated. Modeling of the ISL process indicates that chloride binding accelerates the approach toward a terminal cavity concentration, reducing test duration to practical lengths for moderate permeability concretes. This acceleration can be attributed to maintaining a higher gradient of free chloride near the cavity wall due to the release, during leaching, of previously bound chloride. Consequently, there is a faster chloride buildup in the cavity water compared with the no-binding case. Experimental chloride and pH results obtained by the ISL test in mortar samples show good agreement with those from the pore water expression (PWE) method. Also, examples are presented of application of ISL data to obtain chloride binding isotherms, and pore water chloride to hydroxide ratio relevant to assessing conditions for corrosion of steel reinforcement. The ISL method presents a less costly and less disruptive alternative to PWE for pore water analysis. It is noted, however, that in a few instances ISL could not be implemented because of excessive absorption of cavity water by the surrounding medium.     

Improvement in concrete resistance against water and chloride ingress by adding graphene nanoplatelet

Graphene nanoplatelet (GNP) is a cheap impermeable carbon-based nanoplatelet with large surface-to-volume ratio and has been exploited in polymer materials to improve their transport resistance. Experimental investigation on the transport properties under chloride and water exposure was carried out on concrete containing up to 2.5% of GNP at 0.5% increment. The pore structure was inferred using mercury intrusion porosimetry and significant reduction in pore sizes was measured. Concrete with 1.5% of GNP showed the greatest reduction in transport; water penetration depth, chloride diffusion, and migration coefficients were reduced by 80%, 80%, and 37%, respectively. The barrier effects of GNP were characterized and it was found that more than 50% of the improvement in transport resistance can be attributed to tortuosity while the rest to pore refinement. However, further improvement did not take place at GNP content higher than 1.5% due to limitation in dispersing the nanoplatelet clusters.     

干湿循环下煤矸石混凝土孔结构特性及抗氯离子侵蚀机理

氯离子侵蚀是影响混凝土耐久性的重要因素。通过干湿循环试验,研究了煤矸石混凝土的抗氯离子侵蚀性能,分析了煤矸石体积取代率(0%、20%、40%、60%)对氯离子浓度分布和表观扩散系数的影响。通过压汞试验,测定了煤矸石混凝土的孔结构参数,通过计算其孔隙体积分形维数,研究了孔结构对煤矸石混凝土抗氯离子侵蚀性能的影响。结果表明:随着煤矸石掺量的增加,自由氯离子的浓度先减小后增加,而表观扩散系数先增加后减小;煤矸石掺量为40%时,混凝土密实性最好,孔隙体积分形维数最大;与未添加煤矸石的混凝土相比,掺量40%的煤矸石混凝土氯离子浓度最低,此时抗氯离子侵蚀性能最好,且表观扩散系数下降35.68%。     

The relationship between charge passed and the chloride-ion concentration in concrete using steady-state chloride migration test

The accelerated chloride migration test in this study is a modified version of the ASTM C1202-97 or AASHTO T277-96 (RCPT) method. The current, chloride-ion concentration and temperature were measured during the experiment. Four different concretes used for test had a water to cementitious ratio of 0.4, containing various mineral admixtures. The transport properties were investigated using the accelerated chloride migration test. At a steady-state chloride flux, a good correlation was found between the charge passed (obtained by integrating the current-time curve) and the chloride-ion concentration.     

低温(3℃)养护条件下不同水胶比对引气混凝土孔结构参数及抗渗性的影响

针对西部寒冷以及盐渍土地区的灌注桩混凝土,主要研究了低温(3 ℃)养护环境下不同水胶比对引气混凝土孔结构参数以及抗渗性能的影响.试验结果表明:随着水胶比的增大,引气混凝土的孔隙率与气泡间距系数都呈现增大的趋势,低温养护条件下孔隙率与气泡间距系数大于标准养护条件下;低温养护条件下混凝土主要孔径分布范围明显大于标准养护条件;低温养护条件下混凝土抗渗性能小于标准养护条件下混凝土,随着水胶比的增大,抗氯离子渗透性能下降,水胶比越大,抗渗性能下降越快;混凝土电通量和氯离子迁移系数与混凝土孔结构参数(孔隙率、气泡间距系数、孔径分布)呈现高度正负相关.     

Experimental investigation and numerical modeling of chloride penetration and calcium dissolution in saturated concrete

Chloride penetration and calcium dissolution have been investigated for a saturated concrete after exposure to a 0.5 mol/L NaCl solution for a period of up to 3150 days. Simultaneous ion transport model (SiTraM) that allows the transport of chloride and calcium ions to be simultaneously simulated in a hydrated cement system has been used to verify the experimental results.Self-compacting concrete (SCC) with a water to cement ratio of 0.3 resulted in a limited chloride penetration depth while the calcium dissolution was also reduced within the near surface zone. Increased unit water content for normal concrete resulted in higher chloride penetration depth and larger dissolution front of Ca(OH)₂ regardless of having the same water to cement ratio.It was revealed that the SiTraM can predict the profiles of chloride and calcium for self-compacting concrete. It was also found that the primary factor to control chloride penetration front and the dissolution front of Ca(OH)₂ was the pore structure characteristic of concrete.     

Aggregate influence on chloride ion diffusion into concrete

An attempt is made to predict the probable effect of the aggregate on chloride ion diffusion into saturated concrete. It is shown that if the chloride ion diffusion coefficient of an aggregate ranges from 0.2 to 10 times that of the cement paste matrix, then this could result in variations in the concrete chloride ion diffusion coefficient of up to 10:1. Such a variation is equivalent to a change in free water-cement ratio from 0.77 to 0.45.     

水胶比对混凝土性能及气孔结构的影响分析

通过试验,对不同水胶比下混凝土28 d龄期的抗压强度、氯离子电通量及微观方面的气孔结构和气孔特征参数进行了对比分析,研究了水胶比对混凝土宏观性能及微观孔结构的影响.结果表明:过量的自由水会在混凝土内部产生毛细孔,增大水胶比相当于变相增多了混凝土内部的孔隙数量,能够显著降低混凝土的抗压强度,但较大的水胶比又能够增强局部的水泥水化反应.对氯离子电通量而言,水胶比越大,毛细孔越多,孔含量越多,相对增大了连通孔隙的数量,氯离子电通量会呈现出增大的现象.随着水胶比的减小,孔径分布也有向小孔径方向发展的趋势.此外,抗压强度与较小孔径的孔含量及孔隙率的关联度计算结果较大,氯离子电通量与气孔间距系数的关联度计算结果较大,这说明小孔含量及孔隙率能够用来表征混凝土的抗压强度,气孔间距系数也能在一定程度上表征混凝土的耐久性.