Corrosion Science 44 (2002) 24092424 www.elsevier.

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Accelerated simultaneous determination of the chloride depassivation threshold and of the non-stationary diusion coecient values
M. Castellote *, C. Andrade, C. Alonso
Institute of Construction Science, Eduardo Torroja CSIC, C/Serrano Galvache s/n, 28033 Madrid, Spain Received 14 January 2000; accepted 23 February 2002

Abstract Numerous studies have been already carried out to study the chloride threshold value for depassivation of the steel embedded in concrete. Most of them were based on natural penetration of chlorides, whose main disadvantage is that it is very time consuming and makes necessary a long time to obtain reliable data. Other methods used were potentiostatic tests that, depending on the potential applied, may also be very long. In present paper, a new accelerated method to determine the threshold value of corrosion of steel is tried on a mortar specimen with an embedded rebar. The procedure is based on the use of the mechanism of migration to force the penetration of chlorides into the specimen, but switching o the external voltage and measuring the resulting threshold value in quasi-natural conditions. In spite of some considerations regarding the fact of the acceleration, the thresholds found (total, free Cl and Cl /OH ratio) are in good enough accordance with those found for a twin specimen in natural conditions and within the range reported for mortars in the literature. In addition, this method has the advantage of enabling the simultaneous determination of the non-stationary chloride diusion coecient, Dns from the migration data, which has also been validated in natural conditions. 2002 Elsevier Science Ltd. All rights reserved.

1. Introduction The main aggressive regarding reinforcement corrosion is the chloride ion. The amount of chlorides inducing active corrosion of the steel is named the chloride threshold [1,2]. Up to now, a single value for this threshold has not been found, as it

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varies depending mainly on concrete [2] (pH of pore solution, moisture content in the concrete, temperature, type of cation, C3 A content and nesse of the cement, blended materials, etc.) and on the steel characteristics [3] (composition, impurities, roughness of the surface, aging). Although the expression of this threshold is usually made as total chloride content, either by weight of cement or concrete, it is also accepted that only free chlorides are able to depassivate the steel. At this respect, already in the 60s [1,2] it was proposed to express the threshold in terms of the Cl /OH ratio, that seems to be more rigorous due to the competitive action of both ions and additionally, it accounts for the dierent cement types and their evolution with time. Numerous authors [1,2,431] have reported dierent chloride thresholds to depassivate the reinforcing steel. Most of them have carried out tests based on natural penetration of chlorides, whose main disadvantage is that it is very time consuming and makes necessary a long time to obtain reliable data. On the other hand, more rapid tests have been carried out to determine the threshold value not at a free corrosion potential, but in potentiostatic conditions [27] or by anodic polarisation [2,20]. The wondering of these last kind of methods is, on the opposite, that the threshold value is not measured in natural conditions. In summary, the threshold of depassivation of the steel depends on several factors depending on the concrete and on the steel, being the overall key point the potential of the steel [3]. As the potential varies during the life in the same reinforcement, several thresholds can be found for the same kind of specimens. This fact implies that the best way of dening the threshold value may be a set of values in function of the steel potential, and not a single one, as already pointed out in [32]. In that paper [32], potentiostatic tests were performed which enabled to determine a set of Cl /OH values. However, in spite that the potentiostatic tests at noble values are relatively fast, at more cathodic ones, the tests still resulted too long (several months) for quality control, and therefore, it seems convenient to continue with the search to have a reliable and quick enough test for determining the chloride threshold. This task is undertaken in present paper, where an accelerated test is proposed with the additional advantage of the simultaneous determination of the non-steadystate diusion coecient. The method is based on the use of the mechanism of migration to force the penetration of chlorides into the specimen, but measuring the resulting threshold value in quasi-natural conditions. Through migration, the nonsteady-state diusion coecient, Dns , of the matrix embedding the rebar can be calculated. More work is however needed to take into account the variability of the threshold with the potential of the steel at the time of arrival of chlorides, as well as to take into account, in the value of Dns , the concrete ageing.

2. Experimental 2.1. Materials Two mortar cubic shaped specimens (70 70 mm) were cast with a corrugated steel rebar embedded in the central part. The area of the steel in contact with the

M. Castellote et al. / Corrosion Science 44 (2002) 24092424 Table 1 Dosage of the specimens Cement (kg/m3 ) Mortar 708.3 Sand (kg/m3 ) 1239.4 Water (kg/m3 ) 262.1 Ratio (w/c) 0.37

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Additive (l) 7

Table 2 Summary of the purpose and number of specimens involved Specimens With rebar 2 Container Yes Yes Without rebar 1 Yes Acceleration Yes No No Run until . . . Depassivation Depassivation 90 days Purpose Accelerated threshold and Dns value Natural threshold value Natural Dns value

mortar was 5.6 cm2 . Another specimen without steel was also cast. All the specimens were demoulded 24 h after casting and cured for 28 days into a wet chamber (95% HR). The cement employed was of the type IV-B-32.5 SR/BC. Table 1 contains the mix proportion of the mortar fabricated. A container was sealed on one of the faces parallel to the length of the embedded rebar, in all the specimens, and was lled with a solution 1 M of NaCl. The purpose of each one of the specimens is summarised in Table 2. 2.2. Procedures In one of the specimens with embedded rebar, a stainless steel was placed inside the NaCl solution, and was connected to the negative pole of a power source. The positive electrode (anode) was a steel plate, electrically connected to the specimen by means of a wet sponge. The arrangement used for this test is shown in Fig. 1. Additionally, two Ag/AgCl electrodes (Cl sensors) [33] were also embedded in the path of chlorides through the corrugated bar, in order to better follow them. The position of them can also be seen in Fig. 1. Initially, a series of increasing voltages ranging from 0 to 13 were applied, waiting a few minutes until stabilisation of the potential of the steel for every potential tested, before to take the corresponding value. As a second part of the test, a voltage drop was applied between the electrodes: 3 V during 3 days, 10 V during 6 days and 13 V during 14 days. After this period of 23 days, the power was switched o and the catholyte solution was removed. The specimen was stored in a humid chamber (95% HR), with water in the container, being the potential of the rebar periodically measured. After 30 days of storage, the container was lled with fresh NaCl 1 M solution and a voltage drop of 13 V was applied during 5 days. In this step, the catholyte solution was neutralised with HCl 0.05 M, to maintain the pH permanently around neutral values (68). After, the specimen was again stored in the humid chamber for 15 days.

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Fig. 1. Experimental arrangement used for the accelerated test.

A summary of the procedure followed is given in Table 3. During the test, the electrical potential of the rebar as well as the potentials of the sensors were monitored, by means of reference electrodes (a saturated calomel electrode (SCE) and Mn/MnO electrodes respectively), in order to detect the instant

Table 3 Summary of procedure followed in the case of the accelerated test Container Voltage (V) Period (d) Instantaneous Storage Remarks Series of increasing voltages NaCl 1 M 0 1 2 5 7.5 9.9 13 Determination of the threshold value NaCl 1 M 3 10 13 Water 0 NaCl 1 M 13 Water 0

3 6 14 30 5 15

Without neutralising

95% HR 95% HR

Neutralising

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of depassivation of the steel. Periodically, the power supply was switched o to have also the data of potential without the electrical eld applied. The current circulating between anode and cathode was registered by means of a HP ammeter. Periodic measurements of the corrosion rate of the rebar were carried out (without application of the external potential) by means of the polarisation resistance technique [34], to have a conrmation of its passive or corroding state. For the other two specimens, chloride ions were allowed to enter into the specimen by natural diusion, in order to have a reference for the data obtained in the accelerated test. In the case of the specimen with rebar, the state of it was determined by means of the corrosion potential measurements and the corrosion rate by the polarisation resistance technique [34], and the test was allowed to run until depassivation of the steel. In the specimen without rebar the chlorides were allowed to enter during 90 days. After this period, the chloride prole was determined by milling the specimen, and analysing (by acid extraction), the total chloride concentration at dierent depths. At the end of the threshold experiments (after depassivation of the steel), the specimens were broken and the concentration of free chlorides [35] and hydroxyl ions [36] in the mortar just around the steel was analysed in order to determine the threshold of depassivation. Additionally, in the case of the specimen in which the chlorides penetrated driven by the electrical eld, it was split in two halves following the plane transversal to the face in which was placed the container and the front of penetration of chlorides was measured over one of the halves by using the colourimetric method (spraying uoresceine and AgNO3 ) described in [37]. The other half was used to determine the chloride prole by analysing the total and free chloride concentration at dierent depths by acid extraction and alkaline leaching [35] respectively. 2.3. Dns calculations Accelerated test: The calculation of the non-steady-state diusion coecient, Dns , of chlorides from the proles of the accelerated test has been made by two dierent procedures: (1) Through the tting of the total chloride prole. As a rst step, the natural diusion equivalent time, D teq , corresponding to the accelerated test (based on the concepts given in [38]), has been calculated, having averaged the dierent external voltages applied during the time of the experiment. The averaged voltage resulted to be of 11.28 V. The equivalent time obtained has been of 2254 days. The second step corresponded to the tting of the total chloride prole to the second Ficks law [39], considering the previously calculated equivalent time of test. (2) Through the total amount of current that has passed during the test and the value of the surface concentration, Cs , after the test. This method has been developed in [40], and is based in the fact that according to Faradays law, the amount of chlorides that have penetrated into the specimen, can be calculated, if particularisation for the chloride ions is taken into account, by means of the corresponding

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transference number. Therefore, just from the recording of the current intensity during a non-steady-state migration test, it is possible to calculate the amount of chlorides that have penetrated into the specimen. If additionally, the surface concentration in the specimen, Cs , is analysed, from the integrated form of the second Ficks law, the non-steady-state diusion coecient can be obtained by using, as a nal step in the procedure, the analogy of treatment between migration and diusion in non-steady-state conditions [40]. This analogy is based in the use of a migration coecient, Dmig , which enables to apply to a migration experiment any known solution of a diusion problem [41]. Natural diusion test: Calculation of the Dns from the natural diusion test has made by tting the prole to the integrated form of the Ficks second law for semiinnite media, as given in [39].

3. Results 3.1. Accelerated test 3.1.1. Eect of the applied polarisation In the rebar: The results corresponding to the initial series of increasing voltages is shown in Fig. 2. In this gure, it can be seen that when an external electrical eld is applied through the specimen, even though the steel does not act as electrode, the rebar becomes polarised, evolving its electrical potential according a linear trend in function of the external voltage applied. In Fig. 3, the evolution of the electrical potential of the steel (SCE) in function of the time of test is shown, including data when the power supply was on, as well as the data corresponding to the punctual moments of switch o. In accordance with the results of the rst series of increasing voltages, it can be seen that when the electrical eld is applied through the specimen, the steel becomes

Fig. 2. Electrical potentials of the steel (SCE) in function of the external voltage applied.

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Fig. 3. Evolution of the electrical potential of the steel (SCE) in function of the time of test, in dierent conditions of polarisation.

anodically polarised. It is noticeable that in the step in which the catholythe is maintained neutral by addition of HCl, the polarisation soon becomes much smaller than when it remains alkaline. This lower anodic polarisation is an early warning of the steel depassivation, as will be commented later. It can also seen that when the electrical eld is switched o, the steel recovers the initial values of potential, even in the case of neutralisation of the catholyte. This can be seen better in a zoom of the part of the gure close to the X axis, where a detailed picture of the values of the potential of the rebar without electrical eld applied is shown (Fig. 4). In the Ag/AgCl electrodes: Following the same schema in the presentation of the results than those of the rebar, in Fig. 5 the evolution of the electrical potential, of

Fig. 4. Values of the electrical potential of the steel (SCE) in function of the time of test, but only when the power supply is switched o.

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Fig. 5. Evolution of the electrical potential of the Ag/AgCl electrodes (referred to MnO2 ) in function of the time of test, in dierent conditions.

the each one of the sensors of Ag/AgCl, in function of the time of test is shown. This picture includes data corresponding to electrical eld applied as well as the data corresponding to the punctual moments of switch o. In the gure, it can be seen that when the electrical eld is on, also the Ag/AgCl electrodes become polarised showing, in this case, more negative values of electrical potential than those that they had in natural conditions. As it took place in the case of the rebar, when the electrical eld is switched o, the values of potential fall back, but it can be noticed the moment in which concentration of free chlorides in the pores is high enough to be detected as a drop of their initial electrical potential. As can be seen in Fig. 6, for the electrode at a distance of 5 mm from the Cl exposed surface, this drop takes place in around 8 days, while the

Fig. 6. Evolution of the electrical potential of the Ag/AgCl electrodes (referred to MnO2 ) in function of the time of test, but only when the power supply is switched o.

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Fig. 7. Evolution of the corrosion rate of the rebar along the test.

sensor at 10 mm from this surface detects the presence of chlorides at about 20 days. From this moment, they remained stable. 3.1.2. Corrosion rate of the rebar Fig. 7 depicts the evolution of the corrosion rate of the rebar along the test. It can be seen that, in accordance with the values of corrosion potential measured, the steel has been passive during all the test, being depassivated only after neutralising the catholyte solution and letting it stored for a few days. When the test was nished and the steel bar removed, pitting was conrmed by visual observation. 3.1.3. Chloride threshold value At the end of the experiment, after depassivation of the steel, the specimen was broken and the concentration of total chloride (% of total with respect to the sample), free chlorides and hydroxyl ions in the pore solution of the mortar, just around the steel, were analysed in order to determine the depassivation threshold. The results obtained are given in Table 4. 3.1.4. Calculation of the non-steady-state diusion coecient, Dns The proles of total and free chloride from the surface of the specimen exposed to the chloride solution (catholyte) as well as the position where the colorimetric front appeared are shown in Fig. 8. In this gure, it is also shown the position of the Ag/ AgCl sensors, as well as that of the rebar. The calculation of the non-steady-state diusion coecient, Dns , of chlorides from these proles has been made by two dierent procedures, described in Section 2. The
Table 4 Threshold values of depassivation of the steel in the conditions of the test Total Cl (%) Threshold value 0.152 Free Cl (M) 0.330 Ratio Cl /OH 2.0

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Fig. 8. Proles of total and free chlorides at the end of the test. The position of the Ag/AgCl electrodes and of the rebar are also shown.

diusion coecient obtained by the procedure (1) was of 2:67 108 cm2 /s, and by method (2) of 1:17 108 cm2 /s. 3.2. Natural tests 3.2.1. Corrosion rate of the rebar In Fig. 9(a) and (b), it can be seen the evolution of the corrosion potential of the rebar until depassivation. It can be seen that there is a very good inverse parallelism between the parameters of potential and corrosion rate. Therefore, the moment in which the steel is depassivated can be determined to be around 200 days of the beginning of the test.

Fig. 9. Evolution of the (a) corrosion potential (Ecorr ) and (b) corrosion rate (Icorr ) of the rebar along the natural test.

M. Castellote et al. / Corrosion Science 44 (2002) 24092424 Table 5 Threshold values of depassivation of the steel in the natural test Total Cl (%) Threshold value 0.227 Free Cl (M) 0.364

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Ratio Cl /OH 1.50

Fig. 10. Prole of the total chlorides after 90 days of duration of the natural penetration test.

3.2.2. Threshold value In the same way than in the case of the accelerated test, at the end of the experiment, in order to determine the threshold of depassivation, the specimen was broken and the concentration of total chlorides (% with respect to total sample), free chlorides and hydroxyl ions in the pore solution of the mortar just around the steel were analysed. The results obtained are given in Table 5. 3.2.3. Calculation of the non-steady-state diusion coecient The prole of the total chlorides from the surface of the specimen exposed to the chloride solution during 90 days can be seen in Fig. 10. Calculation of the Dns by tting the prole to the integrated form of the Ficks second law for semi-innite media, gives a Dns of 2:24 108 cm2 /s, in quite reasonably good accordance with the calculated for the same mortar in accelerated conditions.

4. Discussion The present attempt to determine the threshold value, of depassivation of the steel embedded in a cement matrix, arises from the need of developing some kind of accelerated test, as the most commonly used experiments are based in natural diffusion tests, or potentiostatic ones, that are very time consuming. However, when acceleration is tried, modications in the system are introduced, which might

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invalidate the obtained deductions. These modications have to be carefully analysed in order to consider how close of the reality is the accelerated method. 4.1. Polarisation of the rebar under an electrical eld When an electrical eld is applied to concrete with an embedded rebar, the unallocated electrons of the metal are orientated in the most favourable direction of the electrical eld. As a consequence, polarisation of the steel takes place. This polarisation is directly proportional to the voltage applied, as was shown in Fig. 2. This polarisation eect is reversible, and when the electrical eld is switched o, the values of potential of the steel fall back to the initial one, what seems to allow the measure of the resulting threshold value in quasi-natural conditions. However, it can be noticed (Fig. 3) that the last point of electrical potential for the rebar is not in the general trend (very anodic). This is attributed to the fact that a change in the passive layer of the steel may be occurring, not yet noticeable by the Rp measurements (Icorr value at 58 days < 0:1 lA/cm2 in Fig. 7). This behaviour is very interesting because, when this deviation of the polarised potential of the steel is detected, the power supply can be switched o, and the depassivation of the steel (Icorr values > 0:1 lA/cm2 ) will take place in quasi-natural conditions. This fact may be very useful from a practical point of view, as the change in the value of polarised electrical potential registered is an early warning of the depassivation of the steel. 4.2. Chloride threshold value Another point that is necessary to consider is the fact that when chlorides are being forced to penetrate into concrete, driven by the electrical eld applied, the length of the contact time between the penetrating solution and the concrete is dierent that when chlorides penetrate by natural diusion. Therefore, in natural diusion, the time of chloride reaction with the cement phases is relatively much quicker than the transport step, however in migration tests it seems that the transport rate is so rapid that the binding does not occur in the same extension [42]. In addition, it has to be considered the eect that the electrical eld could induce in the double layer of the pore walls. It might happen that the electrical eld applied could alter the double layer potential, and in consequence, induce a dierent interaction between the chlorides and the substrate, and even in the threshold level. In spite of these considerations, the results obtained from the accelerated test are in very good agreement with those of natural diusion (see Fig. 11), may be because of the use of quite concentrated NaCl solution, which provides similar binding of chlorides in diusion and migration experiments [42]. In addition, the ratio Cl /OH obtained in present trials is in good accordance with the usual range of threshold values for mortars found in the literature, as can be seen in Fig. 11. In this gure, the result obtained in present research has been plotted with the results from other authors. It has to be also stressed the fact, that in the accelerated test, the depassivation was only found after neutralisation of the alkalinity generated by the electrodic reaction

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Fig. 11. Threshold values for solutions, mortars and concretes found in the literature [31], in comparison with results of present work.

in the cathoyte. The need of adding HCl was realised when, in spite of the high anodic value of the polarised steel, depassivation did not seem to occur. This was interpreted to be due to the continuous generation of OH which had two eects: (1) decrease in the transference number of Cl [43] that makes it slower its penetration rate and (2) injection of OH ions, which decrease the Cl /OH ratio to keep it below the threshold value. Then, it is expected an important decrease of the duration of the experiment when neutralising from the beginning of the test. Finally, it has to be mentioned that the Ag/AgCl sensors did detect the arrival of chlorides, but as they were placed far away of the steel surface, they have not served to account for the amount of chlorides in the depassivation front. Their placement nearer the rebar is necessary, although still remains to verify the reliability of their potential values when switching o the current, to indicate the chloride concentrations obtained by chemical analysis. 4.3. Proposed methodology The procedure followed in the present research, by steps of increasing voltages, had the aim of nding the better methodology and therefore, is not the optimum way to carry out this kind of test. According to all aforementioned, the methodology proposed to the accelerated and simultaneous determination of the chloride threshold as well as the Dns coecient of the embedding matrix, is the following. A container has to be sealed on one of the faces of the specimen parallel to the length of the embedded rebar, and lled with a solution 1 M of NaCl. Inside the solution, a negative electrode has to be placed. The positive electrode (anode) is placed in the opposite side of the specimen, as can be seen in Fig. 1. A voltage drop in between 10 and 13 V has to be applied between the electrodes, continuously neutralising the catholyte solution with HCl 0.05 M and recording

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the current during the test and the electrical potential of the rebar (by means of a reference electrode). The electrical eld has to be switched o when a cathodic change in the polarisation of the steel is detected, and wait until depassivation in natural conditions. After depassivation of the steel, the specimen has to be broken and the concentration of free chlorides and hydroxyl ions in the mortar just around the steel has to be analysed to determine the threshold value of depassivation. The proposed method to calculate the Dns is the described as number (2) because it does not need the determination of the chloride prole in the specimen. Only the chloride surface concentration has to be also analysed. From this data, the total amount of current passed and the characteristic cathodic accumulative chloride transference number, tcac Cl, corresponding to the Cl concentration used (for NaCl 1 M, tcac Cl 0:534), the Dns can be calculated according to the procedure described in [40]. In addition, if possible, further use of the Ag/AgCl electrodes, placing them close to the rebar, would be convenient, as it has been proved that they are sensitive to the arrival of chlorides in the cementitious matrix, although verication of their reliability in the conditions of this test remains unexplored. This preliminary research has opened a new way to determine a single threshold value of depassivation of a rebar embedded in a cementitious matrix. However, it is necessary to remark that it is a rst approach to the goal. It is necessary to continue in testing this procedure with dierent specimens, with dierent type of binders and dosages of concrete, in parallel to natural diusion penetration tests, and compare the obtained results as the only way to validate this procedure of simultaneous and accelerated determination of the chloride threshold and the Dns values.

5. Conclusions In the present paper, a new accelerated method to simultaneously determine the chloride threshold value for active corrosion of steel and the non-steady-state diffusion coecient is proposed. The procedure is based on the use of the mechanism of migration to force the penetration of chlorides into the specimen, but measuring the resulting threshold value in natural conditions. The threshold value and the Dns found are in good accordance with those obtained in natural conditions for parallel specimens. However, it is necessary to continue in testing this procedure with different dosages and experimental conditions and going on in making the comparison with natural tests.

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