Developments in the Built Environment 8 (2021) 100062

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Developments in the Built Environment

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Chloride ingress rate and threshold content, as determined by the ‘Integral’

test method, in concrete with several w/c ratios in saturated and
unsaturated conditions
Yury A. Villagrán-Zaccardi a, c, *, Carmen Andrade b
a
Magnel-Vandepitte Laboratory for Structural Engineering and Building Materials, Ghent University, Belgium
b
CIMNE, Universitat Politécnica de Catalunya, Spain
c
CONICET, Argentina

A R T I C L E I N F O A B S T R A C T

Keywords: The ‘integral’ test method aims at the simultaneous determination of the chloride migration rate and chloride
Chloride threshold content threshold content. This information is required for durability performance design of reinforced concrete struc­
Chloride migration tures in the marine environment. Standard tests are generally designed to be applied on saturated samples to
Pitting
improve their repeatability and reproducibility, but this condition differs from the actual conditions of depas­
Integral test
sivation in structures in service. This paper compares results of the ‘integral’ test method applied on concrete
made with ordinary Portland cement and a water-to-cement ratio ranging 0.35–0.50, preconditioned for full
saturation and a saturation degree of 77%. Results are contrasted with concrete properties commonly associated
with its performance concerning chloride ingress. The variation in the saturation degree in the range 77–100%
showed a greater effect on the chloride ingress rate than in the chloride threshold content. The determined
chloride threshold decreases with increasing w/c ratio.

1. Introduction applied electric field that facilitates chloride penetration. Migration tests
are completed in a few days, while ponding tests (diffusion tests of
Predicting the onset of rebar corrosion in concrete exposed to chlo­ concrete specimens immersed in a chloride solution) take months to
rides requires short tests that can be performed at an early age of the complete. Using electric fields to shorten the test time is convenient from
concrete. The results of these tests can then be extrapolated to effectively a practical point of view but has a negative effect on the reliability of the
assess the future performance of the concrete. For this purpose, many results. If the current through the concrete is high, there will be a rise in
accelerated methods have been proposed (Whiting 1981; AASHTO T temperature during the test. For a given electrical potential, the lower
277 1993; Andrade 1993; ASTM C1202 2010; Baroghel-Bouny et al., the resistivity of the concrete, the higher the temperature rise. There­
2007; Castellote et al., 2001; Castellote and Andrade 2006; Frederiksen fore, the results of some methods should be interpreted with caution.
2002; Nilsson et al., 1996; NT Build 443 1995; NT Build 492 1999; Oh One method that has the above drawbacks is that of AASHTO T 277
et al., 2003; Ridding et al., 2008; Tang and Sorensen 2001). (AASHTO T 277 1993)), which estimates the resistance to chloride
Quantification of chloride penetration rate and threshold chloride penetration by measuring the electrical cha rge passed through a spec­
content for reinforcement pitting in concrete are particularly complex. imen over a short period of time. The results of this method largely
Many factors affect the chloride penetration rate, the most important of correlate with the results of the 90-day ponding test (Andrade and
which are pore geometry, chemical activity (both related to the cement Whiting 1996). However, this migration method is only qualitatively
type and w/c ratio), environmental conditions, and imperfections such informative because no value can be determined for the chloride ingress
as cracks and compaction voids. rate. The applied high voltage of 60 V DC causes the sample to heat up.
Various migration tests have been developed to evaluate the resis­ The temperature increase depends on the concrete resistivity, which is
tance of concrete to chloride penetration. Test time is shortened by an an issue for the comparability of the results.

* Corresponding author. Magnel-Vandepitte Laboratory for Structural Engineering and Building Materials, Ghent University, Technologiepark-Zwijnaarde 60, 9052
Gent, Belgium.
E-mail address: yury.villagranzaccardi@ugent.be (Y.A. Villagrán-Zaccardi).

https://doi.org/10.1016/j.dibe.2021.100062
Received 13 April 2021; Received in revised form 13 August 2021; Accepted 15 September 2021
Available online 21 September 2021
2666-1659/© 2021 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Y.A. Villagrán-Zaccardi and C. Andrade Developments in the Built Environment 8 (2021) 100062

Another widely used migration test is the CTH method (NT BUILD contrasted not only with chloride diffusion coefficients, but also other
492 1999). This method provides a result in the form of a migration indexes commonly used for durability design, such as resistivity, water
coefficient that can be correlated with the apparent diffusion coefficient penetration under pressure and capillary absorption rate. The dual aim
and used in a performance approach to durability design (Tang and is to contribute to the understanding of the electrochemical processes
Sørensen 2001). The applied electrical potential ranges from 10 to 60 V, during the ‘integral’ test method and their correspondence with the
depending on the concrete resistivity. The potential is applied over 24 h, porous properties of concrete.
except for very resistant concretes, which are tested over 48 or 96 h. River siliceous sands, coarse (CSS) and fine (FSS), served as the fine
Conventional concrete is usually tested at more than 25 V over 24 h as aggregate. The coarse aggregate was crushed granite of nominal size
this potential is high enough. However, chloride binding is an important 6–20 mm (GCS 6–20). The properties of the aggregate are listed in
retarding process for chloride penetration into concrete, which cannot Table 1. In addition, Ordinary Portland Cement (OPC) was used. The
be properly assessed in 24 h (Castellote et al., 1999). Consequently, the chemical and physical properties of OPC are given in Table 2.
value of the CTH coefficient must be corrected to account for the in­ A naphthalene superplasticizer was used. The solid residue by oven-
fluence of chloride binding on the prediction of chloride penetration drying at 60 ◦ C and the density of the superplasticizer were 36.8 wt %
profiles (Martín-Pérez et al., 2000; Glass and Buenfeld 2000). and 1.18, respectively.
Other migration methods have been developed that lie midway be­ The composition of the concrete mixtures and some concrete prop­
tween the earlier migration method and the ponding test. These are the erties are given in Table 3. The numbering in the nomenclature refers to
"multiregime" (Castellote et al., 2001) and the ’integral’ methods the w/c ratio multiplied by 100. Mix proportions were modified to
(Andrade and Rebolledo 2012; Andrade and Rebolledo 2013; Andrade obtain similar relative volume of paste in the four mixes. Workability
and Rebolledo 2014; Pachón-Montaño et al., 2018). Although they use was maintained (slump value in the range 6–10 cm) by adjusting the
an electrical potential of 12V, this value is much lower than the other superplasticizer dosage.
methods. It avoids a temperature rise and allows the binding of chloride. Compressive strength, capillary absorption rate, electrical resistivity,
In addition, any change in the pore fluid due to the electrical potential is water absorption, and chloride ingress rate by the ponding test method
lower compared to other migration methods that require higher po­ were determined.
tentials. Therefore, migration tests with lower electrical potential are Standard procedures in accordance with ASTM C192 were used for
more time consuming but more representative of the spontaneous casting, compacting, and curing of all concrete specimens. Specimens
penetration of chloride into the concrete. were removed from the molds 24h after casting and stored in a curing
The ‘integral’ method is one of the few methods available interna­ room (temperature: 23 ± 2◦ C [73±4F]; RH>95%) until the age of 28
tionally that has the advantage of simultaneous measuring the chloride days.
threshold content of concrete. It requires more complex equipment and Cylindrical specimens with dimensions of 150 × 300mm (diameter x
involves more work than other chloride migration tests. Since the focus height) were used to determine the compressive strength at 7 and 28
is generally on the threshold content as a function of the binder type, it is days according to ASTM C39.
most commonly applied to mortar specimens with an embedded rebar. Capillary absorption rate was measured in 100 × 50mm cylindrical
The application of the method to concrete specimens is scarce in the specimens cut from 100 × 200mm standard specimens, corresponding to
literature and new experimental data is very valuable in this regard. The the sector 30–80 mm from the base. The test procedure was carried out
disadvantage of using concrete instead of mortar is the longer duration in accordance with IRAM 1871 (IRAM 1871, 2004). The cylindrical
of the test; in contrast, using concrete has the advantage of being more surface of these specimens was waterproofed and then oven dried at
representative of the process in real structures. The phenomenologically 50 ◦ C until the weight variation was <0.1 %in a 24 h period. Next, the
based method, which is currently standardized by AENOR (UNE bottom surface of the specimens was brought into contact with water so
83992-2, 2012), has a correlation with the material’s properties. Addi­ that the water level was 3 mm above the bottom surface of the speci­
tional capabilities arise from a correlation with the properties of the mens. The test method consisted of weighing the samples after 0.5, 1, 2,
cover concrete. The performance-based design of concrete structures in 3, 4, 5, 6, 24, 48 and every 24 h until the weight gain in a 24-h period
the marine environment requires experimental input concerning the was <0.1 wt% of the sample. The capillary absorption rate was calcu­
chloride transport rate and chloride threshold content. In addition to lated as the rate of weight gain per unit area as a function of the fourth
determining the chloride threshold under standard conditions, correla­ root of time according to the model proposed in (Villagrán-Zaccardi
tion with other concrete properties and the saturation degree of the et al., 2017). Therefore, capillary absorption rates are expressed in
material provides additional insight for more accurate prediction of the g/(m2⋅s0.25).
durability performance. Electrical resistivity was measured on specimens with the same
Results of the ‘integral’ method on concrete specimens made with previous geometry after they were vacuum saturated in water. The
ordinary Portland cement and w/c ratios between 0.35 and 0.50 are procedure consisted in applying a voltage of 13 V CA 50 Hz through
presented below. The main of objective of the present work is to stainless steel plates pressed with a screw clamp on both sides of the
compare samples were tested for both saturated and unsaturated con­ specimen and measuring the current flowing through the sample.
ditions to account for the influence of pore liquid content on the results In addition, water absorption by immersion and porosity were
of the ‘integral’ test. The results are also compared with hardened determined on cylindrical specimens of 100 × 120 mm according to
concrete properties such as compressive strength, capillary absorption ASTM C642.
rate, electrical resistivity, water absorption and chloride penetration Prismatic specimens of 75 × 150 × 250mm were used to study the
rate using the ponding method. Moreover, continuous registration of the resistance to chloride penetration. The procedure was analogous to the
current and dual measurement of the electrochemical potential were ASTM C1543 method. At the end of curing, all surfaces of these
implemented with the aim of better describing the possible electro­
chemical changes in the samples during the test.
Table 1
The properties of aggregates.
2. Experimental
Properties FSS CSS GCS 6-20
The experimental campaign was designed to show the correlation Density ssd (g/cm3) 2.60 2.60 2.65
between the results of the ‘integral’ test and other properties of con­ Material finer than 75 μm (%) 1.52 0.71 0.55
ventional concrete (i.e. made with ordinary Portland cement). Then, the Absorption (%) 0.8 0.2 0.4
Fineness modulus 1.61 2.62 6.83
results of chloride threshold and migration coefficients can be

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Y.A. Villagrán-Zaccardi and C. Andrade Developments in the Built Environment 8 (2021) 100062

Table 2 ( ( ))
Chemical and physical properties of OPC.
x
C(x,t) = Cs 1 − erf √̅̅̅̅̅̅̅̅̅̅ Eq. 1
2 Dns ⋅t
Properties OPC

Blaine specific surface (m2/kg) 380

Material finer than 75 μm (%) 1.30 2.1. ‘Integral’ test method
Density (g/cm3) 3.11

Compressive strength (MPa) 2d 25.6 Two series with different saturation degrees were analyzed with the
28d 45.2 ‘integral’ method. The ‘saturated’ series was saturated under vacuum.
Chemical analysis (%)
The samples were first stored under vacuum (0.01 mbar) for 2 h, then
Loss on ignition 2.14 water was added in the container to cover them. The vacuum was
Insoluble residue 2.50 removed and the samples were kept under water for 24 h to complete the
SO3 2.41 saturation. This procedure ensures a saturation degree of accessible
MgO 2.76
porosity of 100%. The ‘unsaturated’ samples were stored in a room at
SiO2 19.93
Fe2O3 4.00 95% RH and 23 ◦ C for three weeks. After this period their weight sta­
Al2O3 4.30 bilized. Their moisture content corresponded to a saturation degree of
CaO 60.38 77% (determined by weight loss relative to the weight loss of the satu­
Na2O 0.14 rated series after oven-drying at 105 ◦ C of part of the samples after
K2O 0.85
Cl− 0.012
completion of the ‘integral’ test). All samples were covered with Paraf­
ilm to prevent any moisture loss through the sides.
The test method used is based on the procedure described in UNE
83992-2, 2012 (UNE 83992-2, 2012). This was an adaptation of the
Table 3
standard test setup for the ‘integral’ test, which is described in detail in
Mix proportions and properties of fresh concrete and hardened concrete.
(Andrade and Rebolledo, 2013) and (UNE 83992-2, 2012), with the
N35 N40 N45 N50 purpose of collecting additional data during the experiments. Specimens
w/c 0.35 0.40 0.45 0.50 of 60 × 70 × 100 mm with a 6 mm diameter bar embedded in them were
Materials (kg/m3) tested (Fig. 1). The cover concrete depth was 30 ± 2 mm. One end of the
Water 133 140 144 150
rebar (working electrode) protruded from one side of the specimen to
OPC 380 350 320 300
FSS 189 190 193 193 make the connections to perform the electrochemical measurements.
CSS 749 754 766 767 The rebars were coated near their outer end to protect this zone and
GCS 6-20 980 980 980 980 ensure effective evaluation of depassivation in the embedded zone only
Superplasticizer (l/m3) 6.2 5.9 6.0 3.6 due to chloride penetration through the cover concrete.
Properties of fresh concrete The test method consisted of applying an electric field through the
Air (%) 3.0 3.1 3.0 3.1 specimens. A copper electrode immersed in a 0.6 M NaCl +0.4 M CuCl2
Unitary weight (kg/m3) 2404 2417 2392 2404
catholyte was placed on one side of the specimen. On the opposite side, a
Slump (cm) 8.0 10.0 6.0 6.0
stainless-steel electrode was placed on the concrete surface with a wet
Properties of hardened concrete
sponge in between (Fig. 1). The applied electrical potential was 12 V DC.
Compressive strength 7d 54.2 ± 47.6 ± 37.8 ± 37.4 ±
(MPa) 2.9 0.5 1.1 1.4
The current flowing through each specimen was also recorded contin­
28d 60.2 ± 53.8 ± 46.2 ± 45.6 ± uously while the electric field was active.
3.0 2.5 4.2 1.3 The time required to achieve depassivation of the embedded steel
Porosity 28d (%) 8.0 ± 0.2 8.7 ± 0.4 8.9 ± 0.2 8.9 ± 0.3 was used to calculate the non-stationary apparent migration coefficient.
Electrical resistivity in saturated 17.3 ± 13.6 ± 12.8 ± 10.7 ±
Depassivation was verified by measurements of the half-cell potential
state 28d (kohm⋅cm) 0.8 1.1 0.7 1.2
and corrosion rate. A half-cell potential more negative than − 255 mV
versus Ag/AgCl is considered indicative of the active state (equivalent to
specimens except the top surface (penetration surface) were sealed with − 300 mV vs. SCE specified in (UNE 83992-2)). To record the half-cell
an epoxy paint. This allowed unidirectional chloride penetration in the potential, a data acquisition system was connected to the working
casting direction. The specimens were first immersed in a saturated Ca electrode and to a disposable Ag/AgCl electrode attached to each sam­
(OH)2 solution for 7 days and then in a 30 g/l NaCl solution. The profiles ple. Periodic measurements of half-cell potentials were also made using
of chloride ingress were determined after 6 and 12 months of exposure. a laboratory Ag/AgCl electrode and a voltmeter. The corrosion rate was
First, one half of each specimen was taken for the first evaluation period also determined using the polarization resistance method (Andrade and
and the other halves were sealed, re-exposed, and used for the next González, 1978). The half-cell potentials and corrosion rates were
evaluation. To determine the amount of chloride penetrated as a func­ determined after 60 min the electric field deactivation.
tion of depth, the painted sides of these halves, approximately 1-cm Reference electrodes were placed at two locations. The disposable
thick, were discarded. Dry mechanical grinding was then performed in monitoring electrodes were placed at the level of the working electrodes
the direction of penetration to obtain samples from progressive depth (i.e., in the middle of the electric field), while the laboratory electrode
layers of approximately 5 mm. These samples were analyzed for chloride was located in the chloride pond at the top of the specimens. The dif­
content. ferences between the readings from each electrode are indicative of any
The AFREM method recommended by RILEM TC 174 (RILEM TC influence of the residual electric field after the power was turned off,
178-TMC 2002) was used to determine the water-soluble chloride con­ since any difference in potentials between the two locations was due to
tent. Subsequently, the acid-soluble chloride content of the remaining concrete resistance.
solid sample was determined by potentiometric titration of the filtrate After depassivation was detected, the electric field was turned off,
after hot nitric acid digestion according to ASTM C 1152 M. and the sample was split in the direction of chloride ingress. One half
The fit of the chloride profiles to the widely used solution for Fick’s was sprayed with a 0.1 M NO3Ag solution to visualize the chloride
Second Law (Equation (1)) was observed. Nonlinear regression analyzes penetration front (Fig. 2). The depth of this front allowed the calculation
of the data on this model were performed, and apparent chloride of a migration coefficient for the ingress rate (DINTE) according to Eq.
transport parameters, Dns and Cs, were obtained. (2). Where e is the depth of the chloride penetration front, tlag is the time
required by the rebar to depassivate, and ϕ is the acceleration factor of

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Y.A. Villagrán-Zaccardi and C. Andrade Developments in the Built Environment 8 (2021) 100062

Fig. 1. ‘Integral’ test method for the assessment of chloride ingress rate and chloride threshold content (left: complete set-up; middle: top view of sample; right:
lateral view of sample under testing).

Table 4
Type and number of samples prepared per mix for each test.
Test Type Dimensions Number

Compressive strength Cylinders 150 × 300mm 6

Capillary absorption Cylinders 50 × 100mm 5
rate
Electrical resistivity Cylinders 50 × 100mm 5
Water absorption Cylinders 120 × 100mm 3
Chloride diffusion Prisms 75 × 150 × 250mm 1 (except for N40:
3)
‘Integral’ test Prisms 70 × 70 × 100mm 4

water-reducing admixture to maintain the workability level.

The capillary absorption rates were determined by regression ana­
lyses, considering a linear relationship between the mass of water
Fig. 2. Chloride penetration front in the ‘integral’ test. absorbed per unit area and the fourth root of time (Fig. 3). The capillary
absorption rates depend on the w/c ratio. The range of values obtained
the electrical field computed as in Eq. (3), where z = 1 is the valency of was in a short interval due to the low mixing water content in the four
chloride, F is the Faraday’s constant, R is the universal gas constant, T is mixtures.
the absolute temperature, ΔV is the electrical potential, and L is the The values for the porosity and resistivity in the saturated state
specimen thickness. presented in Table 3 show that, naturally, the concrete porosity in­
creases with the w/c ratio as a result of increased capillary porosity.
e2 However, this increase is not exponential, as is usually assumed, since
DINTE = Eq. 2
2 ⋅ tlag ⋅ ϕ the increase in w/c ratio was not accompanied by a significant increase
in bleeding.
ϕ=
z ⋅ F ΔV
⋅ Eq. 3 The chloride ingress profiles after 6 months of exposure are shown in
R⋅T L Fig. 4. The corresponding profiles after 12-month exposure are shown in
From the other half, the concrete adjacent to the rebar was sampled Fig. 5. The chloride contents are given in wt% relative to concrete
to determine the threshold chloride content. For this, 0.7 g of concrete weight. An ingress profile per exposure time is presented for all mixes,
were collected by drilling a depth of no more than 1 mm along rebar
imprint sector that corresponded with the position of the Ag/AgCl
electrode. Both water-soluble and total chloride contents were analyzed
for these samples. The concrete at the surface adjacent to the catholyte
was also sampled to determine the maximum chloride content of the
ingress profile. Chloride determinations (according to (RILEM TC
178-TMC 2002) and [ASTM C 1152 M]) were made using an automatic
titrator on samples of 0.7 g obtained adjacent to the rebar zone and 0.4 g
for samples from the concrete surface.
The types and number of samples prepared with each concrete mix
are summarized in Table 4.

3. Results

The range of values for the compressive strength showed in Table 3 is

quite narrow for the range of w/c ratios studied. This is related to the
low paste content of the concrete mixes, which was achieved by adding a
Fig. 3. Capillary absorption.

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Y.A. Villagrán-Zaccardi and C. Andrade Developments in the Built Environment 8 (2021) 100062

Fig. 4. Chloride ingress profiles in ponding test (6 months immersed in NaCl 30 g/l).

except for N40, for which three profiles were performed to examine the based on the number of repetitions performed. This procedure is very
variability between repetitions in addition to the variation due to the w/ time-consuming, so accelerated migration tests demonstrate a signifi­
c. To perform a reliable regression analysis, all profiles consist of at least cant advantage in terms of the possibility to perform numerous
eight chloride determinations at different depths. The chloride ingress repetitions.
rates by diffusion were related to the w/c ratio. As expected, the lowest The chloride penetration depths in the ‘integral’ test were used to
chloride ingress rate was that of N35. compute the chloride migration coefficients. Considering that the
Some profiles did not correspond to what is usually referred to as duration of the test was decided upon depassivation of the reinforce­
chloride ingress profiles in saturated concrete. Concrete is a heteroge­ ment, these penetration depths were close to the value of the cover depth
neous material and some local effects such as the wall effect, coarse ([32.3 ± 0.4] mm for the whole group of specimens). The respective
aggregates, and macropores may distort the shape of the ingress profile. (average ± standard deviation) penetration depths for the saturated and
This is the case for the profiles for N50-6 m, N40-12 m, b and c, and N50- unsaturated series were (36.9 ± 10.8) mm and (41.3 ± 7.1) mm. As the
12 m; these mismatched values were not considered for the regression different specimens were exposed for variable durations until depassi­
analyses. For these cases, the computation of Dns was done disregarding vation was confirmed, a direct comparison of the penetration depths is
the atypical surface layer as recommended in (Andrade et al., 2015). not possible, and this comparison is therefore made considering the
The increase in chloride contents in concrete between 6 and 12 migration coefficients. Fig. 6 shows the migration coefficients deter­
months was less than the initial increases between 0 and 6 months. The mined in the ‘integral’ test (DINTE) compared to the w/c ratio of the
chloride ingress rate decreases with time in accordance with the increase respective concrete mix. It is interesting to note that the influence of the
in the hydration degree and the influence of the chloride content at the w/c ratio on the migration coefficients is lower for unsaturated concrete
surface of the concrete. However, a value of the time coefficient calcu­ than for saturated concrete. The pore volume involved in chloride
lated from the two exposure times evaluated is not very reliable and is transport is the volume of liquid in the pores. This volume increases with
therefore not derived from the present data. the saturation degree. Macropores are involved only at full saturation;
Samples N40–1, N40–2 and N40-3 are from the same concrete (N40). they are not to be considered in unsaturated concrete because the vol­
Figs. 4 and 5 show different profiles for these three concrete samples, ume of pore liquid at a given relative humidity depends on the pore size.
demonstrating the variability of the chloride ingress profile due to the Regarding the chloride threshold contents by the ‘integral’ test
heterogeneity of the concrete. In this sense, the influence of the chloride method, Fig. 7 shows the evolution of the half-cell potential (Ecorr disp:
content at the surface is very significant. The concrete porosity and the disposable type and permanently placed at the reinforcement level; Ecorr
roughness of the surface are the main points to be investigated in rela­ pond: discrete measurements with a laboratory electrode in the chloride
tion to the chloride content at the surface. This is the main cause of the pond) and the corrosion rate (icorr) in vacuum-saturated specimens. All
differences in the ingress profiles presented. The present study only measurements were made 60 min after the electric field was
considered one mix to perform the repetition; more research is needed to disconnected.
fully confirm the reliability of the obtained chloride diffusion coefficient The minimal differences found between the two types of reference

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Y.A. Villagrán-Zaccardi and C. Andrade Developments in the Built Environment 8 (2021) 100062

Fig. 5. Chloride ingress profiles in ponding test (12 months immersed in NaCl 30 g/l).

from the beginning of the test. The reason for this behaviour is not fully
clear but it might be connected to the high porosity of the concrete and
the high saturation degree. Thus, for N50-saturated samples depassi­
vation was assumed considering only the values of the corrosion current.
The dual methodology reliably indicated the point at which the test must
be interrupted. Thus, the dual recording of the half-cell potential and
corrosion current in the ‘integral’ test, while beneficial, is not always
essential since duplicated information is provided for most of the cases.
Some short-term drops of the corrosion potential that quickly recovered
were noted. Still, none of these were below the threshold limit of − 255
mV vs Ag/AgCl. The corroboration of the pitting with the concurrent
sudden drop of the corrosion potential and increase in the corrosion rate
prevented to stop the test before the due moment (as demonstrated by
the visual inspection discussed later and presented in Fig. 13). As the
measurement of the half-cell potential is simpler than the measurement
of the corrosion rate, the former can be implemented in a simplified
procedure for the experiment.
Fig. 6. Migration coefficients from ‘integral’ test versus w/c.
The time required for the ‘integral’ test was longer the lower the w/c
ratio, in agreement with the resulting porosity. The times required for
electrodes proved that the electric field was turned off at the time of the the tests were the times used to calculate the DINTE values presented in
half-cell potential measurement, and no significant latent electric po­ the previous section.
tential was active. Duplicate measurements of the half-cell potential are Fig. 8 show the evolution of the corrosion parameters in partially
not necessary. The results show that the electrode in the pond can be saturated concrete. The behavior was similar to that of the vacuum
replaced by a disposable electrode placed on the concrete surface at the saturated concrete. The main difference was the higher time required for
level of reinforcement. Then, a continuous acquisition system for depassivation, which increased by ~50% in partially saturated
measuring the half-cell potential can be implemented for a more accu­ specimens.
rate appreciation of the time for depassivation. Fig. 9 shows the chloride contents in concrete at the end of the ‘in­
The half-cell potential and corrosion rate showed simultaneous evi­ tegral’ test for the (a) saturated and (b) unsaturated samples. These
dence of depassivation. The increase in corrosion rate occurred simul­ contents are expressed in terms of the weight of the dry concrete. The
taneously with the decrease in half-cell potential for all concrete mixes, chloride content at the surface is within a certain range irrespective of
as shown in Fig. 7. The only exception were samples N50-saturated, the w/c. Conversely, the effect of the w/c on the chloride threshold
which demonstrated abnormal behaviour with very negative Ecorr value seems more notorious. The respective threshold values for the

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Y.A. Villagrán-Zaccardi and C. Andrade Developments in the Built Environment 8 (2021) 100062

Fig. 7. The evolution of half-cell potential and corrosion current in vacuum saturated samples.

Fig. 8. The evolution of half-cell potential and corrosion current partially saturated samples.

total chloride contents (wt.% cement) for w/c = 0.35, 0.40, 0.45 and reduced with increasing w/c. The results in the present work are in
0.50, were: saturated samples=(2.44, 1.92), (2.07,1.31), (0.52,0.23), broad agreement with those reported in (Izquierdo et al., 2004) for
(0.64,0.16); partially saturated samples=(2.18,1.67), (2.07,1.94), electrochemical parameters for depassivation in cement mortars, with
(1.73,0.83), (1.20,0.56). It should be noted that these values are com­ values ranging from 0.632 ± 0.112 to 0.771 ± 0.346 wt% of cement for
parable only in terms of the critical chloride content to depassivate the total chlorides. The chloride content next to reinforcement was depen­
reinforcement, whereas the time required to reach such value was dent on the w/c ratio. The chloride content at the surface shows a slight

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Y.A. Villagrán-Zaccardi and C. Andrade Developments in the Built Environment 8 (2021) 100062

Fig. 9. Threshold chloride contents in samples after performing the ‘integral’ test in (a) vacuum-saturated samples and (b) partially saturated samples.

increasing trend with the w/c ratio, except for an outlier for N35. Then,
the w/c ratio is presented as the main factor to consider when inter­
preting the results. The influence is twofold as the w/c ratio determines
the porosity of concrete and also the unit cement content in the mix. For
the same chloride content, a lower porosity and higher cement content
reduce the [Cl− ]/[OH− ] and increase the time for depassivation.
Fig. 10 and Fig. 11 show the evolution of resistivity during the ‘in­
tegral’ test of chloride migration for the vacuum-saturated and partially
saturated concrete, respectively. The periodic variations for each series
are due to the disconnection of the power supply to determine the half-
cell potentials and corrosion rates. When the power supply was con­
nected, the resistivity gradually increased. The variation in resistivity
during the ‘integral’ test is significant. The reduction of copper ions on
the copper cathode in the pond with chloride can increase the resistivity
in the interface between the electrode and the solution and the re­
sistivity of the solution itself. In addition, the steel anode corroded
during the test, and its resistivity increased due to the oxide layer formed
Fig. 11. The evolution of resistivity in the ‘integral’ test, partially satu­
on it. Therefore, the resistivity values at the beginning of the test are
rated concrete.
most representative of the concrete properties.
Fig. 12 shows the minimum resistivity values for vacuum-saturated
and partially saturated concrete. The variability of results increases for
the partially saturated samples in comparison with the saturated sam­
ples. A decreasing trend in resistivity with increase in the w/c ratio can
be seen (a small increase for N50 in comparison with N45 is noted but
given the very similar porosity reported in Table 3, this is attributed to
the variability of the experiment). A high w/c ratio determines a high
porosity of the concrete. The volume of the pore liquid, i.e. the volume of
the conductive phase, is determined by the degree of saturation and the
porosity of the concrete. The minimum resistivity values during the
‘integral’ test were reached about 3 h after the start of the test.

Fig. 12. Minimum resistivity values in the ‘integral’ test.

The bars were visually inspected after removal from the concrete
specimens (Fig. 13). Pitting was found on all bars, but with a varying
degree of severity that cannot be attributed to any particular difference
between specimens. Depassivation is also expected to occur more
frequently at the ends of the rebars, where sharp edges, hardened by
mechanization, were created during sawing. However, the pits on the
rebars are randomly located. The steel surface does not appear to be
preferentially affected by the electric field in any particular zone. In this
sense, the testing of cover concrete is assumed to be homogeneous, and
irregularities in the penetration front are attributed only to the hetero­
Fig. 10. The evolution of resistivity in the ‘integral’ test, vacuum- geneity of concrete.
saturated concrete.

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Y.A. Villagrán-Zaccardi and C. Andrade Developments in the Built Environment 8 (2021) 100062

Fig. 13. Pitting in reinforcement bars after being tested by the ‘integral’ method.

4. Discussion properties than for compressive strength. Capillary absorption is not

essentially tied to the chloride ingress rate in the marine environment.
The present study addresses concrete mixes with reduced paste The capillary water transport is the result of suction through concrete
content. Water reducing admixtures can certainly be a very useful tool pores, whereas chloride diffusion is not dependent on pore size. (Poulsen
for designing durable concrete structures. The paste volume in concrete and Mejlbro 2005). However, since the capillary absorption rate de­
mixes can be limited by reducing the mixing water content. Thus, the scribes the pore structure of the concrete, it is expected to be qualita­
pore volume in concrete is reduced with the paste volume. Therefore, tively related to the chloride ingress rate.
the relative influence of w/c ratio on the concrete strength is reduced. The electrical resistivity of saturated concrete is directly related to
The same results are expected for the transport properties. the accessible pore volume (Whiting and Nagi 2003). This is because
In terms of transport properties, the w/c ratio always plays a key both the ions in the pore liquid and the saturation degree of concrete
role, but bleeding is very sensitive to the fines content of the aggregates, determine the electrical conductivity of concrete. Thus, the inverse
which can vary in the production process. Therefore, the influence of the relationship between resistivity and w/c ratio or porosity is logical.
w/c ratio must be analyzed in conjunction with the amount of bleeding. While these properties involving the whole pore volume relate well with
The relative effect of w/c ratio was more significant for transport results in vacuum saturated specimens, the correlation is reduced for

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Y.A. Villagrán-Zaccardi and C. Andrade Developments in the Built Environment 8 (2021) 100062

partially saturated specimens. ingress. The simplicity and universality of the compression test poten­
Fig. 14 shows the relationship between the ‘integral’ coefficients and tiates it as a tool for quality control. However, compressive strength is
(a) the compressive strength at 28 days, (b) the capillary absorption rate, influenced by several technological parameters in a different way than
and (c) the resistivity. These relationships can be represented by a linear transport properties. Capillary absorption rate describes water transport
regression curve with acceptable scatter. The correlation obtained is throughout the volume of capillary pores and may not be directly related
satisfactory for the saturated state, but for the partially saturated con­ to chloride ingress, especially in unsaturated concrete. The resistivity is
crete the prediction of DINTE from properties of the concrete such as also related to the volume of pore liquid, and this volume is the total
compression strength, capillary absorption rate or electrical resistivity accessible porosity when the concrete is fully saturated. This investi­
seems to potentially result in a significant error. gation shows that there is a strong relationship between the studied
The compressive strength, capillary absorption rate and resistivity parameters, but only at a qualitative level.
are considered as qualitative indexes related to the resistance to chloride Fig. 15 shows the relationship for the group of studied mixes between
the apparent chloride diffusivity from the ponding test and the migra­
tion coefficients from the ‘integral’ test (saturated samples). The diffu­
sion coefficients from the water-soluble chloride profiles were better
correlated with the migration coefficients. The penetration front in the
‘integral’ test was revealed by spraying AgNO3 solution, which forms a
white precipitate upon reaction with free chloride. Therefore, differ­
ences in binding capacity could not be directly inferred from the
colorimetric evaluation of chloride penetration.
The overestimation of the chloride ingress rate in the ‘integral’ test
compared to the ponding test is largely attributed to the younger age (28
days versus 6 and 12 months) and vacuum saturation of the specimens.
However, part of the divergence can be attributed to the lower binding
capacity that the concrete develops in the migration test. The difference
in binding capacity affects the chloride ingress rate and the content in
the pore liquid, which is reflected in Fig. 15.
Furthermore, the ‘integral’ method was found to be more sensitive to
an increase in concrete porosity. At higher w/c ratios, the increase in the
ingress rate was higher for the ‘integral’ method than for the ponding
method. In this respect, the differences in the scatter of the results
require further investigation. The ‘integral’ method ensures full satu­
ration to guarantee a good correspondence with the porous properties of
the concrete, but this can deviate from real conditions. The present re­
sults suggest the effect of the degree of saturation, but additional results
are necessary to investigate this aspect more in detail.
The longer time required for depassivation in unsaturated samples
can be attributed to a lower chloride ingress rate due to migration
combined with the lower pore liquid content. These results demonstrate
the ability of the method to investigate the influence of the saturation
degree on the chloride migration rate. In the present study, the differ­
ence in moisture content between the two conditions was not significant,
and further studies may consider a wider range of moisture contents to
fully account for the influence of the content of free water so that an
accurate calibration tool can be included in durability models.
The threshold values for total chloride content found for N45 and
N50 were similar to those commonly reported in the literature (Thomas

Fig. 14. Migration coefficients from ‘integral’ test versus (a) the 28d
compressive strength, (b) the capillary absorption rate, and (c) the electrical Fig. 15. Apparent chloride diffusion coefficients of the studied mixes: ponding
resistivity. test versus ‘integral’ migration test in vacuum saturated samples.

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Y.A. Villagrán-Zaccardi and C. Andrade Developments in the Built Environment 8 (2021) 100062

1996; Glass y Buenfeld 1997; Taylor et al., 1999; Alonso et al., 2000; Declaration of competing interest
Angst et al., 2019), but the values for N35 and N40 were higher. There is
general agreement on an increase in the value of the critical chloride The authors declare that they have no known competing financial
content by about 30% for w/c ratios below 0.5 (Angst et al., 2019), but interests or personal relationships that could have appeared to influence
the results of the present study suggest that this effect of the w/c ratio the work reported in this paper.
can be more significant. In this respect, the ‘integral’ method, while
considering a more appropriate electric gradient and preconditioning, Acknowledgements
might be more suitable than other methods to show the effect of the
porosity of concrete. The overall porosity does not seem to be the most The authors appreciate greatly the constructive criticism of Prof.
important factor to consider, but the distribution of moisture across the Ángel Di Maio and Prof. Roberto Romagnoli†, who greatly contributed
different pore sizes could be more relevant. to the value of the present paper. Y. Villagrán-Zaccardi thanks the
The variation of total chloride threshold content with the w/c ratio Research Foundation – Flanders (FWO) for the funding through MSCA
was similar for vacuum saturated samples and for partially saturated SoE (12ZZD21N LV).
samples. Therefore, no difference in chloride threshold content can be
inferred in relation to the pore liquid content for each saturation degree. References
Both moisture contents were high enough for corrosion to begin (i.e.
lack of water availability was not the controlling parameter for the Aashto T 277-93, 1993. Standard method of test for electrical indication of concrete’s
ability to resist chloride. In: American Association of State Highway and
depassivation). Transportation Officials (AASHTO), Standard Specifications for Transportation
Materials and Methods of Sampling and Testing, sixteenth ed. Part II-Tests,
5. Conclusions Washington, DC, pp. 876–881.
Alonso, C., Andrade, C., Castellote, M., Castro, P., 2000. «Chloride threshold values to
depassivate reinforcing bars embedded in a standardized OPC mortar». Cement
The ‘integral’ test method has been shown to be effective and truthful Concr. Res. 30, 1047–1055.
in determining both the chloride ingress rate and the chloride threshold Andrade, C., 1993. «Calculation of chloride diffusion coefficients in concrete from ionic
migration measurements». Cement Concr. Res. 23, 724–742.
content in conventional concrete with w/c ratio between 0.35 and 0.50. Andrade, C., Climent, M.A., De Vera, G., 2015. «Procedure for calculating the chloride
The ‘integral’ test method is capable of providing indexes for diffusion coefficient and surface concentration from a profile having a maximum
performance-based design for durability, i.e. chloride ingress rate and beyond the concrete surface». Mater. Struct. 48, 863–869.
Andrade, C., Rebolledo, N., 2012. Accelerated evaluation of corrosion inhibition by
chloride threshold content. The method has also demonstrated a quali­
means of the integral corrosion test. In: Concrete Repair, Rehabilitation and
tative correlation with compressive strength, capillary absorption rate, Retrofitting III – Alexander et al. Taylor & Francis Group, London, ISBN 978-0-415-
water absorption and electrical resistivity. 89952-9.
A significant effect of the w/c ratio on chloride threshold content was Andrade, C., Rebolledo, N., 2013. «Accelerated evaluation of chloride corrosion by
means of the integral corrosion test». In: Conference “Pietro Pedeferri e la scuola di
found. In all cases, values for total Cl− threshold were found to be above corrosione e protezione dei materiali al Politecnico di Milano”. Milan (Italy), 26-27
0.4 wt% of cement. The threshold values increased with decreasing w/c September 2013, Memoria Nro 28, 14 p. (available at. https://digital.csic.es/bitstr
ratio. The respective values for w/c = 0.35, 0.40, 0.45 and 0.50, were: eam/10261/240709/1/508050.pdf.
Andrade, C., Rebolledo, N., 2014. Accelerated evaluation of chloride corrosion by means
saturated samples=(2.44, 1.92), (2.07,1.31), (0.52,0.23), (0.64,0.16); of the integral corrosion test. Structural 186, 09.
partially saturated samples=(2.18,1.67), (2.07,1.94), (1.73,0.83), Andrade, C., González, J.A., 1978. «Quantitative measurements of corrosion rate of
(1.20,0.56). Such an effect of the w/c ratio on the chloride threshold has reinforcing steels embedded in concrete using polarization resistance
measurements». Mater. Corros. 29 (Nº8), 515–519.
been scarcely reported in the literature and further research in this re­ Andrade, C., Whiting, D., 1996. A comparison of chloride ion diffusion coefficients
gard is convenient to establish the probability limits for depassivation. derived from concentration gradients and non-steady state accelerated ionic
When the availability of free water is not the controlling factor of migration. Mater. Struct. ume 29 (Number 8), 476–484.
Angst, U.M., Geiker, M.R., Alonso, M.C., Polder, R., Isgor, O.B., Elsener, B., Wong, H.,
depassivation, the saturation degree showed no significant impact on Michel, A., Hornbostel, K., Gehlen, C., Fraçois, R., Sánchez, M., Criado, M.,
the values determined for the chloride threshold content. Thus, it seems Sørensen, H., Hansson, C., Pillai, R., Mundra, S., Gulikers, J., Raupach, M.,
possible to consider a fixed value for depassivation when the saturation Pacheco, J., Sagüés, A., 2019. “The effect of the steel–concrete interface on chloride
induced corrosion initiation in concrete: a critical review by RILEM TC 262-SCI”.
degree of concrete is above 77%.
Mater. Struct. 52, 88.
The continuous registration of the half-cell potential is useful to Astm C1202, 2010. Standard Test Method for Electrical Indication of Concrete’s Ability
detect depassivation of the reinforcement during the ‘integral’ test. to Resist Chloride Ion Penetration. ASTM International, West Conshohocken, USA.
However, when the corrosion current is measured, both parameters Baroghel-Bouny, V., Belin, P., Maultzsch, M., Henry, D., 2007. «AgNO3 spray tests:
advantages, weaknesses, and various applications to quantify chloride ingress into
provide the same information. Therefore, measuring only one of these concrete. Part 2: non-steady-state migration tests and chloride diffusion
two parameters seems sufficient to detect the depassivation during the coefficients». Mater. Struct. 40, 783–799.
‘integral’ test. Castellote, M., Andrade, C., Alonso, C., 1999. Chloride-binding isotherms in concrete
submitted to non-steady-state migration experiments. Cement Concr. Res. 29,
When comparing accelerated and non-accelerated chloride ingress 1799–1806.
tests, differences due to the dissimilar age of the samples must be Castellote, M., Andrade, C., Alonso, C., 2001. «Measurement of the steady and non-
addressed. Accelerated tests are performed after only 28 days of curing, steady-state chloride diffusion coefficients in a migration test by means of
monitoring the conductivity in the anolyte chamber - comparison with natural
while diffusion tests may require 6 or 12 months. The aging effect on diffusion tests». Cement Concr. Res. 31, 1411–1420.
chloride penetration should always be considered in the comparison. Castellote, M., Andrade, C., 2006. «Round-Robin Test on methods for determining
Pre-conditioning to full saturation prior to the ‘integral’ test is chloride transport parameters in concrete». Mater. Struct. 39 (Nº10), 955–990.
Frederiksen, J.M., 2002. Method for determination of chloride threshold values for steel
required for repeatability. Some additional deviation from natural in concrete. NordTest Report TR 500, 64.
chloride diffusion is possible if lower saturation degrees are achieved. Glass, G.K., Buenfeld, N.R., 1997. «The presentation of the chloride threshold level for
The consideration of the saturation degree appears to be more important corrosion of steel in concrete». Corrosion Sci. 39 (5), 1001–1013.
Glass, G.K., Buenfeld, N.R., 2000. The influence of chloride binding on the chloride
for the chloride ingress rate than for the chloride threshold content.
induced corrosion risk in reinforced concrete. Corrosion Sci. 42, 329–344.
Further research is needed to construct accurate formulations for Iram 1871, 2004. Hormigón. Método de ensayo para determinar la capacidad y la
correction according to the saturation degree of concrete when labora­ velocidad de succión capilar de agua del hormigón endurecido. IRAM, Buenos Aires,
tory results are applied to durability modeling of concrete structures in p. 12.
Izquierdo, D., Alonso, C., Andrade, C., Castellote, M., 2004. Potentiostatic determination
the marine environment. of chloride threshold values for rebar depassivation: experimental and statistical
study. Electrochim. Acta 49, 2731–2739.
Martín-Pérez, B., Zibara, H., Hooton, R.D., Thomas, M.D.A., 2000. A study of the effect of
chloride binding on service life predictions. Cement Concr. Res. 30, 1215–1223.

11
Y.A. Villagrán-Zaccardi and C. Andrade Developments in the Built Environment 8 (2021) 100062

Nilsson, L.O., Poulsen, F., Sandberg, P., Sorensen, H.F., Klinghoffer, O., 1996. HETEK, Rilem TC 178-TMC, Recommendations of Rilem TC, 2002. 178-TMC: ‘Testing and
Chloride Penetration into Concrete, State-Of-The-Art, Transport Process, Corrosion modelling chloride penetration in concrete’. Analysis of water soluble chloride
Initiation, Test Methods and Prediction Models. The Road Directorate, Copenhagen, content in concrete. Mater. Struct. 35 (No. 253), 586–588.
Denmark, p. 151. Tang, L., Sørensen, H.E., 2001. «Precision of the Nordic test methods for measuring the
Nt Build 443, 1995. Concrete, Hardened: Accelerated Chloride Penetration. NORDTEST, chloride diffusion/migration coefficients of concrete». Mater. Struct. 34, 479–485.
Espoo, Finland, p. 5. Taylor, P.C., Nagi, M.A., Whiting, D.A., 1999. Threshold chloride content for corrosion of
Nt Build 492, 1999. Concrete, Mortar and Cement-Based Repair Materials: Chloride steel in concrete: a literature review. Portland Cement Association, PCA R&D Serial
Migration Coefficient from Non-steady-state Migration Experiments. NORDTEST, No 2169, 32.
Espoo, Finland, p. 8. Thomas, M., 1996. «Chloride thresholds in marine concrete». Cement Concr. Res. 26,
Oh, B.H., Jang, S.Y., Shin, Y.S., 2003. «Experimental investigation of the threshold 513–519.
chloride concentration for corrosion initiation in reinforced concrete structures». Une 83992-2, 2012. Spanish Standard. Durability of Concrete. Test Methods. Chloride
Mag. Concr. Res. 55 (2), 117–124. Penetration Tests on Concrete. Part 2: Integral Accelerated Method. AENOR, p. 15.
Pachón-Montaño, A., Sánchez-Montero, J., Andrade, C., Fullea, J., Moreno, E., Villagrán-Zaccardi, Y.A., Alderete, N., De Belie, N., 2017. Improved model for capillary
Matres, V., 2018. Threshold concentration of chlorides in concrete for stainless steel absorption in cementitious materials: Progress over the fourth root of time. Cement
reinforcement: classic austenitic and new duplex stainless steel. Construct. Build. Concr. Res. 100, 153–165.
Mater. 186, 495–502. Whiting, D.A., 1981. Rapid Determination of the Chloride Permeability of Concrete” –
Poulsen, E., Mejlbro, L., 2005. Diffusion of Chloride in Concrete: Theory and Application. Federal Highway Administration – Report. FHWA/RD-81/119.
Spon Press, London, p. 480p. Whiting, D.A., Nagi, M.A., 2003. Electrical Resistivity of Concrete – A Literature Review.
Riding, K.A., Poole, J.L., Schindler, A.K., Juenger, M.C.G., Folliard, K.J., 2008. PCA R&D Serial No. 2457. Portland Cement Association, Skokie, Illinois, USA, p. 57.
«Simplified concrete resistivity and rapid chloride permeability test method». ACI
Mater. J. 105 (Nº4), 390–394.

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