Materials and Structures (2021)54:98

https://doi.org/10.1617/s11527-021-01698-7 (0123456789().,-volV)
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89().,-volV)

ORIGINAL ARTICLE

Estimating service life of reinforced concrete structures

with binders containing silica fume and metakaolin
under chloride environment: durability indicators
and probabilistic assessment
Gustavo Bosel Wally . Fábio Costa Magalhães . Félix Krolow Sell Junior .
Fernando Ritiéle Teixeira . Mauro de Vasconcellos Real

Received: 23 July 2020 / Accepted: 30 March 2021

Ó RILEM 2021

Abstract Pozzolanic additions, especially high
reactive pozzolans, such as silica fume and metakao-
lin, currently stand out as the main alternatives for
increasing the mechanical strength and resistance to
the penetration of deleterious agents in concrete. Thus,
the use of these materials will result in a longer service
life of reinforced concrete structures exposed to
aggressive environments. In this paper, the influence
of silica fume and metakaolin on aspects related to the
durability and service life of concretes subject to
chloride penetration is evaluated. Through the evalu-
ation of durability indicators, a performance-based
approach is used in the analysis of the durability
potential of the produced concrete. In order to cover
the variability that can be assumed by the model
parameters involved in the process of chloride pene-
tration into concrete, a probabilistic assessment is
performed using Monte Carlo Simulation with Impor-
tance Sampling. These calculations indicate that the
use of silica fume and metakaolin generates significant
improvements in the durability-related properties of
concrete. When comparing mineral additions at equal
levels, the most satisfactory results were obtained
when using silica fume. Based on the obtained results,
the importance of a performance-based approach is
discussed and verified instead of the prescriptive
approach. The results indicate that concretes that
follow the same prescriptive parameters may present
different behaviors when evaluated from the perspec-
tive of durability.

G. B. Wally (&) F. K. Sell Junior  F. R. Teixeira

Structural Models and Testing Laboratory (LEME), Graduate Program in Materials Science and Engineering
Graduate Program in Civil Engineering (PPGEC), Federal (PPGCEM), Federal University of Pelotas (UFPel),
University of Rio Grande do Sul (UFRGS), Porto Alegre, Pelotas, Brazil
Brazil e-mail: felixsell@gmail.com
e-mail: gustavo.wally@gmail.com
F. R. Teixeira
F. C. Magalhães e-mail: fernandoteixeira5400@gmail.com
Structures and Building Materials Laboratory (LEMCC),
Federal Institute of Rio Grande do Sul (IFRS),
Rio Grande, Brazil
e-mail: fabiocmagalhaes@gmail.com

F. C. Magalhães  M. de Vasconcellos Real

Graduate Program in Ocean Engineering (PPGEO),
Federal University of Rio Grande (FURG), Rio Grande,
Brazil
e-mail: mvrealgm@gmail.com
98 Page 2 of 16
Keywords Concrete durability  Performance-based
approach  Probabilistic assessment  Silica fume 
Metakaolin
1 Introduction
The use of pozzolanic materials is currently one of the
most common practices in the quest to provide greater
durability and service life to reinforced concrete
structures, especially when exposed to aggressive
environments. Pozzolans work mainly in the refine-
ment of the pore structure of concrete, providing
greater mechanical strength and less penetrability to
harmful agents [1–3]. Two of the main pozzolans used
in concrete are silica fume (SF) and metakaolin (MK).
This is because these materials have high reactivity
and, therefore, significantly increase the compressive
strength of concrete and its resistance to the penetra-
tion of aggressive agents even when used in small
quantities [4, 5].
SF is a by-product of the production of ferrosilicon
alloys or metallic silicon, generated from the reduction
of high purity quartz, which normally has a SiO2
content between 85 and 90% [6, 7]. The particles of
silica fume are mostly amorphous and ultrafine, with
an average size between 0.1 and 0.5 lm, correspond-
ing to approximately one-hundredth of the average
size of a cement particle. Due to its high content of
silicon dioxide, high fineness, and consequent large
surface area, SF is a chemically reactive pozzolan.
Due to the formation of calcium silicate hydrates
(CSH), resulting from the reaction between SiO2 and
Ca(OH)2, and the filler effect generated by the fine
particles of silica fume, its use in a concrete mixture
can considerably reduce the probability of rebar
corrosion in reinforced concrete structures [4, 8].
Bagheri et al. [9] highlight that the replacement of
2.5% of cement by silica fume reduces the diffusivity
of concrete by approximately 50%.
MK, in turn, is obtained from the calcination of the
kaolinite processed at temperatures between 500 and
800 °C, being highly amorphous and showing high
pozzolanic activity. This material normally has a SiO2
content between 50 and 55%, Al2O3 between 40 and
45%, and may also contain, among others, small
amounts of MgO, CaO, and TiO2 [10–12]. Due to its
high aluminate content, metakaolin is capable of
Materials and Structures (2021)54:98
resulting in a substantial increase in the capacity of
concrete to retard the chloride penetration since the
interaction between aluminates and chloride ions leads
to the formation of Friedel’s salt (3CaOAl2O3CaCl2-
10H2O), which will reduce the content of free
chlorides participating in the corrosion initiation
process [13, 14]. Gruber et al. [15] point out that the
use of 12% of metakaolin as a replacement for cement
can reduce the penetration of chlorides in concrete by
up to 60%. Furthermore, because it is a primary
product and not a by-product, metakaolin can be
produced according to demand and in a way that the
desired properties are met.
The increased use of the most diverse types of
additions in concrete admixtures has highlighted the
need for approaches based on the desired performance
of the material in terms of durability, especially in
severe aggressive environments. Performance-based
approaches are favorable because the prescriptive
approach traditionally adopted in durability design is
limited to stipulating parameters such as minimum
cement content, minimum compressive strength, and
maximum w/b ratio. These limits, although they tend
to affect the durability-related properties, do not
establish well-defined conditions for the concrete to
be durable. In a performance-based approach, critical
properties related to concrete durability, called dura-
bility indicators, are evaluated—such as permeability
and diffusivity. In addition to providing information
about the characteristics related to relevant durability
properties of the material and allowing a quantitative
comparison of the durability potential of two or more
concretes, the values obtained from the durability
indicators may ideally also be used as an input
parameter in service life prediction models [16–20].
Additionally to the importance of assessing the
characteristics of a concrete mix from durability
indicators, it is also widely reported in the literature
[21–25] that the uncertainties and nonlinearities
present in the process of chloride penetration into
concrete cause purely deterministic models to show
results inconsistent with reality. In this sense, proba-
bilistic models, which consider the inherent variability
of the parameters involved in the transport process,
stand out as a way to better assess the studied
phenomena. Gjørv [26] highlights that in recent years
there has been an accelerated development of models
and procedures aimed at the design and analysis of the
structural service life based on probabilities. Yu et al.
Materials and Structures (2021)54:98
[27], in turn, point out that the Monte Carlo Simulation
(MCS) method has been widely used in carrying out
probabilistic analyses. However, to reduce the vari-
ability of the results obtained and the number of
simulations necessary for a good representation of the
assessed phenomenon, sampling techniques have been
studied and applied to the MCS [28]. The basic idea of
the Monte Carlo with Importance Sampling is to
concentrate the distribution of sampling points in the
region of the highest importance, that is, in the area
that presents the most significant contribution to the
occurrence of failures, rather than spreading them
evenly over all possible values [29]. More information
about the Monte Carlo Simulation and importance
sampling techniques can be obtained from Melchers
and Beck [28], Haldar and Mahadevan [29], and Ang
and Tang [30].
This paper presents an experimental evaluation of
concrete mixes produced with partial replacement of
Portland cement by silica fume and metakaolin. The
substitution levels adopted were 5, 10, and 20%, by
mass of cement, for each of the mineral additions. The
results obtained from the rapid chloride penetrability
test (RCP), standardized by ASTM C1202 [31], the
bulk diffusion test (BDT), described in ASTM C1556
[32], and the rapid chloride migration test (RCM),
performed according to NT Build 492 [33], were taken
as durability indicators. The correlations between the
diffusivities obtained through the migration (RCM)
and diffusion (BDT) tests are also analyzed. From the
diffusivity of the concretes measured experimentally, a
probabilistic service life assessment of structures made
with these concretes was carried out. The numerical
evaluation was performed using the chloride penetra-
tion model presented by Gjørv [26] associated with
Monte Carlo Simulation with Importance Sampling.
The importance of a performance-based approach for
assessing the quality of concrete using durability
indicators and the use of these indicators as input
parameters in models for predicting the service life of
structures is evaluated and discussed.
2 Methodology
2.1 Materials
For the production of the concretes, Brazilian Portland
cement CP II Z-40 (according to Brazilian NBR 16697
Page 3 of 16 98
[34]), natural quartz sand, gravel, silica fume,
metakaolin, potable water, and a polyfunctional addi-
tive were used.
The cement used has a content of pozzolanic
addition (fly ash) between 6 and 14% in its original
mixture. Thus, this will compromise the analysis of the
exclusive action of silica fume or metakaolin. Never-
theless, this cement was chosen because it is the most
easily found in the local market, being the cement
generally used in local structural works and presenting
superior performance to Portland cement without
additions regarding durability in marine environ-
ments. The cement used has a Blaine specific surface
area equal to 4893.00 cm2/g and specific gravity equal
to 3.00 g/cm3.
The characteristics of the aggregates used are
presented in Table 1.
SF and MK were characterized by energy-disper-
sive X-ray (EDX) and laser granulometry techniques.
The characteristics of these materials are shown in
Table 2.
2.2 Mix design and sample preparation
The mix design was performed using the methodology
presented by IPT/EPUSP [38]. The w/b ratio was set
at 0.45, and the concrete slump at 100 ± 10 mm. It
should be noted that the w/b ratio adopted (= 0.45) is
the maximum value prescribed by the Brazilian
NBR 6118 [39] for structures exposed to splash zones
(exposure class IV). When necessary, the polyfunc-
tional additive was used to increase the workability of
the material. Table 3 shows the material consumption
in each concrete mix.
It is necessary to pay attention to the fact that the
use of some pozzolans in high levels (such as 20% of
SF, for example), strongly affects other properties of
the concrete, being able, for example, to promote
autogenous shrinkage and early-age cracking,
demanding care during concrete curing, as observed
by several authors, such as Shekarchi et al. [40] and
Imam et al. [41]; however, this study does not aim to
evaluate the technical feasibility of high levels of SF
and MK in large concrete plants. The analysis of these
levels is restricted to a laboratory evaluation of its
influence on aspects related to the chloride penetration
in concrete.
The casting and curing of the specimens were
carried out according to the Brazilian NBR 5738 [42].
98 Page 4 of 16 Materials and Structures (2021)54:98

Table 1 Physical characterization of the aggregates used

Parameter Fine sand Medium sand Coarse aggregate

Fineness modulus 1.64a 2.42a 6.71a

a a
Maximum diameter (mm) 2.40 2.40 12.50a
3 b b
Bulk specific gravity (g/cm ) 2.67 2.65 1.46c
a b c
NBR NM 248 [35], NBR NM 52 [36], NBR NM 53 [37]

Table 2 Physical and chemical characterization of silica fume Cylindrical specimens with dimensions /
and metakaolin 100 mm 9 200 mm were molded. After demolding,
Parameter Results the specimens were submitted to submerged curing
until the age of 120 days; thereupon, the proposed
Silica fume Metakaolin
tests were carried out. Although it is unusual in
Specific gravity (g/cm3) 2.22 2.53 common practice at the construction site to apply this
Specific surface área (cm2/g) 26,118.79 28,168.56 curing period, the use of this long period is aimed to
SiO2 88.320 41.150 ensure the occurrence of a large part of the pozzolanic
K2O 6.140 2.330 reactions.
CaO 4.350 0.082 In order to obtain samples having the dimensions
Fe2O3 0.680 16.610 recommended in ASTM C1202 [31],
MnO 0.390 0.370 ASTM C1556 [32], and NT Build 492 [33], the
Cu2O 0.053 – original cylindrical specimens had to be cut. In the
Rb2O 0.040 – bulk diffusion test, samples with dimensions /
SrO 0.032 0.021 100 mm 9 100 mm were used, while for the migra-
Al2O3 – 35.570 tion tests, samples with dimensions /
TiO2 – 2.840 100 mm 9 50 mm were taken. It should be noted
ZrO2 – 0.590 that only the central parts of the original specimens
Nb2O5 – 0.190 were used to obtain the samples, thus disregarding the
V2O3 – 0.140
cover zones of the specimen.
ZnO – 0.067
To avoid the use of samples that presented very
Ga2O3 – 0.042
different gravel and paste contents, the mortar content
of the samples obtained was determined. For this, an
adaptation of ASTM E562 [43] was used, as proposed

Table 3 Material Mix w/b ratio Material consumption (kg/m3)

consumption of the
investigated concrete mixes Cement SF MK Fine sand Medium sand Coarse aggregate

R 45 0.45 400.00 0.00 0.00 128.00 512.00 960.00

SF 5 0.45 380.00 20.00 0.00 128.00 512.00 960.00
SF 10 0.45 360.00 40.00 0.00 128.00 512.00 960.00
SF 20 0.45 320.00 80.00 0.00 128.00 512.00 960.00
MK 5 0.45 380.00 0.00 20.00 128.00 512.00 960.00
MK 10 0.45 360.00 0.00 40.00 128.00 512.00 960.00
MK 20 0.45 320.00 0.00 80.00 128.00 512.00 960.00
Materials and Structures (2021)54:98
by Ribeiro [44]. Through this methodology, it is
possible to estimate the relative quantity of a deter-
mined phase by overlaying a mesh on the sample and
quantifying the nodes that appear in the evaluated
phase. Nodes located on the transition zone are
assigned 0.5 points, while nodes positioned on the
analyzed phase receive 1 point. Finally, the phase
percentage in the sample is obtained by the relation-
ship between the number of points and the total knots
of the mesh used. Figure 1 schematically presents this
methodology.
Before conducting chloride penetration tests, the
samples intended for these tests were saturated in
calcium hydroxide solution. Although
ASTM C1202 [31] and NT Build 492 [33] indicate
that sample saturation must be performed using a
vacuum chamber, the saturation in calcium hydroxide
solution is indicated by ASTM C1556 [32] and,
similarly, aims at ensuring that no chloride penetration
occurs into concrete through capillary absorption.
When removing the samples from the calcium
hydroxide solution, there may be residual lime on
the sample surface. When in contact with air, this lime
may react and form a calcium carbonate layer on the
sample surface, interfering with the results obtained,
as also discussed by ASTM C1556 [32]. To avoid this
carbonation process, the samples were cleaned and
rinsed with tap water after being removed from the
calcium hydroxide solution.
Fig. 1 Methodology used for determining the percentage of
mortar in the samples used in chloride penetration tests
(Adapted from Ribeiro [44])
Page 5 of 16 98
2.3 Physical and mechanical characteristics
of concretes
Initially, aiming to obtain data about the physical and
mechanical characteristics of the concretes, the tests
on compressive strength and capillary water absorp-
tion were carried out, following the codes NBR 5739
[45] and RILEM CPC11.2 [46], respectively. Both
tests were carried out 126 days after casting the
concretes. In each test, three specimens having
dimensions / 100 mm x 200 mm from each mix
were used. The specimens intended for the capillary
water absorption test were previously dried, as
recommended by RILEM CPC11.2 [46].
Bjegović et al. [47] highlight that the results on
capillary absorption obtained by
RILEM CPC11.2 [46] are often expressed as a func-
pffi
tion of t by analogy, for example, with the capillary
action of water in an ideal cylindrical pore, which can
be expressed approximately by Eq. 1.
pffi
mðtÞ ¼ Sc t ð1Þ
where mðtÞ is the increase in the mass of the specimen
(g), due to capillary absorption after an exposure time
t, and Sc is the absorption coefficient (or sorptivity).
2.4 Rapid chloride penetrability test (RCP)
The rapid chloride penetrability test (RCP) was
performed according to ASTM C1202 [31]. Four
samples of dimensions / 100 mm x 50 mm from
each concrete mix were evaluated at the age of
126 days. Although it does not directly provide values
for the diffusion coefficients of a concrete, this is a
highly accelerated test, lasting 6 h, which makes it
possible to infer about the penetrability of chlorides in
concrete. One of the major criticisms imposed on this
method [48], however, refers to the fact that the
voltage indicated in the code (60 V) is extremely high,
possibly resulting in overheating of the system and
consequent damage to the accuracy of the data
obtained. Thus, it was decided to apply a lower
voltage (30 V), and subsequently, the current values
measured in the electrical circuit were corrected using
Ohm’s Law.
During the 6 h duration of the test, current flow
readings were taken every 30 min. After this period,
98 Page 6 of 16
the total electrical charge passed is calculated accord-
ing to Eq. 2.
Q ¼ 900ðI0 þ 2I30 þ 2I60 þ . . . þ 2I330 þ I360 Þ ð2Þ
where Q is the total charge passed (C), I 0 is the current
measured immediately after applying the voltage (A),
and I t is the current measured t minutes after the start
of test (A).
2.5 Bulk diffusion test (BDT)
Through the bulk diffusion test (BDT), standardized
by ASTM C1556 [32], the apparent diffusion coeffi-
cient (Da ) of the concretes was determined. Among
the test methods used in this study, this is the one that
tends to better represent the behavior of concrete when
exposed to marine environments, especially in sub-
merged zones. However, it is necessary to pay
attention to the fact that it is necessary for the
concretes to be immersed in a saline solution for at
least 35 days, thus making it difficult to assess the
diffusivity of the concretes at an early age.
To perform the test, three samples of / 100 mm 9
100 mm from each concrete mix were used. The test
started 126 days after concrete casting. Thereupon, all
samples were continually submerged for 112 days in a
saline solution with a concentration of 165 g of NaCl
per liter of water and at a temperature of 23 ± 2 8C.
After the immersion period, at the age of 238 days, the
samples were dried in the air, at a controlled temper-
ature of 23 ± 2 8C, for 24 h. For the determination of
the chloride profile, 1 g of concrete powder was
extracted by drilling from each 7 subsequent depth
intervals up to a depth of 20 mm. The determination of
chloride content was carried out through potentiom-
etry using a silver/silver chloride electrode, with an
accuracy of 0.01%. From the established chloride
profile, Da can be determined by adjusting Eq. 3 to the
chloride content values measured by non-linear
regression using the least-squares method.
 
x
C ðx; tÞ ¼ CS  ðCS  Ci Þerf pffiffiffiffiffiffiffiffiffiffi ð3Þ
4Da t
where C ð x; tÞ is the chloride content at depth x after the
time t (%), C S is the chloride content at the concrete
surface (%), determined via linear regression, Ci is the
initial chloride content (%), erf is the Gauss error
function, x is the middle depth of the extraction layer
Materials and Structures (2021)54:98
(m), Da is the apparent diffusion coefficient (m2/s),
and t is the exposure time1 (s).
2.6 Rapid chloride migration test (RCM)
The non-steady-state migration coefficient (Dnssm ) was
determined using the rapid chloride migration test
(RCM), initially proposed by Tang [49] and standard-
ized by NT Build 492 [32]. Four samples of dimen-
sions / 100 mm x 50 mm from each concrete mix
were evaluated at the age of 126 days. Tang and Sør-
ensen [50] highlight that this method has high preci-
sion in determining the migration coefficient of
concrete, in addition to being fast, lasting between 6
and 96 h, simple and with results that have a good
correlation with the results obtained in diffusion tests.
Initially, the samples were subjected to an exter-
nally applied voltage of 30 V, which was adjusted
according to the current initially measured. Eventu-
ally, the applied voltage could vary between 10 and
60 V. The temperature of the anodic solution was also
measured at the beginning and the end of the
procedure. After being subjected to ionic migration,
the samples were diametrically broken, and 0.1 M
AgNO3 solution was sprayed on the split concrete
surface to reveal the depth of chloride ion penetration.
Lastly, the Dnssm was calculated using the formu-
lation presented in Eq. 4.
0; 0239ð273 þ T ÞL
Dnssm ¼
ðU  2Þt
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi! ð4Þ
ð273 þ T ÞLxD
xD  0; 0238
U2
In Eq. 4, Dnssm is the non-steady-state migration
coefficient (1012 m2 =s), U is the absolute value of
the applied voltage (V), T is the average value of the
initial and final temperatures in the anolyte solution
(°C), L is the thickness of the sample (mm), xD is the
average value of the chloride penetration depths (mm),
and t is the test duration (h).
2.7 Probabilistic service life assessment
The chloride penetration model presented by Gjørv
[26] was used to assess the service life of concrete
structures. This model is based on the analytical
1
In this case, t = 112 days was introduced.
Materials and Structures (2021)54:98
solution of Fick’s Second Law of Diffusion and was
developed from improvements to the model initially
proposed by the European project DuraCrete [51].
Besides, this model was widely used in probabilistic
service life assessments of structures exposed to harsh
marine environments and underwater infrastructure.
The model is presented in Eq. 5.
" !#
xc
C ðx; tÞ ¼ CS 1  erf pffiffiffiffiffiffiffiffiffiffiffi ð5Þ
2 DðtÞt
where Cð x; tÞ is the chloride content at depth xc after
time t (%), C S is the chloride content at the concrete
surface (%), erf is the Gauss error function, and DðtÞ is
the concrete chloride diffusion coefficient given by
Eq. 6, adopted by Gjørv [26] based on the study
presented by Tang and Gulikers [52].
"   0 1a # a
D0 t0 1a t t0
DðtÞ ¼ 1þ  ke ð6Þ
1a t t t
where D0 is the diffusion coefficient at the reference
time t0 (m2 =s), t0 is the age of concrete at the time of
first chloride exposure (years), a represents the
concrete aging factor, and ke is a parameter that takes
the effect of temperature into account (Eq. 7).
  
EA 1 1 failure, or design point, is a combination of values of
ke ¼ exp  ð7Þ
R 293 273 þ T
where exp is the exponential function, EA is the
activation energy for the chloride diffusion (kJ/mol), R
is the gas constant (J/(mol  K)), and T is the
temperature (8C).
The criterion for initiating corrosion of steel
reinforcement can be defined as Eq. 8.
C ðx; tÞ ¼ CCR ð8Þ
where Cð x; tÞ is the chloride content at depth xc after
time t (%), and C CR is the critical chloride content (%).
As a consequence, the limit state function Gðx; tÞ
for the rebar depassivation can be written as shown in
Eq. 9.
Gðx; tÞ ¼ CCR  Cðx; tÞ ð9Þ
Finally, the Pf can be calculated as Eq. 10.
Pf ¼ PðGðx; tÞ  0Þ ð10Þ
where Pf is the probability of failure, i.e. the
probability of reinforcement corrosion initiation.
Page 7 of 16 98
The probability of corrosion initiation was evalu-
ated for concrete structures having an average cover
depth of 40, 50, 60, and 70 mm. The cases with 40 and
50 mm cover depth refer to the requirements indicated
by the Brazilian NBR 6118 [39] for marine exposure
classes III and IV, respectively. The values of 60 and
70 mm come from case studies presented by the
developers of the probabilistic model [26] for Norwe-
gian harbor structures. For all evaluated xc , the cover
depth variability presented by Magalhães et al. [53]
was used. The D0 values adopted are those determined
experimentally using the methodology described by
NT Build 492 [33]. The CS presented by Guimar-
ães [54] was taken, which was obtained in a harbor
structure in the city of Rio Grande, southern Brazil,
and the temperature considered refers to the annual
average during 2018 in this same city. Furthermore,
the age at which D0 was measured was adopted for
parameter t0 (i.e. 126 days). The values adopted for
each input parameter are shown in Table 4.
The Monte Carlo Simulation with Importance
Sampling was used to determine the Pf . In an adaptive
Monte Carlo Importance Sampling Technique, the
point of failure x is iteratively searched so that these
two conditions, namely Gð xÞ ¼ 0 and maximum
f X ð xÞ; are simultaneously satisfied. The point of
the basic random variables X, that satisfies the limit
state function Gð xÞ ¼ 0. This point also has the
highest value of the joint probability density function
f X ð xÞ over the curve Gð xÞ ¼ 0.
In this study, two hundred updates of the point of
failure were performed, with 1000 simulations being
performed for each update. This number proved to be
sufficient for the statistical convergence of the results.
3 Results and discussions
3.1 Physical and mechanical characteristics
of concretes
The results obtained in the tests of compressive
strength and water absorption by capillarity are
presented in Table 5 and Fig. 2. It is emphasized that
the results presented refer to the average value
obtained from the analysis of three specimens.
98 Page 8 of 16 Materials and Structures (2021)54:98

Table 4 Random variables Parameter Unit Distribution type Mean Coefficient of Variation (CV) Reference
used in the probabilistic
assessment D0 m2 /s Normal Dnssm 0.10 [33]
t0 days Deterministic 126 – This study
xc mm Normal 40.00 0.10 [39, 53]
50.00
60.00 [26, 53]
70.00
CS %a Lognormal 2.07 0.23 [54]
a
T 8C Normal 18.00 0.20 [55]
By mass of cement; bfor
a – Normal 0.43b 0.20 [56]
concrete without mineral
admixtures; cfor concrete 0.50c [56]
containing metakaolin; dfor 0.55d [40]
concrete containing silica C CR %a Normal 0.40 0.15 [57]
fume

It can be seen, based on the data presented in should be noted that, at the end of the test, the use of
Table 5 and Fig. 2, that, in general, silica fume and 5% of silica fume generated a 10% reduction in
metakaolin increased the compressive strength and capillary absorption. The SF 10 and SF 20 mixes, in
reduced the rate of capillary water absorption of the turn, provided reductions of, on average, 12.17% and
evaluated concretes. These improvements occur due to 20.87% compared to the reference concrete, respec-
the pozzolanic reaction between Ca(OH)2 from tively. MK, in turn, only provided the concrete with
cement hydration and SiO2 present in silica fume less capillary absorption when used in the 20%
and metakaolin, providing the formation of secondary content. Even so, this reduction was quite small and
CSH. In addition, SF and MK act as fillers, making the less than that obtained with the use of 5% of SF.
paste more homogeneous and modifying the concrete However, it is necessary to pay attention to the fact
microstructure. When comparing the two pozzolans at that the use of mineral additions promotes a reduction
equal levels, the best results were obtained when using in the pore diameters of the concrete, which may cause
silica fume. The superior performance of concretes a higher suction of water and increase the values
with silica fume compared to those with metakaolin in obtained in the water absorption test, as also observed
terms of compressive strength was also observed by by Teodoro [59]. When this occurs, as in the case of
Meddah et al. [58]. the MK 5 and MK 10 mixes, it does not necessarily
When analyzing the results obtained in the water mean that the concrete is more porous or permeable, as
absorption test, it is highlighted that the use of SF the test result may be expressing a greater water
proved to be beneficial for all the evaluated levels. It suction capacity due to the resistance of the smaller
diameter capillaries.
It should also be noted that the variations in the
Table 5 Compressive strength and sorptivity of concretes average values of compressive strength presented by
pffiffiffi the concretes R 45, MK 5, MK 10, and SF 5 are less
Mix Compressive strength [MPa] Sorptivity [g= h
than 1 MPa. This difference is small when the degree
R 45 63.22 12.37 of precision of the test in question is analyzed, and the
SF 5 63.46 10.70 simple variation between specimens of the same mix
SF 10 70.88 10.59 may be higher than this value.
SF 20 74.51 9.35
MK 5 62.86 12.55 3.2 Rapid chloride penetrability test (RCP)
MK 10 63.55 12.88
MK 20 66.99 11.68 The average electrical charges passed (Q, expressed in
Coulombs) through the concrete samples during the
duration of the test standardized by
Materials and Structures (2021)54:98
Fig. 2 Water absorption by capillarity of the evaluated concrete: a influence of silica fume; b influence of metakaolin
ASTM C1202 [31] are presented in Table 6. It is
noteworthy that, according to the methodology of
classification of the concretes as for the penetrability
of chlorides proposed by this standard, all evaluated
concretes are qualified as ‘‘very low’’ penetrability
(100 C \ Q \ 1000 C).
Unlike the water absorption test, the RCP-test
results in a parameter more directly related to the
movement of chloride ions inside the concrete. Thus,
the RCP results tend to represent better the penetra-
bility and the durability potential of the evaluated
concrete.
Note that the SF again improved the concrete.
Although the SF 5 mixture provides a good reduction
in electrical charge passed (355.3 C), it is noteworthy
that the 10% content reduced the chloride penetrability
of concrete by less than half when compared to the
reference mix. The metakaolin, which had slight
variations considering the reference mixture when
assessing the compressive strength and the absorption
of water by capillarity, provided concrete with signif-
icant improvements in terms of chloride penetrability.
For this property, the use of MK in the content of 5%
implied a reduction of the charge passed by 29.72%.
Table 6 Chloride penetrability of concretes
Mix Total charge passed [C]
R 45 859.44
SF 5 504.14
SF 10 387.54
SF 20 377.94
MK 5 604.02
MK 10 477.63
MK 20 402.45
Page 9 of 16 98
When evaluating the influence of the type of
mineral addition used, it appears that the best results
were obtained when using silica fume. However, this
differs from the results presented by Poon et al. [4],
who also evaluated concretes with silica fume and
metakaolin using the rapid chloride penetrability test.
This difference was more accentuated when compar-
ing concretes with a substitution content equal to 5%,
with the Q presented by the SF 5 being 99.89 C lower
than the Q measured in the MK 5 concrete.
3.3 Bulk diffusion test (BDT)
Figure 3 presents the chloride profiles obtained from
the samples extracted from the specimens submitted to
the bulk diffusion test according to
ASTM C1556 [32]. It should be noted that each
chloride profile shown in Fig. 3 refers to the average
obtained based on three profiles of each concrete mix.
These profiles are necessary for the calculation of Da .
The values of Da , in turn, are presented in Table 7. In
addition, it is necessary to pay attention to the fact that
this test started 126 days after the concrete casting and
that the samples were immersed in a NaCl solution for
another 112 days.
Since the standard that governs this method does
not present any classification of chloride penetrability
in concretes based on the diffusion coefficient, the
classification proposed by Nilsson et al. [60] was used.
It is stressed again that the results obtained in the
immersion test are those that best represent the real
conditions of exposure of the concrete to marine
environments, especially in submerged zones. How-
ever, in order to obtain chloride profiles with a
penetration depth that would allow a satisfactory
evaluation, 112 days of immersion were necessary.
Thus, although this method presents results that are
quite consistent with real exposure situations, the long
98 Page 10 of 16 Materials and Structures (2021)54:98

Fig. 3 Chloride profile of concretes: a influence of silica fume; b influence of metakaolin

Table 7 Apparent Mix Apparent diffusion coefficient (Da ) Resistance to chloride penetration [60]
diffusion coefficient of [1012 m2 =s]
concretes
R 45 3.23 Very high
SF 5 2.85
SF 10 1.91 Extremely high
SF 20 1.81
Extremely high: Da \ MK 5 3.15 Very high
2.5 1012 m2 =s;
MK 10 2.13 Extremely high
Very high: 2.5 1012 m2 =s
MK 20 1.80
\ Da \ 5 1012 m2 =s

test duration and costs make the bulk diffusion test less
attractive to be used as a method for assessing the
quality of concrete at its early age.
3.4 Rapid chloride migration test (RCM)
The non-steady-state migration coefficients (Dnssm )
obtained through the test procedure standardized by
NT Build 492 [33] are presented in Table 8. Again, the
classification proposed by Nilsson et al. [60] was used
to determine the level of resistance of concretes to the
penetration of chlorides.
It is noted that, initially, the use of mineral
additions, with various contents, provided concrete
with resistance to chloride penetration classified as
‘‘extremely high’’. However, even if they have
obtained the same classification, one must pay atten-
tion to the Dnssm value of each concrete, since this is an
input parameter of the service life prediction model
used in this study and frequently used in other models
described in the literature. Thus, even though two or
more concretes have the same classification regarding
diffusivity according to the results of the rapid
chloride migration test, the variation between the
diffusion coefficients can lead to significantly differ-
ent service life predictions.
It is known that pozzolanic materials when used as
a partial replacement of Portland cement in concrete,
act through their physical and chemical effects. The
notable reduction in the diffusivity generated by SF
and MK may, therefore, be related to changes in the
porous structure of the concrete due to the filler effect,
through which the particles of silica fume or
metakaolin create physical barriers that impose diffi-
culties in the entry of ions in concrete, as pointed out
by Wild et al. [2], and to the increase in the resistivity
of the concrete and, consequently, greater difficulty in
the electrical conduction of the ions.
Also noteworthy is the notable difference in
migration coefficient between the mixes R 45, MK
5, MK 10, and SF 5. These concretes, as previously
discussed, present very similar compressive strengths,
with variations below 1 MPa. However, analyzing the
Dnssm values obtained by mixtures R 45 and MK 10,
for example, a reduction of 66.2% is perceived.
The importance of using performance-based
approaches and durability indicators in durability
design and quality control of reinforced concrete
structures is confirmed by these facts, since concretes
that follow the same prescriptive parameters (w/b
ratio, compressive strength, and binder content) can
show significantly different behaviors when their
Materials and Structures (2021)54:98
Table 8 Non-steady-state migration coefficient of concretes
Mix Non-steady-state migration coefficient (Dnssm )
[1012 m2 =s]
R 45 2.84
SF 5 1.40
SF 10 0.90
SF 20 0.27
MK 5 2.14
MK 10 0.96
MK 20 0.62
Extremely high: Da \ 2.5 1012 m2 =s;
Very high: 2.5 1012 m2 =s \ Da \ 5 1012 m2 =s
Fig. 4 Summary of the diffusion coefficients obtained through
the two test methods used
durability-related properties are evaluated. However,
that it is necessary to realize that the values obtained
for durability indicators in laboratory cast con-
crete (labcrete) will be different from those taken in
samples extracted from the structure (realcrete) and,
still, both will be different from the real capacity of the
executed concrete to resist the penetration of harmful
agents, as highlighted by Wally et al. [61].
Figure 4 summarizes the results obtained from the
two methodologies for determining the diffusion and
migration coefficient of concretes. In Fig. 5, the
correlation between these results is evaluated.
Based on Fig. 4, it is noted that the diffusivity
obtained through the migration test standardized by
NT Build 492 [33] is considerably lower than those
obtained in the bulk diffusion test [32]. This is an
expected result that has been observed by other
authors [62]. It is also verified that the difference
between the diffusion coefficients was smaller in the R
45 concrete, which has higher penetrability, and
Page 11 of 16 98
Resistance to chloride penetration [60]
Very high
Extremely high
Fig. 5 Correlation between the diffusion coefficients obtained
experimentally
higher in the concretes, which have a higher resistance
to the ingress of chloride ions, such as the SF 20.
When analyzing the classification of concretes in
terms of their resistance to the penetration of chlo-
rides, it is observed that only the SF 5 and MK 5
obtained different classifications due to the method-
ology used.
It can be seen from Fig. 5, that the rapid chloride
migration test has a good correlation with the diffusion
test (R2 = 0.8772). This good correlation was also
observed by Tang and Sørensen [50] and Castellote
and Andrade [62]. It is noteworthy that the method
presented by NT Build 492 [33] requires less equip-
ment and demands less time than the methodology
standardized by ASTM C1556 [32], being, therefore,
an adequate test for the quality control of concrete
regarding durability. Due to the good correlation
between the results presented by both methods
observed in this paper and other publications available
98 Page 12 of 16
in the literature [50, 62], the Dnssm values were used in
the probabilistic assessment performed. However, it is
necessary to pay attention to the fact that when the
diffusion coefficient is determined through such an
accelerated test, the behavior of the concrete may be
different from what occurs under normal conditions in
the field. Therefore, the value of Dnssm should be taken
as a index that reflects the resistance to the penetration
of ions and the general durability properties of the
concrete, similarly to the compressive strength eval-
uated at the first ages of the concrete, which is also a
simple index, reflecting general mechanical properties
of concrete.
3.5 Probabilistic service life assessment
The results of the probabilistic service life assessment
of the evaluated concretes are presented in Fig. 6. For
this analysis, the values presented in Table 4 were
adopted, and Monte Carlo Simulation with Importance
Sampling was used. It is reiterated that the results
obtained experimentally in the test standardized by NT
Build 492 [33] (Dnssm ) were taken as the reference
diffusion coefficient D0 in the chloride penetration
model presented in Eqs. 5–7.
In general, it appears that the use of mineral
additions will significantly reduce the predicted prob-
ability of corrosion occurring at all ages and cover
depths evaluated. These results are directly linked to
the diffusion coefficients of each concrete since this is
the main parameter related to the characteristics of the
concrete considered in the penetration model used.
Evaluating the results obtained for cover depths of
40 and 50 mm, the importance of a performance-based
approach for concrete durability is again highlighted.
It is noteworthy, for example, that the Pf is approx-
imately 18% at 25 years considering the concrete R 45
and 50 mm of cover depth. However, when 5% of
silica fume is used, even if the cover depth is reduced
to 40 mm, the probability of corrosion is predicted to
reach approximately 2% at the age of 25 years and
approximately 10% at the age of 50 years.
It should also be noted that at the age of 100 years,
for the reference concrete Pf reaches approximately
53% if xc = 60 mm is used and approximately 31% if
70 mm cover depth is taken; if MK 10 concrete is
considered, both percentages are less than 1%. How-
ever, this type of consideration and decision-making,
Materials and Structures (2021)54:98
which can generate economic, structural, and archi-
tectural benefits to the building, requires previous
experiences with the use of durability indicators as a
methodology of evaluating durability-related proper-
ties of concrete and as an input parameter in service
life prediction models.
4 Conclusions
The evaluation of the service life of concretes
containing silica fume and metakaolin as partial
replacement of Portland cement through durability
indicators and using a probabilistic method led to the
following main conclusions:
The use of silica fume and metakaolin led to
improvements in the properties of concretes as deter-
mined by laboratory tests. Although in some cases the
variations in compressive strengths due to the use of
pozzolans have not been significant, the notable re-
ductions obtained in the diffusion coefficient of
concretes stand out, which presented reductions of
up to 90% when using mineral additions. When
compared in the same replacement content, the most
satisfactory results were obtained when using silica
fume;
The migration test standardized by NT Build 492
[33] is a good alternative for the rapid determination of
concrete diffusivity. This method presents results that
have a reasonable correlation with the values obtained
through the bulk diffusion test, besides being simple
and fast. The bulk diffusion test, in turn, despite being
the method that best represents the real situation of
concrete exposure to chloride ions, demands an
extended test period, making it difficult to use in the
quality control of concrete;
The evaluation of concrete characteristics from
performance-based approaches is of great importance
in the durability design and the evaluation of the
service life of reinforced concrete structures. It was
inferred in this study that concretes that follow the
same prescriptive mix design parameters and that
present compressive strengths with variations below
1 MPa can present significantly different behaviors
when evaluated under the perspective of durability in
chloride environments, with reductions of 53% in RCP
and 90% when Dnssm is determined. Thus, it is noted
that the compressive strength has reduced accuracy in
evaluating properties related to the chloride
Materials and Structures (2021)54:98
Fig. 6 Results obtained in the probabilistic service life assessment
penetration in concrete and, therefore, it is not an
adequate durability indicator for structures exposed to
severe aggressive environments.
The evaluation of the service life of reinforced
concrete structures based on probability is of funda-
mental importance since the variability of the param-
eters involved in the process of chloride penetration
into concrete causes significant variations in the
behavior of the probability of failure. As is well-
known, due to numerous parameters involved in the
model, the values of service life obtained from
probabilistic assessments should not be taken as
definitive numbers but rather as a basis for compar-
ative evaluation of the behavior of a concrete structure
throughout its service life and for making decisions
about maintenance;
As a consequence of the variations in the diffusion
coefficient values and other model parameters, notably
the concrete aging factor, different Pf were obtained
Page 13 of 16 98
for concretes when exposed to chloride penetration.
Thus, the importance of the quality control of the
produced concrete through durability indicators is
corroborated. For example, for a reinforced concrete
structure with a cover depth of 50 mm, at the age of
100 years, for R 45 concrete, a probability of corro-
sion initiation of roughly 78% will be predicted.
However, considering the same cover depth and age,
for the MK 10 mix, a probability of about 4%, and for
the SF 10 mix, a probability of only 2% will be
expected.
Acknowledgements This study was financed in part by the
Coordenação de Aperfeiçoamento de Pessoal de Nı́vel
Superior—Brasil (CAPES)—Finance Code 001. The author
M. de V. Real thanks the Conselho Nacional de
Desenvolvimento Cientı́fico e Tecnológico (CNPq) for the
research grant (Process 304211/2018-4).
98 Page 14 of 16
Declarations
Conflict of interest The authors declare that they have no
conflict of interest.
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