ACI MATERIALS JOURNAL TECHNICAL PAPER

Title No. 118-M39

Effect of Different Metakaolins on Chloride-Related

Durability of Concrete
by Oswaldo Cascudo, Rodrigo Teodoro, Andrielli M. de Oliveira, and Helena Carasek

The main purpose of this work is to evaluate which parameters ratio (w/b), in association with the use of mineral additions,
obtained from the characterization of metakaolins (MKs) (physical, producing a poorly interconnected and tortuous pore system
chemical, and mineralogical parameters) have greater relevance with very low permeability.12 Studies by Castro et al.13
in terms of positive impact on concrete durability properties related show that the overall performance of concretes with 10%
to chlorides, and which scientific arguments support these results.
of metakaolin (MK) (in replacement to the cement mass),
In parallel, a comparative study between three different MKs was
regarding the accelerated and natural carbonation processes
carried out to statistically evaluate the ability that each of these
materials must modify and eventually improve concrete dura- (after 14 years), was superior or similar to the reference
bility properties associated with chlorides (electrical resistivity concretes (without mineral additions).
and chloride migration). A discussion of the results was carried Among the SCMs available for use in concrete tech-
out considering evaluations of the microstructure, emphasizing the nology, there is MK. MK is a special artificial pozzolan ther-
cementitious systems’ porosity (by mercury intrusion porosimetry mally activated and obtained by the calcination of kaolinitic
[MIP]). It was found that MKs contributed to reduced porosity and clay at moderate temperatures between 600 and 800°C.14 It
refined pores, which made the transport of chlorides significantly offers numerous technical and economic benefits when used
more complex, and that some characteristics of MK, especially its inside concrete. Further, this mineral addition is also consid-
amorphous content, have been more decisive for that. ered a more sustainable and environmentally friendly mate-
Keywords: amorphous content; chloride migration; durability; electrical
rial, owing to the limited CO2 emission during its production
resistivity; metakaolin; microstructure; performance; porosity. process, because lower temperatures are required for calci-
nation of kaolinite. Unlike ordinary portland cement (OPC),
INTRODUCTION the primary decomposition reaction does not result in CO2.
The demand for durable concrete structures in the civil Primarily, as previously mentioned, this material increases
construction industry is encouraged by reducing the inci- concrete durability, rendering the ingress of chlorides more
dence and costs of maintenance and repairs during its life- difficult10,11; however, MK’s primary disadvantage is likely
time and life cycle. Additionally, from an environmental the high cost of production compared to cement due to its
perspective, an increasing number of laws have been imple- current low production rates. Higher employment in the
mented to reduce carbon footprint and limit greenhouse concrete industry could potentially decrease the production
gas emissions and landfill spaces.1 Simultaneously, a social cost of this pozzolan.15
requirement has been imposed regarding the reduction in Many researchers have presented the effects of MK on
consumption of materials, workforce and energy in repairs, the physical characteristics of concrete. The results have
and the use of more efficient materials.2 evidenced a physical alteration of the cement paste, with
In this sense, the benefits associated with the incorpora- changes in the pore network and pore size distribution (pore
tion of pozzolanic materials in cement matrixes have been refinement occurs).16,17 The cement paste becomes more
studied extensively in recent years.3-10 Among their various dense (less porous) with more tortuous and less intercon-
contributions, it is possible to highlight concrete durability nected pores.18 Besides these physical changes, there are also
improvement, making the ingress of aggressive agents such changes from the chemical point of view in the pore solu-
as chloride ions more difficult.10 Studying the production of tion, which brings about changes in both the electrical prop-
different cements, Maraghechi et al.11 showed, in particular, erties (conductivity and resistivity) and the species and ionic
how the purity and kaolinite content of the raw material concentrations. As a result, the transport properties such as
plays an important role in reducing the transport of chlo- gas and water permeability, capillary absorption, and ion
rides in cementitious systems, both by the mechanisms of diffusion decrease, thus decelerating the ingress of aggres-
chloride binding and, mainly, by the porosity refinement. sive substances.3,10 As mentioned briefly, an important modi-
On the other hand, it is known that when these supplemen- fication in the concrete electrical resistivity occurs, whose
tary cementitious materials (SCMs) are incorporated into values become significantly higher, thus restricting the
concrete, in partial replacement to cement, a dilution effect
ACI Materials Journal, V. 118, No. 3, May 2021.
occurs, with a reduction in the alkaline reserve. As a result, MS No. M-2019-417.R5, doi: 10.14359/51732634, received September 2, 2020, and
there is a tendency to reduce the performance of concretes reviewed under Institute publication policies. Copyright © 2021, American Concrete
Institute. All rights reserved, including the making of copies unless permission is
against carbonation. This trend, however, is not confirmed obtained from the copyright proprietors. Pertinent discussion including author’s
closure, if any, will be published ten months from this journal’s date if the discussion
when the porosity is controlled by limiting the water-binder is received within four months of the paper’s print publication.

ACI Materials Journal/May 2021 3

transport of electrical charges (ionic) through the concrete’s introduced in the concretes (including changes in pore
porous internal structure.5,12,19 Badogiannis et al.15 evalu- systems), which provided scientific argument in terms of the
ated concretes with MK by chloride migration tests. They different behaviors and performances of these MK modified
showed a significant decrease in the chloride migration concretes concerning their chloride-related durability.
coefficient from 21.75 × 10–12 m2/s to 4.79 × 10–12 m2/s for
concrete without and with a 10% replacement to cement for EXPERIMENTAL INVESTIGATION
MK, respectively. Some authors observed the same trend Materials
of reduced chloride migration coefficient by incorporating Concrete mixture proportions used in this investigation
any mineral addition into concrete.3,4,8 In terms of resistivity, are based on commercial concrete compositions from a
Ramezanianpour and Bahrami3 confirmed the effective local ready mix producer. Brazilian Type CP II F-40 port-
increase in concretes’ electrical resistivity with the inclusion land cement (composed of 90 to 94% clinker and calcium
of MK in replacing portland cement (0% up to 15% of MK). sulfate, and 6 to 10% in mass of limestone filler, according
This study concluded that concretes with pozzolan indicated to the Brazilian standard ABNT NBR 16697:2018), similar
an increase from 38 to 60% in electrical resistivity values to the ASTM C150 Type I cement,23 is used throughout the
compared to plain concretes. Based on concrete perfor- investigations. It presents Blaine specific surface area and
mance against corrosion, considering thermodynamic and specific gravity data equal to 493 m2/kg and 3125 kg/m3,
kinetic parameters, de Oliveira and Cascudo20 have stated respectively.
that the electrical resistivity represents an important indi- Additionally, three different types of highly reactive MK
cator for assessing the potential durability of concrete under are used (MK1, MK2, and MK3), all from the same Brazilian
chloride attack. producer. Despite the differences between them, it is known
Physical effects in the cement matrix by incorporating MK that MK1 and MK3 are obtained from the same deposit of
into concrete, and chemical changes including modifications raw kaolin and that MK2 is from another kaolin mine. The
in the pore solution, are expected. McPolin et al.21 have main visual difference between them is the color: MK1 is
confirmed that the initial pH values (approximately 11.2) in gray, MK2 is white, and MK3 is wheat. The MKs’ complete
the pore solution of concretes containing MK are slightly characterization is presented and explained later herein and
lower than those found in concrete without mineral addi- includes the physical, chemical, and mineralogical proper-
tion (approximately 11.7). In parallel, they verified that this ties, for which the methods are presented in the next section.
pozzolan in portland cement blends increased the chloride- Also, four types of aggregates are used in all concrete
binding capacity compared to pure portland cement. The mixtures. Crushed gneiss is used in two different sizes:
authors justified this behavior in forming a larger quantity one with a maximum size of 0.98 in. (25 mm) and fineness
of Friedel’s salt, where MK acted as an additional aluminum modulus of 6.80; the other with a maximum size of 0.49 in.
source.4,9,22 (12.5 mm) and fineness modulus of 5.71. Moreover, two
In this context, this work’s main objective is to eval- different sizes of siliceous river sand are used, with fine-
uate which parameters obtained from the characterization ness moduli of 3.54 and 2.09. The proportions of aggregates
of MKs (physical, chemical, and mineralogical parame- remained constant for all mixtures: for coarse aggregates,
ters) have greater relevance in terms of positive impact on 20% of the finer gravel and 80% of the coarser gravel; for
concrete durability properties related to chlorides, and which fine aggregates, 40% of the finer sand and 60% of the coarser
scientific arguments support these results. Another objective sand. Furthermore, a polycarboxylate-based high-range
of the paper is to present a comparative analysis between water-reducing admixture (HRWRA) is used in the mixtures
three different MKs of high reactivity, statistically verifying to increase the workability without changing the w/b.
their effect on two concrete durability properties: elec-
trical resistivity and chloride migration. These results are MK characterization methods
discussed based on changes caused by MKs in the porosity For the evaluation of MK physical properties, the fineness
and microstructure of concretes, considering two distinct is measured by the BET specific surface area, using nitrogen
w/b. Additionally, the work aims to verify when there are gas adsorption as described in ASTM C1069.24 Additionally,
significant correlations between the results of the evaluated the particle mean diameter is obtained by the SediGraph
durability properties—resistivity and chloride migration— method, based on Strokes’ law, using particle size analysis
and between the characteristics of MKs and the concrete equipment. Further, to analyze their morphologies, MK
properties. particles are placed on a double-sided conductive carbon
tape (0.16 mm thick) covered with a 25 nm gold layer in a
RESEARCH SIGNIFICANCE scanning electron microscope, using a secondary electrons
An important point of contribution of this work is the imaging detector (SE), with a voltage of 15 kV and work
emphasis of discussion on the protection mechanisms of distance of 0.43 in. (11 mm).
concretes modified by MKs, thus bringing a contribution X-ray fluorescence (XRF) obtained the chemical composi-
concerning the influence of some parameters inherent to the tion of the SCMs. Additionally, the qualitative phase compo-
characteristics of MK on aspects of concrete durability related sition was obtained using the data of X-ray diffractometry
to chlorides. The paper identifies the fundamental differences (XRD) performed with copper anodes (30 mA and 40 kV)
between three types of MKs, producing a link between these and 2θ angle varying from 3 to 70 degrees, with a step of
differences and the corresponding microstructural changes 0.02 degrees every 2 seconds. To quantify the amorphous

4 ACI Materials Journal/May 2021

Table 1—Mixture proportions of concrete
Portland Coarse Compressive
cement, MK, Fine aggregate, aggregate, Water, HRWRA, Slump test, strength—28 days,
Mixture w/b kg/m3 kg/m3 kg/m3 kg/m3 kg/m3 kg/m3 in. (mm) ksi (N/mm2)
40R 0.4 450 — 756 1067 180 1.62 4.53 (115) 8.6 (59.3)
40MK1 0.4 405 45 752 1067 180 2.97 5.12 (130) 9.4 (65.0)
40MK2 0.4 405 45 752 1067 180 2.88 5.51 (140) 10.5 (72.5)
40MK3 0.4 405 45 752 1067 180 3.02 5.51 (140) 9.8 (67.6)
60R 0.6 300 — 894 1059 180 0.99 4.72 (120) 5.2 (36.1)
60MK1 0.6 270 30 888 1059 180 1.38 4.53 (115) 5.7 (38.4)
60MK2 0.6 270 30 888 1059 180 1.14 5.51 (140) 5.5 (38.1)
60MK3 0.6 270 30 888 1059 180 1.80 4.72 (120) 6.7 (43.7)

content of MKs, Rietveld-based refinement techniques placed in a saturated solution of water and Ca(OH)2 at room
are employed. Initially, there was a quantification of the temperature of 23°C. In this condition, the specimens are
material’s crystalline phases (they are not quantified indi- cured until the age of 28 days, when they are stored in a
vidually). The crystalline phases’ total content was obtained laboratory environment until the test age is completed.
using the data of the analyses accomplished in the X-ray Temperature and relative humidity in the laboratory environ-
diffractometer with copper anodes (10 mA and 30 kV) and ment, within the storage period (from 28 days to 140 days of
a 2θ angle varying from 5 to 85 degrees, with a step of 0.04 age), are, respectively: 24 ± 4°C and 60 ± 5%. All tests are
degrees per second. In the end, the difference between the conducted with concrete specimens at the age of 140 days,
contents of the total sample and the total crystalline phases and exclusively for the compressive strength, there are
resulted in the amorphous content. Finally, Chapèlle’s modi- also results with 28 days. Additionally, some of the results
fied method, as described in Brazilian Standard NBR 15895,25 are submitted to statistical methods: analysis of variance
measured the pozzolanic activity index, which determines (ANOVA) and multiple mean comparisons (Tukey’s test).
the use of 2 g of lime to react with 1 g of pozzolan. Quarcioni Mercury intrusion porosimetry—Mercury intrusion poro-
et al.26 discussed this method and, especially with regard to simetry (MIP) is performed on samples of mortar extracted
the ratio of 2 g of lime to 1 g of pozzolan, they affirm that from the concretes produced by sieving fresh concrete in a
the method provides a more accurate and reliable result for 0.25 in. (6.3 mm) sieve to remove the interference of the
highly reactive pozzolans such as MK. coarse aggregate on the overall porosity of concrete. MIP
results are very scattered and inconclusive in more complex
Mixture proportions systems containing many interfacial transition zones (at
The primary variables adopted in this research are the coarse aggregate interfaces with cement paste). The proce-
w/b and the MK type. Concrete mixtures are cast with two dure of extracting the mortar directly from the concrete, by
w/b: 0.40 and 0.60, and three different types of MK: MK1, sieving, brings the mortar samples closer to those that would
MK2, and MK3—whose content of MK incorporated in occur in real concrete, insofar as, coming from the concrete,
concrete was always 10% replacing the cement content, by they are subjected to all the steps involved in the production
mass (binary composition)—and a plain concrete (R) with no of concrete, in terms of the mixer used, the mixing mecha-
mineral addition. The 10% MK content was defined based on nism, and the mixing energy and the content of entrained air
previous works from the study group in durability (GEDUR) (during mixing), among others.
of the Federal University of Goiás (UFG),4,8,13,20 consid- The resulting mortars (from concretes) are molded in
ering the lower content given the better technical response 1.58 x 1.58 x 6.30 in. (40 x 40 x 160 mm) prismatic speci-
in terms of durability performance (lower cost/benefit ratio). mens and subsequently demolded and cured, like the other
For all concrete mixtures, the consistency, measured by the specimens. After this, the mortar prismatic specimens are
slump test, was 4.72 ± 0.79 in. (120 ± 20 mm). Therefore, cut into smaller pieces using a high-precision specimen
the content of the HRWRA was variable to each concrete to cutting machine measuring 0.12 x 0.12 in. and 0.39 in. in
maintain consistency. The detailed mixture proportions of the length (3 x 3 mm and 10 mm in length). Before the MIP test,
eight mixtures and the consistency and compressive strength these reduced specimens (mortar samples) are subjected to
at 28 and 140 days are given in Table 1. Further, the volume a vacuum drying for 12 hours, thus ensuring that a weight
of mortar—the content of cement, MK, and fine aggregates in loss of 0.001 g per gram of sample was reached, with the
volume—in the concrete mixtures was kept constant. application and maintenance of a negative pressure equal to
15 × 10–3 Torr during the total drying period. This procedure
Test methods in concrete and mortar follows the D-Drying method’s prescriptions, as discussed
The concretes are mixed in a laboratory environment and by Korpa and Trettin.27 After drying, the samples are tested
3.94 x 7.87 in. (100 x 200 mm) cylindrical test specimens with the following parameters: a contact angle of 140 degrees
are cast. The specimens are covered with a thin plastic film and a mercury intrusion rate of 500 mm Hg/min.
after casting and subsequently demolded 24 hours later and

ACI Materials Journal/May 2021 5

Table 2—Characterization of MKs: chemical composition and physical properties
Chemical composition, by XRF, in wt. %
Loss on
MK type SiO2 Al2O3 Fe2O3 CaO MgO K2O Na2O Other ignition
MK1 56.46 32.17 2.23 0.17 0.7 2.16 0.04 1.65 4.27
MK2 52.58 44.61 0.35 0.06 0.02 0.09 0.04 0.11 1.95
MK3 51.43 42.53 2.00 0.16 0.28 0.95 0.02 1.14 1.28
Physical properties MK1 MK2 MK3
BET specific surface area, m2/g 19.75 8.13 30.99
Particle mean diameter, D50, µm 6.92 12.42 0.61

Surface apparent electrical resistivity—Concrete surface EXPERIMENTAL RESULTS AND DISCUSSION

electrical resistivity is measured as described in ASTM MKs characterization
G5728 by the Wenner four-electrode method. The measure- Despite being from the same manufacturer, the MKs used
ments are conducted in five concrete test specimens, with in this research are different. Their physical properties are
three measurements for each, totaling 15 measures for each shown in Table 2. The manufacturer provides the specific
concrete mixture. As previously described at the beginning gravity as 2600 kg/m3 for all MKs. An important aspect
of the section “Test methods in concrete and mortar,” a cylin- being emphasized is that the MKs’ specific areas are quite
drical specimen of 3.94 in. (100 mm) in diameter by 7.87 in. different; MK2 is the coarser one, followed by MK1 and
(200 mm) in height was used. To maintain the concrete MK3, which presented higher values. The particle mean
humidity constant for all mixtures, the concrete specimens diameter results are coherent to the specific area results,
are stored in a wet chamber, with a relative humidity greater indicating that MK3 particles are significantly smaller than
than 95%, at 23°C, for 15 days before measuring the surface those of the other MKs.
electrical resistivity. In addition, by observing the particle size distribution
All samples had the same geometry and age, as well as (Fig. 1) obtained from the Sedigraph method—which is a
the same storage condition. The equipment used a low- combination of laser granulometry with sedimentation,
frequency signal (40 Hz) and provided surface electrical based on Stroke’s law—the MK3 presents a significantly
resistivity values with accuracy from ±0.2 to ±2 kΩ.cm. The higher number of smaller particles (< 1 µm) than the other
distance between electrodes in the Wenner device was fixed MKs.
between the four electrodes and equal to 1.97 in. (50 mm). The SEM images of the MKs (Fig. 2) indicate that the
Chloride migration (non-steady state)—A few different particles of MK3 (Fig. 2(c)) are less agglomerated and
methods are applicable to evaluate chloride concrete resis- smaller than those in MK2 (Fig. 2(b)). Also, particles of
tance. In this research, the method proposed by Tang and MK1 (Fig. 2(a)) seem to be slightly more agglomerated than
Nilsson29 (that is further described in NT Build 49230) is MK3. Besides that, the MK2 particles (Fig. 2(b)) exhibit
chosen because it results in a parameter closer to the actual a different morphology (needles) and appear to be more
mass transport of ions in concrete—namely, the non-steady- agglomerated, which may lead to higher values of particle
state migration coefficient (Dnssm), and for its ease in mean diameter and lower specific surface area, as shown in
performing the test. Table 2. This may be an explanation for the discrepancies
For the chloride migration test, 3.94 x 1.97 in. (100 x between specific area and particle size distribution results.
50 mm) cylindrical specimens are cut from the middle The chemical compositions of the three MKs are also
of 3.94 x 7.87 in. (100 x 200 mm) cylinders. Further, the shown in Table 2. The silica (SiO2) content of all MKs is
non-steady-state migration coefficient was calculated for in the range of 51 to 56.5%; however, in terms of alumina
each concrete sample using Eq. (1), provided in NT Build (Al2O3) content, a wider range is observed, varying from 32
492.30 The results are the average of four specimens for each to 45%. MK1 has significantly lower alumina content but
concrete mixture the highest silica value; this may be related to raw kaolin
processing, but it is certainly linked with the source and
0.0239(273  T ) L  (273  T ) L.xd  type of clay and its mineralogy. Analyzing the SiO2 + Al2O3
Dnssm   xd  0.0238  content, MK2 shows the highest value, equal to 97.2%,
(U  2)t  U 2  which denotes its purity. Furthermore, MK3 presents high
(1) contents of silica and alumina (94%). Finally, MK1 has
the lowest silica + alumina content, equal to 88.6%, which
where T is the average of the initial and final temperature means the highest impurity content, with a loss on ignition
of the solution, in °C; L is the thickness of the specimen, in of 4.27%.
mm; U is the voltage, in V; t is the test time, in hours; and xd Despite the significance of the MKs’ chemical compo-
is the average of penetration depth, in mm. sition, it is essential and complementary to analyze the
mineralogical characterization of these three SCMs, which
was carried out by means of XRD. Through the X-ray

6 ACI Materials Journal/May 2021

Fig. 1—Particle size distribution of MKs by SediGraph.

Fig. 3—XRD analysis of MKs.

Fig. 2—SEM images of: (a) MK1; (b) MK2; and (c) MK3. Fig. 4—Correlation between Chapèlle’s pozzolanic index
and amorphous content of MKs.
diffractograms obtained from the MKs (Fig. 3), it is also
possible to confirm the purity of MK2, which shows only some analyses are performed to verify any major influence.
kaolinite as a crystalline mineral. In MK3, illite, sericite, Comparing the pozzolanic index results to other physical,
anatase, and quartz are observed. Additionally, no kaolinite chemical, and mineralogical characteristics of all MKs, a
is present in MK3; this may imply that it had been fully relatively strong correlation between Chapèlle’s pozzolanic
calcined compared to MK1, which is produced from the index and amorphous content is observed, as presented in
same raw material. Finally, the MK1 XRD analysis shows Fig. 4. This association between amorphism and pozzo-
all minerals mentioned, with a noticeable peak for quartz. lanic activity is relatively well known in this field of study.
In addition to the X-ray diffractograms, the quantification According to the process of obtaining or producing the
of the three MKs’ amorphous content—as described in the pozzolanic materials, in which there is heating and cooling
section “MK characterization methods”—is performed. (sometimes abruptly), there is usually very little time for the
MK1 comprises 61% amorphous content, while MK2 and structures of the constituent phases of materials to precip-
MK3 comprise 70 and 76%, respectively. itate in an organized manner. Thus, amorphous structures
Finally, the pozzolanic activity index results, measured or crystalline phases containing structural defects charac-
by Chapèlle’s modified test, show the global behavior of terize these materials. Residual stresses can occur in these
mineral additions in a pozzolanic reaction.26 MK1 indicates “imperfect” structures and energy concentration at the points
the smaller value (although still high) of 859 mg of Ca(OH)2 where the structural defects are located. According to ther-
fixed per gram of MK. This MK, despite being fine, indicates modynamics, these accumulated energies generate higher
the lowest amorphous and silica + alumina contents. The enthalpic systems, which spontaneously evolve to lower
MK2 result is intermediate, with 1027 mg of Ca(OH)2/g, and energy levels (lower enthalpic levels, according to thermo-
MK3 indicates the highest value with 1440 mg of Ca(OH)2/g. dynamics). The pozzolanic activity (expressed by a potential
The results are coherent with the other properties presented chemical reactivity of the material) has, therefore, scien-
and analyzed: MK3 is the finer MK and indicates the highest tific support in this energetic level of the material, which
amorphous content with a high silica + alumina content. is related to their structural characteristics (amorphism and
Meanwhile, despite being the coarser MK, MK2 has a high structural defects). The reactivity of a material is not based
amorphous content, and it is the purest, thus explaining the solely on its amorphism, but this issue can be preponderant
high value of the pozzolanic activity. (as in the present study).
Considering that the pozzolanic reactions are complex and Other characteristics such as BET specific surface area,
depend on the SCM’s various factors and characteristics, particle mean diameter, and alumina content do not show

ACI Materials Journal/May 2021 7

Fig. 5—Cumulative mercury intrusion volume on mortar Fig. 6—Mercury intrusion volume distribution on mortar
samples. samples.
significant correlations with the pozzolanic index because
the R2 values of these correlations are 0.46, 0.51, and 0.37,
respectively.

Pore structure
Changes in the concrete microstructure due to pozzolanic
reaction and filler effect (physical effects of microparticles)
generally lead to significant enhancements in the concrete’s
durability properties. Therefore, studying and evaluating
these changes is essential to understand the consequences
of using a SCM such as MK. To better understand the
concrete pore structure, MIP was conducted with mortar
samples. Unfortunately, some tests could not be performed
in the study (samples 40MK1, 60MK2, and 60MK3) due to Fig. 7—Detail of mercury intrusion volume distribution on
operational difficulties with the equipment. The porosimeter mortar samples in range of pore diameter from 0.005 to
damaged during the analysis of the samples of the present 0.05 µm.
work, without the expected return of its operationality in plain concrete samples (40R and 60R) have higher intruded
the research’s total period, which led the analysis to occur volumes in the range of 1 to 5 µm, in comparison to MK
without the three referred samples. Even so, porosimetry concretes. In pore diameter ranging from 0.005 to 5 µm, the
analysis could be performed by comparing MK mixtures behavior is altered, and the results are coherent. The concrete
to reference mixtures in the two w/b (Fig. 5 to 7). These samples without MK have higher mercury intruded volumes
presented results are from three concretes samples with the (especially those with a higher w/b because they have larger
w/b equal to 0.40 (reference, MK2, and MK3) and two with pores), followed by 40MK2 and 60MK1 with close results,
the w/b equal to 0.60 (reference and MK1) samples. and finally, 40MK3, which is the concrete with the finest
The total porosity of the sample is observed through the MK. Comparing samples with different MKs (MK2 and
cumulative intrusion volume (Fig. 5). Thereby, it is clear MK3) and in the same w/b (0.40) in the specified range of
that plain concrete mixtures, 40R and 60R, indicated the the pore diameter, the finest MK (MK3) indicates a lower
highest values, implying that these mixtures are more porous porosity. A detailed mercury intrusion volume distribution
than the others. Additionally, the 60MK1 concrete demon- in the pore diameter range from 0.05 to 0.005 µm is shown
strated a result approximately equal (slightly lower) to that in Fig. 7.
of 40R, thus confirming that MK1 reduced the cementitious The pore refinement promoted by the MK is noticeable,
system’s total porosity, despite the w/b. In addition, 40MK2 especially in the concrete 40MK3. As shown in Fig. 7, in the
and 40MK3 unveiled lower results that are significantly range of micropores (0.05 to 0.005 µm), the MK concrete
better than plain concrete. This indicates that these two MKs samples present larger volumes, indicating that more pores
could reduce the total porosity of concrete due to their high with smaller diameters exist. Additionally, comparing
pozzolanic activities. 40R and 60MK1, both with similar total porosity (Fig. 5),
The results presented in Fig. 6 indicate that, in the range the latter has a larger micropores volume, while the plain
of macropores (approximately 100 µm), 40R and 40MK2 concrete presents larger pores. Therefore, this corroborates
concretes present the highest volumes, which are unex- MK capacity to refine the pore structure and reduce the
pected. This is due to some remaining air voids in the mortar total porosity of concrete, as discussed in the literature.19
samples—that is, some content of entrained air probably This characteristic is essential in hampering mass transport
originated during the concrete mixing procedure, incorpo- mechanisms, especially absorption, permeability, and diffu-
rated by the HRWRA’s action. The graph also reveals that sion, because a denser paste structure (less porous) with

8 ACI Materials Journal/May 2021

finer pores will certainly imply fewer interconnection of the value presented is the limit of the equipment used. The
pores and the occurrence of more tortuous pores.12 Recent Comité Euro-International du Betón (CEB)32 indicates the
advances on this subject are presented by Yio et al.,31 who probability of steel corrosion in concrete (very low, low,
directly observed, using three-dimensional (3-D) images, high, and very high) according to the electrical resistivity,
the effect of SCM (silica fume and blast-furnace slag) in these criteria being represented in the graph of Fig. 8.
altering the porosity of cementitious systems by producing The difference between plain concrete (reference) and MK
less interconnected and more tortuous pores. They also veri- concrete is evident and coherent: concretes with a higher w/b
fied how these modified pore systems influence mass trans- lead to a lower resistivity; further, the use of mineral addi-
port properties. tions can significantly increase concrete electrical resistivity.
Broadly, comparing only the influence of MK type (MK2 In addition, it is possible to observe that even the worse MK
and MK3) in concrete samples with the same w/b (0.40), concrete (60MK1) presents a result that is higher than plain
MK3 produces more homogenous porosity matrixes in a concrete with a lower w/b (40R). The data were submitted to
narrow range of porosity. This shows the high capacity of ANOVA to comprehend these differences, and the results are
the MKs studied in modifying the cement paste’s physical shown in Table 3.
structure, emphasizing MK3. Both variables—w/b and MK type—are statically signifi-
cant in the model evaluated. Their interaction is also relevant
Durability and mass transport mechanisms and significant. Moreover, the coefficient of determination
Mass transport mechanisms primarily guide concrete dura- (R2) of the statistical model is high. As expected, the w/b
bility. Most of the problems that decrease concrete lifetime significantly changes the electrical resistivity of concrete.
are caused or influenced by ions or fluids transport through Concrete mixtures with the lower w/b present lower porosity;
the concrete pore structure. Thus, understanding how mass in other words, these concretes are denser than the other,
transport mechanisms behave in concrete with mineral addi- thus rendering it more difficult for ions to pass through.
tions is essential to enhance concrete durability. These results confirm the importance of controlling the w/b
The results of surface electrical resistivity of all concrete to produce durable concretes. The results, by analyzing the
mixtures are presented in Fig. 8. Before the results influence of the MK type, are shown in Fig. 9, with multiple
analysis, it is noteworthy that in the case of concrete 40MK3, mean comparisons (Tukey’s test).
The MK concretes indicate significantly higher values of
electrical resistivity. MK2 and MK3 demonstrate similar
performance, better than the other concrete mixtures. Two
different theories explain these results: significant pore
structure changes and changes in electrical conductivity and
ion concentration of the aqueous solution in the pores.
The MIP results indicate that the MK concretes present
lower total porosity and pores with smaller diameters (pore
refinement), especially the MK2 and MK3 concretes, in
comparison to the reference ones. Therefore, the difficulty
in passing an electric current is higher because a denser pore
structure exists to serve as a physical barrier. Meanwhile,
once the MK reacts, primarily with calcium hydroxide, the
ion content, especially OH– and Ca2+, will decrease in the
concrete pores’ aqueous solution. Because the electrical
Fig. 8—Mean values and standard deviation of electrical
resistivity is influenced by ion diffusivity in the pore struc-
resistivity of all concrete mixtures, and indication of proba-
ture, the system with a lower concentration of ions will
bility of steel corrosion according to CEB 162.32
Table 3—Analysis of variance (ANOVA) of electrical resistivity results
Effect SS DF MS Fcal Ftab Result
Model 79,830.66 7 11,404.38 2768.69 2.10 Significant
Error (residual) 461.33 112 4.12 — — —
Total 80,291.99 119 — — — —
w/b 25,317.08 1 25,317.08 6146.3 3.93 Significant
MK type 51,372.49 3 17,124.16 4157.3 2.69 Significant
w/b × MK type 3141.09 3 1047.03 254.2 2.69 Significant
Error (residual) 461.33 112 4.12 — — —
Coefficient of determination (R2mod) 0.994 — — —
Coefficient of correlation (Rmod) 0.997 — — —
Note: SS is sum of squares; DF is degrees of freedom; MS is mean square; Fcal is F-statistic (calculated); Ftab is F-statistic (table).

ACI Materials Journal/May 2021 9

 Fig. 10—Mean values and standard deviation of non-steady-
state chloride migration coefficient of all concrete mixtures,
and classification of chloride resistance from Nilsson et al.36
Fig. 9—Electrical resistivity results by type of MK, consid-
ering all mixtures. Dashed vertical lines limit statistically The ANOVA model presents a high coefficient of determi-
different groups, defined by Tukey’s test. nation, meaning that the analysis performed is statistically
reliable. Both variables are significant in the analysis as well
conduct less electrical current. Additionally, analyzing all
as their combination (the interaction of them). Similar to the
MK chemical properties, MK2 and MK3 have higher silica
electrical resistivity results, the w/b is relevant to explain
and alumina quantities compared to MK1. This alters the
changes in chloride migration, owing to the reduction in
hydration reaction kinetics,33 induces a higher reactivity
global porosity, as previously discussed. Figure 11 shows the
with cement paste,34 lowers the quantities of alkalis in the
results of the statistical analysis of the influence of MK type.
solution,35 and increases the values of electrical resistivity.
Tukey’s test segregates the results into three groups
However, MK2 and MK3 have different physical properties.
(Fig. 11). Plain concrete (reference) presents the highest
As mentioned regarding X-ray diffraction, the higher
global mean value, while MK concretes indicate significantly
peaks of the crystalline phases in MK1 denote the low purity
lower values. The chloride migration results are similar
of the raw material and/or that residual materials that are not
to the electrical resistivity results. Thus, the lower total
completely calcined or cooled properly are present. Mean-
porosity (with pore refinement), and a lower ionic strength
while, MK2 has low-intensity peaks of kaolinite, and the
(in the pore solution), typical of MK systems, can explain
absence of other crystalline phases evidences the purity of
the better results. Studies21 have shown that concretes with
its raw material. For MK3, there are no relevant peaks of
SCMs present changes in the pore solution, expressed by
kaolinite; this may imply that the calcination and cooling
a reduction of ionic strength—that is, there is a reduction
process had occurred properly, transforming nearly all the
of the ions in solution as well as changes in the concentra-
kaolinite into metakaolinite, although the presence of other
tions of these ions, including decreases in the concentration
phases is observed.
of OH–. These changes modify the electrical properties of
Unlike other methods that evaluate the concrete resistance
cementitious systems, significantly reducing the pore solu-
to chlorides, the non-steady-state chloride migration test
tion’s electrical conductivity,37 which leads to considerable
yields a coefficient related to the real mass transport mech-
increases in the electrical resistivity of concrete and signifi-
anism of chlorides that occurs preponderantly in concrete,
cant reductions in chlorides’ transport properties.
which is diffusion. The results obtained in this research are
Regarding the differences between the MK types, the
presented in Fig. 10. The classification of chloride resistance
physical, morphological, chemical, and mineralogical prop-
from Nilsson et al.36 is plotted in the graph (low, moderate,
erties of MKs produce different effects on the cement matrix
high, very high, and extremely high chloride resistance).
because of presumable alterations while the hydration of
Before analyzing the results, it is noteworthy that the
portland cement and pozzolanic reactions are occurring.
lower the migration coefficient, the more resistant concrete
Concrete with chemically similar MKs (silica and alumina
is to chloride ingress. The difference between the 0.40 and
contents) and lower quantities of quartz and kaolinite
0.60 w/b concrete is noticeable; as expected, the lower
phases, namely MK2 and MK3, present an almost identical
w/b indicates better performance owing to chloride attack.
non-steady-state chloride migration coefficient, which is
Further, the very positive effect of MK on chloride migra-
observed for two different w/b.
tion is evident, with remarkable reductions in migration
coefficients (of these modified concretes by MK). These
Global discussion
results are similar to those in the literature,19 thereby justi-
Analyzing the durability results with MK characteristics,
fying this behavior as dependent on the physical parameters
it is observed that, for the materials used in this research,
of concretes with MK (a lower porosity and a lower inter-
the SCM’s chemical and mineralogical properties are more
connection of pores with an increased tortuosity of the pore
significant to explain the changes in the concrete properties.
network). Further, the data were submitted to ANOVA, and
In Fig. 12, the relationship between the amorphous content
the results are presented in Table 4.

10 ACI Materials Journal/May 2021

Table 4—Analysis of variance (ANOVA) of non-steady-state chloride migration coefficient results
Effect SS DF MS Fcal Ftab Result
Model 359.27 7 51.32 195.11 2.66 Significant
Error (residual) 6.31 24 0.26 — — —
Total 365.58 31 — — — —
w/b 121.64 1 121.64 462.41 4.49 Significant
MK type 202.09 3 67.36 256.08 3.24 Significant
w/b × MK type 35.55 3 11.85 45.04 3.24 Significant
Error (residual) 6.31 24 0.26 — — —
Coefficient of determination (R 2
mod) 0.98 — — —
Coefficient of correlation (Rmod) 0.99 — — —
Note: SS is sum of squares; DF is degrees of freedom; MS is mean square; Fcal is F-statistic (calculated); Ftab is F-statistic (table).

Fig. 12—Correlation between surface electrical resistivity

Fig. 11—Non-steady-state chloride migration coefficient and chloride migration coefficient with MK amorphous
results by type of MK, considering all mixtures. Dashed content.
horizontal lines limit statistically different groups, defined
are presented. The best correlations are shaded in the table: (a)
by Tukey’s test.
amorphous content and silica content versus resistivity (ρ) and
of MKs and the global mean values of the surface electrical chloride migration coefficient (Dnssm); (b) alumina content and
resistivity and non-steady-state chloride migration coef- (silica + alumina) content versus resistivity; and (c) Chapèlle’s
ficient is evaluated. A high determination coefficient (R2) pozzolanic activity index versus Dnssm.
is verified between these variables, meaning that a signif- The results of durability properties also confirm the better
icant part of the alterations in the durability properties of performance of the MK concretes. The addition of MK
concrete could be explained by the amorphous content of significantly improves both electrical resistivity and chloride
the mineral additions, in which for chloride migration, the resistance. A mathematical relationship exists between the
R2 is 0.99. Additionally, the MK silica content presents high electrical resistivity of concrete and the ion transport through
values of determination coefficients for both electrical resis- concrete, as described by the Nernst-Einstein equation.38
tivity (0.96) and chloride migration (0.97). When Chapèlle’s This means that ions can pass through the pore structure
pozzolanic activity index is correlated with resistivity and of concrete with low resistivity more easily. Thus, concrete
the chloride migration coefficient, the same tendency of rela- with higher electrical resistivity values may present lower
tion observed regarding the amorphous content is observed, chloride migration values, as demonstrated in Fig. 13, with
but with lower values of R2: namely, 0.53 and 0.87 for elec- an extremely high coefficient of determination (R2 = 0.95).
trical resistivity and chloride migration, respectively. Finally, to evaluate the influence of porosity, relation-
Meanwhile, MK physical characteristics—BET fineness ships between electrical resistivity and the chloride migra-
and particle mean diameter—do not demonstrate any signif- tion coefficient with the total volume of mercury intrusion
icant correlation between the concrete properties. Table 5 in mortar samples (from concrete) are carried out (Fig. 14).
presents a summary of the linear correlations obtained in the It is possible to observe that these correlations are signifi-
study between the various parameters of the MKs and the two cantly high (R2 equals 0.99 and 0.94, respectively), which
durability properties. The obtained equations and R2 values means that the porosity of concrete is highly responsible for
changes in the durability properties.

ACI Materials Journal/May 2021 11

Table 5—Linear correlations obtained (equation and R2) between MK parameters and durability properties
of concrete (resistivity and chloride migration)
Surface electrical resistivity, ρ (kΩ.cm) Chloride migration coefficient, Dnssm (× 10–12 m2/s)
Linear correlation Linear correlation
MK’s characteristic parameters Equation R 2
Equation R2
BET specific surface area (SSA), m2/g ρ = 71.1 – 0.0012.SSA 0.000 Dnssm = 3.21 – 0.014.SSA 0.143
Particle mean diameter, D50, µm ρ = 71.82 – 0.11.D50 0.002 Dnssm = 2.74 + 0.030.D50 0.179
Amorphous content (Am), % ρ = –46.04 + 1.70.Am 0.873 Dnssm = 6.75 – 0.055.Am 0.999
SiO2 (Si), % ρ = 341.66 – 5.06.Si 0.956 Dnssm = –5.34 + 0.15.Si 0.969
Al2O3 (Al), % ρ = –9.20 + 2.02.Al 0.973 Dnssm = 5.04 – 0.053.Al 0.723
SiO2 + Al2O3 (Si + Al), % ρ = –200.85 + 2.92.(Si + Al) 0.854 Dnssm = 9.29 – 0.068.(Si + Al) 0.505
Chapèlle pozzolanic index (PI), mg Ca(OH)2/g ρ = 34.22 + 0.033.PI 0.532 Dnssm = 4.38 – 0.0013.PI 0.873

Fig. 13—Correlation between surface electrical resistivity

and chloride migration coefficient. Fig. 14—Correlation between surface electrical resistivity
and chloride migration coefficient with cumulative mercury
CONCLUSIONS intrusion volume from MIP.
After investigating the influence of metakaolin (MK)
characteristics on the durability properties and pore structure 4. An extremely high correlation is found between the
of concrete, the following conclusions can be drawn: electrical resistivity and chloride migration coefficient
1. Mineralogical and chemical parameters of MK, such as (R2 = 0.95), which is coherent to the theoretical proposition
amorphous content and silica content, prove to be represen- by the Nernst-Einstein equation. Thus, the electrical resis-
tative to explain the significant improvement in the durability tivity test is a sensible, accurate, and expeditious method to
properties of concrete (resistivity and chloride migration). evaluate the probability of chloride attack in concrete. One
Other chemical parameters and physical characteristics, indirect conclusion of this work is that resistivity can be
such as specific surface area and the particle mean diameter, used previously as an important performance indicator for
also affect the reactivity of MK, but to a lower degree. assessing the potential durability of concrete under chloride
2. In general, MK3, which indicates the highest values attack.
of specific surface area, amorphous content, and Chapèlle’s 5. Pore structure is highly responsible for improvements in
pozzolanic index, presents the best results for all durability the durability properties. The total porosity results obtained
properties and pore structure of concrete. MK2, despite by MIP indicate very clear correlations with the electrical
having the highest value of particle mean diameter, also resistivity and the chloride migration coefficient, with coef-
demonstrates good results in terms of the durability proper- ficients of determination of 0.99 and 0.94, respectively. This
ties of concrete. Finally, MK1, which is poorer in terms of implies that the MKs, especially MK3, promote significant
purity, presents the worst performance between the MKs but concrete internal structure changes, which makes the trans-
is still significantly better than plain concretes. port of ions (such as chlorides) through concrete signifi-
3. The addition of MKs promotes significant changes cantly more difficult.
in the concrete microstructure. The incorporation of these
supplementary cementitious materials (SCMs) undoubtedly AUTHOR BIOS
ACI member Oswaldo Cascudo is a Full Professor at the Federal Univer-
alters the pore structure. In general, MK promotes a reduc- sity of Goiás (UFG), Goiânia, GO, Brazil. He received his MS and PhD in
tion in total porosity and pore refinement, which mercury civil engineering from the University of São Paulo, São Paulo, Brazil, in
intrusion porosimetry (MIP) verifies. 1991, and 2000, respectively. His research interests include durability of
concrete structures and reinforcement corrosion.

12 ACI Materials Journal/May 2021

Rodrigo Teodoro is a Civil Engineer and Partner at Gilenge Precast 11. Maraghechi, H.; Avet, F.; Wong, H.; Kamyab, H.; and Scrivener,
Concrete and Quiconcreto Ready-Mix Concrete, Quirinópolis, GO, Brazil. K. “Performance of Limestone Calcined Clay Cement (LC3) with Various
He also serves as Professor, Lecturer, and Consultant in engineering. He Kaolinite Contents with Respect to Chloride Transport,” Materials and
received his MS in civil engineering from the Federal University of Goiás in Structures, V. 51, No. 5, 2018, pp. 1-17. doi: 10.1617/s11527-018-1255-3
2016. His research interests include supplementary cementitious materials 12. Ollivier, J.-P., and Torrenti, J.-M., “La Structure Poreuse des Bétons
and durability of reinforced concrete structures. et les Propriétés de Transfert,” J.-P. Ollivier, A. Vichot (direct.), La Dura-
bilité des Bétons: Bases scientifiques pour la formulation de bétons durables
Andrielli M. de Oliveira is a Researcher and Professor at the Federal dans leur environnement. Presses de l’Éc. Nat. Ponts et Chaussées, Paris,
University of Goiás. She received her MS from the Federal University of France, 2008, pp. 51-133.
Goiás in 2007 and her PhD from the Federal University of Rio de Janeiro 13. Castro, A.; Ferreira, R.; Lopes, A. N. M.; and Cascudo, O., “Relation-
(UFRJ), Rio de Janeiro, Brazil, in 2015, both in civil engineering. Her ship between Results of Accelerated and Natural Carbonation in Various
research interests include concrete durability, reinforcement corrosion, and Concretes,” International RILEM Conference of Use of Recycled Mate-
composite materials. rials in Buildings and Structures, RILEM, Barcelona, Spain, V. 2, 2004,
pp. 800-810.
Helena Carasek is a Full Professor at the Federal University of Goiás. She 14. Rashad, A. M., “Metakaolin As Cementitious Material: History,
is currently serving as Director of Technological Transfer and Innovation Scours, Production and Composition—Comprehensive Overview,”
and Vice Pro-Rector for Research and Innovation at UFG. She received her Construction and Building Materials, V. 41, 2013, pp. 303-318. doi:
MS from the Federal University of Rio Grande do Sul, Porto Alegre, Brazil, 10.1016/j.conbuildmat.2012.12.001
in 1990, and her PhD from the University of São Paulo, São Paulo, Brazil, 15. Badogiannis, E. G.; Sfikas, I. P.; Voukia, D. V.; Trezos, K. G.; and
in 1996, both in civil engineering. Her research interests include studies Tsivilis, S. G., “Durability of Metakaolin Self-compacting Concrete,”
on cement-based systems, with an emphasis on sustainability, performance, Construction and Building Materials, V. 82, 2015, pp. 133-141. doi:
and innovation. 10.1016/j.conbuildmat.2015.02.023
16. Wang, Y.; Shui, Z.; Huang, Y.; Sun, T.; and Duan, P., “Properties
ACKNOWLEDGMENTS of Coral Waste-based Mortar Incorporating Metakaolin: Part II. Chloride
The authors acknowledge the contribution of Metacaulim do Brasil Migration and Binding Behaviors,” Construction and Building Materials,
Company, which supported this research. They also thank Eletrobras Furnas V. 174, 2018, pp. 433-442. doi: 10.1016/j.conbuildmat.2018.04.076
for all the support given in the experiments as well as the following labo- 17. Cheng, S.; Shui, Z.; Sun, T.; Yu, R.; and Zhang, G., “Durability
ratories: LEDMa/UFBA for the XRD tests, LABMIC/UFG for the SEM and Microstructure of Coral Sand Concrete Incorporating Supplementary
analysis, and Unisinos for the MIP tests. Finally, the authors would like Cementitious Materials,” Construction and Building Materials, V. 171,
to thank CAPES and CNPq (Brazilian governmental institutions), which 2018, pp. 44-53. doi: 10.1016/j.conbuildmat.2018.03.082
provided grants to researchers. 18. Duan, P.; Shui, Z.; Chen, W.; and Shen, C., “Effects of Metakaolin,
Silica Fume and Slag on Pore Structure, Interfacial Transition Zone and
Compressive Strength of Concrete,” Construction and Building Materials,
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