Construction and Building Materials 156 (2017) 565–573

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Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Chloride ion resistance of self-compacting concretes incorporating

volcanic materials
Diana M. Burgos a,⇑, Álvaro Guzmán b, Nancy Torres b, Silvio Delvasto a
a
Grupo de Materiales Compuestos (GMC), Escuela de Ingeniería de Materiales, Universidad del Valle, Calle 13 # 100-00, Cali, Colombia
b
Escuela Colombiana de Ingeniería Julio Garavito, AK 45 No. 20559 (Autopista Norte), Bogotá, Colombia

h i g h l i g h t s

The incorporation of alternative materials in the production of self-compacting concretes (SCCs) as a great option to increase its acceptance and reduce
the cement consumption.

The incorporation of different volcanic materials had important role in the fresh and hardened properties of the SCCs, and high durability in the presence
of aggressive agents (chlorides).

The use of the volcanic materials as partially replacing the cement provide savings on the use of others additives, like viscosity modifying agents, which
results in a lower production cost.

a r t i c l e i n f o a b s t r a c t

Article history: This paper examines the effect of incorporating considerable amounts of Colombian volcanic material to
Received 4 May 2017 self-compacting concrete (SCC) as a pozzolanic addition for rheological improvement, including the
Received in revised form 1 September 2017 effects on the mechanical properties and chloride resistance. In particular, the volcanic materials used
Accepted 2 September 2017
as parts of binary and ternary concrete mixtures in this study were Tolima (TVM), Puracé (PVM) and
Bocayá (BVM). This paper shows that incorporating volcanic materials, both inert (TVM) and pozzolanic
(PVM and BVM), results in SCCs with good workability, moderate mechanical properties and high dura-
Keywords:
bility in the presence of aggressive agents such as chlorides.
Self-compacting concrete
Blended cements
Ó 2017 Elsevier Ltd. All rights reserved.
Chloride attack
Friedel’s salt
Permeability

1. Introduction
Self-compacting concrete (SCC) has been gaining popularity in
the construction industry in recent years because of its numerous
advantages over conventional concrete. The most important
advantages of SCC include a shorter construction time, improved
conditions for workers because mechanical vibration is not neces-
sary and easier application in complex architectural designs and
densely reinforced structures [35]. Many researchers have studied
the use of alternative materials for the production of SCCs to
increase their acceptance and reduce cement consumption while
maintaining a high fine content to preserve self-compactability.
Rodriguez et al. [43] evaluated the possibility of obtaining lower-
strength SCC using cement kiln dust CKD) as a partial cement
⇑ Corresponding author.
E-mail address: diana.burgos@correounivalle.edu.co (D.M. Burgos).
replacement and found that the use of high percentages of CKD
and different water/fines ratios allowed the amount of cement
required to obtain SCC of medium strength with lower production
costs to be optimized. Several researchers have developed SCCs
with high percentages of marble powders [50], limestone powders
[22] and palm oil and fly ash waste [41].
Volcanic materials are formed during volcanic eruptions, and
their vitreous states depend on the magma composition and the
solidification process [39]. The reactivity of a volcanic material is
determined by its chemical composition, the physical structure of
the particles and their potential to react and form cementing com-
pounds [34]. Volcanic materials have been widely utilized in the
production of blended cements due to their properties and world-
wide availability. Regarding SCC, researchers such as Hossain and
Lachemi [30] investigated the use of volcanic ash as a partial
cement replacement in the production of economical and environ-
mentally friendly SCCs with good mechanical properties and high
durability. Guneyisi et al. [27] evaluated the influence of incorpo-

http://dx.doi.org/10.1016/j.conbuildmat.2017.09.017
0950-0618/Ó 2017 Elsevier Ltd. All rights reserved.
566 D.M. Burgos et al. / Construction and Building Materials 156 (2017) 565–573

rating volcanic pumice stone powder (VP) on the properties of Table 1

fresh SCC. The results demonstrated that the fluidity of the SCC Physical properties and chemical compositions of the materials used in this study.

increased with the VP content without segregation. Characteristic General-purpose TVM BVM PVM
The type of construction and the components of the concrete Portland cement
mixture must meet certain conditions based on environmental Chemical composition (%)
exposure. These conditions are basically expressed in terms of SiO2 20.73 64.36 71.09 87.45
three parameters: mechanical strength, volume stability and SO3 3.14 0.00 0.00 0.00
S 0.00 0.00 0.61 0.04
chemical resistance. This set of features ensures that concrete per- Fe2O3 5.63 4.92 1.98 1.89
forms well during its service time [47]. In regard to concrete, chlo- TiO2 0.24 0.54 0.43 1.16
ride is among the most common and damaging corrosive agents. Al2O3 4.54 15.90 14.16 0.23
The motion of chloride ions is restricted not only by the porosity Ba 0.00 0.08 0.10 0.13
CaO 52.69 4.71 2.14 0.07
of the structure but also by the exposure conditions, the concrete’s
Na2O 0.15 5.38 0.14 0.05
moisture content, the agent concentration, the type and character- MgO 2.24 1.80 0.22 0.05
istics of the concrete components, etc. [5]. For the chloride-induced P2O5 0.14 0.17 0.08 0.03
corrosion being initiated, the passivity layer must be penetrated. K2O 0.41 1.49 1.00 0.02
Chloride ions surrounding the reinforcement react at anodic sites Zr 0.00 0.01 0.02 0.02
Cr 0.00 0.00 0.00 0.01
(such as cracks and defects) and destroys the passive protective
Cu 0.00 0.00 0.00 0.01
film on the steel. This area serve as anode, while the rest of the Sr 0.00 0.09 0.00 0.00
undamaged surface serves as a cathode. This effect is usually called SrO 0.16 0.00 0.00 0.00
pitting corrosion. Finally, the chloride ions and Fe2+ react to form Mn2O3 0.06 0.00 0.00 0.00
Cr2O3 0.03 0.00 0.00 0.00
chloride or oxychloride compounds (FeCl2 and FeOCl) [10, 17].
ZnO 0.01 0.00 0.00 0.00
Chloride ions and the binder hydration components may combine Loss on ignition (%) 9.85 0.40 7.99 8.35
to form Friedel’s salt (Ca3Al2O6-CaCl2-10H2O), which is in equilib- Density (kg/m3) 3,100 2,090 2,290 2,180
rium when the chloride concentration is constant, or be physically Average particle size (lm) 22.00 20.20 26.30 21.00
adsorbed on the surface of an amorphous calcium silicate hydrate
CSH) gel [33]. However, Yuan et al. [51] mentioned that chloride
binding is a very complicated process and is affected by many fac-
In this study, the fine aggregate was river sand (fineness modu-
tors, such as chloride concentration, cement composition, hydroxyl
lus of 2.55, apparent density of 2,581 kg/m3 and water absorption
concentration, cation of chloride salt, temperature, supplementary
rate of 1.89%), whereas the coarse aggregate was gravel (fineness
cementing materials, carbonation, sulfate ions and electrical field.
modulus of 6.38, nominal size of 12.7 mm, apparent density of
Unlike chemically bound chlorides, physically adsorbed chlorides
2,544 kg/m3 and water absorption rate of 2.01%). The latest gener-
move toward lower-concentration areas on a gel surface. However,
ation of superplasticizer (SP) SIKAPLAST 326 (specific gravity of
the free chlorides in the pore water move faster than the absorbed
1,130 kg/m3 and pH of 5) was used in compliance with ASTM
chlorides, which means that the former dominate the diffusion
C494 [7] types A and F.
process. Some of the chloride ions bond, which causes the free
chloride ion concentration to decrease and, therefore, mitigates
the corrosive effect on the concrete structure [32]. 2.2. Selected SCC mixtures
AFm (monosulphate) phases and incoming chlorides interact to
form Friedel’s salt. Therefore, the binding capacity of the chlorides The methodology proposed by the ACI committee 237R-07 [1]
in the hydration products is determined by the binding agent’s was considered for the design of the self-compacting concrete
chemical composition. The amount of C3A in the binding agent (SCC). A slump flow greater than 650 mm was selected; therefore,
and the amount of available SO3 govern the AFm phase composi- a cement content of 480 kg/m3 was established. Five concrete mix-
tion as well as the amount of the Aft (ettringite) phase [23]. tures were developed (see Table 2) based on Burgos [14]. One stan-
Celik et al. [16] utilized natural volcanic pozzolan and limestone dard mixture and four mixtures based on volcanic materials
powder in the production of SCC with high compressive strength incorporating 20% MVT, 30% MVT, 20% MVT + 10% MVP and 20%
and high resistance to chloride ion penetration. Generally, SCC MVT + 10% MVB as a cement replacement (by mass). All the design
has been widely used in the ready-mixed concrete industry for parameters (see Table 2) were determined to reach the target
structural applications. However, this concept has led to a moder- slump flow >650 mm) and to comply with the Self-Compacting
ate development in the use of SCC in some applications or products Concrete European Project Group [48]. However, the SP content
that require lower strength. Therefore, this paper evaluates the was determined by the volcanic material type in the mixture.
mechanical behavior of and the effect of an aggressive medium,
such as chlorides, on SCCs with large amounts of fine powders
2.3. Self-compactability tests
(mineral additions) derived from a Colombian volcanic material.
The self-compactability tests performed on each of the trial
mixtures included tests of the slump flow, T50, V-funnel for filling
ability and L-box for passing ability. These tests were conducted in
2. Experimental methodology
accordance with the guidelines provided by the 2005 European
guide for SCC.
2.1. Materials

General-purpose Portland cement was used in this study.
Tolima (TVM), Boyacá (BVM) and Puracé (PVM) volcanic materials
were used. These materials can be found in the Tolima, Boyacá and
Cauca departments, respectively. The physical properties and
chemical compositions of the Portland cement and the volcanic
materials can be found in Table 1.
2.4. Tests of the properties of hardened SCC
A test of the compressive strength was conducted to evaluate
the mechanical properties of the SCC mixtures. The durability
indices of the SCC mixtures evaluated included the rate of absorp-
tion (sorptivity) of water and the chloride resistance. Additionally,
 D.M. Burgos et al. / Construction and Building Materials 156 (2017) 565–573 567

Table 2
SCC mixtures.

Mixture ID w/b Water Cement TVM BVM PVM Aggregate, kg/m3 SP

3 3 3 3 3
kg/m kg/m kg/m % kg/m % kg/m % Fine Coarse L/m3
Standard 0.47 226 480 0 0 0 0 0 0 950 633 0.55
20% TVM 0.47 226 384 96 20 0 0 0 0 950 633 0.55
30% TVM 0.47 226 336 144 30 0 0 0 0 950 633 0.55
20% TVM + 10% PVM 0.47 226 336 96 20 0 0 48 10 950 633 0.80
20% TVM + 10% BVM 0.47 226 336 96 20 48 10 0 0 950 633 0.70

respectively, even when a higher SP dosage was used to achieve

Table 3
Details of the specimens and test methods utilized to determine the mechanical
properties and the durability characteristics of the developed SCC mixtures.
Property Test Specimen size Age at test/exposure
standard
Compressive ASTM C39 76.2  152.4 mm 3, 7, 28, 90, 180 and
strength [6] cylinder 360 days
Sorptivity EMPA-SIA 60 mm cube 28, 90 and 360 days
162/1 [21]
Chloride ASTM 76.2  127 mm 28, 90 and 360 days
resistance C1202 [8] cylinder
the electrical resistance was directly measured by the testing
device and resistivity was calculated from Eq. (1), as follows:
d ¼ Rk
where R is the resistance of concrete and k is a geometrical factor
which depends on the size and shape of the sample as well as the
distance between the probes on the testing device [37].
The test methods and specimen sizes utilized for the evaluation
of the mechanical properties and the durability characteristics of
the developed SCC mixtures are summarized in Table 3. An analy-
sis of the hydration products of the cement pastes was performed
to detect Friedel’s salt. Both the formulations and the curing condi-
tions (100% RH and room temperature) of the pastes and the SCCs
were identical. The cement pastes were exposed to a 3.5% NaCl
solution for 28 days, after which the specimens were tested using
X-ray diffraction (XRD).
3. Results and discussion
3.1. Self-compactability
Fig. 1 shows the results of the workability tests for the five fresh
SCC mixtures.
Fig. 1a shows that the five mixtures used in this study achieved
the slump flow target of at least 650 mm. Replacing 20% of the
Portland cement with TVM increased the slump flow by 4.29%
compared to the standard SCC slump flow. Additionally, the 30%
TVM replacement increased the slump flow by 2.90% compared
with those of the standard SCC. Because these three mixtures have
the same SP dosage of 0.55%, it can be stated that up to 20% TVM
increases the mixture’s fluidity; after that, the mixture’s cohesive-
ness increases significantly and, therefore, the spreading diameter
decreases. These results are in complete agreement with those of
other authors, who have reported that increasing the volcanic
material content up to a certain value increases the SCC’s spreading
diameter [30,27].
In contrast, the fluidity of the 20% TVM + 10% PVM mixture
decreased by 4.3% compared to that of the 20% TVM mixture,
whereas the spreading diameter decreased by 3% compared to that
of the 30% TVM mixture. Regarding the ternary 20% TVM + 10%
BVM mixture, the spreading diameter decreased by 3.71% and
2.4% compared to those of the 20% TVM and 30% TVM mixtures,
the standard SCC workability. These results show the significant
effect of volcanic materials on fresh SCCs. The difference in the per-
formance of the volcanic materials is related to their physical and
chemical properties. The need to use a higher SP dosage for the 20%
TVM + 10% BVM and 20% TVM + 10% PVM mixtures could be due to
the irregular porous surfaces of PVM and BVM, which enable them
to absorb more of the liquid phase, which, in turn, limits their
workability. In spite of the above, the water/binder ratio was kept
constant while the SP dosage was adjusted to achieve the target
slump flow. In contrast, the binary 20% TVM and 30% TVM mix-
tures required the same SP dosage as the standard SCC to exhibit
increased flow. This phenomenon could occur because finer parti-
cles usually fill the spaces between cement particles, and since
TVM is an inert material, it can decrease the attractive forces
ð1Þ between them. Additionally, the surface of TVM particles is smooth
and non-porous, which means TVM does not absorb water and
flow can be increased according to Burgos et al. [13].
Fig. 1b shows that all five mixtures required less than 2 s to
spread. Because the value of T50 is related to the mixture’s viscosity
and incorporating TVM decreased this value, it can be concluded
that TVM decreases the mixture’s viscosity. It should be noted that
of the five mixtures, 20% TVM + 10% PVM showed the highest value
of T50, which shows that incorporating PVM increases the viscosity.
A similar situation is found when incorporating BVM, which also
increases the viscosity. Regarding Fig. 1c, in a somehow opposite
behavior, the 20% TVM and 30% TVM mixtures showed the highest
values of flow time (TV) (6.3 and 7.3 s, respectively), whereas the
results for 20% TVM + 10% PVM, 20% TVM + 10% BVM and standard
SCC ranged from 3 to 5 s. Although the previous results showed
that TVM increased fluidity, this is not true in confined spaces.
Conversely, incorporating PVM and BVM results in better perfor-
mance in the small section of the V-funnel. It could be argued that,
in this case, since PVM and BVM particles are semispherical, they
act as bearings that facilitate the motion of cement particles. Con-
versely, the irregular geometry of TVM particles renders such
motion more difficult. However, the values of TV for the five mix-
tures were below 10 s, which shows that the viscosity is suitable
for the free flow of SCCs.
Finally, Fig. 1d shows the passing ability for the five mixtures.
These are all satisfactory at above 0.75. However, the value for
the standard mixture is higher (0.99) than those of the other mix-
tures (between 0.87 and 0.89). It should be highlighted here that
these results are acceptable.
3.2. Compressive strength
Fig. 2 shows the compressive strength (given in MPa) for the
different curing times. The SCC’s were designed with a compressive
strength minimum of 21 MPa after 28 days of curing and the target
compressive strength ranged from 25 to 35 MPa.
After a curing time of approximately 3 days, the standard and
the 20% TVM, 20% TVM + 10% PVM and 20% TVM + 10% BVM mix-
tures showed similar compressive strengths, whereas the corre-
568 D.M. Burgos et al. / Construction and Building Materials 156 (2017) 565–573
Fig. 1. Properties of fresh SCC for all five mixtures. a) Slump flow, b) T50, c) V-funnel, and d) L-box.
sponding value for 30% TVM was 53% lower than that for the stan-
dard. After 7 days, the standard SCC’s compressive strength
became higher than that of the others for all curing ages. After
28 days, the results for the 20% TVM, 20% TVM + 10% PVM and
20% TVM + 10% BVM SCCs were 29, 26 and 27 MPa, respectively,
which fall well within the target compressive strength range. Addi-
tionally, the 30% TVM mixture reached the target lowest expected
value of 21 MPa on day 28. Burgos et al. [15] anticipated that for
ratios greater than or equal to 30%, the resistance of the TVM mix-
ture would decrease due to its inert nature.
Bonavetti and Rahhal [12] discussed the effects of incorporating
mineral aggregates to Portland cement. They mentioned three
effects: dilution, the filler effect and pozzolanic activity. The signif-
icance of each is determined by the mixture ratio, the physical and
chemical properties and the elapsed time. All three effects were
observed in this study. Due to MVT is an inert material, it was iden-
tified in 20% TVM SCC a predominant filler effect yielded a com-
pressive strength that was closer to the SCC standard value.
Conversely, for the 30% TVM SCC, the predominant effect was dilu-
tion, which means that the mechanical properties were lower with
respect to the other mixtures, reaching 27 MPa in 360 days. These
results confirm that the TVM mixture ratio has a strong impact on
the physical particle packing effect. In contrast, incorporating 10%
PVM or 10% BVM in ternary mixtures with 20% TVM is different
from replacing 30% of the cement by only TVM, since the poz-
zolanic activity of PVM and BVM overtakes the dilution effect pro-
duced by the inert material (MVT) [14]. The pozzolanic reaction
occurs after the cement’s hydraulic reaction because the calcium
hydroxide resulting from it is necessary [4]. However, the poz-
zolanic reaction rate is determined by the chemical properties of
pozzolans and its specific surface area. In this study, both poz-
zolanic materials (PVM and BVM) developed pozzolanic activity
after 28 days, however after 90 days the increase in the compres-
sive strength was more evident, in agreement with Belaidi et al.
[9]. After 360 days, the 20% TVM, 20% TVM + 10% PVM and 20%
TVM + 10% BVM SCCs reached around of 81% of the compressive
strength of the standard SCC and the 30% TVM SCC reached 60%
of this.
It should be noted that the effectiveness of pozzolanic activity
of PVM and BVM may have been influenced by the composition
of the cements used in the SCC formulation. Calcareous fillers are
added to this type of cement, which results in additional dilution.
Therefore, the amount of calcium hydroxide formed during the
cement hydration process is smaller, and this, in turn, has a direct
effect on the pozzolanic activity. The above explains why poz-
zolanic reactivity may not have compensated the cement replace-
ment [18]. Celik et al. [16] suggests that the incorporation of
natural pozzolans to ternary mixtures with calcareous fillers,
decrease the pozzolanic reaction rate due to dilution effect pro-
duced by the filler. In spite of the lower compressive strength com-
pared to the corresponding standard values, this study shows that
it is possible to add large amounts of Colombian volcanic materials
to SCCs for medium-to-low-resistance applications.
It is usually accepted that SCC is used for high-resistance and
high-complexity applications, which leads to poor development
of medium-to-low-resistance products [43], which is the market
mostly demanded particularly in Colombia. The current study
demonstrates that it is technically possible to develop medium-
to-low-resistance (3000–3500 psi) SCCs using local materials.
These SCCs could be used to make slabs and columns for homes
and mid-height buildings. They could also be used to make walls,
slabs, stairs, etc. for prefabricated houses, as the SCC’s high fluidity
guarantees homogeneous cast filling and uniform surfaces. Obvi-
ously, this would be an advantage for the construction industry,
as there would be no need to use mechanical vibration.
3.3. Sorptivity
The sorptivity or capillary suction test measures the pore struc-
ture connectivity; therefore, it is regarded as a good way to evalu-
 D.M. Burgos et al. / Construction and Building Materials 156 (2017) 565–573
Fig. 2. Compressive strength vs. curing time for the five different SCC mixtures.
ate the resistance of the concrete against the penetration of aggres-
sive chemical species [31]. Fig. 3a and b presents the results of the
sorptivity tests. The water penetration resistance coefficient, m, the
water permeability coefficient, k, and the effective porosity, ee, are
shown in Fig. 3a and b as columns, lines and bars, respectively.
Generally, the results show that incorporating volcanic material
initially 28 days) increases the SCC’s permeability, as the resistance
coefficients were lower and the permeability coefficients were
higher. Dogan and Ozkul [20] consider that incorporating large
amounts of additions increases the paste volume, which increases
the capillary pore volume and, therefore, the SCC’s permeability.
However, the SCC’s permeability depends on the type and quantity
of additions incorporated [26].
The granulometric distribution of the TVM results in improved
mechanical performance, as discussed earlier. However, Fig. 3
shows that, after 90 days, incorporating 20% TVM or 30% TVM
increases the water permeability and the effective porosity com-
pared to the standard SCC. In complete agreement with the results
presented here, Celik et al. [16] describe an increased capillary pore
volume with a dilution effect activated by inert materials during
the cement hydration process.
Authors such as Bonavetti and Rahhal [12] suggest that incorpo-
rating fine mineral additions accelerates the hydration reaction in
the early stages. Nevertheless, if no CSH is formed, dilution occurs
in the later stages. It is clear, however, that after 360 days, the
hydration reactions become dominant and decrease the permeabil-
ity of the 20% TVM and 30% TVM SCCs. The sorptivity results for the
pozzolanic PVM and BVM SCCs show that the permeability
decreases with the curing time. Sadek et al. [44] argue that the poz-
zolanic reaction converts calcium hydroxide into CSH gel, which, in
turn, blocks the capillary pores and modifies the porous structure.
The pozzolanic reactions become more evident after 90 days,
after which time the pore interconnectivity decreases and the por-
ous structure is modified. As stated above, this occurs due to the
reaction between the pozzolanic materials and calcium hydroxide,
which increases the system’s tortuosity [38, 24]. The permeability
and penetration resistance of the PVM and BVM SCCs are similar to
those of the standard SCC after 360 days. This result suggests that
incorporating these volcanic materials could improve the durabil-
ity of SCC [3, 45].
3.4. Chloride resistance
To determine the chloride ion penetration resistance of each of
the five different mixtures, Fig. 4 shows the charge passing through
569
each SCC specimen as a function of the curing time. Following
ASTM C1202 [8], the chloride ion permeability limits were set as
high, moderate, low and very low. It is clear that, after 28 days of
curing, all five mixtures show high chloride permeability
(>4000 coulombs). However, after 90 days, the hydration process
and the pozzolanic reactions decreased the charge that passed
through all five mixtures, resulting in a moderate to low perme-
ability (1000–4000 coulombs). It is clear, however, that, at that
age, more charge passed through the 20% TVM and 30% TVM mix-
tures and less charge passed through the 20% TVM + 10% PVM and
20% TVM + 10% BVM mixtures compared to the standard SCC.
Finally, after 360 days, the permeability of the 20% TVM and 30%
TVM mixtures remained essentially unchanged in the moderate
region. The amount of charge passing through the 20% TVM
+ 10% PVM and 20% TVM + 10% BVM mixtures, in contrast,
decreased to less than 1000 coulombs, which is in the very low
permeability region and even lower than the amount reported
for the standard SCC. The decrease in the permeability over the
curing time has a significant effect on the reinforcing steel’s chlo-
ride corrosion resistance and, therefore, on the concrete’s useful
life [40].
The fast permeability results prove that incorporating inert
TVM promotes dilution that increases the permeability of SCC.
These results are in complete agreement with those of Ramezani-
anpour et al. [42], who found that replacing cement more than
10% with inert materials increases the chloride penetration depth
due to heterogeneous nucleation and dilution effects. In contrast,
incorporating PVM and BVM pozzolanic additions decreases the
chloride permeability compared to the 20% TVM and 30% TVM
mixtures, based on their capacity to increase the system’s tortuos-
ity. Moreover, Hossain and Lachemi [30] found that incorporating
volcanic ash improves the chloride performance as a result of poz-
zolanic refinement action on the porous structure. The ternary
mixtures show that the PVM and BVM pozzolans plus the mineral
filler behavior of TVM give rise to SCCs with moderate resistance
and low chloride permeability compared to standard SCC. This
means an improvement for SCCs in terms of workability or
mechanical properties as well as durability [16, 2].
Fig. 5 shows both the chloride ion penetration resistance and
the sorptivity index (the water absorption rate through intercon-
nected pores) based on capillary suction tests. In general terms,
Fig. 5 shows that the resistivity increases as the sorptivity index
decreases. This fact is a result of the chloride penetration due to
two transport mechanisms: capillary suction and diffusion of the
solution [19]. The results show that the PVM and BVM pozzolans
570 D.M. Burgos et al. / Construction and Building Materials 156 (2017) 565–573

Fig. 3. Sorptivity test for standard, 20% TVM, 30% TVM, 20% TVM + 10% PVM, and 20% TVM + 10% BVM SCCs. a) Water penetration resistance and permeability coefficients; b)
effective porosity.

Fig. 4. Chloride permeability vs. curing time for the five different SCC mixtures.

have a refining action on the porous structure due to the blocking tions promote the formation of CSH, which, in turn, blocks capillary
effect of the CSH gel, which decreases the chloride permeability. pores and decreases the diffusion coefficient. In addition, it was
Authors such as Siad et al. [46] argue that a low sorptivity index observed that 20% TVM + 10% PVM and 20% TVM + 10% BVM SCCs
is associated with low chloride ion diffusion: the pozzolanic reac- show higher chloride resistivity in spite of their similar sorptivity
 D.M. Burgos et al. / Construction and Building Materials 156 (2017) 565–573 571

Fig. 5. Correlation between the resistivity and the sorptivity index after 360 days of curing time for the five SCC mixtures.

Fig. 6. X-ray diffractograms for pastes of all five SCC mixtures after 28 days of curing time (reference) and after being exposed to a 3.5% NaCl solution for 28 days.
E = Ettringite; M = Monosulfate; Fs = Friedel’s salt; Co = Cordierite; Al = Albite.

indexes to standard SCC. This shows that the effect on the chloride
resistivity is related not only to pore blockage but also to the chem-
ical interaction of binder and chloride ions, allowing the chloride
binding in cementitious systems [33].
Ipavec et al. [32] mentioned that it is well-known that chemical
binding between chloride ion and AFm compounds results in Frie-
del’s salt (calcium monochloroaluminate hydrate). Fig. 6 shows X-
ray diffractograms of the SCC pastes after 28 days of curing time
(reference) and after the SCCs were exposed to a 3.5% NaCl solution
for 28 days. The highest peaks in the X-ray diffractograms corre-
spond to Friedel’s salt at d = 7.9 Å 2h = 11.18°) [49]. Nonetheless,
an increase in the chloride ion concentration can decrease the
interplanar distance to 7.83 Å due to the transformation of AFm
into rhombohedral Friedel’s salt [32].
Fig. 6 shows that Friedel’s salt was detected after the SCCs were
exposed to a 3.5% NaCl solution. As a matter of fact, the concentra-
tion is higher in the 20% TVM + 10% BVM, 20% TVM + 10% PVM and
30% TVM, 20% TVM SCCs than in the standard SCC. This means that
incorporating volcanic materials promotes chloride ion binding
due to the presence of reactive alumina in spite of the dilution
effect that decreases the cement’s C3A content when part has been
replaced [36]. These results are confirmed by authors such as Hos-
sain and Lachemi [28, 29] who report that, when incorporating vol-
canic ashes, it is possible to decrease the chloride permeability in
spite of the lower C3A content of the cement. Two factors con-
tribute to this: pozzolanic reactivity and the subsequent effect of
Friedel’s salt formation. They also concluded that the formation
of Friedel’s salt is related to the presence of aluminum in the vitre-
ous fraction of the volcanic ash.
Burgos [14] found that in blended cement pastes with different
volcanic materials, TVM is not completely inert, and some of the
alumina reported in the chemical composition contributes to the
hydration of calcium aluminates. In the presence of gypsum, this
promotes the formation of AFt phase. Under some circumstances,
such as when the sulfates provided by the gypsum in the cement
are exhausted, the AFm phase may form [11]. The composition of
both aluminic phases and their ferric equivalents) can change, even
after the setting time, in the presence of certain chemicals such as
572 D.M. Burgos et al. / Construction and Building Materials 156 (2017) 565–573
chlorides and sulfates [25]. The interaction of incoming AFm
phases and chloride explains the presence of Friedel’s salt in the
20% TVM and 30% TVM SCCs shown in Fig. 6. However, the TVM’s
binding capacity is unable to balance the high sorptivity indexes of
the 20% TVM and 30% TVM SCCs to reduce the chloride permeabil-
ity. The 20% TVM + 10% PVM mixture showed the lowest Friedel’s
salt concentration. PVM includes sulfates that stabilize the ettrin-
gite component, which means there are not enough available
monosulfates to react with the chloride ion to form Friedel’s salt.
Nevertheless, the results suggest that both the increased tortuosity
of the system (due to PVM) and the binding effect (due to TVM)
increase the resistance to chloride penetration. On the other hand,
the 20% TVM + 10% BVM SCC showed the highest Friedel’s salt
peak. BVM includes alumina, which, when added to the alumina
in TVM, forms the largest quantity of Friedel’s salt.
4. Conclusions
Based on the experimental results of this study, the following
conclusions are drawn:

The fresh state properties and workability (slump flow, T50, V-
funnel and L-box) of all five mixtures comply with the European
SCC guidelines. The difference in performances is related to the
specific chemical and physical properties. The ternary mixtures
require larger amounts of SP.

Incorporating volcanic materials (TVM, PVM and BVM) pro-
motes chloride ion binding (Friedel’s salt formation) due to
the presence of reactive alumina.

Incorporating pozzolans (PVM and BVM) results in refinement
of the porous structure. This increases durability, rendering
the permeability coefficients and water penetration resistance
similar to the corresponding standard values for SCCs. The
refinement of the porous structure due to pozzolanic action also
leads to low chloride permeability.

The synergy of inert (TVM) and pozzolanic (PVM and BVM) vol-
canic materials results in SCCs with good workability, moderate
mechanical properties and high chloride penetration resistance.
Acknowledgments
The authors of this research would like to thank the Vicerrecto-
ria de investigaciones (Vice Dean for Research) at Universidad del
Valle (Valley University) (Cali, Colombia) for financial support
through internal project announcement C.I. 2785, ‘‘Self-
compacting concrete with volcanic materials,” and the Grupo de
materiales compuestos (GMC) (Compound materials group
(CMG)) of Universidad del Valle (Valley University), the Centro
de Excelencia en Nuevos materiales (Centre of Excellence in New
Materials) and the Centro Administrativo de Ciencia, Tecnología e
Innovación (Department of Science, Technology and Innovation;
COLCIENCIAS-Colombia) and its program of National Doctorates
for all their support.
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