Study of Variation in Surface Chloride of Concrete Containing

Different Pozzolans When Exposed to a Tidal Climate in the

Persian Gulf Region

Mahdi Valipour 1
Farhad Pargar 2
Mohammad Shekarchi 3
Sara Khani 4

ABSTRACT

The most common form of deterioration is caused by chloride ingress through concrete, resulting in
corrosion of the reinforcing steel. One of the factors affecting the penetration of chloride ions is the
amount of surface chloride (Cs). In this paper, the amount of chloride on the surface of concrete
specimens made with different pozzolan in tidal and splash zones is considered. The results show that
the amount of surface chloride in the specimens of concrete sited in splash zone is more than tidal
zone.

KEYWORDS

Corrosion, Surface chloride, Splash zone, Tidal zone.

1
Research Assistant Construction Materials Institute (CMI), University of Tehran
2
Research Assistant Construction Materials Institute (CMI), University of Tehran
3
Director of Construction Materials Institute (CMI), University of Tehran
4
Research Assistant Construction Materials Institute (CMI), University of Tehran
Shekarchi, Valpour, Pargar and Khani

1 INTRODUCTION

Chloride diffusion is known to be a major cause of deteriorating concrete structures exposed to marine
environments such as the Persian Gulf which is characterized as one of the most aggressive
environments for concrete in the world because of its high relative humidity and elevated temperature
that can be as high as 50 degrees on some days and may lead the a rise in surface temperature of up to
75 degrees [Ramezanianpour et al., Shekarchi et al.]. Reinforcing steel can be greatly corroded due to
attack of aggressive ions such as chloride and thus reduce the life span of steel reinforced concrete
structures [Bader 2003, Sandberg et al.]. Therefore, the severity of this environment is of concern to
those who maintain concrete structures located in this specific region.

However, to determine chloride ingress and estimate the time to corrosion, the amount of surface
chloride (Cs) must be known. It is interesting to note that when solving Fick’s second law, a constant
value for surface chloride has been widely used whereas the accumulation of chloride on the surface of
concrete can vary in accordance with different exposure conditions [Ann et al. 2009, Nokkena et al.
2006].

According to a study completed by Bruce [2001] on reinforced concrete structures located in the
Eastern Province of Saudi Arabia, the values for Cs are greatest in areas subject to wetting and drying.
When salty water evaporates, any chloride in the water will remain in a crystalline form on the surface
of the concrete. In marine structures, the value of Cs will reach a maximum just above the sea water
level in the splash zone. For reinforced concrete bridge and building structures, the value of Cs will
attain a maximum just above ground level where water is drawn through the concrete and then
evaporates from the surface. When estimating the time to corrosion of reinforced concrete structures,
for which values of Cs are required, engineers should use actually measured values of Cs taken from
samples collected from existing structures; ideally this should be done in those seasons when the daily
temperatures attain the annual average temperature. He determined the surface chloride of 0.6-0.9% by
weight of concrete to simulate the exposure condition of extreme. The majority of samples were taken
from the cover zone which had cracked as a result of the expansion of rusting steel reinforcement.
Concrete mix design may also influence the value of Cs as modern dense concretes typically have
finer pore structures and reduced chlorides are absorbed. On the other hand, the use of pozzolans in
the concrete mix may either increase or decrease the surface chloride content of the concrete
depending on their ability to bind chloride ions.

In other words, the degree of exposure with chlorides in a marine environment is a key factor that
determines each different level of surface chloride content. The values of Cs for a concrete exposed to
seawater may not be changed over time due to chemical equilibrium, but at the tidal zone the chloride
content on the concrete surface can increase in relation to the number of wet and dry cycles to which it
is exposed. Also it is seen that the degree of contact with seawater greatly influences the value of Cs.
For example, the value of Cs obtained from concrete placed in submerged conditions in seawater was
higher than that for exposure to tidal or splash zones and specimens and structures exposed to airborne
chloride ions produce the lowest values for Cs. However, the value of Cs from published data does not
provide a clear relationship in respect to the time of exposure due to various factors that affect chloride
ion transport including binder type, free water/binder ratio (W/B), curing conditions, location of
sampling in the structure and weathering [Song et al. 2008].

For this purpose a study is conducted at Qeshm Island (Iran), in which four concrete specimens were
made using different water to cement ratios of 0.35, 0.4, 0.45 and 0.5 respectively. Also, the
performance of concrete specimens containing silica fume (5%, 7.5% and 10% of replacement level),
metakaolin (5%, 10% and 15% of replacement level) and zeolite (10%, 20% and 30% of replacement
level) with constant w/c ratio of 0.4 were also examined. The surface chloride of concretes were
determined and compared for two exposure conditions, specifically the splash and tidal zones. The
compressive strength of specimens was also determined for all exposed specimens.

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2 EXPERIMENTAL PROGRAM

2.1 Materials

Type II Portland cement was used throughout the investigations. The chemical and physical properties
of cement and pozzolanic materials used in preparing the concrete specimens are shown in Table 1.

Table 1. Composition of cement, silica fume, metakaolin and zeolite.

Oxide
composition %by PC Silica Fume Metakaolin Natural Zeolite
mass
SiO2 21 93.16 51.58 67.79
Al2O3 5 1.13 43.87 13.66
Fe2O3 3.5 0.72 0.99 1.44
CaO 63 - 0.2 1.68
MgO 1.8 1.6 0.18 1.2
SO3 1.6 0.05 - 0.5
Na2O 0.5 - 0.01 2.04
K2O 0.6 - 0.12 1.42
L.O.I 2 1.58 0.57 10.32

2.2 Mixture Proportions

The investigation was carried out on 13 concrete mixes, in which, as previously mentioned, there were
four different water to cement ratio, and other mixtures incorporating different replacement levels of
silica fume, metakaolin and natural zeolite. The mix proportion of concrete samples are presented in
Table 2. Crushed limestone (largest size of 19 mm) was used as coarse aggregate and the fine
aggregate was river sand. Also, to achieve the desired workability the use of poly carboxilate-based
superplasticiser was necessary. All specimens were moist cured for 3 days and then placed at the
respective tidal and splash zones located on the shores of Qeshm Island in the Persian Gulf’s.

2.3 Test Procedure

Concrete prisms of 150×150×600 mm in size that had been prepared for determination of chloride
penetration were placed at the tidal and splash zones for a 9 month period. Concrete cores of 70 mm
diameter were then taken from each specimen and powder samples were obtained from these cores.
The samples were examined to determine their compressive strength and the amount of chloride ion at
a depth of 20 mm. Compressive strength tests were carried out on three cubes of 150×150×150 mm at
7and 28 days of moist curing.

After 3 days of curing, five sides of the concrete prism specimens were sealed with an epoxy coating
to ensure that diffusion would occur only in the direction of the exposed side of the specimens. Then
they were then exposed to two different conditions in the Persian Gulf region: the tidal zone and the
spalsh zone. The tidal zone is that area between the minimum and maximum level reached by the tide
water whereas above this zone resides the splash zone. In this zone seawater washes out the concrete
surface.

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Shekarchi, Valpour, Pargar and Khani

Table 2. Mix Proportions for concrete samples.

Content of Cement Super

W/B Cement Water Slump
Sample replacement Material plasticizer
Ratio (kg/m3) (kg/m3) (cm)
(kg/m3) (kg/m3)
C1 0.35 400 _ 140 0.35 8
C2 0.4 400 _ 160 0.2 7
C3 0.45 400 _ 180 0.1 15
C4 0.5 400 _ 200 0 18
SF5 0.4 380 20 160 1.2 6
SF7.5 0.4 370 30 160 1.4 5
SF10 0.4 360 40 160 1.6 8
MK5 0.4 380 20 160 0.8 5
MK10 0.4 360 40 160 1.4 5.5
MK15 0.4 340 60 160 1.6 8
ZE10 0.4 360 40 160 4 6
ZE20 0.4 320 80 160 8 8
ZE30 0.4 280 120 160 14 6

After nine months of exposure in seawater of the Persian Gulf, powder samples were prepared for
chloride analysis using a Profile Grinder to grind off a layer of concrete parallel to the exposed
surface; samples were extracted with the grinder at 9 different depths to an accuracy 0.1 mm. It should
be noted that 1 mm of the concrete surface was removed before sampling. Also, the initial samples
were not included in calculations as it was considered that this might be affected by actions such as
those of the skin effect, as shown in Figure 3. Using this technique, a sample of 10g at each depth was
collected and analyzed separately for acid-soluble chloride according to the methods described in
ASTM C 114 [Shekarchi et al. 2009].

A commercially available, curve-fitting software program was used to determine the value of Cs
(surface chloride concentration) and Da (apparent diffusion coefficient) from the data using a non-
linear, least-squares method, with Fick’s Second Law of diffusion using Crank’s solution. The best fit
curve was determined by adjusting both the unknowns to achieve the highest coefficient of
determination (r2).

3 RESULTS AND DISCUSSION

3.1 Compressive Strength

Figure 1 illustrates the compressive strength of all specimens at ages of 7 and 28 days. As it can be
seen, increasing the w/c ratio reduces the compressive strength for specimens cured for at both 7 and
28 days. Specimen C4 with the highest w/c ratio showed the lowest compressive strength whereas
specimen C1 with the lowest w/c ratio obtained the highest compressive strength. Lowering the w/c
ratio can bring about improvements in the microstructure of concrete leading to the development of
higher compressive strengths.

Using pozzolan as a cement replacement resulted in an increase in compressive strength at ages of 7

and 28 days in comparison to the results obtained for the control concrete specimens. However, this
was not true for specimens ZE20 and ZE30 at an age of 7 days or for specimen ZE30 at an age of 28
days. Based on the results, lower compressive strength was achieved when greater amounts of zeolite
were used in the mix; given that the ZE30 specimens had the lowest compressive strength this likely
can be attributed to the fact that at a high dosage of zeolite, the hydration process remains incomplete.

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 Surface Chloride of Concrete

For concretes incorporating silica fume, the concrete mix having a replacement level of 7.5% of silica
fume reached the highest compressive strength after 7 days whereas SF10 attained the highest 28 day
compressive strength. For specimens containing metakaolin the compressive strength at both ages
increased with an increase in replacement level noting that MK10 attained the highest compressive
strength.

60
Compressive strenght (MPa)

7-day
50 28-day

40

30

20

10

0
5

10

15

10

20

30
10

5
5
C1

C2

C3

C4

K
7.
SF

ZE

ZE

ZE
SF

M
SF

Sample M

Figure 1. Compressive strength of specimens at ages of 7 and 28 days.

3.2 Surface Chloride

The surface chloride contents are given in Table 3 and Figure 2. The amount of surface chloride (by
weight of concrete) in specimens not containing pozzolan did not follow any specific trends. The
variation of surface chloride amount at tidal and splash zones show that the amount of surface chloride
present in concretes exposed to the splash zone is greater than that of specimens exposed to the tidal
zone. The highest percentage increase belongs to specimen C1 which has the lowest w/c ratio (0.35). It
can be noted that although the surface chloride of specimens exposed to both the tidal and splash
zones fluctuates, the amount of chloride in concrete specimens at a depth of 20 mm exposed to the
tidal zone is almost constant with the exception of specimenC1 which has lower chloride content as
compared to other specimens. Whereas concrete specimens exposed to the splash zone shows a
tangible increase in chloride content with increasing w/c ratio.

Specimens containing silica fume (SF) exposed to both tidal and splash zones have higher surface
chloride contents and lower chloride contents at a 20 mm depth than those concrete mixes not
containing pozzolans. Therefore, it can be observed that among specimens containing silica fume, with
additional dosage of pozzolan there is reduction in the amount of surface chloride content and in the
amount of chloride at a depth of 20 mm. For those specimens incorporating with silica fume and
exposed to the splash zone an increase in surface chloride content of 5 to 10% is evident whereas the
amount of chloride at a depth of 20 mm decreases. A comparison of results obtained for concrete
specimens exposed to these two exposure conditions shows that the amount of surface chloride content
in all silica fume specimens is higher for specimens exposed to in the splash as compared to those in
the tidal zone.

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Shekarchi, Valpour, Pargar and Khani

Surface chloride (% by wt. concrete) 1.6 1.6

Tidal zone Splash zone

Surface chloride (% by wt. concrete)

Tidal zone Splash zone

1.2 1.2

0.8 0.8

0.4 0.4

0.0
0.0
C1 C2 C3 C4
C2 SF5 SF7.5 SF10
Sample
Sample

1.6 1.6
Tidal zone Splash zone Tidal zone Splash zone

Surface chloride (% by wt. concrete)

Surface chloride (% by wt. concrete)

1.2 1.2

0.8 0.8

0.4 0.4

0.0 0.0
C2 MK5 MK10 MK15 C2 ZE10 ZE20 ZE30
Sample Sample

Figure 2. Surface chloride of concretes with different w/c and pozzolanic materials exposed to
tidal and splash zone conditions.

For specimens containing metakaoline (MK), an increase of replacement level from 5 to 15% in
specimens exposed to either zones results in increases in the amount of surface chloride content
whereas the amount of chloride at a depth of 20 mm decreases. It is clear that the amount of surface
chloride content in specimens exposed to the splash zone is greater than that of specimens exposed to
the tidal zone. In contrast with specimens incorporating SF, an increase in the replacement level of
MK, produces a sharp increase in the amount of surface chloride content, whereas the chloride content
at a depth of 20 mm decreases with the proportional reduction similar to that observed for SF concrete
at the same replacement level.

For specimens containing natural zeolite (ZE), the performance of specimens having a 10%
replacement level of zeolite and exposed to the splash zone was found to be similar to that of concrete
specimens SF5. By increasing the replacement level up to 30% of ZE the surface chloride content for
specimens exposed to the tidal zone fluctuates whereas the degree of chloride penetration was
somewhat reduced. The surface chloride content for specimens exposed to the splash zone increased
whereas the reduction of chloride penetration was not noticeable. The results obtained for surface
chloride content for specimens exposed to either marine zone confirms that for replacement levels of
10, 20 and 30%, the surface chloride content and chloride penetration were higher for specimens
exposed to the splash zone as compared to those exposed to the tidal zone.

The comparison of natural zeolite (ZE) with MK and SF shows that higher replacements of ZE are less
effective and do not noticeably change the chloride resistance of the concrete.

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Table 3. Surface chloride and chloride content at a depth of 20 mm in different specimens.

Tidal zone Splash zone

Code Chloride content Chloride content
Surface chloride Surface chloride by
at the depth of 20 at the depth of 20
by weight of concrete weight of concrete
mm mm
C1 0.01 0.26 0.15 0.76
C2 0.15 0.34 0.19 0.66
C3 0.15 0.35 0.25 0.77
C4 0.16 0.29 0.33 0.8
SF5 0.06 0.75 0.10 0.79
SF7.5 0.05 0.69 0.07 1.08
SF10 0.03 0.62 0.04 1.11
MK5 0.06 0.75 0.10 0.87
MK10 0.03 0.92 0.03 1.07
MK15 0.02 1.01 0.02 1.48
ZE10 0.05 0.58 0.11 0.79
ZE20 0.05 0.68 0.10 0.90
ZE30 0.04 0.51 0.09 1.00

4 CONCLUSIONS

(1) In specimens without pozzolan, increasing the w/c ratio caused an increase in the amount of
chloride penetration into the concrete with no perceptible trend in the amount of surface chloride
content for specimens exposed to either the tidal or splash zones.

(2) Surface chloride content and the amount of chloride at a depth of concrete is found to have an
inverse relation in specimens containing pozzolans; increasing the replacement level increases the
amount of surface chloride content but decreases the amount of chloride at a depth of 20 mm.

(3) Increasing the replacement level of pozzolans in concrete specimens exposed to either the splash
or tidal zones had a positive effect on reducing the degree of chloride ingress yet an increase in the
amount of surface chloride content was evident.

(4) All specimens showed higher degree of chloride penetration and surface chloride content for
specimens exposed to the splash zone as compared to those exposed to the tidal zone; this
indicates that a greater concentration of surface chloride may induce a higher degree of chloride
ion penetration into the concrete.

(5) Among the specimens investigated in this study that were cured for a short term (3days), the
performance of natural zeolite in terms of chloride diffusivity was significant in comparison to the
other well known pozzolans such as silica fume and metakaolin. The 10% replacement level for
zeolite and for specimens exposed to the tidal zone showed a better result as compared to those
having 5% replacement of silica fume and metakaolin. For specimens exposed to the splash zone
the performance of these specimens was similar to that of specimens containing silica fume and
metakaolin.

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Shekarchi, Valpour, Pargar and Khani

REFERENCES

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Bader, M.A. 2003, ‘Performance of concrete in a coastal environment’, Cement & Concrete
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Nokkena, M., Boddy, A., Hootonc, R.D. & Thomas M.D.A. 2006. ‘Time dependent diffusion in
concrete—three laboratory studies’, Cement and Concrete Research, pp. 200– 207.

Ramezanianpour, A.A., Ashrafi, H.R. & Ramezanianpour, A.M. ‘Chloride diffusion models for
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Smith, B. G., 2001.‘Durability of silica fume concrete exposed to chloride in hot climate’, ASCE
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Shekarchi, M., Ramezanianpour, A.A., Ghods, P., Chini, M., Alizadeh, R. & Hoseini, M. ‘The effect
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1503.

Song H. W., LEE C. H., Ann, K. Y. ‘Factors influencing chloride transport in concrete structures
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Shekarchi, M .Rafiee, A .Layssi, H .2009 .‘Long-term chloride diffusion in silica fume concrete in
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8 XII DBMC, Porto, PORTUGAL, 2011