International Journal of Civil Engineering and Technology (IJCIET)

Volume 8, Issue 1, January 2017, pp. 418425, Article ID: IJCIET_08_01_047

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ISSN Print: 0976-6308 and ISSN Online: 0976-6316
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DETERMINATION OF APPARENT CHLORIDE

DIFFUSION COEFFICIENT FOR SELF COMPACTING
CONCRETE CONTAINING NANO SILICA UNDER
EFFECT OF SULFATE ATTACK
Dr. Ghalib Mohsin Habeeb
Professor, Civil Engineering Department, College of Engineering,
University of Babylon, Iraq

Zahraa Dhurgham Hashim Hadi

MSc Student, Civil Engineering Department, College of Engineering,
University of Babylon, Iraq

ABSTRACT
The objective of this work is devoted to determine the apparent chloride diffusion coefficient of
self compacting concrete (SCC) with Nano Silica which is subjected to severe saline conditions
contain sulfates and chlorides at concentrations similar to those existing in soils and ground water
of the middle and southern parts of Iraq. Four basic mixes of SCC were performed with and
without addition of Nano Silica, and with two types of cement (ordinary Portland cement and
sulfate resistance Portland cement). The workability properties of mixes were evaluated by fresh
tests such as slump-flow test, T50cm, L-box and V-funnel tests. The apparent chloride diffusion
coefficient was determined at90 and 180 days. Test results exhibited that the presence of Nano
Silica in concrete decreases the apparent chloride diffusion coefficient at age of 180 days which
was ranged between (50.83-54.40)% measured relative to its reference mixes without Nano silica
addition. Also, the results revealed that SRPC specimens have higher chloride content than OPC
mixes especially at 90 days. while at 180 days, SRPC specimens have lower chloride content than
OPC specimens.
Key words: Nano Silica, sulfate attack, chloride diffusion, concrete, Self compacting, Ficks
second law, fresh properties
Cite this Article: Dr. Ghalib Mohsin Habeeb and Zahraa Dhurgham Hashim Hadi, Determination
of Apparent Chloride Diffusion Coefficient for Self Compacting Concrete Containing Nano Silica
under Effect of Sulfate Attack. International Journal of Civil Engineering and Technology, 8(1),
2017, pp. 418425.
http://www.iaeme.com/IJCIET/issues.asp?JType=IJCIET&VType=8&IType=1

1. INTRODUCTION
The Chloride ions are in advertently associated with sulfate in the attack of groundwater on concrete.
Chloride reacts with the hydrates of cement and form Freidels salt (3CaO.Al O . CaCl . 10H O)that does
not have any harmful effects on concrete, but when chloride content in concrete reaches more than the

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 Determination of Apparent Chloride Diffusion Coefficient for Self Compacting Concrete Containing
Nano Silica under Effect of Sulfate Attack

threshold value, the protective alkaline layer of steel reinforcement is broken and in the presence of oxygen
and humidity, steel reinforcement gets corroded. Presence of chloride in sulfate solution affects the
deterioration of concrete under sulfate attack (Prasad et al., 2006).
The chloride diffusion test is used to determine the apparent chloride diffusion coefficient of hardened
concrete by bulk diffusion. The apparent chloride diffusion coefficient is considered as an indication of the
capacity of any type of concrete to resist chloride penetration and also can use to predict the service life of
reinforced concrete structures. The resistance to penetration of chloride is affected by many factors such as
the environment, finishing, mix composition, workmanship, curing and age.
Apparent chloride diffusion coefficient is a chloride transport parameters calculated from acid soluble
chloride profile data obtained from saturated specimens exposed to chloride solutions (without correction
for chloride binding).Diffusion is a process by which ions can pass through a saturated concrete. The
driving factor in diffusion is the concentration gradient. The aggressive ions, such as chloride, when they
are in contact with the surface of concrete will diffuse through the concrete from regions of a high
concentration to a low concentration until a state of equilibrium in ion concentration is achieved. If the
concentration of ions at the surface is very high, diffusion may result in corrosion-inducing concentrations
at the level of the reinforcement (Moradi, 2014).
On the other hand, the concrete structures subjected to sulfate attack which is likely to suffer from two
types of deterioration; loss of strength of the matrix resulting from degradation of calcium silicate hydrate
(C-S-H), and volumetric change leading to expansion due to the formation of gypsum or ettringite that
leads to the cracking(AL-Rawi, 1985).The protection against sulfate attack and chloride diffusion requires
to reduce the permeability of concrete and improve the microstructure of concrete. So, the addition of
Nano Silica to concrete can consume calcium hydroxide crystals, reduce the size of the crystals at the
interface zone and transmute the calcium hydroxide feeble crystals to C-S-H crystals and improve the
interface zone and cement paste structures (Khanzadi et al., 2010) and (Saloma, 2015).
This research focuses on the effect of Nano Silicaon the apparent chloride diffusion coefficient for
SCC exposed to sulfate solutions.

2. EXPERIMENTAL PROGRAM
2.1. Materials and SCC Mix Design
In this research, two types of Portland cement were used: Ordinary Portland Cement (OPC) (ASTM type I)
and Sulfate Resistance Portland Cement (SRPC) (ASTM type V) manufactured by united cement
company, commercially known (TASLUJA-BAZIAN). These types complied with the Iraqi specification
(IQS No.5, 1984). The sand used from Al-Ekadir region in Iraq with a fineness modulus (2.51). Rounded
gravel of 14 mm maximum size from Al-Nebai quarry was used as a coarse aggregate in all mixes. Sand
and gravels conform to the Iraqi specification (IQS No.45, 1984).Nano Silica used in this work was
produced in China by precipitation method in powder form making Nano Silica to have a high degree of
purity about 99.96% and diameter for the particles (35nm). Silica fume used as a replacement with (5%) by
weight of cement. Super plasticizer was also used, which is known commercially Glenium 54 to achieve
high workability needed to produce SCC.
Four mixes were investigated, all based on the same control mixture. These mixes were designed
according to (European Project Group, 2005) and divided into two series each one with different type of
cement (I or V).The main details of SCC mixes used in this study are presented in Table (1)

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 Dr. Ghalib Mohsin Habeeb and Zahraa Dhurgham Hashim Hadi

Table 1 The main details of SCC Mixes used in the present study

Cementitious

Nano Silica
Silica fume

( / )

w/b ratio
( / )
( / )

( / )
( / )
Notation

Material
Cement

Gravel

Water
SP %
Sand
Mix

/
(

(
OPC- 0%NS (OR) 475 25 500 ---- 780 820 0.7 180 0.36
OPC- 3%NS (ON3) 475 25 500 15 780 820 2.0 180 0.35
SRPC- 0%NS (SR) 475 25 500 ---- 780 820 0.7 180 0.36
SRPC- 3%NS (SN3) 475 25 500 15 780 820 2.0 180 0.35

2.2. Mixing Procedure

Mixing process is conducted in pan mixer with a capacity of 0.05 . The 3/4 dosage of super plasticizer
was added to mixing water and mixed about 30 second in a small pan mixing separately from other
material then the Nano Silica was stirred with this solution and mixed about 3 minutes in order to disperse
uniformly and avoid agglomerations of Nano Silica since it has a high surface energy. before 2 minutes
from the end of pervious mixing, the cement and silica fume had been added in pan mixer and mixed for
1minute in dry state.The fine aggregate was added to the drying materials and mixed for 1minute.The
prepared solution of (superplasticizer, water and NanoSilica) was added and mixed for 3 minute.
Thereafter, gravel was added and mixed for 1 minute, Then the remaining dosage 1/4 of super plasticizer is
added and mixed for 2 minute. The mixture is then discharged, tested and placed. The total time of mixing
process was about 8 minutes.

3. TESTING METHODS
3.1. Fresh Concrete Tests
The fresh concrete tests are required to assess filling ability (flow ability), passing ability (passibility) and
segregation resistance (stability) of SCC. But, there is no unique test to measure the three properties
together. So, different test methods have been developed in attempts to characterize the properties of SCC.
In this study three tests were used slump flow test, V-funnel test and L-box test.

3.2. Hardened Concrete Test- Chloride Diffusion Test

The average of three specimens for chloride diffusion test was used (concrete cylinders, diameter of 100
mm and height of 100 mm). Diffusion test was determined at the age of 90 and 180 days. This test was
performed according to (ASTM C1556, 2003). All sides of the test specimens were coated with epoxy
paint with two layers except for the finished surface which left uncovered in order to allow the chloride to
penetrate the samples just from one surface. After that, the specimens were placed in tap water for 28 days
in a plastic container, then the specimens immersed in the exposure solution (sulfate-chloride solution in
this research which consists of pure salts, these salts were 1.5% MgSO . 7H O, 0.325 % Na SO ,
0.7% CaCl . 2H O and 5% NaCl by weight of cement).After a specified exposure period, thin layers were
obtained from the test specimens by grinding the materials in layers parallel to the exposed surface. The
produced powder was collected by using rotary impact drill for the determination of the total chloride
concentration profile. Figure (1) illustrates the details of grinding process for test specimens. The total
initial chloride concentrations are determined at 28 days and total concentrations at different depths after
an exposure to chloride solutions were also determined through acid-soluble chloride content that
described in (ASTM C 1152/ C 1152M, 2003), Plate (1) represents the powder collection process to

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 Determination of Apparent Chloride Diffusion Coefficient
Coefficient for Self Compacting Concrete Containing
C
Nano Silica under Effect of Sulfate Attack

determine the chloride on content. The obtained chloride concentration profiles were fit to the solution of
Ficks second law by means of a non-linear regression analysis using least squares of error, in order to
determine the apparent chloride diffusion coefficient and the chloride concentration in the surface layer of
concrete.

Figure 1 Sketch of Grinding Process for Test Specimens

pecimens

Plate 1 Powder Collection Process and Determination the Acid-Soluble

Soluble Chloride Content

4. RESULTS AND DISCUSSIONS

DISCUSSI
4.1. Fresh Concrete
Fresh concrete tests were carried out to ensure that the mixes satisfy the requirements of SCC. Table (2)
illustrates the results of the fresh properties for each mix. These results explain that the SCC
SC used is
conformed to the requirements of (European Project Group, 2005) (i.e. has a good consistency and
workability at fresh state).

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 Dr. Ghalib Mohsin Habeeb and Zahraa Dhurgham Hashim Hadi

Table 2 Results of Fresh Properties of SCC Mixes

4.2. Hardened Concrete Test- Chloride Diffusion Test

In Figures (2) and (3) the obtained apparent chloride diffusion coefficients (Da)
(Da for SCC mixes exposed to
chloride solution (sulfate-chloride
chloride solution in this work), at 90 and 180 days respectively are illustrated. It
I
can be observed at 90 days of exposure that ON3 specimensspecimens exhibited a lower chloride concentration
profile than SN3, also OR specimens have also lower chloride content than SR specimens. In other words,
SRPC specimens have lower resistance to chloride than OPC specimens. This is due to low C3A content in
SRPC specimens compared with OPC specimens, hence the high C3A content binds with high amount of
chloride ions to form further amount of stable chloro complexes
complexes which called Freidels salt ( 3CaO.Al2O3.
CaCl2.10H2O) that cannot penetrate the concrete, so the total chloride content is reduced, therefore, SRPC
specimens have higher total chloride contents which can diffuse to the steel rapidly and exacerbate the
corrosion problem, that is relative to OPC specimens. WhenWhen the higher chloride content reaches more than
threshold value, the protective alkaline layer of steel reinforcement is broken and in the presence of oxygen
and humidity, steel reinforcement gets corroded. The same conclusion is obtained by (Hussein, 2003) and
(Rodriguez et al., 2013).
Whereas, it is clear at 180 days that SRPC specimens showed a lower chloride concentration profiles
as compared with OPC specimens. This may be related to the formation of expansive salts result from
sulfate attack in OPC specimens such as gypsum and ettringite in a high amount when compared with
SRPC specimens, these compounds result in expansion, cracking and deterioration of concrete; so, the
cracking permits to penetrate more amount of chloride ions to the concrete (Br (Breke et al., 1990) and (Wang
and Ueda, 2011).
Also, from the results, it has been shown that the presence of Nano Silica in concrete mitigates the total
chloride content especially at deeper depths relative to corresponding reference mixes regardless of the
type of cement. So, Tables (3)) and (4) explain this reduction in the chloride content of SCC mixes
containing Nano Silica for both 90 and 180 days of exposure ages relative to corresponding reference
mixes (without Nano Silica). The reduction is due to physical
physical effect of fine Nano particles, which were
responsible for formation of less porous, denser microstructure and a discontinuous pore system.
Additionally, the Nano particles acted as filler to enhance the density of concrete, which reduced the
porosity of concrete. Also, the addition
addi of Nano Silica created a finer particle size distribution. The finer
particle size distribution of Nano Silica enhanced the pore structure of concrete and filled the voids at
various size levels. As well as Nano Silica particles
particles were able to enhance the concrete pastes chemically by
their rapid reaction with free calcium hydroxide, which seemed to be able to create a discontinuous pore
system more readily by consuming free calcium hydroxide. Nano particles acted also as nucleus nuc in cement
paste to make calcium hydroxide crystals smaller and accelerated the cement hydration due to their high
activity.

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 Determination of Apparent Chloride Diffusion Coefficient for Self Compacting Concrete Containing
Nano Silica under Effect of Sulfate Attack

Figure 2 Chloride diffusion profiles of SCC mixes at 90 days of exposure

Figure 3 Chloride diffusion profiles of SCC mixes at 180 days of exposure

Table 3 Percent of Decrease in Chloride Content at 90 Days of Exposure at Selected Depths of SCC Mixes

Reduction in Chloride Content (%) from Reference Concrete at 90

Mid-layer Depth Days of Exposure
(mm)
OR ON3 SR SN3
1 ----- 1.84 ----- 2.67
3 ----- 20.21 ----- 12.81
5 ----- 27.91 ----- 22.40
7 ----- 27.06 ----- 33.33
9.5 ----- 46.70 ----- 27.23
12.5 ----- 56.15 ----- 12.86
15.5 ----- 54.40 ----- 60.42

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 Dr. Ghalib Mohsin Habeeb and Zahraa Dhurgham Hashim Hadi

Table 4 Percent of Decrease in Chloride Content at 180 Days of Exposure at Selected Depths of SCC Mixes

Reduction in Chloride Content (%) from Reference Concrete at 180

Mid-layer Depth Days of Exposure
(mm)
OR ON3 SR SN3
1 ----- 5.83 ----- 10.17
3 ----- 5.35 ----- 6.49
5 ----- 7.95 ----- 6.94
7 ----- 27.80 ----- 29.96
9.5 ----- 25.62 ----- 22.33
12.5 ----- 23.74 ----- 28.42
15.5 ----- 32.67 ----- 44.25
18.5 ----- 62.00 ----- 55.47

It is also clear from these results that lowest chloride diffusion was computed for ON3 (Da = 3.50 *10-
12
m2/s) at 90 days, while (Da = 2.66 *10-12 m2/s) at 180 days for SN3. So, this refers to the influence of
Nano Silica in reducing the diffusion coefficients for SCC mixes because the Nano particles increase the
density of concrete. The percentage of decrease of chloride diffusion coefficient after 180 days found for
SN3 specimens was (50.83%), while for ON3 specimens was (54.40%). This is in agreement with (Quercia
et al., 2012).

5. CONCLUSIONS
The presence of Nano Silica in concrete mitigates the total chloride content especially at deeper depths
relative to corresponding reference mixes regardless of the type of cement.
The chloride diffusion coefficient for SCC with Nano Silica was lower than that without Nano Silica. The
percentage of decrease in chloride diffusion coefficient after 180 days was found for SN3 specimens was
(50.83%) while for ON3 specimens was (54.40%).
Generally, the results reveal that SRPC specimens have higher chloride content than OPC mixes especially
at 90 days. while at 180 days, SRPC specimens have lower chloride content than OPC specimens.

REFERENCES
[1] Al-Rawi R.S., ( 1985), Internal sulfate attack in concrete related to gypsum content of cement with
pozzolan addition, ACI-RILEM, Joint Symposium, Monterey, Mexico, pp. 543 .
[2] ASTM C1152 /C 1152M, 2003), Standard test method for Acid-Soluble chloride in mortar and
concrete" ASTM international west Conshohocken, PA, www.astm.org.
[3] ASTM C1556, (2003), " Standard test method for determing the apparent chloride diffusion coefficient
of cementitious mixtures by bulk diffusion", ASTM international west Conshohocken, PA,
www.astm.org.
[4] Berke, N.S., Chaker, V., and Whiting, D., (1990)," Corrosion rates of steel in concrete", No. 1065,
ASTM International.
[5] European Project Group, (2005), ''The European Guidelines for Self-Compacting Concrete:
Specification, Production and Use'', may, 2005, PP.63.
[6] Hussein, M.T., (2003), " The effect of cement Type on the potential and corrosion behavior of steel
Reinforcement ", Ph.D. thesis, University of surrey.
[7] Iraqi Organization of Standards, (IQS), No.45/1984, for Aggregate.

http://www.iaeme.com/IJCIET/index.asp 424 editor@iaeme.com

 Determination of Apparent Chloride Diffusion Coefficient for Self Compacting Concrete Containing
Nano Silica under Effect of Sulfate Attack

[8] Iraqi Organization of Standards, (IQS), No.5/1984, for Portland Cement.

[9] Khanzadi, M., Tadayon, M., Sepehri , H., and Sepehri, M.,(2010), " Influence of Nano-Silica Particles
on Mechanical Properties and Permeability of Concrete", HBRC Journal, vol.20, No. 20, April 2010,
p.p. (1-13).
[10] Thallapaka Vishnu Vardhan Rseddy, K. Rajasekhar and Seelanani Janardhana. Study and Performance
of High Strength Concrete Using with Nano Silica and Silica Fume. International Journal of Civil
Engineering and Technology (IJCIET), 6(11), 2015, pp. 184-196.
[11] Moradi, B., (2014),"Transport Properties of Nano-Silica Contained Self-Consolidating Concrete", M.Sc.
Thesis, University of Nevada, Las Vegas.
[12] Prasad, J., Jain, D.K., and Ahuja, A.K., (2006)," Factors Influencing the Sulfate Resistance of Cement
Concrete and Mortar", Asian Journal of Civil Engineering, Vol. 7, No. 3 (2006), pp. (259-268).
[13] Quercia, G., Spiesz, P., Husken, G., & Brouwers, J. (2012), "Effects of amorphous nano-silica additions
on mechanical and durability performance of SCC mixtures", In Proceedings of the International
Congress on Durability of Concrete (ICDC 2012), (pp. 18-21).
[14] Rodriguez, G.R., Aperador, W., Delgado, A., (2013), " Calculation of concrete structures ", International
Journal electrochemical science, No. 8, pp. (5022-5035).
[15] Saloma, Nasution, A., Imran, I., and Abdullah, M., (2015)," Improvement of concrete durability by
nanomaterials" Procedia Engineering, Vol.125,( 2015), pp. (608 612).
[16] Arun Nishchal Guleria and Sandeep Salhotra, Effects of Silica Fume (Micro Silica or Nano Silica) On
Mechanical Properties of Concrete: A Review. International Journal of Civil Engineering and
Technology (IJCIET), 7(4), 2016, pp.345357.
[17] Wang, L., and Ueda, T., (2011), "Mesoscale modeling of the chloride diffusion in cracks and cracked
concrete", Journal of advanced concrete technology, Vol. 9, No. 3, pp.(241-249), October 2011,
copyright 2011 Japan concrete institute.

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