Construction and Building Materials 51 (2014) 225–234

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Construction and Building Materials

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Chloride and chemical resistance of self compacting concrete containing

rice husk ash and metakaolin
V. Kannan a,⇑, K. Ganesan b
a
Department of Civil Engineering, National College of Engineering, Tirunelveli, Tamil Nadu, India
b
Department of Civil Engineering, Sudharsan Engineering College, Sathiyamangalam, Pudukkottai, Tamil Nadu, India

h i g h l i g h t s

 Rice husk ash (RHA), metakaolin (MK) and their combination are used as cement replacement materials.
 The ternary systems of OPC, RHA and MK, enhance the mechanical properties of self compacting concrete.
 The RHA and RHA in combination with MK showed a considerable resistance against acid attack.
 Up to 30% the combination of RHA and MK as may be used as supplementary cement replacement materials.
 Strong interrelationship occurred between weight loss due to acid attack and Silica ratio of blended SCC.

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

Article history: In this paper, the durability properties of self-compacting concrete (SCC) containing rice husk ash (RHA),
Received 18 July 2013 metakaolin (MK) and a combination of MK and RHA (1:1 ratio) were evaluated and their relationships
Received in revised form 9 October 2013 discussed. The durability properties of the various mixtures were studied. The results showed that SCC
Accepted 31 October 2013
blended with RHA and a combination of RHA and MK showed a considerable improvement in durability
Available online 27 November 2013
than unblended SCC (100% OPC). However, the performance of SCC blended with MK was unsatisfactory
in an acid environment. In addition, it was found that resistance to acid attack was directly related to the
Keywords:
silica ratio (SR).
Self compacting concrete (SCC)
Rice husk ash
Ó 2013 Elsevier Ltd. All rights reserved.
Metakaolin
Chloride permeability
Acid attack
Silica ratio

1. Introduction ment), which can be reduced by the use of various mineral

Self-compacting concrete (SCC) was first developed in 1988 in
Japan as a partial response to the gradual reduction of skilled labor
in the construction industry. The concrete’s qualities can be
achieved without segregation and high deformability in three
ways, which consist of limiting aggregate content, ensuring a low
water-powder ratio and the use of superplasticizer [1]. Nowadays,
SCC is gaining much popularity throughout the world because of
some of its interesting structural properties [2]. However, it is
not completely accepted due to higher cost as well as the lack of
standard specifications and testing procedures. In most cases, it
is treated only as a special concrete [3]. The reason for the increas-
ing cost of SCC production is the use of higher powder content (ce-
⇑ Corresponding author. Tel.: +91 4630 261481, mobile: +91 9787211014; fax:
+91 4630 261108.
E-mail addresses: kannan_civil81@yahoo.in (V. Kannan), ganesanhari@yahoo.
com (K. Ganesan).
admixtures such as rice husk ash, fly ash, and metakaolin, etc. as
partial replacement of the cement. The mineral admixtures addi-
tions also improve the structural properties of the SCC as well as
reducing the CO2 emission [4,5].
RHA is an agro-waste and used as it enhances the excellent
properties of concrete; presently, it is well known as a cement-
replacing pozzolanic material and there are also a number research
projects being conducted on it. Usually, it can be obtained by burn-
ing rice husks at about 600–800 °C in a controlled manner, which
causes the formation of amorphous silica with a high surface area
[6]. Finely ground RHA is responsible for the high reactivity in ce-
ment and is used to reduce the porosity as well as the width of the
inter-facial transition zone (ITZ) [7,8].
However, when the replacement level of RHA is increased
(more than 10%), the high surface area decreases the workability
of the SCC [9,10]; this property is unfavorable when it comes to
generating the SCC. Therefore, to increase the workability and

0950-0618/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.conbuildmat.2013.10.050
226 V. Kannan, K. Ganesan / Construction and Building Materials 51 (2014) 225–234

Table 1 ratio of fine and coarse aggregate was fixed at 1.1, with a W/B (W/(C + RHA or
Sieve analysis and physical properties of fine and coarse aggregate. MK or RHA + MK) ratio of 0.55 and 2% of the superplasticizer; the only variable
was RHA and MK to OPC.
Sieve size (mm) Fine aggregate Coarse aggregate The mix design was carried out to produce SCC without segregation and bleed-
(% of passing) (% of passing) ing, with the target mean compressive strength of 38.5 N/mm2 (as M30 graded nor-
20 100 100 mal vibrated concrete) at 28 days. For this study, a total of seventeen concrete
12.5 100 90.1 mixtures (RHA, MK with a range of 0%, 5%, 10%  30%, and a combination of RHA
10 100 10.4 and MK with a range of 10%, 20%, 30% and 40% with one normal SCC) were prepared,
4.75 99.9 0.00 and all the mixtures satisfied the target mean strength. These mixes were desig-
2.36 99.1 0.00 nated as OPC (100%) and RHA5/MK5/RHA5 + MK5  RHA30/ MK30/RHA20 + MK20.
1.18 83.1 0.00 The mix proportions are presented in Table 2.
0.60 58.3 0.00 During the production of SCC, the mixing order is very important to obtain
0.30 10.0 0.00 homogeneity and uniformity in all mixtures [17–19]. Initially, the batching process
0.15 0.70 0.00 is carried out and all the materials were separately placed on a nonporous plate.
Pan 0.00 0.00 Mixing sequences consisting of FA and CA are mixed for 30 s in the laboratory mix-
Bulk density (kg/m3) 1752 1640 ing machine to achieve homogeneity, then about 50% of the mixing water is added
Specific gravity (g/cm3) 2.53 2.78 to the mixer machine and mixing is continued for one more minute. Thereafter, the
Water absorption (%) 2.01 0.36 mixing process is stopped to allow the aggregates to absorb the water for one min-
ute. Before adding the cement and admixtures (RHA or MK or RHA + MK), they are
mixed in the dry state, then added to the mixing drum. Finally, the SP is poured in
the remaining water and introduced to the mixture, and mixing is restarted for
quantity of the total cement replacement level of the SCC, the 5 min. The mixed concrete is assessed to check its fresh state properties and then
water-to-binder (W/B) ratio was increased with 2% superplasticiz- placed in the required molds for curing.
For all mixes, three specimens of 100 mm3 were cast for a compressive strength
ers (SP) and RHA was used with MK to make ternary blended SCC.
test; six specimens of 100 mm3 were cast for acid attack tests (H2SO4 and HCl); nine
MK is an amorphous material that is obtained by dehydrating cylindrical specimens with a diameter of 100 mm and height of 50 mm were cast
kaolin at a temperature of about 800 °C [11]. The high reactivity for permeability-related property tests (WA, Sorptivity and chloride penetration).
of MK with cement and its usability to accelerate the cement After casting, all of the specimens were left in their casts for 24 h and then they
hydration differentiates it from other pozzolanic materials [12]. It were unmolded and immersed in a water curing tank until they were required
for testing.
also accelerates the initial setting time and improves the mechan-
ical and transport properties, especially since it can also attain high
compressive strength at an early age [13,14]. 2.3. Testing methods

From the previous studies, concrete blended with RHA and MK
shows better performance in strength and in some properties of
durability. However, few studies have investigated the durability
of SCC containing RHA and MK, especially in an acid environment
[15]. Therefore, the objectives of this study were to investigate the
performance of binary and ternary blended SCC containing RHA
and MK in sulfuric and hydrochloric acid solutions. The effects of
RHA, in combination with and without MK, on durability were
determined experimentally. In addition, the relationships between
the various durability properties were explored. Furthermore, the
relationship between the silica ratio (SR) of the binder, SiO2/(Al2-
O3 + Fe2O3) and the resistance to acid attack on SCC was evaluated.
2. Materials and methods
2.1. Materials
Ordinary Portland cement (OPC) conforming to ASTM C 150 (Type1) was used.
The sieve analysis of fine aggregate (FA) and coarse aggregate (CA) was carried out
in accordance with the ASTM C136 standard provision. The results of the sieve anal-
ysis of FA and CA were tabulated in Table 1. The physical properties of FA and CA
were also presented in Table 1. Commercially available MK was used for this study.
Boiled fired RHA residue was collected from a modern rice mill. The mill-fired
husk residue ash was further burnt in a laboratory muffle furnace at a temperature
of 650 °C over a period of one hour [11]. The burnt material was ground in a labo-
ratory pulverizer with a disc diameter of 175 mm for 1 h to a mean particle size of
6.27 micron meters (lm) before it was used as a cement replacement material.
The physical and chemical analysis of OPC, RHA, and MK was carried out
according to relevant Indian standard (IS) code provisions. Superplasticizers (SP)
were used to increase the workability of SCC [16]. For this work, Sulphonated Nap-
thalene Polymers based SP with the specific gravity of 1.220–1.225 was used as a
high range water reducer (conforming to IS: 9103:1999 and ASTM-C-494 Type ‘F’
depending on the dosages used) to improve the performance of SCC.
2.2. Mix proportion and preparation of the specimens
The mix design, which was based on previous studies, was modified using EFN-
ARC guidelines [17]. In general, self-compactability can be greatly affected by the
material properties and the mix proportion. In the trail mix, the fine and coarse
aggregate contents are fixed so that self-compactability can easily be achieved by
adjusting the water powder ratio and the superplasticizer dosage only. From the
trail mix, a suitable mix proportion was taken for further study. In this study, the
To check the fresh state properties such as filling ability, viscosity, and passing
ability of concrete, slump flow, V-funnel, and L-box tests were conducted according
to European Federation of National Associations Representing the producers and
applicators of specialist building products for Concrete (or EFNARC) specifications
[17]. Mineralogical and mean particle size analyses of RHA and MK were carried
out by X-ray diffraction (XRD). In addition, Scanning electron microscopic (SEM)
with energy dispersive X-ray analysis (EDAX) were carried out to study the mor-
phological behavior of concretes.
The compressive strength, permeability related tests (WA, Sorptivity and chlo-
ride penetration) and the acid attack tests were conducted after 28 days of water
curing. The compressive strength tests were carried out according to IS 9013-1997.
Saturated water absorption values of RHA, MK and a combination of RHA and
MK blended SCC specimens were measured according to ASTM C 642 and previous
studies [20].
Three specimens were used for sorptivity measurement. Measurements of cap-
illary sorption were carried out using specimens preconditioned in the hot air oven
at about 50 °C until a constant weight was obtained. Then the concrete specimens
were cooled down to room temperature. As shown in Fig. 1, the test specimens
were exposed to the water on one face by placing them on a pan. The side faces
of the specimens were coated with epoxy resin. The water level in the pan was
maintained at about 5 mm above the base of the specimens during the experiment.
At suitable time intervals, each specimen was removed from the water, with ex-
cess water removed by damp paper towel, and then the specimen was weighed. It
was then replaced in the water and the stopwatch started again. The gain of mass
per unit area over the density of water is plotted versus the square root of the
elapsed time. The slope of the line of best fit of these points was taken as the sorp-
tivity value. The sorptivity values of RHA, MK and the combination of RHA and MK
blended SCC specimens after 28 days of water curing were evaluated by the follow-
ing expression (Eq. (1)):
i ¼ S t 1=2 ð1Þ
where i is the cumulative water absorption per unit area of inflow surface (m3/m2),
S is the sorptivity (m/s 1/2), and t is the time elapsed (s).
The chloride ion penetration in all SCC specimens was determined by a rapid
chloride ion penetration test (RCPT). The resistance to chloride ion penetration in
terms of total charge passed in coulombs of RHA, MK and the combination of
RHA and MK blended SCC specimens was measured according to the ASTM C
1202 standard.
The acid resistance of the SCC specimens was assessed by immersing them into
sulfuric acid (H2SO4) and hydrochloric acid (HCl) solutions. The specimens were
tested after 28 days of curing and all the specimens were cleaned using a brush,
in order to remove any loose material before testing. The initial weight was mea-
sured and then the specimens were immersed into either a 5% sulfuric acid
(H2SO4) or 5% hydrochloric acid (HCl) solution. A separate plastic beaker was used
for each specimen for identification purposes. The solutions were replaced at regu-
lar intervals (every week) to maintain a constant concentration throughout the test
 V. Kannan, K. Ganesan / Construction and Building Materials 51 (2014) 225–234 227

Table 2
Mix proportions of RHA, MK and combination of RHA and MK blended SCC.

Mix ID Mix description Mix systems W/B ratio Quantities (kg/m3)

Water Binder OPC RHA MK SP FA CA
M1 OPC (100%) Control 0.55 220 400 400 0 – 8 880 800
M2 RHA5 Binary 0.55 220 400 380 20 – 8 880 800
M3 RHA10 Binary 0.55 220 400 360 40 – 8 880 800
M4 RHA15 Binary 0.55 220 400 340 60 – 8 880 800
M5 RHA20 Binary 0.55 220 400 320 80 – 8 880 800
M6 RHA25 Binary 0.55 220 400 300 100 – 8 880 800
M7 RHA30 Binary 0.55 220 400 280 120 – 8 880 800
M8 MK5 Binary 0.55 220 400 380 – 20 8 880 800
M9 MK10 Binary 0.55 220 400 360 – 40 8 880 800
M10 MK15 Binary 0.55 220 400 340 – 60 8 880 800
M11 MK20 Binary 0.55 220 400 320 – 80 8 880 800
M12 MK25 Binary 0.55 220 400 300 – 100 8 880 800
M13 MK30 Binary 0.55 220 400 280 – 120 8 880 800
M14 RHA5 + MK5 Ternary 0.55 220 400 360 20 20 8 880 800
M15 RHA10 + MK10 Ternary 0.55 220 400 320 40 40 8 880 800
M16 RHA15 + MK15 Ternary 0.55 220 400 280 60 60 8 880 800
M17 RHA20 + MK20 Ternary 0.55 220 400 240 80 80 8 880 800

3.2. Fresh state properties

The fresh state properties of SCC containing RHA, MK or a com-

Fig. 1. Sorptivity test setup.
period. The specimens were weighed at regular intervals (every week) for 12 weeks.
At the end of the immersion period the total weight loss for each specimen was
calculated.
Water absorption was chosen as an indicator of durability and its correlation
with other durability properties was determined using linear and exponential
regression. In order to ascertain the type and nature of interdependence between
acid resistance (H2SO4 and HCl) and the silica ratio, SiO2/(Al2O3 + Fe2O3) the total
weight loss due to sulfuric and hydrochloric acid attack were correlated with the
silica ratio, SiO2/(Al2O3 + Fe2O3) by linear regression.
3. Results and discussion
3.1. Physical and chemical analysis of OPC, MK and RHA
The physical and chemical properties of the OPC, RHA and MK
that were tested are presented in Tables 3 and 4. Additionally,
the particle size distribution curve for the binding materials is pre-
sented in Fig. 2. From the particle size distribution curve, it is
clearly noted that RHA, MK and their combinations are finer than
OPC. It is also confirmed from the fineness and particle size of
the binder materials in physical properties results (Table 3).
The XRD patterns of RHA and MK that were used for this study
are shown in Fig. 3. By comparing with other sources [8,12,13,20],
XRD analysis showed that the RHA was mainly in amorphous silica
form; the MK was also in an amorphous form, but deviated slightly
to a crystalline form at an angle of 26.8092°. Silica in the RHA ini-
tially exists in an amorphous form, but may become crystalline
when rice husk is burnt about 650 °C for 1 h. In addition, the silica
in the RHA does not remain amorphous when combusted for a pro-
longed period (1 h) under oxidizing conditions and then the quartz
phase may be formed [21].
bination of RHA and MK were studied and are presented in Figs. 4–6,
respectively.
The slump flow values of SCC with RHA, MK, and RHA + MK are
shown in Fig. 4. From the results, the slump flow values for differ-
ent concrete mixes were calculated in the range of 495–740 mm.
According to values recommended by EFNARC for fresh state prop-
erties of SCC as presented (Table 5), all the mixtures examined fall
under the categories of slump flow classes 1 and 2 (SF1 and SF2)
except RHA30 and RHA20 + MK20 mixes. The SF1 and SF2 classes
in concrete mixes are used to indicate that these mixes are suitable
for applications such as deep foundation construction (SF1) and for
normal applications such as the building of columns (SF2). The
RHA30 and the RHA20 + MK20 mixes did not meet the EFNARC
standard specifications. From the results, it can be clearly noted
that the slump flow (or filling ability) value gradually reduced with
the increments of the replacement level of RHA, MK and RHA + MK.
This condition may be caused by the high reactivity and higher sur-
face area of RHA and MK when compared to OPC. It also may be
due to the lowest fineness modulus of fine aggregate (FA) (see
Table 1). Similar trends in the slump flow values were reported
in previous studies [7,12,22].
The V-funnel times for different concrete mixes appear in Fig. 5.
From the results, it can be noted that the V-funnel times varied in
the range of 3.9–8.4 s; all concrete mixes could be categorized into
the VF1 class except for the 20% RHA + 20% MK mix. According to
the EFNARC guidelines, a V-funnel time when exceeding 25 s only,
it is not recommended (Table 5). From the results, the V-funnel
times for all concrete mixes were satisfied this requirement.
The L-box test results are shown in Fig. 6. From the results, the
blocking ratio for different mixes varied from 0.59 to 0.94. A satis-
factory blocking ratio was observed in up to 15% RHA, 15% MK, and
30% RHA + MK mixes; the value of the ratio for the rest of the mixes
was found to be outside the EFNARC-recommended values. In a
previous study, Felekoglu et al. [23] concluded that a blocking ratio
from 0.6 to 1 is acceptable for SCC to obtain satisfactory filling abil-
ity. In this regard, all concrete mixes were satisfactory (that is,
within the prescribed range) except for the 30% MK mix. In sum-
mary, all of the mixes exhibited satisfactory fresh state properties
(according to the criteria established by EFNARC and previous
studies) except for the 30% RHA, 30% MK, and 20% RHA + 20% MK
mixes.
228 V. Kannan, K. Ganesan / Construction and Building Materials 51 (2014) 225–234

Table 3
Physical properties of OPC, RHA and MK.

Materials Bulk density in (g/cm3) Specific gravity Fineness passing Specific surface Area Mean particle size in
(g/cm3) 45l sieve (%) 2 2 micron meter (lm)
Loose Dense Blain’s in (m /kg) BET’s in (m /g)
OPC 1.18 1.27 3.13 86 318 – 23.4
RHA 0.46 0.51 2.08 91 943 36.47 6.27
MK 0.50 0.52 2.58 99 2350 – 3.79

Table 4
Chemical composition of OPC, RHA and MK (%).

Material SiO2 Al2O3 Fe2O3 CaO MgO Na2O K2O LOI

OPC (%) 20.25 5.04 3.16 63.31 4.20 0.08 0.51 3.08
RHA (%) 87.89 0.19 0.28 0.73 0.47 0.66 3.43 4.36
MK (%) 51.80 43.75 0.82 0.09 0.03 0.07 0.02 0.34

LOI- Loss on ignition.

Fig. 3. X-ray diffraction pattern of RHA and MK.

Fig. 2. Particle size distribution curve for OPC, RHA, MK and RHA + MK.
3.3. Compressive strength
From the results, it can be seen that SCC blended with MK and
MK + RHA have a higher compressive strength than normal SCC
(SCC with 100% OPC) (Fig. 7). The strength improvement of SCC
blended with MK deteriorates with age; a finding that is confirmed
by previous studies [6]. The compressive strength of SCC blended
with 15% RHA was higher than that of normal SCC. However, the
compressive strength of SCC decreased when the quantity of RHA
was greater than 20%. This may occur due to the decreasing work-
ability of the SCC blended with RHA, because of the higher surface
area of RHA and its relative water demand [13,14,24]. The adverse
self-compactibility of the SCC blended with RHA (exceeding 15%
RHA) may be responsible for permeable voids in the concrete
and a subsequent reduction in strength. This demonstrates the
benefit of using RHA in combination with MK to produce SCC with
a higher cement replacement of around 40% (20% MK + 20% RHA).
A comparison of the results shows that the compressive strengths
improved up to 15% with RHA, up to 20% with MK and up to 30%
with RHA + MK.
3.4. Water absorption
respectively) and was lower than that for unblended SCC (100%
OPC) [6]. However, SCC blended with RHA tended to show adverse
performance with respect to water absorption when the replace-
ment level exceeded 15% by weight of binder. This adverse perfor-
mance is attributable to RHA’s higher surface area, lower fineness
modulus value of FA, and subsequent water demand in the con-
crete mixing process in comparison with unblended SCC. With
fresh state SCC blended with RHA, the workability gradually re-
duced when RHA exceeded 15%. This reduction in the workability
of RHA-blended SCC creates voids on the concrete, and may be
responsible for subsequent poor resistance to water absorption.
3.5. Sorptivity
The sorptivity is a key parameter in controlling the liquid trans-
port in concrete and improving its durability [15]. From the test re-
sults, (Table 6), it can be seen that the sorptivity progressively
decreases with increasing RHA content up to 15%, MK content up
to 20% and RHA + MK content up to 30%. SCC blended with MK
and RHA + MK showed significant sorptivity due to the fact that
MK is finer than OPC, RHA and produce an additional calcium sili-
cate hydrate (C–S–H) gel. In addition, MK blocks existing pores and
alters pore structure [25], confirming that the addition of MK leads
to a reduction in the pore space. While considering RHA blended
SCC, the sorptivity values were increased for RHA20–RHA30 mixes.
It implies when the replacement levels of RHA exceed 15%, the mi-
cro pores may be developed on the concrete due to the lack of
workability than other mixes. It was also observed from the sorp-
tivity data that SCC specimens blended with 30% MK and 20%
RHA + 20% MK showed a 18.82% and 19.10% reduction in sorptivity
at 28 days respectively, compared to unblended SCC.

Results for permeability properties (water absorption, sorptivi- 3.6. Chloride penetration
ty, and chloride penetration) are presented in Table 6. When MK
and RHA + MK were used to partially replace OPC in SCC, the water Chloride penetration for all concrete mixes in terms of the total
absorption improved considerably (up to 30% and 40%, charge passed is also presented in Table 6. Results for chloride
 V. Kannan, K. Ganesan / Construction and Building Materials 51 (2014) 225–234 229

Fig. 4. Slump flow values for different mixtures.

Fig. 5. V-Funnel times for different mixtures.

Fig. 6. Blocking ratio (L-box test) for different mixtures.

penetration were compared with ASTM C1202 standards. As per 100 and 1000, 1000 and 2000, 2000 and 4000, and 4000 and
ASTM C1202, total charge-passed values of between 0 and 100, 5000 are considered to correspond with ‘‘negligible’’, ‘‘very low,’’
230 V. Kannan, K. Ganesan / Construction and Building Materials 51 (2014) 225–234

Table 5
EFNARC recommended values for fresh state properties of SCC.

Slump flow test V-funnel test L-box test

Slump flow classes Slump flow (mm) Viscosity classes V-funnel times (s) Passing ability classes Blocking ratio (H2/H1)
SF1 550–650 VF1 68 PA1 P0.8 with 2 bars
SF2 660–750 VF2 9–25 PA2 P0.8 with 3 bars
SF3 760–850

‘‘low,’’ ‘‘moderate,’’ and ‘‘high possibility’’ of chloride penetration,

respectively, through the concrete specimen. The chloride ion per-
meability of the SCC blended with RHA, MK and RHA + MK de-
creased up to 15%, 30% and 40%, respectively. The SCC blended
with MK and RHA + MK showed the best performance for chloride
ion penetration. The total charges passed values of 28.23, and
25.43 coulombs for SCC blended with MK and RHA + MK, respec-
tively, with these values being rated as ‘very low’ for chloride ion
penetration. As reported in previous studies [9,26], the resistance
to chloride ion penetration is significantly improved through the
pozzolanic reaction of MK with Ca(OH)2 and the discontinuity of
the porosity network due to the fineness and chemical properties
of the material. The mixtures with a higher content of MK and
RHA + MK (with high amounts of alumina contents) exhibited a
much better resistance to chloride ion penetration. From the re-
sults, it was also noted that the total charge passed for all blended
mixes were lower (in the category of low) than the unblended SCC.
Previous studies have also confirmed that the chloride ion perme-
ability of SCC with pozzolanic admixtures is lower than that of un-
blended SCC [27].
Fig. 7. Compressive strength of RHA and MK blended concrete.

Table 6
Permeability related properties of RHA, MK and combination of RHA and MK blended SCC.

Mix designation MK/RHA/MK + RHA (%) Water absorption (%) Sorptivity  106 (m/s1/2) Total charge passed by RCPT (C)
OPC (100%) 0 4.54 3.56 1486.28
RHA05 5 4.53 3.64 438.62
RHA10 10 4.1 3.43 389.18
RHA15 15 3.93 3.31 306.22
RHA20 20 3.92 4.06 876.96
RHA25 25 4.47 6.41 904.7
RHA30 30 4.92 9.2 1089
MK5 5 3.59 1.75 431.23
MK10 10 3.57 2.69 299.32
MK15 15 3.48 2.5 292.98
MK20 20 2.88 2.29 59.74
MK25 25 2.83 2.5 34.67
MK30 30 2.78 2.89 28.23
RHA5 + MK5 10 3.23 3.38 286.72
RHA10 + MK10 20 3.02 2.71 173.6
RHA15 + MK15 30 2.98 2.64 86.3
RHA20 + MK20 40 3.17 2.88 25.43

Fig. 8. Weight losses due to immersion in 5% sulfuric acid solution of (a) RHA concrete (b) MK concrete (c) RHA + MK concrete.
 V. Kannan, K. Ganesan / Construction and Building Materials 51 (2014) 225–234 231

more resistant against sulfuric acid attack than was SCC blended
with MK (Fig. 8). The lowest weight losses in SCC blended with
RHA, MK and RHA + MK were obtained at replacement levels of
25% for RHA, 5% for MK, and 40% for RHA + MK. From the results,
it can be also noted that the weight of the specimen increases grad-
ually between 7 and 14 days depending on the mix. Weight gain
may occur due to the filling of specimen pores by acid solutions.
Upon visual inspection (Fig. 9), it was clear that the surface of
the specimens in which SCC was blended with MK started to dete-
riorate after 2 weeks in the acid solution; the level of deterioration
gradually increased for up to 12 weeks. Weight loss and deteriora-
tion in specimen condition was greatest in the SCC blended with
MK due to the high concentration of alumina in MK, which pro-
duces calcium sulfoaluminate (ettringite). Previous studies have
confirmed that the formation of ettringite depends purely on the
reaction between alumina (Al2O3) and sulfate (SO4) and the ratio
of the two compounds [28]. The formation of ettringite leads to
expansion in the concrete, which causes disruption of the set ce-
ment paste [29]. In contrast, RHA and RHA + MK contain lower alu-
mina content with higher silica content compared to MK. It is also
confirmed by the EDAX spectra analysis results (Table 7). The SCC
blended with RHA and RHA + MK showed better resistance to sul-
furic acid attack for this reason.

Fig. 9. Deterioration of (a) RHA blended SCC, (b) MK blended SCC and (c) RHA + MK 3.8. Hydrochloric acid attack
blended SCC specimens after 12 weeks of immersion in 5% sulfuric acid solution.
The results of the blended SCC specimens exposed to 5% hydro-
chloric acid (HCl) solutions show that the lowest weight losses
Table 7 were obtained at the replacement level of 20% RHA, 5% MK and
EDAX spectrum results.
40% RHA + MK (Fig. 10). Similar to the sulfuric acid attack, SCC
Elements Mass (%) blended with RHA and RHA + MK performed best in the hydrochlo-
100% OPC 15% RHA 20% MK 15% RHA + 15% MK ric acid solution. SCC blended with MK was less resistant to the
hydrochloric acid compared to SCC blended with RHA and
CK 3.32 1.68 3.05 4.6
OK 18.75 30.56 21.57 15.3 RHA + MK. It was also observed that the weight loss for all mix-
Mg K 0.78 9.59 – – tures in the hydrochloric acid solution was lower than in the sulfu-
Al K 5.37 6.47 8.76 3.76 ric acid solution. Other than SCC blended with 30% MK, all
Si K 14.79 23.23 19.75 38.03 mixtures showed better resistance (lower weight loss) to the
Ca K 52.04 22.56 51.78 33.64
Fe K 3.07 4.77 4.94 –
hydrochloric acid attack than unblended SCC (100% OPC). This is
Cu K 1.88 – – 3.25 due to the fact that the RHA and MK in fresh state SCC reduce
KK – 1.14 – 1.43 the capillary pores by the formation of a new C–S–H gel from the
pozzolanic reaction and portlandite hydrate resulting from the ce-
ment hydration [30]. In the visual inspection, the differences in the
degraded state of the various specimens after 12 weeks of immer-
3.7. Sulfuric acid attack sion in 5% hydrochloric acid solutions were apparent (Fig. 11).
While most of the concrete mixtures had undergone a small
The results from the specimens exposed to 5% sulfuric acid change, the cubic form of the SCC-MK25 and the SCC-MK30 was
(H2SO4) showed that the SCC blends with RHA and RHA + MK were lost.

Fig. 10. Weight losses due to immersion in 5% hydrochloric acid solution of (a) RHA concrete (b) MK concrete (c) RHA + MK concrete.
232 V. Kannan, K. Ganesan / Construction and Building Materials 51 (2014) 225–234
Fig. 11. Deterioration of (a) RHA blended SCC, (b) MK blended SCC and (c)
RHA + MK blended SCC specimens after 12 weeks of immersion in 5% hydrochloric
acid solution.
3.9. Scanning electron microscopic (SEM) analysis
SEM images and the EDAX spectra of unblended SCC (100%
OPC), 15% RHA, 20% MK, and 15% RHA + 15% MK mixes are shown
in Fig. 12 and Table 7 respectively. From the SEM image in
Fig. 12(a), it can be observed that the unblended concrete sample
Fig. 12. Scanning electron microscopic (SEM) image of (a) unblended SCC (100% OPC), (b) 15% RHA blended SCC, (c) 20% MK blended SCC and (d) 15% RHA + 15% MK blended.
consisted of irregular particle with micro pores; this may be the
main reason for the poor performance in relation to strength and
durability compared to blended concretes. However, in the case
of the SEM images of blended concrete with RHA and MK
(Fig. 12b–d), it can be seen that the samples were not porous.
Due to the hydration progress, the pore structure of the RHA and
MK blended concretes were greatly reduced, giving a more uniform
structure than in the unblended SCC. The SEM image also shows
that the ettringite (a spine-like crystal present in unblended SCC)
is much reduced due to the pozzolanic reaction of RHA and MK
(see Fig. 12) [31]. From the EDAX spectrum analysis (Table 7), it
can be clearly noted that the silica content of blended concrete
with RHA and MK is greater than that of unblended SCC. The higher
silica content observed in the 15% RHA + 15% MK mix indicates
that a good pozzolanic reaction and synergic effect has occurred
in OPC + RHA + MK [32].
3.10. Relationships between durability properties and the effect of
silica ratio (SR)
The relationships between the various durability properties are
important in correlating mix formulations with long term durabil-
ity parameters [15]. The regression of water absorption with other
durability parameters shows a poor correlation for binary blended
SCC containing RHA + MK, whereas ternary blended SCC containing
RHA + MK showed a very good correlation between water absorp-
tion and the other durability properties (R2 = 56.03% with sorptiv-
ity, R2 = 99.60% with chloride penetration, R2 = 98.27% with weight
loss from sulfuric acid attack and R2 = 99.33% with weight loss
from to hydrochloric acid attack) (Table 8). This implies a beneficial
synergistic effect of RHA + MK replacement on different durability
related properties.
The synergic effect may have occurred because of the good
packing behavior of granular materials (RHA and MK) in cement,
as well as the cement hydration process. In previous studies
[12,33], it has been reported that the particle size of the pozzolanic
materials may play an important role in the packing density of the
concrete. Since the RHA and MK particle size (see Table 3 and
 V. Kannan, K. Ganesan / Construction and Building Materials 51 (2014) 225–234 233

Table 8
Regression between other durability properties (y) and Water absorption (x) of RHA, MK and RHA + MK blended SCC.

Mix Fit Sorptivity in Chloride penetration Weight loss due to Weight loss due to
(m/s1/2) In (C) H2SO4 in (%) HCl in (%)
RHA blended SCC Linear y = a + bx A 1.371  105 1.927  103 0.063 1.153
B 4.262  106 624.28 1.927 1.074
R2 0.41474 0.149 0.179 0.110
Exponential y = a  bcx A 5.811  104 1.2421  104 9.960 6.291
B 5.951  104 1.4692  104 6.017  1029 5.093  1015
C 0.992 0.947 3.933  108 1.100  104
R2 0.267 0.063 0.175 0.155
MK blended SCC Linear y = a + bx A 1.115  106 2.260  103 39.505 9.967
B 4.842  107 779.79 5.808 0.654
R2 0.475 0.880 0.706 0.125
Exponential y = a  bcx A 2.470  104 3.093  105 14.969 6.867
B 2.459  104 3.116  105 2.327  103 6.469  1018
C 0.998 0.997 0.140 2.730  107
R2 0.343 0.849 0.881 0.579
RHA + MK blended SCC Linear y = a + bx A 1.418  106 2.556  103 12.729 1.181
B 4.841  107 889.64 6.341 2.197
R2 0.525 0.997 0.740 0.911
Exponential y = a  bcx A 3.606  106 2.600  105 15.483 8.934
B 0.001 2.625  105 1.137  105 601.262
C 0.079 0.996 0.043 0.180
R2 0.560 0.996 0.982 0.993

Fig. 13. Relationship between weight loss due to sulfuric acid attack and silica ratio Fig. 14. Relationship between weight loss due to hydrochloric acid attack and silica
of RHA, MK and RHA + MK blended SCC. ratio of RHA, MK and RHA + MK blended SCC.

Fig. 2) is less than that of cement, RHA and MK can fill the cement
particle gaps effectively. It should also be noted that the synergic
effect may have occurred due to the effect of SCM’s (RHA and
MK) on the cement hydration process [7,12]. With the addition
of RHA to cement, the hydration is increased at a later stage [34],
whereas in MK blended cement, hydration increases earlier than
RHA [35]. Therefore, the combination of RHA and MK blended ce-
ment may increase the hydration at both the early and late stages.
This indicates that the combination of RHA and MK can have a
good synergic effect on the strength and durability properties of
SCC.
The linear regression of the total weight loss due to sulfuric acid
attack and the silica ratio (SR)(SiO2/Al2O3 + Fe2O3) shows that they
are well correlated with each other (R2 = 71.11% for SCC blended
with RHA, 82.53% for SCC blended with MK, and 99.85% for SCC
blended with RHA + MK) (Fig. 13). From the analysis, it is to be
noted that the sulfuric acid resistance is dependent on the SR for
RHA, MK, and RHA + MK blended SCC, implying that the SR signif-
icantly influences concrete’s resistance to sulfuric acid. While con-
sidering weight loss due to sulfuric acid attack for various mixes
(Fig. 8), considerable resistance against sulfuric acid attack was ob-
served in the SR range between 2.1 and 5.5. When the SR is less
than 2.1 (mainly obtained in MK-blended SCC), the sulfuric acid
resistance of concrete considerably decreased in this study and
deterioration occurred. Conversely, the correlation between SR
and weight loss due to hydrochloric acid attack is not perfectly cor-
related (R2 = 34.93% for SCC blended with RHA, 54.93% for SCC
blended with MK, and 80.23% for SCC blended with RHA + MK)
(Fig. 14). From this analysis, it is noted that the correlation be-
tween SR and weight loss due to HCl attack is strong only for
SCC blended with RHA + MK. In the same way, when considering
weight loss due to HCl attack (Fig. 10), all mixes showed stronger
resistance against HCl in comparison with unblended SCC (100%
OPC). Hence, the useful SR range for blended SCC with RHA, MK,
and RHA + MK to help maximize HCl acid resistance is from 1.7
to 4.8.
234 V. Kannan, K. Ganesan / Construction and Building Materials 51 (2014) 225–234
4. Conclusions
Based on the experimental studies presented in this paper, the
following conclusions may be drawn:
(1) As high as 40% by weight of OPC can be replaced with a com-
bination of RHA and MK without any adverse effect on the
durability of SCC.
(2) Replacement with 30% MK in blended SCC mixtures leads to
a beneficial improvement in the strength and permeability,
when compared to those of unblended SCC. However, in an
acid environment the SCC blended with MK gave an unfavor-
able performance.
(3) Even though the compressive strength of SCC blended with
RHA was lower than SCC blended with MK at a 30% replace-
ment level, it showed a beneficial improvement in durability
(especially acid attack).
(4) From the regression analysis, strong correlations were found
for SCC blended with RHA + MK as follows:
These strong correlations clearly indicate that the combination
of MK and RHA caused them to act as highly reactive pozzolanic
materials in SCC.
(a) Water absorption and chloride penetration (R2 = 99.73%).
(b) Water absorption and weight loss due to sulfuric acid attack
(R2 = 98.27%).
(c) Water absorption and weight loss due to hydrochloric acid
attack (R2 = 99.33%).
(d) The silica ratio and sulfuric acid attack (R2 = 99.85%).
(1) There was a good synergistic effect between RHA and MK on
the mechanical properties and durability of SCC. The SCC
mixture with 15% RHA and 15% MK was the most durable
and it may be considered as an optimum level of replace-
ment for OPC as supplementary cementitious materials.
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