11

CHAPTER 2
LITERATURE REVIEW
2.1 USE OF SECONDARY RAW MATERIALS IN CONCRETE
Manufacturing of PC is an energy intensive process and releases a
very large amount of green house gas into the atmosphere. It has been
reported that 13,500 million tons of PC are produced from this process, which
accounts for about 7% of the green house gas produced annually (Malhotra
2002). Concrete is a composite material which has a complex microstructure
and exhibits a wide range of scale lengths from nanometers to millimeters
(Garboczi 1993). Aggregates are the biggest materials in concrete and have
particle size in millimeters.
At the micrometer scale, the cement paste is a composite of
unhydrated residues of cement grains and hydration products (CSH, Ca(OH)
2
)
and capillary pore. Hydrated cement paste contains large capillary pores with
diameters between 5010,000 nm, medium capillary pores with diameters of
1050 nm and gel pores with diameter of less than 10 nm (Mindess et al
1981). It is well known that the service life of a concrete structure is strongly
dependent on its material transport properties, which are controlled by the
microstructure characteristics of concrete. It is generally recognized that the
incorporation of pozzolanic materials as a partial replacement for PC in
concrete is an effective means for improving the properties of concrete.
12
Pozzolanic materials react with calcium hydroxide during hydration
reaction and forms calcium silicate hydrate. This can reduce the size of the
pores of crystalline hydration products, make the microstructure of concrete
more uniform and improve the impermeability and durability of concrete.
These improvements can lead to an increase in the service life of a concrete
structure (Chindaprasirt et al 2007). The use of reactive RHA as
supplementary cementitious material may lead to reduction of the emissions
of carbon dioxide caused by the cement production. It can also improve the
mechanical and durability properties of concretes (Mehta 1994). Moreover,
the replacement of cement by RHA has another environmental advantage: the
carbon remaining in the ash, which could be released to the atmosphere
during a long storage period, is trapped in the concrete. The same effect of
RHA is expected in other SCMs such as fly ash and LP.
2.2 FLY ASH
2.2.1 General
Other than the environmental advantages fly ash improves the
performance and quality of concrete. Fly ash affects the plastic properties of
concrete by improving workability, reducing water demand, reducing
segregation and bleeding, and lowering heat of hydration. Flyash increases
strength, reduces permeability, reduces corrosion of reinforcing steel,
increases sulphate resistance, and reduces alkali-aggregate reaction. Flyash
reaches its maximum strength more slowly than concrete made with only
portland cement. As pozzolan greatly improves the strength and durability of
concrete, the use of ash is a key factor in their preservation.
Owing to its pozzolanic properties, fly ash is used as a replacement
for some of the Portland cement content of concrete (Scott Allan et al 2007).
The use of fly ash as a pozzolanic ingredient was recognized as early as 1914,
13
although the earliest noteworthy study of its use was in 1937 (Halstead 1986).
Use of fly ash as a partial replacement for Portland cement is generally
limited to Class F fly ashes. It can replace up to 30% by mass of Portland
cement, and can add to the concretes final strength and increase its chemical
resistance and durability. Recently concrete mix design for partial cement
replacement with High Volume Fly Ash (50 % cement replacement) has been
developed. Due to the spherical shape of fly ash particles, it can also increase
workability of cement while reducing water demand ().
2.2.2 Microstructure of fly ash
The SEM image of as-received fly ash and fine fly ash shows the
spherical shape of the fly ash particles as shown in Figure 2.1.
As-received fly ash Fine fly ash
Figure 2.1 SEM image of RHA (Chindaprasirt 2008)
It is generally realized that the use of fine fly ash improves the
properties of mortar and concrete (Erdogdu et al 1998, Lee et al 1999).
Although the porosity of the paste is increased as a result of the incorporation
of fly ash, the average pore size is reduced. This results in a less permeable
paste (Poon et al 1997, Chindaprasirt 2005). The interfacial zone of the
14
interface between aggregate and the matrix is also improved as a result of the
use of fly ash (Wong 1999, Kuroda 2000).
2.3 RICE HUSK ASH (RHA)
RHA is an agro-waste material abundantly available in all rice
producing countries. It constitutes 20% of the 500 million tons of paddy
produced in the world (Bhanumathidas et al 2004). It is reported that for every
ton of rice produced, approximately 0.23 tons of RH, which, on combustion
produces about 0.04 tons of ash (Das et al 1986 and Mehta 1986). Nowadays,
the rice-producing countries are challenged by the problem of disposing off
the rice husk, and have been trying to use it in an economical manner (Mehta
1994).
Studies on RHA for use as a pozzolan have been carried out during
the last three decades (Das et al, 1986, Goncalves et al 2007, Sharma et al
1984). Most of these studies concern ashes produced by controlled burning
conditions, at specified temperature, time of burning, heating rate, type of
furnace, and oxidizing conditions. In such conditions, a white highly reactive
pozzolan with non-crystalline silica, small carbon content, and high specific
surface area is produced.
2.3.1 Properties of RHA
The chemical composition of RHA is found to vary from sample to
sample. A number of studies (Goncalves et al 2007, Sharma et al 1984) have
reported the chemical composition of RHA obtained in different parts of the
world. The average particle size of rice-husk ash ranges from 5 to10m. RHA
is very rich in silica content. Silica content in RHA is generally more than 80-
85%.
15
For RHA to be used as pozzolan in cement and concrete, it should
satisfy requirements for chemical composition of pozzolans as per ASTM
C618. The combined proportion of silicon dioxide (SiO
2
), aluminium oxide
(A1
2
O
3
) and iron oxide (Fe
2
O
3
) in the ash should be not less than 70%, and
LOI should not exceed 12% as stipulated in ASTM requirement.
Most of the studies report that the organic content in RH is 72% of
the husk by weight, but with the wide variation of the constituents such as
cellulose, moisture content and ash as expected with any natural material.
Sharma et al. (1984) have analyzed the organic constituents in rice husk after
excluding silica and reported as in Table 2.1 and the chemical composition of
RHA as given in Table 2.2.
Table 2.1 Organic constituents in rice husk (Sharma et al 1984)
Constituents Amount present in rice husk (wt %)
-cellulose 43.30
Lignin 22.00
D-xylose 17.52
I-arabinose 6.53
Methylglucuronic acid 3.27
D-galactose 2.37
Total 94.99
16
Table 2.2 Chemical composition of RHA (Sharma et al 1984)
Weight of ash (%)
Constituents
Vietnamese USA South India
Silica (SiO
2
) 96.7 94.5 91.40
Alumina (Al
2
O
3
) 0.08 Trace 1.12
Iron oxide (Fe
2
O
3
) 0.03 Trace 0.54
Calcium oxide (CaO) 0.30 0.25 0.17
Magnesium oxide (MgO) 0.16 0.23 1.30
Sodium oxide (Na
2
O) --- 0.78 trace
Potassium oxide (K
2
O) 0.73 1.10 trace
Sulfur trioxide (SO
3
) 0.78 1.13 trace
Loss on ignition at 850

C 8.56 --- 5.40

2.3.2 Processing of RHA
Recently, a large amount of rice husk has been used as fuel to power
the boilers of modern rice milling factories. It is used to produce steam, either
for drying and parboiling (i.e., precooking) of the rice grains or for the
production of electricity in cogeneration systems. Within these processes, the
RHA generally has physical-chemical characteristics different from those of
the ones produced under controlled conditions (Stroven 1999). For example,
the burning temperature in the boiler, which should be less than 900C to
avoid the formation of a-cristobalite (a crystalline polymorph of quartz) (Jain
et al 1997), is not always effectively controlled. Moreover, if sufficient
oxygen is not available, and if the residence time for the husk in the boiler is
not long enough, organic material in the form of unburnt or partially burnt
rice husk, will remain within the bulk RHA after the burning process. It was
indicated by X-ray diffraction analyses (James et al 1986) that RHA by-
products from different parts of India presented silica in distinct phases.
Another study by Patel et al (1986) demonstrated the great variability in the
RHA characteristics, mainly carbon content and silica structure, of the by-
17
products generated in different rice plants in Brazil. Hence, RHA produced in
unsatisfactory conditions usually presents high-carbon content and a part of
silica in crystalline state, which could compromise its pozzolanic activity. In
this particular case, the mechanical ultrafine grinding of the RHA may
minimize the effect of the residual carbon and presence of the crystalline
compounds.
The use of RHA in concrete was patented in the year 1924 (Stroven
et al 1999). With proper burning and grinding, the amorphous reactive RHA
could be produced and used as a pozzolan. Rice husk consists of about 40%
cellulose, 30% lignin group and 20% silica and hence the ash contains a large
amount of silica (Mehta 1979). The silica exists in two forms: amorphous or
crystalline silica depending on the temperature and duration of burning. Silica
of amorphous form is reactive and suitable for use as a pozzolan to replace
part of PC. Amorphous silica is obtained by burning rice husk at temperature
lower than 700
o
C (Della et al 2002).
Even for higher burning temperature with some crystalline formation
of silica, good result could be obtained by fine grinding (Ismail et al 1996).
The reactive RHA can be used to produce good quality concrete with reduced
porosity and reduced Ca(OH)
2
(Zhang 1996). Combustion of rice husk with
fire duration of 30 minutes, air supply duration of 60 minutes and chilling
duration of 2 days was found to produce good quality ash (Zain et al 2010).
Air ducts in the furnace were useful in supplying necessary oxygen for proper
burning of rice husk and, thus, helped in producing good quality ash.
Although grinding for 30 minutes produced good result, grinding for 60
minutes or more is recommended for achieving standard fineness of RHA.
Deepa.G.Nair (2008) came to the conclusion that the most reactive RHA is
produced after incineration for 12 hours at 500C and subsequently quickly
cooling the sample down by directly removing it from the oven.
18
Effect of three parameters (acid treatment, temperature and heating
rate) on the formation of black (carbon fixed) particles in rice husk silica ash
was studied by Krishnarao et al (2001). The black particles in the rice husk
silica are due to the carbon fixed in them. This happens due to surface melting
of silica in the presence of K
2
O impurity. In the acid treated samples, the
impurity is removed and hence no carbon appears in the silica ash.
In untreated samples, rapid heating does not allow the oxidation of
carbon before the surface melting occurs, resulting in a higher amount of
black particles. On the other hand, slow heating allows oxidation of carbon
before surface melting of silica, resulting in a silica ash with negligible black
particles. Utilization of rice husk as a resource of silica is based on removal
of impurities with low effort. At present, rice husks are the raw material for
the production of a number of silicon based materials, including silicon
carbide, silicon nitride, silicon tetrachloride, pure silicon and Zeolite (Stroven
1999).
Matori (2009) informed that by heat treating RHA at 800 C for 2h,
all the carbon contained in RHA (black ash) was removed and an amorphous
white ash was produced. From XRD traces, it was shown that acid does not
affect the amorphicity of the silica. The peaks (cristobalite) obtained from
untreated husk was caused by the metallic elements that contained in the
sample which might affect the structure of SiO
2
.
2.3.3 Pozzolanic reactivity and pore structure refinement of RHA
The most important property of RHA that determines the pozzolanic
activity is its amorphous phase content. RHA is a highly reactive pozzolanic
material suitable for use in lime-pozzolan mixes and for PC replacement.
RHA contains a high amount of silicon dioxide, and its reactivity related to
lime depends on a combination of two factors, namely the non-crystalline
19
silica content and its specific surface area. Research on producing RHA that
can be incorporated to concrete and mortars are not recent.
In 1994, Mehta investigated the effect of pyroprocessing on the
pozzolanic reactivity of RHA. Reactivity of RHA is attributed to its high
content of amorphous silica, and to its very large surface area governed by the
porous structure of the particles (Sensale 2006, Mehta 1978, 1994, Cook
1984). Generally, reactivity is favored also by increasing fineness of the
pozzolanic material (James et al 1986, Kraiwood et al 2001, Paya et al 1995,
1997). However, Mehta (1979) has argued that grinding of RHA to a high
degree of fineness should be avoided, since it derives its pozzolanic activity
mainly from the internal surface area of the particles.
Similar to silica fume, RHA also contains about 90% silica by mass.
A well-burnt and well-ground RHA, with most of its silica in an amorphous
form and with N
2
-specific surface varying between 40 and 60 m
2
/g, and the
average particle size ranges from 5 to 10 m and is very active and can
considerably improve the strength and durability of concrete (Inoue et al
1996, Sugita et al 1997, Mazlum et al 1992).
Regarding the strengthening mechanism of RHA-blended concrete,
Sugita et al (1997) suggested that (i) the average pore size of RHA concrete,
compared with that of control concrete, is decreased; (ii) the practical water-
to-cement (w/c) ratio of RHA concrete is less than the used one because a
portion of free water has been adsorbed in the great number of mesopores
existing in RHA particles and having an average pore diameter of about 80;
(iii) cement hydration is improved; and (iv) more CSH gel may be formed in
RHA concrete due to the reaction that probably occurs between the silica in
RHA and the Ca
2+
, OH

ions, or Ca(OH)
2
in hydrating cement. However,
until now, no direct evidence for such a reaction has been observed.
20
By burning the rice husks under a controlled temperature and
atmosphere, a highly reactive rice ash is obtained (Zhang et al 1996, Sousa
Coutinho 2003). In fact the ash consists of non-crystalline silica and produces
similar effects in concrete as silica fume. However, unlike silica fume, the
particles of RHA possess a cellular structure as shown in Figure 2.2, which is
responsible for the high surface area of the material even when the particles
are not very small in size.
Figure 2.2 Cellular structures responsible for the high surface area
(Sousa Coutinho 2003)
The utilization of RHA as a pozzolanic material in cement and
concrete provides several advantages, such as improved strength and
durability properties, reduced material cost due to cement saving and
environmental benefits related to the disposal of waste materials and to
reduced CO
2
emissions.
2.3.4 Microstructure of RHA
Mehta (1987), showed the addition of fly ash or RHA, whose
particles are finer than those of PC will, in most cases, cause a segmentation
of larger pores and increase the number of nucleation sites for the
precipitation of the hydration products of the cementitious paste. This will
21
accelerate the reactions and form smaller calcium hydroxide crystals. The
chemical action of the pozzolanic reactions enhances the physical effects
because of the higher segmentation of pores and the refinement of CH grains
as the curing time progresses. The SEM image of as-received RHA and
ground RHA in Figure 2.3 shows the reduction in particle size by grinding.
Unground RHA Ground RHA
Figure 2.3 SEM image of RHA (Chindaprasirt 2008)
RHA has been used as a highly reactive pozzolanic material to
improve the microstructure of the Interfacial Transition Zone (ITZ) between
the cement paste and the aggregate in High Performance Concrete (HPC).
Mechanical experiments of RHA blended PC concretes revealed that in
addition to the pozzolanic reactivity of RHA (chemical aspect), the particle
grading (physical aspect) of cement and RHA mixtures also exerted
significant influences on the blending efficiency.
The relative strength increase relative to the concrete made with
plain cement, expressed in percentage is higher for coarser cement (Bui et al
2005). Results indicated that such a pozzolana can be produced with varying
pozzolanic activity index depending on the degree of grinding and the burning
22
temperature. The effect of RHA content as partial replacement of cement on
compressive strength and volume changes of different mixes was
investigated. Test results showed that up to 40% replacement can be made
with no significant change in compressive strength compared with the control
mix (Moyad et al 1984). It is also reported that the microstructure of the
cement paste can be significantly improved by adding RHA (Yu et al 1999).
Fig. 2.4(a) CSH gel observed in paste, 8,000x
Fig. 2.4(b) CSH gel formed in pores, 8,000x
Figure 2.4 SEM images of C-S -H gel in the paste with 10% (Yu et al 1999)
23
Figure 2.4(a) and Figure 2.4(b) show the SEM images of CSH gel in
the paste with 10% RHA added and hydrated at 20 1C for 28 days, with
CaO to SiO
2
molar ratio of about 1.43 determined by X-ray microanalysis (Yu
et al 1999). The high silicon content of RHA also makes it more favorable to
be used as part substitute for OPC in low cost concrete for rural housing
(Ajiwe et al 2000, Cisse et al 2000). The RHA rich in silicon content was
obtained by burning RHA to remove the volatile organic carbon such as
cellulose and lignin. Studies by James et al (1986) have shown that a
complete destruction of the organic matter from the RHA was achieved at a
minimum temperature of around 400
0
C. The silica exists in two forms:
amorphous or crystalline silica depending on the temperature and duration of
burning. Silica of amorphous form is reactive and suitable for use as a
pozzolan to replace part of PC. Amorphous silica is obtained by burning rice
husk at temperature lower than 700 C (Della et al 2002). With proper
burning and grinding, the amorphous reactive RHA could be produced and
used as a pozzolan. Even for higher burning temperature with some
crystalline formation of silica, good result could be obtained by fine grinding
(Ismail et al 1996).
The reactive RHA can be used to produce good quality concrete
with reduced porosity and reduced Ca(OH)
2
(Zhang et al 1996). RHA has
been used successfully in such applications as concrete with controlled
permeability formwork and roller compacted concrete (Coutinho 2003 and
Kajorncheappunngam et al 1992).The amorphous silica in the ash begins to
transform to crystalline, which does not exhibit pozzolanicity when the rice
husk was burnt at temperature above 750
0
C (Yu et al 1999, Hanafi et al 1980,
Ibrahim 1981).
The RHA contains strong concentration of silica occurring in
crystalline (quartz) and amorphous forms. The amorphous silica occurs
24
principally on the external face of the husk and in a lesser concentration on
the inner surface. This amorphous silica and to a lesser extent the fine grained
quartz explains the previously observed pozzolanic role. The crystalline silica
found on the husk before calcinations indicates that its presence, in the ash, is
probably due to contamination by sand. This material is an agricultural waste
product that is already used as a fuel source. From the above research works,
it can be concluded that this ash can be used as cement replacement thereby
achieving a more efficient use of resources.
It is proposed that a lightweight concrete can be produced by the
inclusion of rice husk into the mix, good material characteristics can be
achieved together with a reduction in density due to the husks fibrous nature
and its pozzolanic effect. Several research works have been conducted on the
use of RHA as mineral additive to improve the performance of concrete
(Jauberthie 2000). By blending RHA with coarser cement, higher packing can
be expected, leading to improved behavior of blended systems (Stroeven et al
2002).Similar to silica fume, RHA also contains about 90% silica by mass. A
well burnt and well-ground RHA, with most of silica in an amorphous form
and with specific surface varying between 40 and 60m
2
/g, is very active and
can considerably improve the strength and durability of concrete (Mazlum et
al 1992).
A thermal analysis (TG-DTA) was initially undertaken by Sousa
Coutinho (2003), on a sample of rice husk and the graph in Figure 2.5 was
obtained. Rice husk was incinerated in an oven at a heating rate of 10
o
C per
minute up to 650
o
C, maintaining this temperature for 8 hours, and then
allowed to cool down to room temperature and then the ash was grinded.
Figure 2.6 and 2.7 shows the particle size distribution and X-ray diffraction of
RHA (Sousa Coutinho 2003). SEM/EDAX testing was undertaken on samples
of RHA with a JEOL JSM 35C microscope system, NORAN, Voyager and
25
semi-quantitative standardless analysis was carried out and given in Figure
2.8. The specific gravity of the ash was also evaluated and a value of 2.15
g/cm
3
was obtained.
Figure 2.5 Thermal analysis curves for rice husk (Sousa Coutinho 2003)
Figure 2.6 X-Ray Diffraction of RHA (Sousa Coutinho 2003)
26
Figure 2.7 Particle size distribution of the RHA (Sousa Coutinho 2003)
Also Sousa Coutinho (2003) ascertained that using RHA as a partial
cement replacement enables higher compressive strength than control
concrete (0% RHA).
Figure 2.8 Semi-quantitative standardless analysis of rice husk
(Sousa Coutinho 2003)
27
Results of the rapid determination of chloride permeability of
concrete test by American Association of State Highway and Transportation
Officials (AASHTO) and of the CTH Rapid Migration test method show that
using RHA as a partial cement replacement drastically enhances resistance to
chloride penetration compared to control concrete (on average, around seven
times higher for the AASHTO test and about eight times higher for the CTH
method). The effect of using 10% cement replacement by RHA enhances
concrete performance.
2.3.5 Sulphate resistance of RHA blended concrete
Sulphate attack is one of the most important problems concerning
the durability of concrete structures. Under the sulphate environment, cement
paste undergoes deterioration resulting from expansion, spalling and softening
(Lauer 1990, Collepardi 2003). It is generally recognized that addition of
pozzolan reduces the calcium hydroxide in cement paste and improves the
impermeability of concrete. This helps to increase the resistance of concrete
to the attack of sulphate and other harmful solutions (Mehta 1994). The
increase in the service life of the structure made from the blended cement
containing pozzolan would further reduce the amount of PC use. The
knowledge of the use of lignite fly ash and RHA to increase the resistance of
concrete to the harmful solutions, especially sulphate solution, would be
beneficial to the understanding of the mechanism and to the applications of
these materials.
Chindaprasirt et al (2007) have studied the effect of sulphate attack
on blended cement. Based on the obtained data, it can be concluded that the
incorporation of lignite class F fly ash and ground RHA into normal PC result
in a significant improvement in the resistance to attack by 5% sodium
sulphate solution. Better dimension stability is obtained with blended cements
containing FA and RHA. Despite having higher water demand characteristics,
28
RHA at a dosage of up to 40% cement replacement is very effective in
providing sulphate resistance. Class F lignite fly ash is only slightly less
effective at both 20% and 40% replacement levels in comparison to that with
RHA. The pH levels of the sulphate solutions after immersion for 6 months
are significantly different, indicating the different levels of calcium
hydroxide. Fly ash and RHA mortar are of lower pH levels and thus less
susceptible to sulphate attack. SEM examination confirms that ettringite is not
a pronounced feature in the microstructure of the blended cement mortars
exposed to sodium sulphate solution, in comparison to that of PC mortar. Up
to 40% of PC could be replaced with fly ash and RHA in making blended
cement mortar with reasonable strength development and good sulphate
resistance. This would reduce the amount of PC use and the greenhouse gas.
Service life of the mortar would also be increased owing to the higher
sulphate resistance.
2.3.6 Corrosion resistance of RHA blended concrete
It is known that the corrosion of reinforced steel is an important
problem in the reinforced concrete structure. One of the most important issues
in the corrosion of reinforced steel is the ingress of chloride ion into concrete
(Veera Horsakulthai et al, 2011). Although reinforced steel embedded in
hydrating cement paste forms a thin passive film around the embedded steel
that tightly adheres to the steel and gives it complete protection from reaction
with oxygen and water, unfortunately the chloride ion can destroy the passive
film and initiate the corrosion of reinforced steel bar. This showed that the
resistance to chloride penetration of concrete increases with higher SCMs
replacement. This was due to the reduction of Ca(OH)
2
and the improvement
of pore size distribution resulting in the pore refinement to a narrower channel
and thus made it difficult for electrolyte flow to reach the embedded steel.
29
Saraswathy et al. (2007) carried out various electrochemical studies
on RHA blended concrete to understand the corrosion behavior of reinforcing
steel embedded in concrete and found that the incorporation of RHA up to
25% replacement level reduced the chloride ion penetration, decreased the
coefficient of permeability, improved the corrosion resistance properties.
Ganesan et al. (2008) reported that up to 30% of RHA could be
advantageously blended with cement without adversely affecting the strength
and permeability properties of concrete.
The enhancement of the resistance to chloride penetration is one of
the benefits of incorporation of pozzolans. It is generally accepted that
incorporation of a pozzolan improves the resistance to chloride penetration
and reduces chloride-induced corrosion initiation period of steel
reinforcement. The improvement is mainly caused by the reduction of
permeability/diffusivity, particularly to chloride ion transportation of the
blended cement concrete (Thomas et al 1999, Bijen 1996, Tumidajski 1996).
2.3.7 Strength and Workability of RHA blended concrete
Alireza Naji Givi et al (2010) showed that the use of RHA
especially with coarser average particle size reduces the water demand more
than fly ash mixtures. The workability observed from the slump test
increased from 50% to 100% for proportionate replacement of RHA from 5%
to 20%. Therefore, the cement particles are effectively dispersed and they
could trap large amounts of water that results in the reduction of water
requirement of the system to achieve an acceptable consistency. The particle
packing effect is also associated with the reduced water demand.
Partial replacement of cement with RHA improved workability of
fresh concrete for both 95m and 5m particle sizes. However, the RHA
with average particle size of 95m gave rise to higher slump values for
30
comparable cases. Ultimately it was found that 10% ultra fine RHA-blended
concrete could be considered as an optimum formulation because of its high
value of compressive strength, less water permeability and acceptable
workability. It is concluded that partial replacement of cement with RHA
improves the compressive strength and workability of concrete and decreases
its water permeability. In addition, decreasing RHA average particle size
provides a positive effect on the compressive strength and water permeability
of hardened concrete but indicates adverse effect on the workability of fresh
concrete.
Nasser et al (2010) concluded in their investigation that the rate of
clinker hydration governs the rate of pozzolanic reaction contribution to the
strength in the case of high reactivity pozzolanic materials. In the absence of
a superplasticizer the improvement in the strengths of cement blends is due to
the pozzolanic reaction and the improvement of the structure and morphology
of the hydration products in spite of the persistence of agglomerates.
Givi et al (2010) studied the effects of RHA particle size on
strength, water permeability and workability of binary blended concrete. They
reported that partial replacement of cement with RHA improved the
compressive strength and workability of concrete and decreased the water
permeability. In addition to that decreasing RHA average particle size
provides a positive effect on the compressive strength and water permeability
of hardened concrete but indicates adverse effect on the workability of fresh
concrete. The optimal level of RHA content for average particle sizes were
achieved with 10% replacement.
Therefore using RHA as a cement replacement material will pave
the way for large scale utilization in concrete thereby reducing the
environmental effects and also increases the service life of the structure.
31
2.4 LIMESTONE POWDER (LP)
2.4.1 Properties of LP
Giuseppe et al (2010) showed the effect of the extended exposure of
quicklime to water, confirming a shape change from prismatic crystals of
portlandite, Ca(OH)
2
, into platelike ones. The shape change and the broader
particles size distribution of portlandite crystals upon aging seem to contribute
to a better plasticity of lime putty. Voglis et al (2005) made a study in the
properties and hydration of PLC compared to those of other composite
cements and has informed that the cement containing limestone demands less
water than cements with pozzolana and fly ash. Limestone could be used
only as a filler (up to 3% w/w), but since 2001 (application of EN 197-1) it
can also be used as a main cement constituent. Pozzolana, fly ash, GGBS and
limestone are the main materials that are permitted by the EN 197-1 (2000).
The results of Menadi et al 2009 proved that up to 15% of fines (particles
whose diameters are less than 80m) content in crushed sand could be used
without adversely affecting concrete strength. It also reduces the water
permeability and increases the gas and chloride-ion permeability.
2.4.2 Strength and durability of LP blended cement concrete
Bentz, (2006) has informed that in 2004, the ASTM-C150 standard
specification for PC was modified to allow the incorporation of upto a 5%
mass fraction of limestone in ordinary PCs. Ramezanianpour et al (2009)
have concluded that the PLC concretes having up to 10% limestone, provide
competitive properties with PC concretes. Adding higher percentages of
limestone to cement produces less competitive concrete properties. The PLC
concretes indicate satisfactory compressive strength and generally demand
less water than PC concretes. Absorption decreases with the period of curing
and increases with the limestone replacement percentage. Also, there is no
32
significant difference between the absorption of specimens containing 0% and
5% limestone. PLC concretes decrease water penetration depth with
limestone contents up to 10%. The partial replacement of cement with
limestone reduces the electrical resistivity of concrete. PLC concrete
containing 10% and 20% limestone replacement have maximum and
minimum values respectively. Chloride ion permeability is increased
considerably when the water/binder ratio is increased from 0.37 to 0.55. For
the materials in this study, the optimum replacement of limestone is between
10% and 15%.
Arandigoyen et al (2007) studied the pore structure and mechanical
properties of cementlime mortars. From the results for Young's modulus, he
stated that the lime-rich mortars present a plastic zone that does not appear in
the other blended mortars. Therefore, lime-rich mortars are able to absorb a
high degree of deformation before the breakage. Due to this, these mortars
have great potential as materials for restoration work. They can accommodate
the movements of ancient buildings. Barbara Lothenbach (2008) from
their study on influence of limestone on the hydration of PCs reported that
blending of PC with limestone was found to not only accelerate the initial
hydration reaction but also to influence the hydrate assemblage of the
hydrating cement pastes.
2.4.3 Microstructure of LP
Arandigoyen et al (2006) studied the microstructure of blended
pastes of lime and cement. An increment of complexity of the microstructure
was found when pastes increased their percentage in cement. The porosity
decreases in a high degree with the increment of cement in the paste.
Study by Pipilikaki et al (2009) has proven that limestone, when
used in blended cements, changes hardened cements pore structure by
33
increasing the capillaries pore size from 20 nm to 40 nm when the maximum
amount (35%) of limestone that is allowed by EN 197-1 is used. On the other
hand, it reduces the threshold diameter of the paste and presents a more
uniform pore size distribution. This behavior can be attributed to the better
packing of particles due to the filling effect of the LP, indicating that chemical
species enter the hardened cement with difficulty but transport easier inside
the cement paste because the pores have approximately the same size.
Furthermore, a better performance against freezethaw and salt decay is
acquired. As gel pores are concerned, addition of limestone in cement
produces smaller gel pores and that is related to higher hydration rates.
Hence, the use of limestone in cement produces a material that is structurally
adequate to be used in construction.
Torres et al 2006 made a study on microstructure of 5-year-old
mortars containing LF damaged by thaumasite and informed that in OPC
prisms, the mode of attack changed with time, from being ettringite based at
early age to the thaumasite form of sulphate attack at later ages.
2.4.4 Sulphate and chloride resistance of LP blended cement concrete
Irassar (2009) had made a review on Sulphate attack on
cementitious materials containing LF and had come to the following
conclusion: External sulphate attack of mixtures containing LF is firstly
governed by mixture resistance to sulphate ions penetration. When LF is used
as cement replacement, effective w/c ratio is the main variable affecting ions
transport. Therefore, a low proportion (10%) of LF causes no significant
change in sulphate resistance of parent PC, while a large proportion (15%)
may worsen sulphate performance. Ghrici et al (2007) showed that the
penetration of chloride ion increases in concretes containing 15% limestone.
Also, Bonavetti et al. (2000) reported that the penetration of chloride ion
34
increased from 43% to 114% for concretes containing 10% and 20% of
limestone, respectively.
Studies by Skaropoulou (2009) have shown that the Ca/Al ratio
changes while the limestone replacement increases. This ratio for cement
pastes containing 0%, 10% and 20% limestone is 5.51, 7.1 and 13.62
respectively. Ye et al (2007) showed that small limestone particles still exist
in the pastes even after 28 days of hydration. Although the principal
hydration products in composite cements are almost similar to those found in
pure PC, the added minerals affect the ettringite transformation to
monosulphate hydrate. In limestone cements, 3CaO.Al
2
O
3
.CaCO
3
.11H
2
O is
formed from the first days of hydration and is still present after 28 days.
Bouasker et al (2008) made a study on the effect of LF and granular
inclusions on chemical shrinkage of cement pastes and mortars at very early
age. The study reported that the presence of LF causes an acceleration of the
chemical shrinkage and the hydration process since the very first hours. This
filler effect is generally explained by the supplementary surface area provided
by the filler particles, playing the role of nucleation sites for hydrates.
Consecutively, the Vicat setting time is also accelerated in the presence of LF.
Thomas Schmidt et al (2009) made a study on the physical and
microstructural aspects of sulphate attack on ordinary and limestone blended
PCs and reported, that damage due to sulphate interaction can result in the
cracking and softening, with loss of strength of the concrete. The role in such
damage of the precipitation of certain sulphate phases such as ettringite
(3CaOAl
2
O
3
3CaSO
4
32H
2
O), gypsum (CaSO
4
2H
2
O) and thaumasite
(CaSiO
3
CaCO
3
CaSO
4
15H
2
O) and the effect of internal carbonate such as
LF in cement is still not understood in detail.
35
The addition of 5% limestone in PC systems led to a decrease in
sulphate uptake due to its lower initial capillary porosity. Especially at
ambient temperatures (20C) the sulphate induced deterioration was reduced.
In the case of 25% limestone addition the initial porosity was increased and
the sulphate induced deterioration was accelerated. Skaropoulou et al (2009)
made a study on the thaumasite form of sulphate attack in limestone cement
mortars and the long term efficiency of mineral admixtures. The status of
the samples after a storage period of 5 years was reported based on visual
inspection, compressive strength, mass measurements, Ultrasonic Pulse
Velocity (UPV) measurements and analytical techniques. It is concluded that
the use of specific minerals, as partial replacement of cement, inhibits
thaumasite formation in limestone cement mortar. Limestone cement mortar
is susceptible to thaumasite sulphate attack at low temperature. The use of
specific mineral replacements retards thaumasite formation in limestone
cement mortar. The use of fly ash seemed to retard sulphate attack.
Performance of limestone cement mortars in a high sulphates
environment was studied by Pipilikaki et al (2009). The sulphates attack in
the case of the PC mortar in aggressive laboratory conditions is not obvious
even if deterioration products are present in porosity. The higher total porosity
and larger interconnected pores of limestone cement paste can explain this
difference. However, even if the clinker of both cements were the same, the
products of deterioration were actually different in the two mortars: in the
limestone cement mortar, mostly gypsum was formed due to the fact that
ettringite formation was restricted by the smaller amount of C
3
A, while in the
PC mortar mainly ettringite was formed. Hence, the addition of limestone in
the cement leads to a totally different behavior than PC with respect to the
resistance in high sulphates environment. Some authors (Sbabi et al 2004,
Maurenbrecher 2004) concluded that LF could increase the sulphate
resistance of cement, while other researchers (Lanas et al 2004, Manita et al
36
2003) found a decrease of sulphate resistance of this cement depending on the
replacement level and clinker composition.
Irassar et al (2005) studied on thaumasite formation in LF cements
exposed to sodium sulphate solution at 20
o
C have come to the following
conclusions:
1 The attack in mortars containing LF is characterised by an
inward movement of the reaction front leading first to the
formation of ettringite, later to gypsum deposition and finally to
thaumasite formation when the decalcification of the mortar
leads to the breakdown of CSH gel providing the required silica.
2. The reaction sequence in LF cement is essentially the same as in
the case of PC. The main change is that at later stages,
thaumasite is formed with decomposition of the first formed
ettringite.
The test results emphasized the negative effect of 10% to 30% LF
replacement of non-sulphate resistant Type I cement on the resistance of
mortar specimens when they are subject to sodium and magnesium sulphate
attack at ambient temperature. Gypsum formation as well as thaumasite
formation is primarily responsible for the deterioration of cement systems
incorporating higher replacement levels of LF under magnesium sulphate
attack.
Blanco-Varela (2006) made a study on effect of cement C
3
A
content, temperature and storage medium on thaumasite formation in
carbonated mortars. Thaumasite forms in mortars are made with C
3
A-low
cement, whereas mixed crystals or solid solutions of thaumasite and ettringite
form in mortars are made with high C
3
A content cements. The amount of C
3
A
is a parameter to be considered for internal and external sulphate attack in
terms of thaumasite formation. Low C
3
A cement produces higher amounts of
37
thaumasite than high C
3
A cement independent of immersion medium. Calcite
addition decreases thaumasite formation in samples of high C
3
A.
2.4.5 Carbonation of LP blended cement concrete
The carbonation of air lime mortars appears to affect the pore
structure of the mortars in two distinct ways (Robert M. Lawrence et al 2007).
There is an increase in the volume of pores at around 0.1 m in diameter
which is associated with the change of state of the binder from portlandite to
calcite. For pores smaller than about 0.03 m the difference in the volume of
pores penetrated between carbonated and uncarbonated mortar increases
monotonically with decreasing pore size. This is likely to be associated with
the attachment of calcite crystals to the surface of aggregate particles and
occasionally to the surface of portlandite crystals. Both of these phenomena
involve the reduction of pores larger than 0.1 m. This is significant because
pores below 0.1 m are not involved in the carbonation process. This is
therefore evidence of the self-limiting nature of the carbonation process, and
might explain why the carbonation of air limes can continue for many years.
Matschei et al (2007) gave the role of calcium carbonate in cement
hydration. Calcite additions affect the amount of free calcium hydroxide as
well as the balance between AFm (Monosulphate C
3
A.CaSO
4
.12H
2
O) and
AFt (Trisulphate C
3
A.3CaSO
4
.32H
2
O) hydration phases, although CSH is
unaffected in much of the range of compositions. Calcite has two functions,
one as an active participant in the hydration process, the other as inert filler.
The calculations also disclose that sulphate, liberated from sulfoaluminate in
the course of carbonation, reacts with water, calcium hydroxide, etc., with
formation of ettringite. The additional ettringite formation increases the molar
volume of paste solids and it is proposed that this mechanism can be deployed
to enhance the space-filling properties of paste, possibly leading to reduction
of porosity and permeability of hardened cement pastes. Finally, the study of
38
Li Beixing et al (2009) concludes that the durable concretes can be made from
sand with at least 10% limestone fines.
2.5 TERNARY AND QUATERNARY BLENDING OF SCMs
At all ages, the ternary blend of LF, Blast Furnace Slag (BFS) and
PC present an optimum strength, better than binary LF or BFS cement and
plain PC (Irassar et al 2005). It is attributed to the complementary behavior of
both admixtures: LF improves early strength while BFS improves later
strength by its cementing reaction. The isoresponse method highlights the
significance of the effect of the mineral addition and their interactions, and it
permits to obtain the optimum combination to make a composite cement that
meets with the standard or the user requirement regarding the environmental
regulations (energy saving and emission reducing). During the 1990s, the use
of cements made with Portland clinker and two additions, called ternary or
composite cements, has grown because they present some advantages over the
binary cements (Elkhadiri et al 2002).
According to Isaia's (1997, 1999) studies, when a less reactive
pozzolan is employed in ternary mixtures together with another more reactive
mixture such as silica fume or RHA, there is a synergy between these
pozzolans, thus the obtained result is higher than those verified in the
respective binary mixtures; this result is called synergic effect. This fly ash
effect may be explained by its physical effect, because it is related to the
cement grain deffloculation provided by fly ash which is higher than that
provided by silica fume or RHA particles.
This higher deffloculation increases the specific cement surface
contacting water, being enhanced by the electrokinetic potential (zeta
potential) between the particles. These mechanisms propitiate more quantity
of nucleation sites to begin the hydration reactions, and the final result would
39
be a higher amount of hydrated products and, consequently, higher calcium
hydroxide consumption, pozzolanic activity and, finally, unitary strength gain
(per mass unit of PC in the mixture) or the enhancement of other variables
linked with durability. The physical action enhances the chemical one, and the
concrete global performance is increased.
Chindaprasirt (2008) studied the effect of strength, porosity and
corrosion resistance of ternary blended PC, RHA and fly ash and found that
the corrosion resistance of ternary blend mortar is higher than that of mortar
containing single pozzolan. The use of ternary blend OPC, RHA and FA is
very effective in enhancing chloride induced corrosion of mortar. Figure 2.9
shows the time to initiation of crack of mortars subjected to ACTIV, as
studied by Chindaprasirt (2008).
Figure 2.9 Time to initiation of crack of mortars subjected to ACTIV
(Chindaprasirt 2008)
The improvement of chloride induced corrosion resistance of the
ternary blend OPC, FA and RHA mortar is thus the result of reduced
permeability and reduced calcium hydroxide, which is evidenced from Figure
40
2.9, where all the ternary mixes perform better than the binary mixes in the
ACTIV test (Chindaprasirt 2008).
Ghrici et al (2007) studied the mechanical properties and durability
of mortar and concrete containing Natural Pozzolana (NP) and limestone
blended cements, and arrived at the conclusion that the point of maximum
strengths is around 10% of LF and low NP replacement level at the early
ages. After 28 days, this point moves toward the high level of NP replacement
and low LF content. NP can be used to improve Hydrochloric acid (HCl)
resistance and LF can be used to improve Sulfuric acid (H
2
SO
4
) resistance.
Blent (2008) made studies on cement and mortar containing low-
calcium fly ash, LS, and Dolomitic Limestone (DLS) and came to the
conclusion that the compressive strength of the mortar gradually decreases
with the increasing fly ash content. However, incorporation of fly ash with LS
and DLS resulted in an increase in the strength of the mortar in comparison
with the FA mortar. Also the setting time and soundness of the fly ash, LS,
and DLS cements are satisfactory and similar to those observed in PC. When
combined in ternary system OPCfly ashDLS mortar, the expansion of
mortar prism decreases as the DLS content increases.
Weerdt et al (2011) studied the synergy between fly ash and LP in
ternary cements. The findings were that LP interacts with the AFm and AFt
hydration phases, leading to the formation of carboaluminates at the expense
of monosulphate and thereby stabilizing the ettringite. The effect of LP on
OPC may be restricted due to the limited amount of aluminate hydrates
formed by the hydration of OPC. The additional aluminates brought into the
system by fly ash during its pozzolanic reaction amplify the mentioned effect
of LP. This synergistic effect between LP and fly ash in ternary cements is
confirmed in this study and it translates to improved mechanical properties
that persist over time.
41
The presence of limestone leads to the formation of mono- or
hemicarboaluminate hydrates instead of monosulphoaluminate hydrate and
stabilizes thereby the ettringite. This leads to an increase in the volume of
hydrates and a subsequent decrease in porosity and an increase in strength.
Fly ash, on the other hand, can provide additional aluminates which will
lower the sulphate/aluminate ratio and thereby amplify the impact of the
limestone.
The effect of the presence of 5% LP seems to be more pronounced
for the fly ash cements than for the ordinary PC. As the fly ash reacts,
aluminates are liberated by dissolution of fly ash, thereby decreasing the
sulphate/aluminate ratio. Therefore more ettringite will decompose after
sulphate depletion and react with the additional aluminates to form calcium
monosulphate hydrate. The presence of limestone will then have a larger
impact as this will stabilize the ettringite by reacting with the additional
aluminates provided by the fly ash to form calcium carboaluminate hydrates.
The net result is more ettringite, more chemically bound water and a larger
volume of hydrates leading to less porosity and thereby higher strength, i.e. a
true synergistic effect exists and can be used to advantage.
Pipilikaki et al (2009) made a study of the hydration process of
quaternary blended cements and durability of the produced mortars and
concretes. Blended cements have a lower amount of C
3
A due to the reduction
of clinker. This is the first factor that controls sulphate resistance.
Furthermore, the blended cements contain pozzolanic additives that react with
portlandite reducing it in that way so that it would not react with sulphates.
The conclusion of the above study is that quaternary blended cements can
perform as well as cement as far as compressive strength are concerned and
they produce durable mortars and concretes.
42
2.6 SULPHATE ATTACK ON SCMS
2.6.1 General
Sulphate attack is one of the most important problems concerning
the durability of concrete structures. Under the sulphate environment, cement
paste undergoes deterioration resulting from expansion, spalling and softening
(Collepardi 2003). Sulphate attack is defined as deleterious action involving
sulphate ions. If sulphates interact with cement and cause damage to it, the
action is physical and a similar action can occur with salts other than
sulphates. Then the damage is considered to be physical attack or physical
sulphate attack (Maltais et al 2002). Calcium sulphate reacts with C
3
A to
form ettringite and reacts also with sodium and potassium hydroxides (Adam
Neville 2004). Magnesium sulphate reacts with all products of hydration of
cement; the important resulting compounds are calcium sulphate and
magnesia. Calcium sulphate can proceed to react with C
3
A. Concrete
subjected to sulphate attack can undergo a progressive and profound
reorganization of its internal microstructure (Maltais et al 2002). Concrete
exposed to negligible sulphate concentrations (i.e., soils containing less than
0.1% of water soluble sulphate or solutions for which the SO
4
concentration is
less than 150ppm) are relatively vague.
Deterioration of concrete by sulphate attack is commonly observed
in structures exposed to soil and ground water containing a high concentration
of sulphate ions (Hanifi Binici et al 2005). Sulphate resistance of blended
cements were significantly higher both against sodium sulphate and
magnesium sulphate attacks than ordinary Portland cements. Generally the
compressive at 3, 7, 28, 90 and 180 days and sulphate resistance of blended
cements are investigated and the reduction ratio in compressive strength is as
given in Equation 2.1.
43
Reduction ratio in compressive strength = S
solution
/ S
w
(2.1)
where,
S
solution
= average compressive strength of specimen cured in pure water.
S
w
= average compressive strength of specimen cured in test solution.
Compressive strength is the main feature that allows an appreciation
of cement quality. Compressive strength of mortars decreases roughly by 50%
showing the significance of sulphate attack.
2.6.2 Actions on Calcium Hydroxide[CH] (Menashi D. Cohen et al
1988)
Sodium Sulphate (Na
2
SO
4
) and Magnesium Sulphate (MgSO
4
) can
react with Calcium Hydroxide (Ca(OH)
2
) to produce gypsum (CSH
2
), Sodium
hydroxide and magnesium hydroxide or brucite.
Ca(OH)
2
+ Na
2
SO
4
+ 2H CSH
2
+ NaOH (2.3)
Ca(OH)
2
+ MgSO
4
+ 2H CSH
2
+ Mg(OH)
2
(2.4)
Formation of gypsum is known to be destructive. It is also indicated
in the literature that damage due to gypsum formation is limited to a softening
action. The gypsum in Equations 2.3 and 2.4 can react with hydrated calcium
aluminates (i.e.C
4
AH
13
), hydrated calcium sulpho aluminates (i.e.
monosulphate C
4
ASH
12-18
), or unhydrated tricalcium aluminates (C
3
A) as
shown in Equations 2.5, 2.6 and 2.7.
C
4
AH
13
+ 3 CSH
2
+ 14H C
6
AS
3
H
32
+ CH (2.5)
C
4
ASH
12-18
+ 2CSH
2
+ (10-16)H C
6
AS
3
H
32
(2.6)
C
3
A + 3CSH
2
+ 26H C
6
AS
3
H
32
(2.7)
44
Formation of trisulphate hydrate or ettringite C
6
ASH
32
is believed to
be expansive by crystal growth/crystallization pressure mechanism.
2.6.3 Mechanism of Sulphate Attack
The term sulphate attack denotes an increase in the volume of
cement paste in concrete or mortar due to the chemical action between the
products of hydration of cement and solution containing sulphates. When
hardened concrete is exposed to soil or ground water containing sulphate
compounds, the sulphates in solution are likely to react with hydrated C
3
A in
the hardened cement paste to form a new chemical called ettringite. This new
compound causes expansion and disruption of the concrete. It is therefore
necessary to limit the permeability of concrete, to reduce the penetration of
the sulphates in solution. Sulphate attack is again related to the permeability
of the concrete. Solid salts do not attack the concrete severely but when the
chemicals are in solution they find their entry into porous concrete and react
with the hydrated cementing products.
Of all the sulphates, magnesium sulphate causes maximum damage
to concrete. A characteristic whitish appearance is the indication of sulphate
attack. The deteriorating effect usually starts at the surface and corners and
progressively enters into the concrete by causing scaling and spalling and
finally reduces the concrete into a friable mass. The attack of sodium
sulphate on concrete is due to two principle reactions: the reaction of Na
2
SO
4
and Ca(OH)
2
to form gypsum and the reaction of the formed gypsum with
calcium aluminate hydrates to form ettringite. The formed gypsum from the
above two reactions react with calcium aluminate hydrate (C
4
AH
13
) and
calcium monosulpho aluminate hydrate (C
4
ASH
12
) to form ettringite (Hekal
et al 2002).
45
The typical reaction is shown in Equations 2.8 and 2.9.
Ca(OH)
2
+ Na
2
SO
4
.10H
2
O CaSO
4
.2H
2
O + 2NaOH + 8H
2
O (2.8)
4CaO.Al
2
O
3
.19H
2
O + 3(CaSO
4
.2H
2
O) + 16H
2
O
3CaO.Al
2
O
3
.3CaSO
4
. 31H
2
O + H
2
O (2.9)
The extent to which the first stage reaction proceeds depends on the
ambient condition and the concentration of sulphates. Gypsum also forms
calcium sulpho aluminate directly as per the second stage of the reaction. MS
has a far more reaching action than other sulphates because it reacts not only
with calcium hydroxide and hydrated calcium aluminates like other sulphates
but also decomposes the hydrated calcium silicates completely.
The products gypsum and calcium sulpho aluminates have a
considerably greater volume than the compounds they replace; and hence the
chemical reactions with sulphates lead to expansion and disruption of the
concrete. Because of the very low solubility of magnesium hydroxide this
reaction proceeds to completion, so that under certain conditions, the attack
by MgSO
4
is more severe than other sulphates. The rate of sulphate attack
increases with the increase in the strength of solution.
A saturated solution of MgSO
4
can cause serious damage to
concrete with higher water cement ratio in a short time. However, if the
concrete is made with low water cement ratio, the concrete can withstand the
action of magnesium sulphate for 2 or 3 years. The most aggressive chemical
that affects the long term durability of concrete structures are the chlorides
and the sulphates (Shannag 2002). The rate at which the hardened cement
paste is deteriorated due to the exposure to harmful chemicals depends mainly
on the concentration of chemicals in water, the time of exposure and the
chemical resistance of the concrete.
46
2.6.4 Modes of sulphate attack
The first mode of deterioration is akin to eating away of the
hydrated cement paste and progressively reducing it to cohesionless granular
mass leaving the aggregates exposed. This type of deterioration may lead to
reduction in the cross-sectional area of the structural component (i.e., loss in
weight of concrete) and decrease in strength. This mode of failure is attributed
mainly to the formation of gypsum, and is known as the acidic type of
sulphate attack. The second mode of deterioration, which is normally
characterized by expansion and cracking takes place when the reactive
hydrated aluminate phases, present in sufficient quantities, are attacked by
sulphate ions, thereby forming tricalciumsulfo aluminate hydrate, also called
ettringite or Candlots salt. The third mode of sulphate attack is the onion
peeling type that is characterized by scaling or shelling of the surface in
successive layers in the form of delamination.
2.7 WATER SORPTIVITY
When a homogeneous porous material has a constant hydraulic
potential at wet front, liquids can mount to considerable heights due to the
capillary absorption. If evaporation takes place, equilibrium between capillary
absorption and evaporation is reached at a certain height. This is the measure
of water sorptivity. Water absorption is a measure of permeability, which in
turn is the measure of durability. The absorption coefficient of concrete is
found to decrease, when the compressive strength of concrete increases
(Canan 2003). Absorption coefficient of concrete is very sensitive to the
curing condition. The effect of curing condition on the sorptivity coefficient
of concrete seems to be higher in low strength concretes. Curing environment
has a significant influence on sorptivity development. In general water-cured
concrete gives lower sorptivity than equivalent concrete that has been air
cured (Bai 2002).