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Blended cements
Historical developments
The term blended cement is defined as a hydraulic binder
composed of Portland cement and one or more inorganic
materials that take part in the hydration reactions. It is
generally understood that the term blending bestows a
product with some superior property over the original
constituents. Similar is the case with blended cements which
denote those Portland cements which have been blended
with some mineral addition in fairly large proportion. Blended
cement is a hydraulic cementitious product, characteristically
similar to the portland cement, but from many considerations,
a vastly improved product.
The concept of blending natural siliceous materials in
lime mortar and concrete is age-old, and can be traced to the
ancient history. Romans and Greeks have utilised this concept
to construct monumental structures. They found that finelyground volcanic ashes, when mixed with lime and water,
result in giving stable and durable structures. Even after two
millennia, a number of ancient structures, including the
Pantheon and the Colosseum, stand testimony to the ancient
wisdom of the Romans and the Greeks.
1009
1010
OPC
PPC
PBFS
Others
Total
93.61
56.06
24.50
10.34
0.71
(62.02)
(26.17)
(11.05 )
(0.76)
57.68
32.29
11.89
0.74
(56.32)
(31.53)
(11.61)
(0.74)
102.4
Fly ash
In India, fly ash is available in abundance. It is estimated that
nearly 80-90 million tonnes of fly ash is annually produced
from around 75 major coal-based thermal power stations.
Out of this only a small fraction is today fruitfully utilised.
The availability of the ground granulated blast furnace slag
in the country is limited and most of it is currently utilised by
the cement manufacturers in the production of PSC. Besides
this, condensed silica fume has recently been used but its use
has remained limited to high performance concretes.
Amongst the remaining two SCMs, high reactive metakaolin
is just being made available commercially, while rice husk
ash is yet to be commercialised. Thus, there is a considerable
scope to further increase the use of fly ash in construction,
including the enhancement of the share of fly ash-based
PPC. It may therefore be worthwhile here to have a look at
some of the salient aspects of fly ash as a material.
Fly ash is a solid fine-grained material resulting from the
combustion of pulverised coal in power stations. It is a waste
product of a power plant and the ash is collected in mechanical
1011
10
11
12
Specific gravity
2.35
2.31
2.39
2.32
2.52
2.17
2.17
2.30
2.38
2.15
2.28
2.43
3400
5475
6670
5620
4200
4130
3340
3500
3250
3305
3825
3850
88
87
81
84
78
80
83
71
68
77
75
81
45
89
44
43
27
40
53
61
29
61
60
54
Chemical composition
SiO2
55.5
55.9
55.8
57.0
50.1
60.7
59.8
56.4
54.1
54.7
56.0
53.0
Al 2O3
28.9
32.3
33.0
31.9
25.8
29.0
26.4
25.2
21.9
31.1
30.8
26.0
Fe2O3
4.1
5.5
4.3
4.2
9.7
4.3
7.0
6.4
6.2
3.6
4.0
5.2
CaO
1.8
1.7
1.9
2.0
3.7
1.2
1.7
1.9
1.9
0.6
0.6
0.8
MgO
0.6
1.1
1.0
1.0
0.8
0.9
1.1
1.1
1.1
0.2
0.2
0.2
LOI
5.5
0.4
0.8
0.7
7.8
0.7
0.9
5.4
11.7
6.9
5.7
12.2
SO3
0.1
0.1
0.3
0.3
1.0
0.1
0.1
0.1
0.1
0.2
0.2
0.2
Na 2O
0.01
0.07
0.11
0.12
0.29
0.08
0.07
0.09
0.09
0.15
0.11
0.08
K 2O
1.55
0.72
0.96
0.94
0.84
1.00
1.22
1.87
1.70
1.40
1.21
1.16
Characteristics
13
14
15
16
17
18
19
20
21
22
23
24
Specific gravity
2.16
2.55
2.23
2.34
1.95
2.32
2.35
3.04
2.63
2.28
2.27
2.8
7300
4530
3325
3765
3500
3655
3225
3085
3670
3910
3675
5460
95
83
80
79
76
80
81
82
93
80
73
53
57
53
52
20
25
24
54
57
60
49
44
Chemical composition
SiO2
59.7
58.0
58.1
61.1
60.0
59.8
59.1
55.4
62.0
60.8
65.4
Al 2O3
25.5
28.2
23.6
22.3
21.9
29.1
30.4
28.8
26.8
21.0
19.5
Fe2O3
3.7
4.4
5.1
6.1
8.8
4.3
4.1
3.2
6.1
6.8
4.1
CaO
1.0
3.4
3.4
0.8
0.9
0.7
0.6
1.0
1.2
3.2
0.6
MgO
0.7
0.4
0.6
0.8
0.6
0.8
1.0
1.2
0.8
1.5
0.1
LOI
5.9
3.3
5.9
5.5
6.5
1.7
1.1
7.2
0.8
4.2
4.2
0.3
SO3
0.1
0.1
1.0
0.2
0.1
0.1
0.1
0.1
0.2
0.1
Na 2O
0.13
0.05
0.18
0.12
0.11
0.06
0.05
0.07
0.07
K 2O
1.65
0.77
0.74
1.05
1.00
1.32
1.25
0.90
0.64
1012
Fig 1 Water requirement of fly ashbased cement and OPC for equal
workability in concrete 10
Workability
The small and relatively spherical fly ash particles in blended
cement act as solid particulate plasticiser and hence influence
the rheological properties of the cement pastes, causing a
reduction in the water requirement. Thus, there is an
improvement in the workability when compared with that
of an equivalent paste of OPC. This improved workability, in
turn, allows a reduction in the amount of water used in the
concrete when fly ash-based cement is used, Fig 1. As
compared to the OPC concrete the reduction of water
requirement is 7.59.4 percent10. Thus, at lower water content
the concrete made using fly ash-based cement would show
higher compressive strength characteristics. The use of fly
ash-based cement also shows reduced segregation and
bleeding. This can be attributed to the more cohesive concrete
mix obtained with fly ash-based cement.
Heat of hydration
The hydration chemistry of the cementitious minerals is based
on a reaction between acidic and basic constituents, which
manifests their courses of dissociation and/or associations to
formulate into mineralogical phases, which render strength,
hardness and impermeability to the matrix.
OPC hydration
The tri-calcium silicate (C3S) and di-calcium silicate (C2S) get
hydrated to form a family of calcium-silicate hydrates, which
are structurally similar but have different CaO/SiO2 ratios
and varied content of chemically-combined water. Complete
reaction of hydration of the phases to produce the ultimate
reaction product can be shown as follows:
2C3S + 6H
C3S2H3 + 3CH
2C2S + 4H
C3S2H3 + CH
CSH
1013
50 55 cal /g at 3 days
65 68 cal / g at 28 days.
This low heat of hydration of these cements can be used
to good advantage during hot-weather concreting.
Incorporation of fly ash reduces the temperature rise in
concrete almost in direct proportion to the amount of OPC
replaced, partially by delaying heat evolution and partially
by reducing the total heat evolved. However, the fly ash
absorption levels in cement needs to be optimised to balance
the compressive strength and heat of hydration requirements
at different ages.
Improvement in durability
One of the most important benefits of using fly ash-based
cement is the improvement in the long-term durability of
concrete structures resulting mainly from the lower
permeability of concrete and improved microstructure of
concrete.
Pozzolanic action
In hardened concrete, calcium hydroxide (CH) is weaker than
calcium silicate hydrates (CSH), and the presence of CH is
known to be contributing to many durability problems.
Pozzolanas, which are siliceous or siliceous and aluminous
materials possess little or no cementitious value but will, in
finely-divided form and in the presence of moisture,
chemically react with calcium hydroxide at ordinary
temperatures to form compounds possessing cementitious
properties. This secondary pozzolanic reaction increases the
amount of C-S-H at the expense of CH. Also, C-S-H formed
is denser. The presence of CH can also cause many other
problems and these are mitigated in concrete containing
pozzolanic materials.
Coefficient of
Average pore
permeability,
radius, A o
-11
10 cm/s
(age: 180 days ) (age: 90 days)
Chloride
Electrical
diffusivity,
resistivity
-9
10 cm/s
k ohm-cm
(age: 90 days) (age: 120 days )
OPC
8.70
240
24.5
13.14
FAC
1.77
166
4.1
29.08
1014
Fig 3 Free calcium hydroxide content Fig 4 Heat of hydration of OPC and fly
of cement pastes at different ages of ash-based cement at different ages of
hydration 10
hydration 10
(a)
(b)
(c)
(d)
Corrosion resistance
A plethora of literature is available on the phenomenon of
premature deterioration due to corrosion of
13,14,15
. It is well known that if the concrete cover
reinforcement
over the reinforcement is sufficiently thick and impermeable
it provides adequate resistance to corrosion. The protective
effect of concrete is both physical and chemical and functions
in three ways :
(i) it provides alkalinity in the vicinity of the steel.
(ii) it provides physical and chemical barrier to the ingress
of moisture, oxygen, carbon dioxide , chlorides and
other aggressive chemicals
(iii) it provides electrical resistivity around the steel.
The corrosion process of the reinforced steel can be
described in a simplified way by an equivalent electrical circuit
11
and the corrosion current (Icorr) can be expressed as
lcorr =
Uc Ua
Ra + Rc + RL
where,
Icorr = corrosion current ,
1015
Reactions
++
Anode : 2 Fe( s ) 2 Fe + 4e
Oxygen
Resultant effect
Corrosion of steel .
Formation of
2 Fe ++ + 4OH 2 Fe(OH ) 2 protective
passive film of
Cathode: H: 2O + O2 + 4e 4OH
nano-meter
thickness of iron
hydroxide / oxides
Chloride
(2 Fe ++ + 2Cl ) + 2 H 2O 2 Fe(OH ) 2
+ 2 H + + 2Cl
In presence of oxygen at anode
6( Fe ++ + 2Cl ) + O2 + 6 H 2O 2 Fe3O4
+ 2 H + + 2Cl
The chloride acts as a catalyst
in the corrosion of steel
and generates again to
continue corrosion reaction
Attack on hydrated pastes
Ca (OH ) 2 + MgCl 2
Chloride ions
breakpassivating
film formed on the
steel
External penetration
causes differential
concentration and
sets up micro-cell.
Presence of microcells increases
ectrical
conductivity
CaCl 2 + Mg (OH ) 2
CaO. Al 2O2
CaCl 2 .10 H 2O
C-S-H + Mg
CO2
Reduces alkalinity of
pore increasing risk
of corrosion.
Releases more water
1016
corrosion
Corrosion probability
> 20000
More negative
Negligible
10000 to 20000
Low
More positive
5000 to 10000
High
than - 220
Very high
Active
than - 270
- 220 to - 270
Passive
Active or passive
Friedel salt
Friedel salt
Resistivity,
ohm-cm
<5000
3CaO. Al 2 O3 + CaCl 2 + 4 H 2O
Cement
type
Total chlorides
addition
percentage
Cl in
pore
percentage
Unbound chlorides
percentage of total
Cl-
2.43
OPC
0.6
74.4
50.7
2.43
FA-cement
0.6
44.1
33.9
2.43
OPC
1.2
94.1
61.8
2.43
FA-cement
1.2
64.4
49.3
14.0
OPC
0.61
8.1
11.6
14.0
FA-cement
0.6
11.7
8.3
14.0
OPC
1.2
38.4
24.4
14.0
FA-cement
1.2
33.5
23.3
1017
1018
R = (C-5)/F
where, C = CaO , F = Fe2O3 contents of the fly ash.
The selection of fly ashes (25 percent absorption level) in
terms of R limits for sulphate resistant concretes are reported
to be as follows :
R Limits
Sulphate resistance*
< 0.75
Greatly improved
0.75 - 1.5
Moderately improved
1.5 - 3.0
No significant change
> 3.0
Reduced
These results indicate that the low lime class F fly ashes
are compositionally better suited for improved sulphate
resistance of the resultant concrete.
As a preventive measure for sulphate attack, it is essential
that the concrete has low permeability and is not prone to
cracking on account of shrinkage, thermal effects, corrosion,
etc20. Further, additional safeguards need to be provided by
the use of SCMs or fly ash-based blended cement. It should
be noted that merely by controlling the chemistry of cement
( such as low C3A content) it is not possible to provide longterm protection to permeable concrete subjected to moderate
to high sulphate attack.
and volcanic or artificial glasses and the second with quartzbearing rocks. Amongst these two types, ASR is the most
widespread.
It is widely recognised that three conditions must be
present to initiate and sustain AAR in concrete. These are:
sufficient alkalis in concrete; aggregate containing an alkalireactive component; and high moisture level within the
concrete. The source of alkalis in concrete could be either
from the cement, from alkali-bearing aggregates used in the
concrete, or from external source, say for example, from use
of deicing salts. The moisture level needed for the reaction to
occur need to be very high, say of the order of over 80-85
percent relative humidity. High ambient temperature to
which concrete is subjected to during service is sometimes an
important causative factor. Some aggregates which are
normally relatively unreactive, reportedly showed
o
o
deleterious expansion at temperature of 35 - 40 C.
Alkalis in hardened concrete react with the reactive
aggregates forming high volume gel products. Although the
actual reactions are still to be understood completely the
common accepted formations are summarised below:
Fig 14 Sulphate resistance of concrete at different Rvalues of fly ash23
Reactive silica
of aggregates
alkalis
alkali silicates
1019
Concluding remarks
The aspects discussed in the paper illustrate that the use of
low-lime fly ash in cement and concrete is beneficial in view
of the ecological and energy saving benefits on the one hand
Acknowledgement
The authors would like to thank the management of ACC
for permitting to use the laboratory investigation results
included in the paper. Particular thanks in this regard are due
to Mr Ashok K. Tiwari, Manager, Concrete Division, ACCRCD, Thane.
References
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The Indian Concrete Journal, July 2000, Vol 74, No. 7, pp. 383-393.
2. ______Indian standard code for blast furnace slag based blended cement, IS 455
: 1989, Bureau of Indian Standards, New Delhi.
1020
3. ______Indian standard code for flyash based blended cement, IS 1489 : 1991 Part
I, Bureau of Indian Standards, New Delhi.
4. ______Indian standard code for plain and reinforced concrete,IS 456: 2000, Bureau
of Indian Standards, New Delhi.
17. ______Technical data sheet on pulverised fuel ash for concrete, United
Kingdom Quality Ash Association.
18. ______Results of the work done in ACC-RCD laboratory on the evaluation of
fly ash-based cement, Internal report, Research & Conslutancy Directorate,
The Associated Cement Cos. Ltd, Thane.
19. SARASWATHY,V. , MURALIDHARAN,S., THANGAVEL, K. and SRINIVASAN, S, Activated
fly ash cements . Tolerable limits of replacements for durable steel concrete.
Advances in Cement Research, January 2002, Vol. 14, No. 1, pp 9-16.
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of Concrete, Edited by Jan Skalney, The American Ceramic Society, pp. 105130.
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Leon Monterrey, March 1981, pp. 35-50.
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the sulphate resistance of concretes, Cement, Concrete and Aggregates, Vol 2,
1980, pp. 20-30.
24. BHATTY, M.S.Y and GREENING N.R . Some long time studies of blended cements
th
with emphasis on alkali aggregate reaction, Proceedings of the 7 International
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on expansion due to ASR, 3rd Beijing International Symposium, Cement Concrete,
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ACI Materials Journal, 1987, 84, No 6, 525 553.
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1021