Chapter 2

LITERATURE REVIEW

2.1 Introduction
Concrete is the most widely used building material now-a-days. Its properties greatly depend on
the proportions and properties of its constituents. As cement is the major component of concrete
and usually has relatively low unit cost, the selection of its proper type and use has vital
importance in obtaining the balance of its desired properties in most economical way for any
particular concrete mix. Type I/II Portland cements, which can provide sufficient levels of
strength and durability, are the most common cements used by concrete users. However, some
situations require the use of special cements to provide advanced levels of properties. For
example, the need for high-early strength cements in pavement repairs and the use of blended
cements in hostile environments with aggregates subjected to alkali-aggregate reactions are
examples of such situations. The selection involves the exact knowledge of the connection
between cement and performance required and, in particular, between kind of cement and either
strength or durability or both the properties of concrete.
ASTM C 150 defines Portland cement as "hydraulic cement (cement that not only hardens by
reacting with water but also forms a water-resistant product) produced by pulverizing clinkers
consisting essentially of hydraulic calcium silicates, usually containing one or more of the forms
of calcium sulphate as an inter ground addition." Clinkers are small balls (diameters, 5-25 mm)
of a fused material that is formed when a raw mixture of prearranged composition is heated to
very high temperatures. The low cost and common availability of the limestone, shale and other
naturally occurring raw materials make Portland cement one of the most economical materials
extensively used over the previous century throughout the world. Concrete becomes one of the
most adaptable construction materials available in the world. The production and composition of
Portland cements, its hydration processes, and its chemical and physical properties have been
frequently studied and researched, with numerous reports and papers written on all aspects of
these properties.

10

2.1.1 Cement manufacturing process

Since calcium silicates are the primary constituents of Portland cement, the raw material for the
production of cement must provide calcium and silica in suitable forms and proportions.
Naturally occurring calcium carbonate materials such as limestone, chalk, marl, and sea-shells
are the common industrial sources of calcium, but clay or dolomite (CaCO3.MgCO3) are usually
present as impurities. Clays and shales, rather than quartz, are the preferred sources of additional
silica in the raw-mix for making calcium silicates because quartizitic silica does not react easily
with lime.
Clay minerals contain alumina (Al2O3), iron oxide (Fe2O3), and alkalies. The presence of
aluminum, iron and magnesium ions, and alkalies in the raw mix has a mineralizing effect on the
formation of calcium silicates; that is, they facilitate the formation of the calcium silicate at
considerably lower temperatures than would otherwise be possible. Therefore, when sufficient
amounts of iron and alumina minerals are not present in the primary raw materials, these are
purposely incorporated into the raw mix through addition of secondary materials such as bauxite
and iron ore. As a result, besides the calcium silicate compounds, the Portland cement clinker
also contains aluminates and aluminoferrites of calcium (Mehta & Monteiro 1993). To facilitate
the formation of the desired compounds in Portland cement clinker it is necessary to homogenize
the raw-mix before heat treatment. That is why the materials are subjected to a series of crushing,
grinding, and blending operations. From chemical analyses of the stockpiled materials, their
individual proportions are determined by the compound composition desired in the clinker; the
proportioned raw materials usually inter ground in ball or roller mills to particles below 75 m.
In the wet process of cement manufacture, the grinding and homogenization of the raw mix is
carried out in the form of slurry containing 30 to 40 percent water. Modern cement plants favors
the dry process, which is more energy efficient than the wet process because the water in the
slurry must be evaporated before clinkering. For the clinkering operation, the dry-process kilns
equipped with multi-stage suspension pre-heaters, which permit efficient heat exchange between
hot gages and the raw-mix, require a fossil-fuel energy input on the order of 800 kcal/kg of
clinker compared to about 1400 kcal/kg for the wet-process kilns. Figure 2.1 shows a simplified
11

Figure 2.1 Manufacture of Portland cement.

12

flow diag
gram of the wet & dry processes
p
fo
or Portland ccement manuufacture. Ann aerial view
w of a
modern cement
c
plantt is shown in
n Figure 2.2.

Figure 2.2 Aerial vieew of a moddern cement pplant

mical reactio
on taking plaace in the cem
ment kiln maay be expresssed as follow
ws:
The chem
Limesstone

CaO
O + CO2

Clay

SiO2 + Al2O3 +

-----------------Fe2O3 -------

((2.1)
((2.2)

3CaaO. SiO2
2CaaO. SiO2

Clay + Limestone

------------------- ((2.3)

3CaaO. Al2O3
3CaaO. Al2O3.Fee2O3
n the Portlaand cement manufacturiing process consists off pulverizingg the
The finaal process in
clinker to
o an averagee particle beetween 10 an
nd 15 m. T
The operation is carried out in ball m
mills,

13

also called finish mills. Approximately 5 percent gypsum or calcium sulfate is usually inter
ground with clinker in order to control the early setting and hardening behavior of the cement.

2.2 Types of Portland cement

Different types of Portland cement are manufactured to meet up various physical and chemical
needs for definite purposes, such as durability and high-early strength. In order to facilitate the
discussion, a list of various generic types of Portland cement produced around the world is
summarised in Table 2.1. It is to be noted that the descriptions given in this Table are very
general and National Standards may have specific limits for the contents of constituents and
there may be several different sub-types of cement with different levels of pulverised fuel ash
and ground granulated blast-furnace slag and mixes of slag, pulverised fuel ash and limestone
powder.
The composite cements are those in which a proportion of the Portland clinker is replaced by
industrial by-products, such as Ground Granulated Blast-Furnace Slag (GGBS) and pulverised
fuel ash (pfa, also known as fly ash), certain types of volcanic materials (natural pozzolans) or
limestone. Table 2.2 gives the characteristics of the constituents of composite cements. In
addition, microsilica (MS) and metakaolin (MK) are also used as supplementary cementitious
material in concrete to improve various physical and durability properties of concrete. The
characteristics of MS and MK are summarized in Table 2.3.

14

Table 2.1 Main types of cement produced around the world (Shetty 1982)
Type

Designation

BS EN
notation
CEM I

Constituents

Normal
Portland cement

Pure

Sulphateresisting
Portland cement

Pure

BS EN
197-4

Low C3A clinker and

calcium sulphate

Pure

CEM I

Portland
pulverised fuel
ash cement

Composite

CEM II

Special low iron

content clinker and
calcium sulphate
Clinker, pulverised
fuel ash and calcium
sulphate

Portland slag
cement

Composite

CEM III

Portland
limestone
cement
Pozzolanic
cement

Composite

CEM II

Composite

CEM II

Masonry
cement

Composite

BS EN
413-10

White Portland
cement

Clinker and calcium

sulphate

Applications
All types of
construction except
those exposed to
sulphate exposure.
Concrete exposed to
sulphate attack.
Architectural finishes.

All types of
construction, where
concrete is required to
have improved sulphate
resistance and
protection against
alkali-silica reaction,
mass concrete.
Clinker, granulated
All types of
blast-furnace slag and construction, where
calcium sulphate
concrete is required to
have improved sulphate
resistance and
protection against
alkali-silica reaction,
mass concrete.
Clinker, limestone and All types of
calcium sulphate
construction.
Clinker, natural
pozzolan and calcium
sulphate

All types of
construction,
particularly where
concrete is to improve
the durability.
Clinker, limestone and Brickwork, blockwork
air-entraining agent
and rendering.

15

Table 2.2 Nature of composite cement constituents (Newman & Choe 2003)
Constituents
Reaction type

Natural pozzolan
Pfa
Pozzolanic

SiO2 (%)
Al2O3 (%)
Fe2O3 (%)
CaO (%)
MgO (%)
SO3 (%)
Na2O (%)
K2O (%)
Loss of ignition (%)
Specific gravity
Specific surface area
(m/kg)

60-75
10-20
1-10
1-5
0.2-2
<1
0.5-4
1-6
2-12
2.30-2.80
300-600

38-64
20-36
4-18
1-10
0.5-2
0.3-2.5
0.2-1.5
04-4
2-7
2.30
300-600

Ggbs
Latently
hydraulic
30-37
9-17
0.2-2
34-45
4-13
0.05-0.2
0.2-1
0.3-1
0.02-1
2.90
300-500

Limestone
Hydration
modifier
3
0.5
0.5
51
2
0.3
0.2
0.1
42
2.70
400-900

Table 2.3 Characteristics of Microsilica and Metakaolin (Newman & Choe 2003)
Oxides (%)
SiO2
Al2O3
Fe2O3
CaO
MgO
SO3
Na2O
K2O
Loss of ignition
Specific gravity
Specific surface area (m/kg)

Microsilica
92.0
0.70
1.23
0.30
0.21
0.33
1.23
0.82
3.18
2.20
15000-20000

16

Metakaolin
52.1
41.0
4.3
0.09
1.4
0.01
0.62
0.48
2.40
12000-15000

The mineralogical composition of cement used in special purposes varies, as can be seen from
Table 2.4. In this table, the typical chemical composition of normal, sulphate resisting and white
Portland cements is summarised.
Table 2.4 Typical composition (%) of normal, sulphate-resisting & white Portland
cement ((Newman & Choe 2003)
Normal
SiO2
20.4
Insoluble residue
0.6
Al2O3
5.1
Fe2O3
2.9
CaO
64.8
MgO
1.3
SO3
2.7
Na2O
0.11
K2O
0.77
Loss of ignition
1.3
Free lime %
1.5
LSF %
96.6
SR %
2.55
AR %
1.76
Calculated mineral composition
C3S
57
C2S
16
C3A
9
C4AF
9

Sulphate-resisting

White

20.3
0.4
3.6
5.1
64.3
2.1
2.2
0.10
0.50
1.3
2.0
97.3
2.33
0.71

24.6
0.07
1.9
0.3
69.1
0.55
2.1
0.14
0.02
0.85
2.3
95
11.2
6.3

62
12
0.9
16

67
20
4.5
0.9

2.3 Physical properties of Portland cement

ASTM C 150 has notified certain requirements regarding physical properties for each type of
cement. These properties comprise: (i) fineness (ii) specific gravity (iii) soundness, (iv) standard
consistence, (v) setting time, (vi) compressive strength, (vii) heat of hydration and (viii) loss of
ignition. All of these properties have an effect on the functioning of cement in concrete. Out of
these properties only those which are important are discussed in the following section.

17

2.3.1 Fineness of cement

Fineness of cement is the total surface area of cement grains available for hydration. It
determines the level of grinding of cement clinker in grinding mill of plant and affects the rate of
hydration. Greater the fineness more is the surface available for hydration, resulting greater early
strength and more rapid release of heat (the fineness of Type III is greater than that of Type I
cement) (U.S. Department of Transportation 1990). The Wagner Turbidimeter and the Blaine air
permeability test for determining cement fineness are both required by the American Society for
Testing Materials (ASTM) and the American Association for State Highway Transportation
Officials (AASHTO). Average value of fineness of modern cement ranges from 3,000 to 5,000
cm2/g (Higginson 1970).

2.3.2 Specific gravity

Specific gravity is not a sign of the quality of the cement, but is required for calculations during
concrete mix design. The specific gravity of Portland cement is approximately 3.15 (Neville
1995).

2.3.3 Soundness
Soundness refers to the capability of the cement paste to maintain its volume after setting, and is
associated with the existence of extreme amounts of free lime or magnesia in the cement or
supplementary cementitious material. A cement paste should not undergo a large change in
volume once it has been set. However, some expansion may occur due to gradual hydration or
due to some other reactions of some compounds there in the hardened cement, namely free lime,
magnesia and calcium sulfate. Free lime absorbs moisture and expands many times to its original
volume and develops considerable heat and thus causes disintegration of concrete in which this
cement is used. Expansion in OPC is limited to 10 mm or 0.5%.

18

It is essential that cement concrete does not undergo large changes in volume after setting. This
change in volume is known as unsoundness and may cause cracks, distortion and disintegration
of concrete. Bektas et al. (2008) investigated the effect of Portland cement fineness on the results
of ASTM C1260 tests. He concluded that mortar-bar expansion was promoted with increased
cement fineness regardless of clinker alkali, aggregate reactivity or soak solution normality.

2.3.4 Standard consistency

Consistency indicates the degree of density or stiffness of cement. Therefore, it is necessary to
determine the amount of water content for a given cement to get a mixture of required
consistency. Consistency of cement is measured by vicat apparatus. The paste is said to be of
standard consistency, when the penetration of plunger, attached to Vicat apparatus, is 33-35 mm.
The moisture content of the standard paste is written as a percentage by weight of the powdered
cement. The normal range is between 26-33%. This test precedes the test of cement for
soundness, setting time, tensile strength or for compressive strength (Neville 1995).

2.3.5 Setting Time

To enable the concrete to be laid in position properly the initial setting of cement should not start
too quickly. Once the concrete has been laid it should harden rapidly so that the structure could
be put to use early. Initial setting of cement is that step in the process of setting, after which if
any cracks appear do not reunite. Final setting is that when it has occurred, sufficient strength
and hardness is attained.
As soon as water joins the cement, it forms gel that causes the paste to stiffen. However, this
stiffening does not affect workability until initial set takes place. Thus, setting describes The
strength of the cement paste. Setting may also be understood as setting refers to a
transformation from a fluid to a hard state. During setting, the paste attains some strength. But it
is different from hardening, which refers to the increase of strength of a set cement paste.The
setting process is associated with temperature changes in the cement paste. Initial set is related to
a quick increase in temperature and final set to the highest temperature. Setting time decreases
19

with rise in temperature. Setting time of cement can be increased by adding some admixture, as
sodium carbonate. The setting time of cement is measured using vicat apparatus with different
penetrating attachments.

2.3.6 Compressive Strength

The compressive strength of concrete is one of the most important mechanical properties. In
most structural applications, concrete is employed primarily to resist the compressive forces. In
those cases where other stresses (for e.g. tensile) are of primary importance, the compressive
strength is still frequently used as a measure of the resistance because this strength is the most
convenient to measure. For the same reason, the compressive strength is generally used as a
measure of the overall quality of the concrete, when strength itself may be relatively
unimportant.

2.4 Chemical composition of Portland cement

Different types of cements are differentiated from each other on the basis of their chemical
composition. ASTM C 150 imposes the standard chemical needs for each type. AST defines the
following phase compositions in Portland cement: tricalcium silicate (C3S), dicalcium silicate
(C2S), tricalcium aluminate (C3A), and tetracalcium aluminoferrite (C4AF). However, these
phases would occur at an equilibrium state of all constituents in the mix and do not present
effects of burn temperatures, quenching, oxygen availability, and other practical kiln conditions.
The actual compounds are mostly multifaceted chemical crystalline and amorphous
compositions, named by cement chemists as "elite" (C3S), "belite" (C2S), and different forms of
aluminates (Mehta & Monteiro 1993). The performance of each type of cement depends on the
concentration of these components. Role of these compounds, their hydration behaviour, and
their effect on the behaviour of cements are given in full detail in literature. Some of the most
comprehensive references regarding the chemistry of cement consists of those written by Bogue
(1955), Taylor (1964), and Lea (1970). Various analytical methods such as X-ray diffraction and
analytical electron microscopy are used by scientists in order to explain in detail the reaction of
cement with water (hydration process) and to enhance its properties.
20

In simplest way, results of these researches have shown that early age hydration of cement is
mainly controlled by the content and action of C3A, counterbalanced by the ratio and type of
sulphate ground together with the cement. C3A hydrates very speedily and will affect early
bonding characteristics. Anomalous hydration of (C3A) and less control of this hydration by
sulphate can result in such problems as flash set, false set, slump loss, and cement-admixture
incompatibility (Previte 1977; Whiting 1981; Meyer and Perenchio 1979).
Growth of the internal structure of hydrated cement (referred to by many researchers as the
microstructure) starts after the concrete has set and continues for months (and even years) after
placing. The mechanical performance and durability of the concrete is affected by the
microstructure of the cement hydrates. In terms of cement composition, the C3S and C2S contents
will have the main effect on long term growth of structure, although aluminates may contribute
to development of compounds such as ettringite (sulfoaluminate hydrate), which can bring about
expansive disruption of concrete. Cements with high content of C3S (especially those that are ore
finely ground) will hydrate more and lead to increased early age strength. However, the
hydration products formed will, actually, make it more difficult for hydration to continue at
mature ages, resulting in an ultimate strength lower than required in some cases. Cements high in
C2S content will hydrate much more slowly, resulting in a compact final structure and a higher
long-term strength. Due to competition, the relative proportion of C3S to C2S, and the overall
fineness of cements, has been increasing over the past few decades. Indeed, Pomeroy (1989)
notes that early age strengths of concrete achieved today could not have been tested in the past
except at very low water-to-cement ratios (w/c's), which would have declared concretes
unworkable in the absence of HRWR. This aptitude to achieve required strengths at a higher
workability (and hence a higher w/c) may cause many durability problems, as it is now proved
that higher w/c consistently leads to higher permeability in the concrete (Ruettgers, Vidal, and
Wing 1935; Whiting, 1988).
One of the main aspects of cement chemistry interesting for cement users is the effect of
chemical admixtures on portland cement. Since the early 1960s most authorities have allowed or
required the use of water-reducing and other admixtures in highway pavements and structures
21

(Mielenz 1984). A broad category of chemical admixtures have been inducted in the concrete
industry over the last three decades, and civil engineers are more and more concerned about the
positive and negative influences of these admixtures on cement and concrete operations.
Substantial research concerned with admixtures has been carried out in the United States. Airentraining agents are extensively used in the highway industry in North America, where concrete
will have to face repeated freeze-thaw cycles. Air-entraining agents have no considerable
influence on the rate of hydration of cement or on the chemical composition of hydration
compounds (Ramachandran and Feldman 1984). However, a raise in the cement fineness or a
reduction in cement alkali content normally enhances the dose of an admixture required for a
given air content (ACI Comm. 225R 1985). Water reducers or retarders affect cement
compounds and their hydration. Lignosulfonate-based admixtures influence the hydration of
C3A, which affects the setting and early hydration of cement. C3S and C4AF hydration is also
affected by water reducers (Ramachandran and Feldman 1984). Research conclusions presented
by Polivka and Klein (1960) showed that alkali and C3A contents affect the necessary admixtures
to attain the desired mix. It looks that set retarders, for example, are more useful with cement of
low alkali and low C3A content, and that water reducers appear to enhance the compressive
strength of concrete having cements of low alkali content greater than that of the concrete having
cements of high alkali content.

2.5 Variation in cement properties

Cement has several varying properties. These are for example:
1. Composition of clinker minerals
2. Microstructure of clinker minerals
3. Amount and form of calcium sulphate
4. Amount and form of alkalies
5. Material temperature
6. Particle size gradation (fineness)
7. Particle shape

22

Until now, the most observed single property of cement has been the fineness that is expressed in
specific surface according to the Blaine method. Several tests and long time monitoring,
however, have shown that Blaine fineness is not a sufficient parameter for explaining the
variations in the properties of fresh concrete mix or early age properties of hardened concrete.
This seems to be the case especially with superplasticized mixes where superplasticizer and
cement compatibility reportedly can cause problems or at least differing workability with various
combinations.

2.6 Effect of cement fineness on concrete properties

Sufficient research has been carried out investigating the relationships between Portland cement
particle size distribution (PSD), the hydration kinetics and set cement paste strength properties
(Frigioine and Marra, 1976; Osbaeck and V. Johansen, 1989; Pommersheim, 1987; Knudsen,
1984; Wakasugi et al., 1998 and Taylor, 1997). For a specified water-to-cement (w/c) ratio, a
drop in median particle size generally outcomes in an enhanced hydration rate and, therefore,
improved early qualities such as higher early strengths. For to this, Portland cement finenesses
have normally improved over the years. However, Mehta (1997) has recommended that on
durability basis, finer cements may not always be preferred over coarser ones. Moreover, it has
freshly been pointed out that in high-performance concretes with comparatively low w/c ratios,
coarser cements may show equal long-term performance to finer cements (Bentz and Haecker,
1999), resulting in considerable economy of energy due to a decrease in grinding time. This
recommendation was based on simulation studies of the degree of hydration vs. time
performance of a collection of cements ground to different finenesses.
In common situations, cements with a greater fineness level will tend to hydrate rapidly and
result high early age strength, due to this fact, use of finer cements in the mix. design of high
early strength concrete is common, although the strength development at greater ages may be
lesser as compared to coarser cements. Moreover, finer cement causes a stronger reaction with
alkali reactive aggregate, and makes the cement, though not necessarily concrete, display a
higher shrinkage and a greater proneness to cracking (Neville, 1995)

23

According to Jaspers (1951), a given specific surface in cement could be produced with a variety
of particle-size distributions. Basically, strength and other properties of cements are functions of
the amount hydrated and initially this will be related to the specific surface rather than to particle
grading. As hydration proceeds, however, the finest particles become completely hydrated and
the surface area of the remaining anhydrous material will become progressively less related to
the original value, and more dependent on the original particle size distribution. Their work
indicates that there, at 1-day, strength is related more or less linearly to the specific surface, but
at longer ages it is influenced also by the kind of particle-size distribution. The maximum
strength at relatively short ages with a given specific surface would be produced by particles of
roughly uniform size, but this is not necessarily true at longer ages nor, in fact, could such a
gradation be produced with existing types of grinding machinery.
Celik (2009) studied the effect of particle size distribution and surface area upon strength
development of cement. He correlated variation in fineness of cement on the basis of its particle
sizes and strength of cement and concluded that fineness has a great effect on 2 days strength. At
increased ages, strength is affected more by the concentration of coarser particles as compared to
finer ones. Zhang and Napier (1995) also worked on effect of particle size distribution, chemical
composition and surface area upon strength development of cement. He correlated particle size
distribution, chemical composition and surface area and by modelling, optimized clinker
grinding by simulation modelling.
Bentz, et al. (1999) conducted research over effects of cement particle size distribution on
operational properties of Portland cement-based materials. He recommended that coarse grains
require more time to set, although they practically set at a lower degree of hydration. Their gain
in strength will go slowly than that of finer cements, also, coarser cements will show a lower
initial heat release rate. The authors also gave argument for using coarser cements as far as
development of high performance concretes is concerned. Beuselink et al., (1998) discussed
different techniques of determining particle size distribution of cements and compared their
salient features.

24

2.7 Hydration of cement

2.7.1 Significance
Anhydrous Portland cement cannot bind sand and rock; it acquires the adhesive property only
when mixed with water. This is because the chemical reaction of cement with water, commonly
referred to as the hydration of cement, yields products that process setting and hardening
characteristics. The chemistry of concrete is essentially the chemistry of the reaction between
Portland cement and water. In any chemical reaction the main features of interest are the changes
in matter, the changes in energy, and the speed of the reaction. These three aspects of a reaction
have great practical importance for the user of Portland cement. Knowledge of the substances
formed when Portland cement reacts is important because the cement itself is not a cementing
material; its hydration products have the cementing action. Knowledge of the amount of heat
released is important because the heat is sometimes a help and sometimes a hindrance.
Knowledge of reaction speed is important because it determines the time of setting and
hardening. The initial reaction must be slow enough to enable the concrete to be poured into
place. On the other hand, after the concrete has been placed rapid hardening is often desirable.

2.7.2 Mechanism of hydration

The hydration of Portland cement (PC) involves the reaction between clinker minerals, calcium
sulphate and water. Although extensive research has been conducted on the hydration of PC, the
hydration mechanism is still not fully understood.

The hydration process has been

comprehensively reviewed by Taylor (1997). It is believed that the general principle of hydration
is the dissolution of anhydrous phases to the precipitation of much less soluble products,
typically colloidal and micro-crystalline hydrates which form the hardened paste (Bensted and
Barnes, 2002). The process can be divided into four consecutive periods, as summarised in
Table 2.5.

25

2.7.3 Hydration of aluminate phases

The reaction of C3A with water is immediate. Crystalline hydrates, such as C3AH6, C4AH19, and
C2AH8, are formed quickly, with liberation of a large amount of heat of hydration. Unless the
rapid hydration of C3A is slowed down by some method, Portland cement cannot be used for
most construction applications. This task is generally accomplished by the addition of gypsum.
Therefore, for practical purposes, it is not the hydration reactions of C3A alone but the hydration
reactions of C3A in the presence of gypsum which are important.
From the standpoint of hydration of Portland cement, it is also convenient to discuss the
hydration reactions of C3A and ferroaluminate together because when the latter reacts with water
in the presence of sulfate, the products formed are structurally similar to those formed from the
hydration of C3A. For instance, depending on the sulfate concentration, the hydration of C4AF
produces either C6A(F)S3H32 or C4A(F)SH18, which, in spite of differences in chemical
composition, have crystal structures that are similar to ettringite and low sulfate, respectively.
However, the part played by the ferroaluminate compound in the early setting and hardening
reactions of the Portland cement paste depends mainly on its chemical composition and
temperature of formation. Generally, the reactivity of the ferrite phase is somewhat slower than
C3A, but it increases with increasing alumina content and with decreasing temperature of
formation during the clinkering process. In any case, it may be noted that the hydration reaction
of the aluminates described below are applicable to both the C3A phase and the ferrite phase in
Portland cement through, for the sake of simplicity, only C3A is discussed.
Several theories have been postulated to explain the mechanism of retardation of C3A by
gypsum. According to one theory, since gypsum and alkalies go into solution quickly, the
solubility of C3A is depressed in the presence of hydroxyl, alkali, and sulfate ions. Based on the
contents of aluminate and sulfate ions in the solution, the crystalline product which is
precipitated may be either calcium aluminate trisulfate hydrate or the calcium aluminate
monosulfate hydrate. In solutions saturated with calcium and hydroxyl ions, the former
crystallizes in the form of short prismatic needles and is also known as high-sulfate or by its
mineralogical name, ettringite.
26

Table 2.5 The principal hydration stages of Portland cement

(Bensted and Barnes, 2002)
Relevance to physical
properties of concrete
First minutes
Rapid dissolution of Large initial bust of Rapid formation of
heat, mainly from
aluminate hydrates, plus
(wetting and
free lime, sulphate
dissolution of
gypsum and syngenite
mixing,
and aluminate
aluminate phases,
influences rheology and
0-15 minutes)
phase; immediate
plus some from
may also affect the
formation of Aft;
alite and CaO.
subsequent
superficial
microstructure.
formation of C3S.
Induction period Nucleation of C-S- Low heat evolution Continued formation of
(agitation,
H; rapid decrease in rate;
Aft and AFm phases;
transport, placing SiO2 and Al2O3 to
slow formation of
can influence
and finishing,
very low levels;
early C-S-H and
workability, but it is
15-120 minutes) CH becomes
more AFt leads to
formation of C-S-H that
supersaturated and
continuous increase usually leads to the
portlandite
of viscosity.
onset of normal setting.
nucleates.
Acceleration
Hydration of C3S
Rapid formation of Change from plastic to
period
accelerates and
hydrates leads to
rigid consistence (initial
(setting and early reaches maximum; solidification and
and final set); early
hardening,
CH supersaturation decrease in
strength development.
2 to 14 h)
decreases.
porosity;
Post-acceleration Decelerating rate of Decrease in rate of Continuous strength
period
formation of C-S-H heat of evolution;
increase due to
(demoulding,
and portlandite
continuous
decreasing porosity; but
continued
from both C3S and
decrease in
as an ever-diminishing
hardening,
C2S;
porosity;
rate; hydration
> 20 h)
Renewed hydration particle to particle
continues for years if
of aluminates to
and paste to
water is available;
give AFm phases.
aggregate bond
paste will shrink due to
formation.
drying.
Processing stage

Chemical process

Physical process

The monosulfate is also known as low-sulfate and crystallizes in the form of thin hexagonal
plates. The pertinent chemical reactions may be written as follows:
Ettringite
[AlO4]- + 3[SO4]2- + 6[Ca]2+ + aq.

27

C6AS3H32

-------------------- (2.4)

Monosulfate
[AlO4]- + [SO4]2- + 4[Ca]2+ + aq.

C4ASH18

-----------------------

(2.5)

Ettringite is normally the first hydrate to be crystallized because of the high sulfate/aluminate
content in the solution stage during the first hour of hydration. In normally retarded Portland
cements, which contains 5 to 6 percent gypsum, the precipitation of the ettringite imparts
stiffening (loss of consistency), setting (solidification of the paste), and early strength
development. Then, after the exhaustion of sulfate when the proportion of aluminate ions in the
solution goes high again due to changed hydration of C3A and C4AF, ettringite becomes unstable
and is slowly converted into the monosulfate phase, which is the final product of hydration of
Portland cements containing more than 5 percent C3A:
C6AS3H32 + 2C3A + 22H

3C4ASH18 -------------------- (2.6)

Since the aluminate-to-sulfate balance in the solution phase of a hydrated Portland cement paste
primarily determines whether the setting behavior is normal or not, various setting phenomena
affected by an imbalance in the A/S ratio, which have practical significance in the concrete
construction practice, are illustrated in Table 2.6, and are discussed below (Mehta & Monteiro
1993):
Case I: When the rates of availability of the aluminate ions and the sulfate ions to the solution
phase are low, the cement paste will remain workable for about 45 min; thereafter it will start
stiffening as the water-filled space begins to get filled with ettringite crystals. Most so-called
normal-setting Portland cement belong to the category. The paste becomes less workable
between 1 and 2 h after the addition of water, and may begin to solidify within 2 to 3 h.
Case II: When the rates of availability of the aluminate ions and the sulfate ions to the solution
phase are high, large amount of ettringite form rapidly and cause a considerable loss of
consistency in 10 to 45 min, with solidification of the paste between 1 and 2 h. Freshly produced
high-C3A cements containing more than normal amounts of alkali sulfates or calcium sulfate
hemihydrate are generally characterized by this type of behaviour.
28

Case IIII: When am

mount of reaactive C3A is
i high but the soluble sulfate preesent is less than
required for normal retardation, hexagonal-p
plate crystalls of monosuulfate and caalcium alum
minate
hydrates form quicklly and in larrge amounts causing thee cement passte to set in less than 455 min
after the addition of water.
w
The phenomenon
p
is known ass quick set.
Case IV
V: When littlle or no gyp
psum has beeen added too a ground Portland cem
ment clinkerr, the
hydration
n of C3A is rapid and th
he hexagonaal-plate calccium aluminaate hydratess start forming in
large am
mounts soon
n after the addition
a
of water, caussing almostt an instantaaneous set. This
phenomeenon, know
wn as flash
h set, is associated
a
w
with large heat evolution and poor
ultimatettrength.
Tab
ble 2.6 Influence of the aluminate/ssulphate rattio in the soolution phasse on settingg
charracteristics of
o Portland cement passtes (Locherr et al. 19800)

29

Case V: When the C3A in cement is of low reactivity, as is the case in partially hydrated or
carbonated cements which have been improperly stored, and at the same time a large amount of
calcium sulfate hemihydrate is present in the cement, the solution phase will contain a low
concentration of aluminate ions but will quickly become supersaturated with respect to calcium
and sulfate ions. This situation will lead to the rapid formation of large crystals of gypsum with a
corresponding loss of consistency. The phenomenon, called false set, is not associated with large
heat evolution and can be remedied by vigorous mixing of the cement paste with or without
additional water.
Although gypsum is added to cement to serve as a retarder, what is known as the optimum
gypsum content of cement is generally determined from standard tests which show maximum
cement strength and minimum shrinkage at given ages of hydration. As discussed next, the
sulfate ions contributed to the solution phase by gypsum have a retarding effect on the hydration
of the aluminate compounds but an accelerating effect on the hydration of the silicates that are
the principal compounds in Portland cement. Therefore, depending on the composition of
cement, a specific gypsum content is indicated for optimum performance of the cement.
Lea (1971) has shown that, unlike the suppression of solubility of the aluminate compounds, the
solubility of the calcium silicate compounds is actually increased in the presence of sulfate ions
in the solution phase. Typical data on the effect of gypsum addition on the strength development
rate of pure alite cements are shown in Table 2.7. In conclusion, although the primary purpose of
gypsum in Portland cement is to retard the hydration o aluminates, a side effect is the
acceleration of alite hydration without which the industrial cements would harden at a slower
rate.

2.7.4 Hydration of silicate phases

The hydration of C3S and C2S in Portland cement produces a family of calcium silicate
hydrates which are structurally similar but vary widely in calcium/silica ratio and the content of
chemically combined water.

30

Table 2.7 Accelerating effect of gypsum on setting time, heat of hydration and strength of
alite (Mehta et al. 1979)
Physical Properties
Setting time (h)
Initial
Final
Heat of hydration (cal/kg)
3 days
7 days
28 days
Compressive strength [MPa]
3 days
7 days
28 days
90 days

Type I/II Portland

Cement

Alite Cement*
No gypsum
3% gypsum

3.0
6.0

8.5
11.5

4.5
7.5

61
75
83

59
61
85

63
66
81

13.4
21.4
34.9
36.9

8.62
14.2
26.2
36.9

11.0
16.8
27.6
37.0

Since the structure determines the properties, the compositional differences among the calcium
silicate hydrates have a little effect on their physical characteristics.
The microstructure and properties of calcium silicate hydrates formed in Portland cement pastes
were described earlier. In general, the material is poorly crystalline and forms a porous solid
which exhibits characteristics of a rigid gel. In the literature, this gel has sometimes been referred
to as tobermorite gel, after a naturally occurring mineral of seemingly similar structure. The use
of this name is no longer favoured because the similarity in crystal structures is rather poor. Also,
since the chemical composition of the calcium silicate hydrates in hydrating Portland cement
pastes varies with the water-cement ratio, temperature, and age of hydration, it has become rather
customary to refer to these hydrates simply as C-S-H, a notation that does not imply a fixed
chemical composition. On complete hydration the approximate composition of the material may
be assumed as C3S2H3; this composition is therefore used for stoichiometric calculations.
The stoichiometric reactions for fully hydrated C3S and C2S pastes can therefore be expressed as

31

2C3S + 6H

C3S2H3 + 3CH

---------------------- (2.7)

2C2S + 4H

C3S2H3 + CH

---------------------- (2.8)

In addition to the fact that similar reaction products are formed on hydration of both the
tricalcium silicate and the dicalcium silicate present in Portland cement, the following points
should be noted.
First, stoichiometric calculations show that the C3S hydration would produce 61% C3S2H3 and
39% calcium hydroxide, whereas the C2S hydration would produce 82% C3S2H3 18% calcium
hydroxide. As the high specific surface area and, consequently, the adhesive property of the
hydrated cement paste are essentially due to the formation of the calcium silicate hydrate, it is to
be expected that the ultimate strength of a high- C3S Portland cement would be lower than a high
C3S cement. This, indeed, is confirmed by the data from several research investigations (Lea
1971).
Second, if the durability of a hardened cement paste to acidic and sulfate waters is reduced due to
the presence of calcium hydroxide, it may be expected that a cement containing a high
proportion of C3S will be more durable to acidic and sulfate environment compared to a cement
containing a high proportion of C3S. This conclusion is also generally confirmed by laboratory
and field experience. From the standpoint of durability to chemical attacks, some cement
standards attempt to limit the maximum permissible C3S in cement, others recommend the use of
pozzolans in order to remove the excess calcium hydroxide from the hydrated cement paste.
Third, it can be calculated from the above stoichiometric equations that C3S and C2S require 24
and 21 percent water, respectively, for complete hydration.
The stoichiometric equations of C3S and C2S hydration do not tell anything about the reaction
rates. From the standpoint of instability of the crystal structure described earlier and the heat of
hydration data given below, it is apparent that C3S would hydrate at a faster rate than C2S. in the
presence of gypsum, C2S in fine particles of cement begins to hydrate within an hour of the
addition of water to cement, and thus contributes to the final time of set and the early strength of
hydrated cement paste. The relatively quicker rate of C3S hydration in finely ground Portland
32

cements has become an important factor in the production of high-early-strength Portland

cements.

2.7.5 DTA and TGA Techniques

Differential Thermal Analysis (DTA) and Thermo Gravimetric Analysis (TGA) techniques are
of great significance in cement research. DTA and TGA is not only used in identifying various
materials but also has been successfully used to follow reactions by heating the reactions
gradually

to

elevated

temperatures.

Almeida

and

Sicheri

(2006)

also

performed

thermogravimetric analysis of polymer modified mortars with silica fume.

Principle:
Differential Thermal Analysis (DTA) is the analytical technique in which temperature
differential between the sample and a non-reactive reference material is monitored while the two
substances are subjected to the identical heating program. The thermal curve is a plot of the
temperature difference as a function of the temperature of one of the two substances. Normally
the temperature difference is recorded as a function of the temperature of the reference
substance. The sample and reference substance are kept in separate containers with in the same
furnace. To ensure identical heating the containers are kept close (with in 1 cm) to each other.
The reference substance is usually thermally inert throughout the temperature interval used for
the study. Alumina (Al2O3) is used as reference material. DTA can be used to study any process
in which heat is absorbed or evolved. Among the endothermic process that can be studied by
using DTA are melting, boiling and sublimation. Absorptive processes are often exothermic and
can be studied using DTA. Thermal curves obtained with DTA show peaks corresponding to
processes in which the temperature of the sample is increased or decreased relative to the
temperature of the reference substance. Upward deflections usually correspond to exothermic
reaction and downward deflections to endothermic reactions. The temperatures at which the
peaks are observed in the thermal curve can be used for qualitative analysis by comparison with
curve recorded under similar conditions with known materials. Peak areas or peak heights are
used for quantitative analysis. DTA is simpler and quicker to perform than X-ray diffraction but
suffers from several experimental limitations, of which the overlapping of adjacent peaks is
perhaps the greatest. A technique often useful for quantitative analysis is to add to the reference
33

sample different amounts of one component already identified in the test sample until the peaks
for that component disappear, indicating approximately equal amounts of that component in both
samples. This so-called double differential technique sometimes allows quantitative
identification to less than 1% or a sensitive similar to that of X-ray diffraction (Ivindra et al.
2005).
With the completion of the thermal change, the specimen usually retains the temperature of the
inert material. In some cases, the zero line shows a drift after a thermal transformation and is
attributed to the differences in characteristics between the specimen and the inert material. Metal
sample holders reduce baseline drift but the peaks in that case tend to be small because of rapid
heat transfer through the sample holder. In comparison to metal holders, ceramic holders give
larger peaks because of their lower thermal conductivity, thus permitting the same sensitive with
a smaller sample or less sensitive recording device.
Atmospheric control in the furnace is sometimes used to suppress an undesired reaction, to
enhance desired reaction or to resolve overlapping peaks by varying the pressure of a gaseous
reaction product. Rapid heating rates are claimed to have certain advantages, they certainly
enable larger peaks to be obtained with small samples, but may also have certain disadvantages.
Particle size can influence the curve and it is recommended that all specimen should pass a 100
mesh sieve. Uniform and reproducible packing of the specimen in the sample cup is essential.
Careful tempering by hand has been claimed to give reproducibility to within 1%. For
quantitative work, each specimen should be diluted to less than 30% with inert material.
Enhanced response can be obtained from a small specimen by placing the active material in a
thin layer around the thermocouple junction, with inert material above and below. So far as the
selection of inert material is concerned, the inert material should be of same particle size as the
material being investigated.
In thermo gravimetry, the mass of the sample is measured either as a function of temperature or
time. The plot of the mass or the percentage of the initial mass as a function of temperature or
time, is a thermal curve, generally, the mass changes are caused by loss of a volatile component,

34

such as water
w
from th
he sample. The
T change in
i mass can be used for quantitativee analysis annd the
temperatu
ure at which
h the change takes place is useful forr qualitative analysis.
nd TGA)
Apparattus (DTA an
Basic DTA
D
equipm
ment consistts of a furrnace, a teemperature regulator, a sample bblock,
thermoco
ouple and a temperaturee recording system. In the third caavity of the block a sepparate
thermoco
ouple is emb
bedded to measure
m
the temperaturre of the specimen. Thee block with the
specimen
n is placed in
i the furnaace. Temperaature regulat
ation is accoomplished byy a motor ddriven
autotranssformer whicch controls voltage
v
to the furnace wiires, which aare usually m
made of nichhrome
(to 1000oC) or platinum alloys (tto 1750oC).

Figure 2.3 Schematic diagram off DTA apparratus

The appaaratus that simultaneous
s
sly heat the sample andd monitors itts mass is a thermo ballance.
Mass measurement
m
ts are mad
de with a highly ssensitive m
microbalancee which iss an
electromechanical deevice.

35

Fiigure 2.4 Ex
xtrapolation procedure to determine transformattion onset tem
mperature

The beam
m of the baalance is con
nstructed fro
om quartz. It is attacheed to a metaallic arm hooused
between the poles of
o an electro
omagnet. Motion
M
of the balance iss detected bby observingg the
deflection
n of a high beam
b
on a photosensitiv
p
ve null detecctor which iss attached too the beam oof the
balance. A deflectio
on of the beam is autom
matically com
mpensated bby a changee in current flow
through the
t electrom
magnet which
h restores th
he beam to itts original pposition. Thee electrical ssignal
related to
o the mass on
n the balance and is disp
played on thee read-out deevice.

2.7.6 Water
W
rem
moval techn
niques to stop
s
hydraation
ut after stopp
ping hydratiion reactionss at specifieed curing ages by
Hydration studies arre carried ou
removing
g pore waterr that is avaiilable for hy
ydration reacctions in the cement passte. Four metthods
are used by research
hers all over the world: These are the solventt replacemennt of water by a
y referred too as solventt replacemeent method
d, and
hydrophiilic organic liquid, moree commonly
oven, vacuum or freeeze drying of water. However,
H
eacch of these m
methods of w
water removaal has
been proved to alter the delicate microstructture of the haardened cem
ment paste annd may causse the
structural and physiccal disintegraation of som
me of the cem
ment hydratees, especiallyy ettringite (AFt),
monosulp
phate (AFm
m) and CSH
H, because more
m
water is linked wiith these phaases. In harddened

36

cement pastes containing large amounts of AFt, as in calcium sulphoaluminate cements, the
dehydration of ettringite has been proved to result in shrinkage cracking.

1. SOLVENT REPLACEMENT
In this method, bound/pore water present in cement pastes is replaced with the help of organic
liquids such as propanone (acetone), methanol, and isopropanol. By this method, composition
and microstructure of the hydrating paste is changed. Organic liquids are not completely
removed but absorb onto the surface of hydrating C3S and present there without affecting the
microstructure or phases. There may be a reaction with CH leading to aldol condensation, and as
aresult, thermogravimetric analysis (TGA) results are affected. Thermogravimetric (DTG) peaks
for calcium carbonate at about 630 C are influenced by applying acetone to stop cement
hydration. These outcomes could be due to an aldol reaction catalysed due to presence of CH.
It was recommended by some other researchers that presence of organic matter such as acetone,
does not have any influence when carrying out X-ray diffraction (XRD) works. Solvent
replacement with isopropanol formed samples in which fine pores were slightly broken and that
this method best conserved the finest pores as compared to oven drying and freeze drying.
Methanol and isopropanol caused least stress to the microstructure of the hardened cement
pastes. By taking into account changes in length and weight of grains in cement pastes dipped in
isopropanol and methanol, Methanol reacts with hydrated cement by penetrating the CSH, but
observed that there was no reaction between isopropanol and hydrated cement. Methanol reacts
with hardened cement paste and that the length of CH crystals increased when dipped in
methanol, isopropanol, and acetone.
2. FREEZE DRYING
Freeze drying technique is a sufficient drying method for use with MIP, it most likely produces
major loss in the CSH related to thermo mechanical stress. Pores of hardened cement pastes
were broken by freeze drying method. Freeze drying leaves a large amount of water in the
microstructure of the hardened cement paste, while for thermogravimetric analysis and scanning
electron microscopy, freeze drying was reasonable.
37

3. OVEN DRYING
In oven dying method, drying of paste in oven at 105 C partially dehydrates the CSH and
pores present in the hardened cement samples are smashed. After oven drying, cracks are visible
in the microstructure of the hardened cement sample with the crack density increasing as the
drying conditions turn more difficult. In oven drying at 105 C, ettringite and CSH perhaps
leave a noticeable amount of non-evaporable water, so that oven drying at 105 C and even
60 C is inappropriate for preserving the fragile microstructure of hardened cement paste.
4. VACUUM DRYING
High vacuum drying degraded ettringite and monosulphate, and severely damaged the pore
structure, escalating the pore volume of hardened cement paste. Vacuum drying samples of
hardened cement paste formed stresses and microcracks similar to those observed for samples
dried in an oven at 60 C and 105 C, while vacuum drying removed considerably less water
than oven drying at 105 C. Knapen, et al. (2006) performed a comparison between Vacuum
Drying and Solvent Exchange Techniques.

2.8 Heat of hydration

The compounds of PC are non-equilibrium products of high-temperature reactions and are,
therefore, in a high-energy state. When PC is hydrated, the compounds react with water to
acquire stable low-energy states, and the process is accompanied by the release of energy in the
form of heat. In other words, the hydration reactions of PC compounds are exothermic.
According to Mehta and Monteiro (1993) for a typical PC, approximately 50% of the potential
heat is liberated within the first 3 days and 90% within the first 3 months of hydration. The
significance of heat of hydration in concrete is that the heat of hydration studies can be used for
characterising the setting and hardening behaviour of PC, and for predicting the temperature rise
in concrete. These measurements are also useful in predicting the strength development of
concrete.

38

2.9 Effect of cement variations on workability of concrete

The properties of fresh concrete are very vital because they help to decide the techniques needed
for its handling and compaction. Also these properties influence the properties of hardened
concrete to a great extent. The different aspects of the class of fresh concrete need different
requirements. So, a number of definitions are in common practice, each concentrating over a
different aspect of concrete behaviour: consistency, flowability, mobility, pumpability,
compactability, finishability and harshness. These definitions are, however, one-sided and
qualitative referring different things to different people. The term workability is commonly used
to represent all of the properties mentioned above. To be a little more exact, workability is often
defined in terms of the quantity of mechanical work or energy required to make full compaction
of concrete without segregation. Recent studies have shown that the cement variations have a
greater influence on the workability and on the early reactions of concrete than is generally
thought of. These variations are greater with superplasticized mixes but problems can exist also
with normal concrete mixes. The unexpected variations may lead to serious disturbances in
production in the form of poor compaction, too low early strength and strand slippages. This is
causing increased waste in production and considerable economical losses particularly at hollow
core slab factories. Cement variation is difficult to measure or control at a precast plant. The
quality information presently available from the cement supplier is not detailed enough to predict
the behaviour of cement in a concrete mix.
As per A. M. Neville (1971, 1995), more the water content of paste of standard consistency, finer
the cement is, but on the other hand an increase in the Blaine value of cement slightly increases
the workability of a concrete mix. W.H. Price (1951) and US BUREAU OF RECLAMATION
(1956) also verified this. Wuherer et al., (1950) concluded that increase in fineness may slightly
increase the amount of water required to give a neat cement paste of standard consistence but, in
contrast, reduce slightly the amount needed to obtain a given workability in a concrete mix.
According to E. C. Higginson (1970), the workability of concrete is increased by increasing the
cement fineness. For airentrained concretes, the effect of fineness of cement on workability is
not too much pronounced. He also claimed that increasing the fineness of cement from 2700 to
about 4000 cm2/g, reduces the water requirement of concrete. However, increasing the fineness
39

of cement beyond a certain optimum limit increases the water requirement of concrete. Kwan
and Wong (2008) worked on determining belongings of packing density, excess water and solid
surface area on plasticity of cement pastes. As per results, increase in packing density will
increase excess water content and workability is governed by excess water to solid volume and
excess water to solid surface area ratios.

2.10 Effect of cement variations on compressive strength

The strength of a hardened concrete largely depends upon the (i) water-cement ratio, (ii) the
quality and characteristics of cement, (iii) the degree of compaction obtained in the concrete, (iv)
curing and (v) the age of the concrete. The strength increases, as the concrete becomes older.
Generally speaking, strength is largely independent of the type of grading of the aggregate and
the mix proportions. These factors influence the water content required to produce a given
degree of workability and therefore affect the strength indirectly. Although the improvement in
compressive strength for a defined increase in cement content depends mainly on the type of
aggregate used and the cement content itself, on average, for lightweight aggregate, a 10%
higher cement content will give just about 5% higher strength (Clarke, 1993).
F. M. Lea (1971) concluded that more finely the cement is ground, greater is the strength, and
particularly the early age strength, it yields. The author conducted research on fineness versus
tensile strength of cement pastes. Tensile tests on neat cement pastes show that beyond a certain
limit, which lies between 1 and 10 % residue on a 170-mesh, the strength decreases with finer
grinding, and a similar effect has occasionally been observed for the tensile and compressive
strength of mortars of dry consistency, i.e. with a water: cement ratio below 0.35. Kuhl (1931)
suggested that there exists a definite optimum limit of fineness, such tests do not, however,
provide any adequate measure of the influence of blaine values on the strength of mortars and
plastic concretes and for these there is, in general, an increase in strength as a given cement is
more finely ground, at least as far as present practical limits of fineness are concerned.
W. H. Price (1951), H. C. Entroy 91964) and M. Venuat (1965) developed curves for 7 days, 28
days, 90 days and 1 year compressive strength verses fineness of cement separately. The effect
40

of fineness of cement on compressive strength varies with the cement and concrete mix. An
improvement in fineness from 1800 to 2500 cm2/g (equivalent to 3200 to 4500 by air
permeability method) enhances the compressive strength at 1 day by 50-100%, at 3 days by 3060%, and at 7 days by 15-40%. However, improvement in specific surface beyond about 5000
cm2/g (by air-permeability apparatus) only results in a relatively small increase in strength at less
than 1 day. As per Locher et al., (1966), the grain size tiny proportion below 3 m has been set
up to have the predominate influence on the compressive strength at 1-day while the 3-25 m
fraction has major effect on the 28 day strength. E. C. Higginson (1970) claimed that 28-days
compressive strength of concrete increases with an enhancement in fineness. The difference in
compressive strength due to difference in fineness of cement is significantly less at 1 years age.
The author has also claimed that for concrete containing no entrained air, there is a slight
decrease in the static modulus of elasticity at 28 days age, as the fineness of cement is
improved. The modulus of elasticity of concrete persistent by sonic method decreases as the
fineness of cement increases.
Svinning et al., (2008) worked on calculation of compressive strength up to 28 days from
microstructure of Portland cement. Alexander (1972) correlated statistics from new research
work and from results published during the past 40 years and conducted regression analysis to
determine the connection between strength, composition and fineness of cement. Haraste and
Bejzjak (1974) conducted a study on the likelihood to resolve the effect of grain size of cement
on the compressive strength of cement mortars by concentrating over all the particles in a set,
under the belief that apart of the individual effect of every particle in the course of hydration
there is an instantaneous and midway effect of all the particles on the same physical property.
Oner et al., (2003) studied the effect of components fineness on compressive strength of blast
furnace slag cement. He concluded that in the manufacturing of blast furnace slag cement
(BFSC), it is not only the particle size of the clinker-slag mix, but also of the separate parts,
which govern the choice of the mix composition for a target strength.

41

2.11 Deterioration of cement with storage

Cement has a great avidity for water and will readily absorb moisture from the atmosphere or
from damp material in contact with it. Cement exposed to the atmosphere gets hydrated and loses
strength. When cement is stored in sacks (made of jute), absorption takes place from the air and
strength of the cement is considerably reduced. The absorption by cement, of 1 or 2 percent of
water, has no appreciable effect, but further amounts of absorption retard the hardening of
cement and reduce its strength. If the absorption exceeds 5 per cent, the cement is ruined for all
ordinary purpose.
Cement stored in bulk or in air-tight containers does not deteriorate. It can be stored in covered
barrels or bins. Cement thus stored up to about 2 meters or more in depth can lie for longer than
a year with no more damage than the formation of a crust on the surface about 5 cm thick, which
should be removed before cement is taken for use. Special care is necessary during the rainy
season. Bags should not be opened until cement is to be emptied into the mixer.
The following figures show the average reduction of strength in a 1:2:4 mix. as a result of
storage:Storage duration

Reduction in strength

(Months)

(Percentage)

03

20

06

30

12

40

24

50

Ordinary Portland cement which has been stored for over six months, and rapid hardening
cement which has been stored over two months from the time of leaving the factory, should
always be tested before use. If deterioration is suspected, the test for setting time, described
before, should be applied.

42

Test for freshness of cement

Indication of a damaged cement are given by the presence of large lumps of set cement, and
when this happens, the lumps should be screened out unless they are soft enough to be powdered
when pressed in the fingers. It needs to be considered if this cement is to be rejected.
When cement is rubbed between fingers and thumb it should feel like a smooth powder, such as
floor. Grittiness may indicate deterioration. Such cement should be tested for setting time. If
caked material is screened out and the balance used with 10 percent extra cement, the concrete
will be good for common small works, though it will be slow setting.
Storage of cement
Portland cement may be stored indefinitely without loosening its cementing qualities, if it is
protected from moisture. For this reason, it should be stored in dry under tight location as far as
possible. Bulk cement should be stored in weather proof bins. If bagged cement is to be stored
out of doors, the sacks should not be placed directly on the ground and should be covered for
protection against rain.

2.12 Portland cement concrete - general

Portland cement concrete is a hard material cast by allowing a carefully balanced mixture of
Portland cement, fine aggregate, coarse aggregate, and water to set in formworks of the shape
and size of the desired members. The mass of the concrete consists of fine and coarse aggregate.
Cement and water react chemically to unite the aggregate particles into a solid volume. Extra
water, over and above that required for this hydration reaction, is essential to impart the mixture
the workability that makes it to fill the formwork and cover the entrenched reinforcing steel
earlier than setting. Concrete in a broad choice of properties can be cast by suitable modification
of the proportions of the constituent materials. Special cements, special aggregates, admixtures,
and special curing methods permit an even wider variety of properties to be obtained.

43

These properties depend to a considerable level on the ratio of the mix. It also depends on the
carefulness with which the various individual constituents are mixed with each other, and on the
moisture and thermal conditions, in which the mix is subjected throughout its life up to fully
hardening. The mechanism of managing such conditions is known as "Curing". To avoid the
unplanned production of poor concrete, a high level of skillful control and management is
necessary throughout the concreting process.
As already mentioned, main constituents of concrete are cement, fine aggregate, coarse
aggregate and water. In addition, there are a host of other materials, called additives that may be
added to obtain special properties. These include air entraining agents, accelerators, decelerators,
carbon black, fly ash, pozzolans, silica fume, water-reducing agents, superplasticizers, among
others. The use of these admixtures is a specialized subject for experienced professionals and,
therefore, was generally not deemed suitable for inclusion in body of this literature survey. In
section 2.1 to 2.3, we have discussed cement in detail. Now we will study the other main
constituents of Portland cement concrete.

2.12.1 Water
Water initiates the chemical reaction that produces the binding qualities of cement. Without it,
cement is unusable powder and concrete is impossible to make
Effect of impure mixing water
In order to hydrate, cement must have proper amount of water in the paste. It is important to
know the source of this mixing water. Impurities concentrated in sufficient quantity in water
could seriously reduce the strength of concrete, and cause wide variation in setting time. Certain
other chemical compounds may cause unattractive discoloration in concrete surface,
efflorescence (movement of salts to the surface), and excessive corrosion of reinforcing steel.
Testing water for mixing
If the water to be used for mixing is, in any way questionable, it should be submitted for
laboratory analysis before using. There are two ways for this, one practical method is to prepare
44

mortar cubes using the questionable water and compare the 7 and 28 days compressive strength
of these cubes with others, made using water known to be satisfactory. If the strength of the
questionable cubes is at least 90% of the other cubes, the water is judged to be acceptable.
Usually analysis of a citys water supply is always available from the Municipal Water
Department. It will list dissolved salts (silica, iron, sodium and sulphate) in the water as so many
milligrams per liter (ppm). Water containing less than 2000 milligrams per liter of total dissolved
solids can generally be used satisfactorily for making concrete. Although higher concentration
are not always harmful. They may affect certain cements adversely and should be avoided where
possible. A good thumb rule to follow is, if water is pure enough for drinking, it is suitable for
mixing concrete.
Impurities in mixing water
The following impurities in water may obstruct the setting of cement, may badly influence the
strength of the concrete or produce discoloration of its surface, and may also cause rusting of the
reinforcement:
(1) Carbonates and bicarbonates
While present in water have significant effects on the setting time of different cements, sodium
carbonate may cause very rapid setting, bicarbonate may either accelerate or retard set.
Miscellaneous inorganic salts may be present in mixing water. If it is suspected that significant
amounts of salts are dissolved in the water, it is good policy to test the concrete for retarded
setting times or reduced strength. In general, concentration of salts up to 2000 mg/ltr can be
tolerated in mixing water.
(2) Sewage & industrial substances in mixing water
Sugar, citrates, various types of acids, oils, sewage, and peat fibers can delay the setting of
concrete or lower its strength. These materials are found in water carrying sanitary sewage in
45

industrial waste. Waters containing sewage or industrial waste usually has less than 400 gm. of
total solids per ltr. When such water is used in mixing concrete, the reduction in strength is
generally not greater than 10%. However, waste water from paper pulp mills, tanneries, paint
factories, coke plants mills, and chemical and galvanizing industries may contain harmful
impurities.
(3) Oils
Oils of various kinds are occasionally present in mix water. Generally such water makes poor
concrete.
(4) Silt
Silt in mixing water is permissible to a tolerance level of 2000 mg/ltr. Higher concentrations may
not affect strength, but could influence other properties of concrete.

2.12.2 Aggregate
The quality of concrete chiefly depends upon the quality of aggregate because these are the
aggregates that cover at least 3/4th of the total volume of concrete. The main property of concrete
is strength and this property is limited by the strength of aggregates as weak aggregates can
never produce strong concrete. Also the aggregate greatly influence the durability and structural
performance of concrete.
Cement is the most costly constituent of concrete and aggregates were previously assumed as an
inert substance spread throughout the cement paste mainly for economic reasons. As an opposite
view, aggregates may be taken as a building material connected into a cohesive total by means of
the cement paste in a way similar to masonry construction. Actually, aggregate is not purely inert
and its physical as well as chemical properties somehow has an influence on the properties of
concrete.

46

As already mentioned, aggregate is cheaper than cement and it is, therefore, economical to put
maximum of it with minimum of cement on economy grounds. But economy is not the only
motive for using aggregate; it possesses considerable technical advantages on concrete, which
include a higher volume stability and better durability than the cement paste alone.
Depending upon their size, the aggregates are classified as under:
(a) Coarse Aggregate
(b) Fine Aggregate

(a) Coarse aggregate

The material whose particles are of such size as are retained on a 3/16// in B.S. test sieve, is
termed as coarse aggregate. The size of the coarse aggregate used depends upon the nature of
work. The maximum size may be 20 cm (9//) for mass concrete work, such as dams etc, and
62.5mm (2.5//) for plain concrete work. For R.C.C. Construction, the maximum (1//) although
20mm (0.75//) of aggregate is commonly adopted.
Crushed hard stone and gravel are the common materials used as coarse aggregate for structural
concrete. Coarse aggregate are usually obtained by crushing granites, gneiss, crystalline lime
stones and good variety of sand stone, etc. Broken brick is a cheap aggregate for plain concrete
but it renders the mix weak in strength. It is not used in R.C.C. work on account of the possibility
of the reinforcement getting rusted due to the high porosity of the aggregate. Clinker slag, coal
ashes, coke breeze also used as aggregate for lightweight & insulating concrete.

(b) Fine aggregate

The material, which passes 3/16" B.S. sieve size, is termed as fine aggregate. Natural sand is the
fine aggregate chiefly used in concrete mix. Sand may be obtained from sea, river, lake, etc, but
when used in a concrete mix, it should be properly washed and tested to ascertain that it is free
from clay, silt, and such organic matters.
47

Commonly used fine aggregate in R.C.C. work is sand. It is either round or angular in grains and
is often found mixed in various gradation of fineness. The sand used for mortars should consist
of sharp (angular) grains of various sizes. It is generally considered that rounded particles
(grain), do not interlock sufficiently to produces strong mortars.
Bulking of sand
When dry sand comes in contact with moisture or water, thin film is formed around the particles,
which causes the particles to get apart from each other. This results in an increase in volume of
sand. The volume of damp sand may exceed by more than 30% of the volume of same sand
when dry. This phenomenon is known as bulking of sand. It increases with addition of water up
to about 50% by weight. Further addition of water causes films around the particles to break and
thus the volume of sand gets reduced. It is important to note that dry and fully saturated sand
occupies the same volume.

Factors governing selection of aggregate

a) Strength
A strong aggregate makes strong concrete. Granite aggregate will produce a strong
concrete, whereas pumice or burnt clay aggregate, which are sometimes used where
saving of weight is desired, produce concrete of lower strength.
b) Size
Besides the minimum limit of 3/16" for coarse aggregate there arises the question of
maximum size. Clearly the aggregate must be small enough to enable it to work able in
between and around all reinforcements and into all corners of the work.
c) Particle shape
Suitable particle shape vary between rounded, irregular and angular. For a given
workability, of any concrete mix, angular aggregates require the highest water-cement
ratio and rounded aggregates the lowest. Since the strength of concrete depends so greatly
on water-cement ratio, the selection of particle shape is all important.

48

d) Surface texture
Other things being equal, a rough surface gives a stronger concrete than a smooth one. It
is clear that when concrete is subjected crushing, there is tendency for smooth surfaced
particles to slide past one another and to act as wedges disrupting the concrete. Whereas
aggregates with rough surface do not lend themselves so readily to these actions.
e) Grading
For a concrete to be dense and impervious, it is necessary for there to be sufficient water
to fill the voids in the coarse aggregates and sufficient cement to fill the voids in the fine
aggregates. If all the particles were of the same size, the percentage of voids would be
high up to the about 50%. Whereas when the particles are graded the percentages of voids
is considerable reduced. Such grading results in a reduction in the amount of mortar
required to fill the voids.
f) Impermeability
It is essential that aggregate used in concrete for reservoirs, water towers, and other
water-retaining structures, should be impermeable. This is equally important in all
reinforced works because moisture will result in rusting of reinforcements or to the
wedging action of frost, or water contained within the aggregates.
g) Cleanliness
Aggregate must be free from clay, silt, fine dust or other adherent coatings likely to
interfere with the proper mixing of the materials, or likely to weaken the adhesion
between the individual particles in the hardened state.
h) Chemical inertness
Some materials contain traces of sulpher, unburned coal. As a result of chemical actions
of these materials, it causes swelling or disruption of concrete, or may attach the
reinforcement.
i) Cost
In practice an engineer has to balance the value of the aggregate based on the foregoing
considerations against their cost. This, generally, accounts, on their availability and

49

location to the site of the work. Thus a granite which has to be hauled a 100 miles may
not be economic, if local stone will give 80% strong concrete at a greatly reduced cost.

Properties of aggregates
a) Bond of aggregate:
The bond between aggregate and cement paste is a factor of vital importance as far as the
strength of concrete is concerned. This bond is created due to the interlocking between
aggregate and the cement paste and depends mainly on the roughness of the surface of
aggregate. The strength of this bond increases with the increasing age of concrete.
b) Specific gravity
Specific gravity is defined as the ratio of weight of the solid to the weight of an equal
volume of pure distilled water. Since aggregate normally have voids in them, absolute
specific gravity may be designated to the volume of the solid material excluding all such
voids.
c) Porosity and absorption
The porosity, permeability, and absorption of aggregate influence the following
properties of aggregate on the bond between it and the cement paste: resistance of
concrete to freezing and thawing, its chemical stability and resistance to abrasion.
d) Strength of aggregate
Strength of aggregate affects greatly the strength of concrete. The effect of aggregate on
the strength of concrete is not only due to the strength of aggregate but also a substantial
level, to its absorption and bond characteristics. Generally strength of aggregate depends
greatly on its compositions, texture and structure.
e) Other mechanical properties of aggregates
These are properties, which are to be measured when the aggregate is to be used in
pavement construction or is to be subjected to high wear & tear:
i.

Toughness
Toughness is defined as the resistance of aggregate to failure by impact.

ii.

Hardness
It is defined as the resistance to wear.
50

2.13 Properties of fresh concrete

2.13.1 Workability
Workability of concrete mixture may be defined as the ease with which it may be mixed,
handled, transported and placed into the final position with a minimum loss of homogeneity".
Different site conditions required different degree of workability. If for example, concrete is to
be placed by hand in formwork in which there is a great deal of congested reinforcement, the mix
would require a high degree of workability i.e. it would have to be very wet; if, however, a
mechanical vibrator is to be used, a drier mix could be placed satisfactorily
The workability of concrete depends on many factors, the amount of cement, the fineness of
cement and its chemical composition, the amount of water, the grading and shape of fine
aggregate, the grading, shape and surface texture of the coarse aggregates, the ratio of fine to
coarse aggregates and the presence of entrained air or other admixtures.
A workable concrete mix must be fluid enough so that it can be compacted with minimum labor.
A workable concrete does not result in bleeding and segregation. Excellent workability, for
example, normally requires high cement and fine aggregate contents with a low coarse aggregate
content and relatively high water content.

Factors affecting workability

(1) Water
The workability of a concrete increases as the water content of the mix is increased. But increase
in water content would cause a decrease in strength. Excess of water weakens concrete, produces
shrinkage cracks (shrinkage increases with increase in water content), and decreases density.
Water occupies space in concrete and as it evaporates, it leaves voids and cracks. The volume of
water voids may be as much as 10% of the total volume of concrete. Generally speaking, lower
51

the water content, the stronger the concrete but the quantity of water must be sufficient to
produce a workable mix required for the particular method of compaction to be adopted.
Concrete made with low water-cement ratio is unworkable. If stuff or dry concrete is used
honey-combing will result decreasing density and strength. An unworkable concrete results in
incomplete compaction giving rise to air voids. Pressure of 5% air voids will cause a 30%
strength loss. Therefore, there is an optimum value of the water-cement ratio for every mix. The
quality of water has to be restricted within certain minimum limits. Concrete should be around
the reinforcement rods. Sometimes strength has to be sacrificed by adding more water to obtain a
higher degree of workability where concrete has to be placed in narrow and thin section. The
best mix is one which gives the maximum workability with minimum amount of water.
(2) Aggregates
Other things being equal, the workability of concrete is greater with aggregates of larger
maximum sizes. For dry mixes workability is generally greater with rather a coarser aggregates
grading, but for wet mixes better results are often obtained with finer grading.
A smooth and rounded aggregate will produce more workable concrete than sharp angular
aggregate (crushed rock or crushed gravel). A flaky aggregate produces the harshest or most
unworkable concrete. Aggregates producing more workable concrete need less water and hence
give higher strength.
(3) Cement
Cement ground to the upper limits of fineness makes more workable concrete because it is more
cohesive and has less tendency to segregate and bleed. Coarser cement on the other hand,
reduces the stickiness of the mix.
A mix with a very little cement (a lean mix) is harsh and difficult to finish. Flash set occurs,
when hot cement contacts the mixing water; it is actually accelerated hydration. Flash set can
occur in winter when hot water is added to the cement in the mixer. The higher the cement
content, the greater the workability and less the effect of grading.
52

(4) Effects of time and temperature

Concrete stiffens because some of the water from the mix is absorbed in the aggregate, some is
lost in evaporation and some is combined in the hydration process. Hot days require the water
content of a mix to be increased to maintain constant workability. As the temperature of the
concrete is increased the percentage of water required to effect a one-inch change in slump also
increases.
Concrete should remain plastic for at least quarter-to-half hour after water is added without
unusual precautions. Continuous agitation will maintain workability for three hours or more but
may cause a significant slump loss. Water added to restore the original slump, will often cause
strength reductions.

2.13.2 Compaction
Concrete must be workable enough to allow compaction to maximum density. Compaction is
important because density is one of factors directly related to strength. It eliminates voids,
bubbles or fissures of entrapped air. Compaction of concrete should proceed immediately after
placing. The concrete mass should be compacted till the cream of the cement starts appearing on
the surface. Over compaction may leave air voids in concrete. Compaction may be done by hand
or mechanical device.
Hand compaction may be done by rodding, tamping, or hammering. Tamping is usually adopted
in compacting concrete for slabs or other such surfaces. Rodding is done for thin vertical
members. While, hammering is done for massive plain concrete works.
Mechanical compaction is done by the use of vibrators. Vibrators are of three general types:
(a) Internal

(b) External

and

(c) Surface.

Internal vibrators are commonly used on large works for plate surface compaction. External
vibrators are placed against the formwork and are only adopted for thin sections of members or
53

in place where internal vibrators cannot be used with ease. Surface vibrators are generally
employed in concrete road construction works.

2.13.3 Segregation
Segregation is the separation of the coarse aggregate from the rest of the mix or the separation
of the cement-water paste from the aggregate. Segregation generally indicates poor aggregate
grading or mix design. Segregation may occur in mixes, which are too wet or too dry.
Segregation can generally be reduced by altering the water or sand content or by using a finer
sand. Even with a mix of satisfactory design, segregation may be caused by mishandling during
transport, faulty placing, or over-compacting honey-combing which reduces the strength and
durability of the structures.

2.13.4 Bleeding
Bleeding is a type of segregation in which mix water tends to rise to the surface of fresh
concrete, as solid constituents settle downwards, after compaction. When bleeding occurs in the
top portion of a lift that portion should be removed before another is placed. It is an indication
that there is too much water or deficiency of fine material in the mix, or that too much tamping,
floating or trowling had been done. The result is a porous, dusty and weak (concrete) surface.
Bleeding makes weak joints between successive lifts in structural work. Bleeding can be reduced
by causing less water, a finer sand or by adding a finely ground inert material (stone just).
Small size of aggregate needs more water than big size and angular aggregate need more than
rounded aggregate. In other works, a concrete containing a finely graded aggregate will require
more water for a given workability than one containing an aggregate with a coarser grading.
Bleeding can be controlled by proper mix design. No more water should be used than that
required to produce a workable mix.

54

2.13.5 Effects of admixtures

Poor workability caused by badly shaped aggregate or poor gradation can be improved by the
addition of an air-entrainment agent. The agent provides reduced segregation, lower bleeding
rate and easier finishing. Air entrainment is helpful not only when the aggregate is less
satisfactory; it is beneficial for the workability of concrete containing well-graded, well-shaped
aggregate as well.
Lean, harsh mixes can be improved by the addition of fines, such as pozzolanas, fly ash and rock
dust improve plasticity. Small additions of bentonite or diatomaceous earth may also be helpful.
Hydrated lime, added to the clean mix (10% to 15% by weight of cement) will also increase
workability.

2.14 Strength of hardened concrete

The strength of a hardened concrete largely depends upon the (i) water-cement ratio, (ii) the
quality and characteristics of cement, (iii) the degree of compaction obtained in the concrete, (iv)
curing and (v) the age of the concrete. The strength increases, as the concrete becomes older.
Generally speaking, strength is largely independent of the type of grading of the aggregate and
the mix proportions. These factors influence the water content required to produce a given
degree of workability and therefore affect the strength indirectly.
A round aggregate requires a lower water-cement ratio than does an angular aggregate to obtain
the same workability, therefore, a round aggregate gives a higher strength. Similarly a coarser
aggregate grading will permit a lower water-cement ratio than a finer grading for a given
workability and will thus give a higher strength. Greater strengths are also possible with rich
mixes or more thorough.

55

Factors affecting strength

a)

Water cement ratio

The ratio of the volume of mixing water to that of cement is termed as water cement ratio.
Water-cement ratio is a yardstick to obtain a concrete mix of desire strength. The lower the ratio
the greater is the strength of the mix. A rich mix of concrete gives a higher strength, because
more cement is used but it is on account of the fact that concrete can be used with a lower water
cement ratio.
b)

Compaction

Compaction (consolidation) of concrete should proceed immediately after placing. The function
of consolidation of concrete is to expel the air bubbles in the mass and make it impermeable in
addition to its securing desired strength. The concrete mass should be compacted till the cream of
the cement starts appearing on the surface. Over compaction may lead to segregation of concrete
while under-compaction may leave air voids in concrete. As little as 5 percent voids in a volume
of concrete can reduce strength as much as 39 percent while 2 percent voids can reduce overall
strength more than 10 percent. Compaction may be done by hand or mechanical device.
c)

Curing

Curing of concrete is one of the essential requirements of the process of concreting. Curing is the
process of keeping the set concrete damp for some days in order to enable the concrete gain more
strength. It has been established that the strength of concrete increases with the age provided it is
kept damp. During the process of curing, the concrete absorbs the water necessary for its
complete action to reach its required strength. The strength of concrete increases more rapidly in
the first few days after setting and afterwards, the rate of increase in strength goes on retarding.
The period for which the curing should be continued depends upon atmospheric condition such
as temperature, humidity and wind velocity. In general, the process of curing should be
continued for 7 to 10 days in cold weather, however, the concrete should be cured for at least 14
days as the rate of hardening of cement is low in such conditions. It has been discovered that
during the process of curing, increase in temperature increase the rate of strength if concrete.
This property is used in curing of small pre-cast members by stream. This enables the concrete to
gain required strength in less time.

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Materials affecting strength

1.

Cement

Modern cements are made under close quality control and seldom cause poor concrete if handled
properly. Among reasons why cement might be at fault in poor concrete are, the presence of
moisture and carbon dioxide contamination caused by improper sealing of bags or excessive
storage time. Good cement is flour-like and contains no lumps that cannot be broken easily with
fingers.
Fineness and finish-grinding temperature of cement affects concrete strength. Finer grinding
increases cement strength development, especially at early stages. High early strength cement
produces concrete with greater strength at 7, 14, and 28 days than do the other (Neville 1995).
2.

Water

If there is any doubt so as to the quality of the mix water to be used in concrete, it should be
tested in mortar cubes. Strength deficiency can be caused by as little as 0.2% organic material in
mix water. In general, if the water is considered drinkable, it can be used in concrete.
3.

Aggregate

The potential strength of concrete is determined by properties of the aggregate as well as the
amounts used. Aggregate is usually stronger than the cement paste that surrounds. However,
some characteristics of aggregate i.e. particle shape, texture maximum size, soundness, grading
and freedom from harmful materials, affect bonding strength. Aggregate quality is probably
more influential to concrete durability, while shape and gradation are very important to strength.
Well graded aggregate containing many elongated pieces can be used in concrete, but it is not
economical. It requires extra sand, water and cement to make it workable. Strength generally
decreases as the amount of sand in mix increases beyond the level needed to fill voids in the
coarse aggregate because of increased water requirements and their effect on the water-cement
ratio.
4.

Admixture

The effect of admixtures on concrete strength depends on the properties of the admixtures and
the characteristics of the concrete mix. There are admixtures that are designed to sieve in many
capacities, water reduces, accelerators, and air entrainers, for example.

57

Calcium chloride is one of the most commonly used. It increased early strength during cold
weather and protects concrete from damage due to freezing by shortening the time needed for
hardening: however, it should never be considered as an antifreeze concrete. The amount of
calcium chloride used be limited to that necessary to produce the desired results. In any case it
should never exceeded 2% by weight of cement. Fly ash, up to 30% by weight of cement,
reduces compressive strength at 7 and 28 days but may increase it after three months. In
admixture such as a retarder can delay the setting of concrete. Retarders are often used when hot
weather causes early strength graining or early setting and reduction in slump to higher concrete
temperature.

2.15 Durability of hardened concrete

Durability of concrete refers to its ability to endure weathering action, attack by various chemical
substances, freezing and thawing, abrasion and many other Aside from architectural potential,
concrete is employed as a building material because of its strength and lasting qualities. These
qualities are incorporated into concrete by the use of suitable materials, good mix proportioning,
careful batching, mixing, handling and placing, adequate consolidation and sufficient curing.
Many of the conditions that cause concrete to lack durability are not immediately apparent. Some
of them are harmful materials in the aggregate that cause large deflections and cracking, use of
highly absorptive aggregate that expands when moist and exerts sufficient force to disrupt
concrete when frozen, and impure mixing water.
When concrete is placed in lifts it is essential that each lift be prepared properly before the next
one is placed. Improper clean up between lifts or construction joints contributes to weak,
permeable joints. Reinforcing steel must be well embedded in durable concrete to protect it from
corrosion. Quality concrete must be dense, made with sound aggregates and pure water, and
mixed in proportions suitable for the planned use. It must be placed and cured with utmost care.
Concrete handled in this way will give good service for many years.

58

Weathering of hardened concrete

Weathering is defined as the inherent change of hardened concrete in terms of texture, strength,
colour and other physical and chemical properties due to action of the elements. All concrete
weathers but good concrete does so gradually and evenly. Gradual weathering shows up in
rounded edges and/or slight or erosion of the surface. This is a natural phenomenon that gives an
interesting appearance to the concrete. Sound concrete that will break clean (through both the
aggregate and paste) withstands weathering. Poor concrete that will break crumbly is subject to
accelerated weathering. Accelerated weathering shows up in cracks roughly parallel to the edges
of the concrete. These cracks are known as D-line cracks. They fill with calcium carbonate and
dirt. Sound concrete that will not subject to accelerated weathering depends on good mixture
proportioning, a low water-cement ratio, and good workmanship.

Permeability to liquids
If concrete were completely solid, it might be water tight: however, air voids are always present.
They make concrete permeable to outside influences. Materials in rain or ground water may
penetrate concrete with adverse effects.
Destruction from freezing and thawing in the presence of water and corrosion of reinforcement
subjected to moisture and air, are problems related to the permeability of concrete: permeability
is subjected to movement of water from one surface to the other, when there is difference in the
humidity on either surface.
Permeability is caused by pores in both the cement paste and the aggregate. Larger voids found
in poor quality concrete are caused by poor compaction and by bleeding. In every extreme case,
the voids may occupy as much as 10% of the volume of the concrete.
Fresh concrete is more permeable than hardened concrete. In fresh paste, the flow of water is
controlled by the size, shape and concentration of the original cement grains. Hydration reduces
permeability as gel fills the original water filled spaces.

59

In mature paste, permeability depends on the size, shape and concentration of the gel particles
and on whether or not, the capillaries in the cement paste stop. The permeability is lessened with
a high cement content in the concrete. This means less permeable concrete has a lower watercement content. Air entrainment reduces permeability because it reduces seggregation and
bleeding.

Effects of various substances on hardened concrete

(a)

Acids

Some acids attack the cement paste in concrete causing disintegration at the surface or if they
enter in crack, causes internal damage. Some ores, coal or cinders are sources of mineral acids
when they become wet. Concrete used in contact with such materials must be protected.
Unprotected concrete subjected to acid funes in the atmosphere may be dissolved into a soft
mass. This sometimes occurs in chimneys, steam railway tunnels, and other industrial situations.
Concrete in food processing plants is attracted by bacteria and fungi, that grow at floors and
walls. These growths cause damage by mechanical action and by secretion of organic acids.
Antibacterial cement is available. The active ingredient in this cement is usually Assenic or
Copper. This type of cement is used in food plants, kitchens, dairies and pharmaceutical plants as
well as show rooms, boat houses and swimming pools.
(b)

Sulphate and chlorides

Salts in solution can react with hardened cement paste. Ground water may contain dissolved
mineral salts like alkalies, magnesium and Calcium sulphates. Sulphates react with calcium
hydroxide and calcium aluminate hydrate. The products of the reaction (gypsum and calcium
sulfoaluminaate) require a wider space than the reactants they replace resulting in expansion and
disruption of the concrete. Sulphare attack produces a whitish deposit. Damage usually starts at
the edges and corners, with progressively spalling and cracking. Eventually the entire concrete
mass is reduced to a soft state.

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Calcium chloride is a commonly used deicing agent when applied to ice or snow; it lowers the
freezing point of the frozen material creating a salt solution. Temperature is high, sulphur
compounds contained in the effluent can be reduced to hydrogen sulphate by anaerobic bacteria.
When hydrogen sulphate is dissolved in moisture, this film, on the exposed surfaces of concrete,
produces sulphate acid, strong enough to attack lime compounds in the concrete.
(c)

Sea water

Sea water contains chemicals such as chlorides and sulphates. Crystallization of salts in the pores
of concrete may cause disruption from the pressure exerted by the salt crystals. This takes place
above the water level because crystallization occurs at the point of water evaporation.
Permanently immersed concrete is attacked less than that which is alternately wetted and dried,
and disintegration is more rapid in tropical climate than in temperate regions.
To protect against sea water attack, concrete should have well graded, first class, non-reactive
aggregate. Air should be entrained to increase workability and slump in a low water-cement ratio
mix.

2.16 Previous research

(a)

(i)

Strength of cement & concrete

As per A. M. NEVILLE (1995), the rate of hydration depends on the blaine values of the
cement particles, and for a fast improvement of strength more grinding is required. W.
H. PRICE (1995) also claimed the same.

(ii)

F. M. LEA (1971) concluded that more finely the cement is ground, larger is the
strength, and chiefly the early age strength, it yields.

(iii)

F. M. LEA (1995) conducted research on fineness versus tensile strength of cement

pastes. Tensile tests on neat cement pastes show that ahead of a certain limit, which lies
between I and 10 per cent residue on a 170-mesh, the strength lessens with finer
grinding, and a similar effect has occasionally been observed for the tensile and

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compressive strength of mortars of dry consistency, i.e. with a water: cement ratio below
0.35.
(iv)

KUHL (1931) and some others recommended that there exists a specific optimum limit
of fineness, such tests do not, however, provide any suitable measure of the influence of
blaine values on the strength of mortars and fresh concretes and for these there is, in
general, an improvement in strength as a given cement is more finely ground, at least as
far as present realistic limits of fineness are concerned.

(v)

W. H. PRICE (1951), H. C. ENTROY (1964), and M. VENUAT (1965) developed

curves for 7 days, 28 days, 90 days, and 1 year compressive strength verses fineness of
cement (Wagner), independently. The effect of fineness (wagner) on strength changes
with the cement and concrete mix. An increase in specific surface from 1800 to 2500
cm2/g (Wagner, equivalent to 3200 to 4500 by air permeability method) enhances the
compressive strength at 1 day by 50-100 percent, at 3 days by 30-60 percent, and at 7
days by 15-40 percent. However, enhancement in fineness after about 5000 cm2/g (by
air-permeability apparatus) only causes a relatively small increase in strength at less than
1 day.

(vi)

As per LOCHER, et al. (1966), the particle size fraction below 3 has been found to
have the dominated effect on compressive strength at 1-day while the 3-25 fraction has
key effect on the 28 day strength.

(vii)

E. C. HIGGINSON (1970) claimed that

28-days compressive strength of concrete increases with an increase in fineness. The

divergence in compressive strength due to variation in fineness of cement is
significantly less at 1 years age.

For concrete containing no entrained air, there is a minor reduction in the static
modulus of elasticity at 28 days age, as the fineness of cement is increased. The
modulus of elasticity of concrete determined by sonic method decreases as the
fineness of cement increases.

(viii) SVINNING, et al. (2008) worked on forecast of compressive strength up to 28 days

from microstructure of Portland cement.

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(ix)

ALEXANDER (1972) interrelated results from new research and from results published
in the last 40 years and with the help of regression analysis to fix the association between
strength, composition and fineness of cement.

(x)

HARASTE AND BEJZJAK (1974) conducted a research on the possibility to measure

the effect of particle size distribution of cement on the strength of cement mortars by
considering all the particles in a set, under the belief that apart of the independent effect
of every particle in the course of hydration there is an instantaneous and central effect of
all the particles on the same physical property.

(xi)

ONER (2003) worked on the effect of components fineness on compressive strength of

blast furnace slag cement. He accomplished that in the manufacturing of blast furnace
slag cement (BFSC), it is not only the particle size of the clinker-slag mix. but also of the
separate parts, which manage the choice of the mix. ratio for a target strength.

(b)

Water demand of cement & concrete

(i)

As per A. M. NEVILLE (1995), more the water cement ratio of the paste of standard
consistency, finer the cement is, but on the other hand an increase in the blaine value of
cement slightly increases the workability of a concrete mix. W.H. PRICE (1951) and US
BUREAU OF RECLAMATION (1956) also verified the same.

(ii)

J. WUHRER, et al. (1950) accomplished that an enhancement in fineness may somewhat

increase the quantity of water required to give a neat cement paste of standard
consistence but, in contrast, lower slightly the amount needed to obtain a given
workability in a concrete mix.

(iii)

As per E. C. HIGGINSON (1970), the workability of concrete may be increased by

increasing the cement fineness. For airentrained concretes, the effect of fineness of
cement on workability is is not too much prominent. He also recommended that
increasing the fineness of cement from 2700 to about 4000 cm2/g, decreases the water
requirement of concrete. However, increasing the fineness of cement more than an certain
optimum limit increases the water requirement of concrete.

(iv)

KWAN AND WONG (1995) worked on determining relations between packing density,
excess water and solid surface area on plasticity of cement pastes. As per results, increase
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in packing density will increase excess water content and workability is governed by
extra water to solid volume and extras water to solid surface area ratios.
(c)

Grinding of clinker

(i) JORGENSEN AND SMIDTH (2005) made a comparison between clinker grinding in
vertical roller mill and ball mill and found out that ball mill is economical in initial
cost and erection while vertical roller mill has low weight as compared to ball mill.
(ii) KATSIOTI, et al. (2009), studied categorization of a variety of cement grinding aids
and their influence on grinding behaviour and cement functioning.
(iii)LIDSTROM AND WESTERBERG (2003) studied a new technique Sala Agitated
Mill in wet grinding pattern and focused on the effect of fineness on compressive,
tensile, and bond strength of hardened concrete and found out that to get a certain
development in concrete properties, fine grinding has the potential to be an
environmentally and economically sound replacement to increased cement content.
(iv) OPOCZKY (1996) made a study of the grinding of composite cements produced from
clinker and two additional grinding additives and focused on strength, water demand,
and particle size distribution of complex cements.
(v) CHEN AND HUANG (2007) conducted empirical research on performances of drygrinding fine cement (DFC) of grouting. The measurement of its grinding effort and
simultated test for injectibility proved that this cement could be used to inject rock
mass with mico-fissures.
(vi) BANDOPADHYAY, et al. (1999) made a comparison between measurement of
cement fineness by Blaine permeability and laser Granulumetry and found out their
merits and demerits.
(d)

Hydration studies
(i) HATZITHEODOROU, et. al. (2007) conducted series of experiments to study effect
of increasing temperature from 20 C0 to 50 C0 on heat of hydration of concrete.

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(ii) KNAPEN, et. Al. (2006) made a comparison of solvent Exchange and Vacuum drying
techniques to remove free water from early age cement-base construction materials.
(iii) COLLIER, et al. (2008), studied the effect of different water removal techniques on
the composition and microstructure of hardened cement pastes.
(iv) IVINDRA, et. al. (2005) worked on study of blended cement hydration by isothermal
calorimetry and thermal analysis.
(v) LANGAN, et. al (2002) investigated the effect of silica fume and fly ash on heat of
hydration of Portland cement.

2.17 Concluding remarks

From economic, technological and ecological points of view, cement has an undisputed role to
play in the future of the construction industry. Therefore, the variation in cement characteristics
and their effects on concrete properties had been a major area of research in concrete technology
for last two decades. However, in the context of Pakistani cements, no study can be found in the
literature on the variation of cement characteristics and their effect on concrete production.
Therefore, a thorough research was required to investigate these aspects and the different
properties of cement and concrete discussed in this chapter need to be investigated.

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