An Introduction to Concrete

Technology
 Concrete as a Composite
• Concrete is a composite: like any composite the
properties of concrete depend on the properties and
relative proportions of its constituents.
• The properties of concrete also depend on the
temperature and humidity at which it is ‘placed’ and
‘cured’
• Each constituent of concrete (cement, water, fine
aggregate, coarse aggregate and admixtures) has an
important contribution to the overall properties of the
composite.
• None of the constituents can be wholly replaced by the
other.
• For instance, could we use a combination of cement and
water alone as a building material and not use any
aggregate? The answer is no. 2
 Constituents
• The reason is not just because of the added expense,
cement being much more expensive than aggregate.
• It is because hydrated cement paste undergoes large
volume changes due to shrinkage and creep
• Thus a building made of hardened cement paste will contain
a large number of cracks and pores due to shrinkage and
creep, making it practically useless.
• Next we examine briefly each constituent and their individual
properties 3
 Cement
• Cement is a material which acquires cohesive and
adhesive properties in the presence of water.
• In the presence of water, bonds form between individual
cement particles, as well as between cement particles
and other constituents of concrete such as fine and
coarse aggregates.
• Since water is essential for cement to acquire its
cohesive and adhesive properties, such cements are
called hydraulic cements.
• They consist chiefly of silicates and aluminates of lime
obtained from limestone (largely CaCO3) and clay
(largely oxides of silica).
4
 Chemical constituents of Cement
• The mixture of limestone and clay (roughly in the ratio of
3:1) is ground, blended and fused together in a kiln at
about 1400oC to form a produce called clinker.
• The clinker is then cooled and ground with gypsum
(Calcium Sulphate Dihydrate, CaS04.2H20) to get
cement.
• However the decomposition of limestone (CaCO3) at high
temperature leading to release of CO2, leads to a
massive carbon footprint, and accounts for about 8% of
the world's CO2 emissions.
• The main chemical constituents of cement are:
Tricalcium Silicate (Alite) 3CaO.SiO2
Dicalcium Silicate (Belite) 2CaO.SiO2
Tricalcium Aluminate 3CaO.Al2O3
5
Composition of typical Cement
Compound % by weight
Alite (Tricalcium Silicate) (C3S) 55
Belite (Dicalcium Silicate) (C2S) 20
Tricalcium Aluminate (C3A) 10
Tetracalcium Alumino-Ferrite (C4AF) 8
Gypsum (Calcium Sulphate Bihydrate) (CSH2) 5
Sodium Oxide (Na)
2
Potassium Oxide (K)
6
 Hydration of Cement
• As mentioned, for cement to acquire its adhesive and
cohesive properties water is essential. Why is it so?
• This is because in the presence of water, the silicates
and aluminates in cement form products of hydration or
hydrates.
• These hydrates, with time, produce a firm and hard mass
– which is the hardened cement paste.
• The hydration reactions for Tricalcium Silicate (Alite) and
Dicalcium Silicate (Belite) are as follows:
2C3S + 6H → C3S2H3 +3CH + heat
2C2S + 6H → C2S2H3 + CH + heat 7
 Calcium Silicate Hydrate Structure
• At the nano-scale C-S-H, as in hardened cement,
is an extremely variable and poorly ordered phase
that does not have a well defined stoichiometry
• The underlying atomic structure of C-S-H consists of complex layers
of central octahedral calcium oxide sheets with tetrahedral silicate
chains on both sides, attached with a periodicity of three tetrahedra.
 The layers of octahedral calcium oxide sheet
(CaO6) are drawn in dark grey.
 The light grey triangles are SiO44- tetrahedra.
 The interlayer contains water (blue circles)
 The interlayer also contains positively-charged
species (green squares) that can neutralize
the structure (e.g. Ca2+ and/or K+)
(Bonaccorsi et al., 2005)
• The space between two complex layers contains additional
calcium cations and H2O. 8
 Hydration of Cement
• Alite and Belite are, by far, the largest contributors to the
compressive strength of concrete.
• Alite reacts relatively rapidly with water and is responsible for
most of the early strength development in concrete.
• Belite is less reactive at early ages, but can contribute
appreciably to strength at later ages. 9
 Comparison of hydration rates
• While a higher percentage of Alite leads to faster gain in strength,
cements with higher Alite contents also have a larger
environmental impact.
• This is because higher quantities of limestone are required to form
Alite, which results in higher associated CO2 emissions from
calcination.
• Therefore if cements with higher Belite content could be
developed with improved strength gain characteristics, the
environmental impact of cement production could be reduced.
10
 Hydration of Cement
• The hydration reaction of tricalcium aluminate is:
C3A + 6H → C3AH6 + heat
• The amount of tricalcium aluminate in most cements is
comparatively small. During cement production its role is
mainly to act as a flux in the kiln, significantly lowering the
cement burning temperature and time.
• The hydration reaction of tricalcium aluminate with water is
very rapid – it may lead to what is known as “flash set”, or very
rapid setting of cement.
• Gypsum is added to cement clinker to prevent this.
• Gypsum reacts with C3A rapidly to generate calcium
sulfoaluminate hydrate (ettringite) which deposits in the form of
needles and forms a surface film. This slows down the
hydration of tricalcium aluminate and avoids “flash set”. 11
Role of Ettringite
12
The Hydration Process
Initial set:30 min
Final set: 10 hrs
13
 The Hydration Process
• There are four distinct stages in the hydration process.
• Stage I is a short period of fast reaction and heat output
as the cement dissolves and the concentrations of ionic
species in the pore solution increase rapidly.
• Eventually the pore solution is supersaturated, i.e. it
becomes energetically favourable for some of the ions to
combine into new solid phases rather than remain
dissolved.
• This results in precipitation of hydration products.
Precipitation relieves the supersaturation of the pore
solution and allows dissolution of the cement minerals to
14
continue.
 The Hydration Process
• At the end of Stage I, an amorphous layer of hydration
products form around the cement particles, comprising a
metastable C-S-H phase which is different from C-S-H gel.
• This impermeable layer separates the cement particles
from the pore solution and prevents further rapid
dissolution.
• It gives rise to the incubation period (Stage II) when the
rate of reaction becomes nearly zero.
• When the metastable C-S-H phase converts to stable C-S-
H gel, the layer becomes permeable and the rate of
hydration increases as more C-S-H gel nuclei form and
15
grow.
 The Hydration Process
• Therefore, during Stage III, the rate of hydration is
controlled by the rate at which the hydration products
nucleate and grow.
• The rate of reaction increases rapidly and reaches a
maximum.
• Both the maximum reaction rate and the time at which it
occurs depend strongly on the temperature and the
average particle size (𝑑 ) of the cement.
• At the end of Stage III, final set of the concrete has
occurred.
• A relatively thick layer of hydration product now surrounds
the unhydrated cement particle. 16
 The Hydration Process
• For further hydration to take place, the dissolved ions from
the unhydrated cement must diffuse outward and precipitate
in the capillary pores, or water must diffuse inward.
• The diffusion processes become slower and slower as the
layer of hydration product around the cement particles
becomes thicker and thicker.
• The final period (Stage IV) is therefore called the diffusion-
limited reaction period: the rate of hydration is controlled by
the rate of diffusion.
• At the end of Stage III about 30% of the initial cement has
hydrated. So 70% of the hydration occurs in Stage IV.
• Also, during Stage IV, since the rate of the hydration reaction
17
is slow, the heat of hydration is much reduced.
 The Hydration Process
a) hydration has not yet occurred and the pores are filled with water
b) beginning of hydration
c) hydration continues
d) nearly hardened cement paste
18
 Heat of Hydration of Cement
• Heat released during hydration causes rise in temperature
during concrete hardening
• If temperature rise is sufficiently high, and the temperature
distribution is nonuniform, significant thermal gradients arise.
• This tends to cause thermal expansion of the hydrated
cement paste.
• Free thermal expansion is however opposed by the presence
of internal and external (boundary) restraints to thermal
movement. This gives rise to thermal stresses.
• If the thermal stresses are tensile they may give rise to
significant cracking in concrete
• However high heat of hydration is useful if concrete is being
cast in near freezing temperatures.
• It prevents ice formation in the pores and enables hydration to
occur and concrete to gain its desired strength 19
 Thermal stresses in concrete
T1 >T0 , 𝛼𝑚𝑜𝑟𝑡𝑎𝑟 𝛼𝑎𝑔𝑔𝑟𝑒𝑔𝑎𝑡𝑒
T
T T1 𝛼𝑎𝑔𝑔𝑟𝑒𝑔𝑎𝑡𝑒 T1 T
𝛼𝑚𝑜𝑟𝑡𝑎𝑟
T
Mismatch in thermal
strains gives rise to
strain incompatibility
𝑣𝑜𝑙
𝜖𝑚𝑜𝑟𝑡𝑎𝑟 in this region
Strain
𝑣𝑜𝑙
incompatibility gives 𝜖𝑎𝑔𝑔𝑟𝑒𝑔𝑎𝑡𝑒
rise to tensile
stresses which can
cause cracking in
mortar
20
𝑣𝑜𝑙 𝑣𝑜𝑙
𝜖𝑚𝑜𝑟𝑡𝑎𝑟 𝜖𝑎𝑔𝑔𝑟𝑒𝑔𝑎𝑡𝑒
 Portland Cement
• The cement that we have talked about till now is usually
known as Ordinary Portland Cement (OPC), because of
its resemblance upon hardening to Portland stone
• This cement was the most commonly used type of
cement in the past and it is still widely used.
• Comprises about 59-64% lime (CaO), 19-24% silica
(SiO2), 3-6% alumina (Al2O3), 1-4% iron oxide (Fe2O3)
• However there are various other types of cement which
are also used, some widely, others for specialized
purposes.
• One of the other commonly used cements is Portland
21
Pozzolona Cement (PPC)
 Portland Pozzolona Cement
• Pozzolana, a silica based material (major constituent SiO2),
is used to replace a portion of cement in a concrete mix.
This can result in significant economy.
• Pozollona by itself possesses no cementitious properties.
• However in finely divided form, in the presence of water, it
can react with calcium hydroxide to form compounds that
possess cementitious properties.
• Recall calcium hydroxide is formed during the hydration of
dicalcium silicate and tricalcium silicate.
• Portland pozollona cement is prepared by grinding cement
clinker with pozollona.
• IS:1489 requires that the % age of pozollana vary between
22
10%-25% by weight of cement.
 Portland Pozzolona Cement
• The Pozzolona used mostly comprises fly ash
• Fly ash is one of the residues generated during combustion
of coal and comprises fine particles that rise with flue gasses.
• Depending upon the type of coal burnt, the components may
vary considerably but usually contains substantial amounts of
silicon dioxide (SiO2) and calcium oxide (CaO)
• In the past fly ash was generally released to the atmosphere:
pollution control requires that it be captured prior to release.
• About 43% is recycled and used for Portland cement
23
production
 Rapid Hardening Cement
Other types of specialized cements include:
• Rapid hardening cement: more finely ground than OPC,
but same chemical constituents.
• Since more finely ground more surface area available for
formation of hydration products.
• Thus it acquires cohesive and adhesive properties faster:
24 hour strength of rapid hardening cement is nearly equal
to 3 day strength of OPC
• Allows quicker removal of shuttering – suitable for road
24
work or bridge construction
 Specific Surface Area
V1, A1 V2, A2
𝑉1 𝑉2 , 𝐴1 𝐴2
𝐴2 ⁄𝑉2 𝐴1 ⁄𝑉1
𝑉 total volume of particles
𝐴 total surface area of particles
𝐴⁄𝑉 specific area of particles
25
Specific area increases with reduction in particle size
Early strength vs normal strength
concrete
σc
σ c28 1.2
Early strength
1.0
Normal strength
0.8
0.6
0.4
0.2
time
7 days 28 days 5 years
26
 Portland Slag Cement
• Portland slag cement: Blast furnace slag contains oxides
of lime, alumina and silica and is used to replace clay
used in the manufacture of OPC.
• Economical, since it allows reuse of blast furnace by-
product while replacing some of the ingredients of OPC.
• The properties are similar to OPC. However it has lower
heat of hydration (the heat generated during the
hydration reactions) and ensures greater durability.
• It is often used in mass concreting structures such as
retaining walls – since the lower heat of hydration allows
maintenance of proper placing and curing temperatures.27
 Hydrophobic cement
• Hydrophobic cement is formed by adding water repellant
chemicals (such as Oleic acid and Stearic acid) during the
grinding process to clinker.
• These chemicals form a coating over cement particles and
prevents moisture and air from being absorbed by the cement
during storage for long periods in wet climatic conditions.
• This prevents initiation of hydration reactions while the
cement is in storage, which might otherwise occur in wet
climatic conditions, and make the cement unusable.
• However once the coating is broken during the mixing of
concrete, normal hydration processes occur to the same
28
extent as in OPC
 Sulphate Resisting cement
• This cement contains a low amount of tricalcium aluminate in
order to avoid sulphate attack.
• Tricalcium aluminate reacts with sulphates to form ettringite,
hydrous calcium aluminate trisulphate, with chemical formula
Ca6Al2(SO4)3(OH)12ꞏ26H2O, and gypsum.
• Ettringite and gypsum cause expansion and cracks in
hardened concrete.
• Sulphate resisting cement is therefore used for marine works,
mass concreting in aggressive waters, and concrete
construction in sulphate bearing soils. .29
 Sulphate Resisting cement
• Sulphate resisting cements are also designed to reduce the
susceptibility of concrete to sulphuric acid attack.
• Sulphuric acid dissolves and removes a part of the hydrated
cement paste, leaving behind a soft and very weak mass.
• Sulphuric acid also reacts with the calcium hydroxide (CH)
produced during the primary reaction to precipitate gypsum
(CaSO4 2H2O), on and below the concrete surface, which
causes further cracking and spalling.
• Sulphate resisting cements therefore usually contain some
pozzolanic materials.
• These materials increase resistance to sulphuric acid attack,
since pozzolona reduces the amount of free lime that can
react with sulphuric acid. .30
 High Alumina Cement
• The main active constituent of high alumina cements is
monocalcium aluminate (CaO ꞏ Al2O3).
• It also contains other calcium aluminates as well as smaller
quantities of iron oxides and silica
• Note that the use of monocalcium aluminate rather than
tricalcium aluminate avoids the problem of flash set.
• High early strength
• High durability against chemical attack, because of
replacement of tricalcium aluminate, and hence is useful for
concreting in hostile environments, where concrete may be
exposed to sulphates.
• High heat of hydration – useful for concreting in freezing
31
weather.
 Super Sulphated cement
• Super sulphated cement is formed by grinding a mixture of 80-
85% granulated slag, with 10-15% gypsum and about 5%
Portland cement clinker. This cement is ground finer than OPC.
• It is known as super sulphated because of the high percentage of
gypsum (CaS04.2H20) present.
• Gypsum acts as an activator. In an alkaline environment,
sulphates (gypsum) accelerate the pozzolonic reaction of slag
with alkali and increases the strength of the resulting
cementitious material.
• Why does gypsum act as an activator? One possible answer is
that the sulphate in gypsum attacks the Al203 in slag to form
ettringite.
• This speeds up the decomposition of slag leading to the release
of lime and silica, which then react with C-H to form C-S-H.
32
 Super Sulphated cement
• The pozzolonic reaction of slag with Ca(OH)2 leads to formation of a
more crystalline phase of CSH known as tobermorite.
• The tobermorite gel has a smaller gel particle size than the CSH gel
formed from ordinary cement (e.g. OPC).
• Hence it fills up the open pores in the CSH gel formed from OPC,
leading to the formation of a more compact hardened cement paste
which can resist sulphate and chloride attack
• The composition of super sulphated cement, by itself, also makes it
highly resistant to chemical attack. Because of the increase in the slag
content vis-à-vis OPC there is reduction in the amount of C3A. This
increases the sulphate resistance of the cement.
• Also, the increase in slag content decreases the amount of free
Ca(OH)2 in concrete.
• Another advantage of super-sulphated cements is their low total heat
of hydration. They are therefore very useful for mass concrete works. 33
 Geopolymer concrete
•As noted earlier, cement has a massive carbon footprint and
accounts for about 8% of the world's carbon dioxide emission.
•Is it possible to find an alternative binder for concrete that is
more environment-friendly?
•The use of pozzolanic materials like fly ash as a partial
replacment of cement, has already been discussed.
•The use of fly ash, however, slows down the rate at which
concrete gains strength. This is because CH has to be
produced in sufficient quantities during the primary hydration
reaction due to the cement.
•Current research in the use of geopolymers, pioneered by
Davidovits (2008), attempts to overcome this problem by
eliminating the need for the primary hydration reaction. 34
 Geopolymer concrete
•Geopolymers, such as metakaolin (Al2Si2O7), provide a source
of silicon and aluminium.
•They are directly dissolved in an alkaline activating solution
which subsequently polymerises and becomes the binder.
•Geopolymers do not require additional water, unlike cement.
Therefore with the use of geopolymers one can cut down on
the volume of water in concrete.
•This can have major implications on durability– it makes
concrete less permeable and hence less susceptible to attack
by ingress of harmful external agents.
•However, since polymerisation generally occurs at high
temperatures, heat must be applied to facilitate polymerisation.
•Current research aims to develop geopolymers which can
35
polymerise at room temperature
 Geopolymer concrete
•Geopolymer concrete is a new version of an old idea. Roman
concrete, used by the Romans since about 150 BC widely in
construction, is essentially geopolymer concrete.
•The binder in Roman concrete was usually obtained by mixing
volcanic ash (rich in pozzolona) with quicklime and water (alkaline
activating solution).
•The resulting hydration product had excellent binding properties.
Examples of Roman concrete structures survive, the most well
known example being the Pantheon in Rome from around 125 AD.
36
 Aggregate
•Aggregates occupy about 80% of the total volume of concrete.
Thus their properties greatly influence the behavior of concrete
•Aggregates are classified as fine aggregates (materials passing
through an IS sieve that is less than 4.75 mm gauge) and coarse
aggregates (material that do not pass the 4.75 mm IS sieve)
•For maximum strength and durability of concrete, the aggregates
must be packed and cemented as compactly as possible.
•Thus the gradation of particle sizes is important. If aggregates span
a range of sizes – the smaller aggregates can occupy the interstitial
spaces between larger aggregates and reduce the volume of void.
37
 Aggregate Gradation
• Good gradation also reduces the cement requirement for
the concrete – since it reduces the available void space
that must be filled with cement.
Fuller’s Curve (Fuller, W.B. and
Thompson, S.E. “The laws of
proportioning concrete," Transactions of
the ASCE,159, 1907)
opening in the sieve being considered
• Reducing 𝑛 increases the percentage of fines and vice
versa. 38
 Typical gradation curves

Retained
Passing

The Fineness modulus (FM) is an empirical figure obtained by adding the cumulative
percentage weight of aggregate retained on each of a specified series of sieves, and dividing
the sum by 100. The sieve sizes are 150 μm, 300 μm, 600 μm, 1.18 mm, 2.36 mm, 4.75 mm,
9.5 mm, 19.0 mm, 38.1 mm. FM values range from 2.00 to 4.00 for fine aggregates, and 6.50 to
8.0 for coarse aggregates smaller than 38.1 mm. Thus higher FM implies a coarser gradation.
39
Fineness Modulus calculation
40
 Aggregate Properties
• Aggregates must also have good strength, durability and
resistance to harsh weather.
• Their surface must be free of impurities e.g. organic matter
which may weaken the bond with cement paste.
• Aggregates are often classified into lightweight aggregates,
normal weight aggregates and heavy weight aggregates
• Light weight aggregates e.g. slag and sintered fly ash are
primarily used for insulating purposes or masonry units
• Normal weight aggregates include natural material such as
sand, gravel and crushed rock such as granite, basalt and sand
stone.
• Artificial material such as broken brick and air cooled slag 41
are
also used.
 Influence of aggregate type on
concrete stress-strain behaviour
σ ( psi) σ ( psi)
12 Light wt
Normal wt
8
4
ε ε
.001 .002 .003 .004 .001 .002 .003 .004
42
 Aggregate classification
• Normal weight aggregates are classified based on particle
shape (angular, rounded, flaky etc.) and surface texture
(smooth, granular, honeycombed and porous)
Classification by shape
Classification by texture
Rough texture Smooth texture
• Heavy weight aggregates are used for making heavy weight
concrete manufactured for specialized purposes such as
nuclear reactors where there is a need to screen out harmful
radiation.
• They typically consist of heavy iron ores or hard rocks such as
43
barite, crushed to suitable sizes.
 Water
•Water is an essential requirement in concrete: it is essential
during both the mixing and curing of concrete
•Water equal to about 25% of the weight of cement is required
for the hydration reactions
•Additional water is required to ensure proper workability of
concrete.
•However this additional water usually has a detrimental effect
on the compressive strength and durability of hardened
concrete.
•The water used must be free from injurious chemicals and
substances that may be harmful to concrete or reinforcing
steel.
•Potable water is considered satisfactory for mixing concrete. 44
 Admixtures: Accelerators
• Materials known as admixtures are sometimes added to the
concrete mix, just before or during mixing, to modify the
properties of the concrete. Some commonly used admixtures
are discussed below.
• Accelerators act in two ways. They speed the setting time.
• They also lead to an increase in the rate of strength
development in concrete at early ages.
• Calcium chloride is the most widely used accelerator and is
cheapest.
• Calcium chloride however lowers the alkalinity of the
concrete mix. As a consequence rebars in reinforced
concrete become more susceptible to corrosion.
45
 Accelerators
• Alternative accelerators such as calcium nitrate, calcium formate
and sodium nitrate are now being preferred instead.
• Most accelerators (such as calcium chloride) tend to act as
catalysts.
• They facilitate the production of a more permeable C-S-H gel that
permits faster diffusion of ions and thus a faster hydration of
cement particles at early ages.
• Other accelerators, e.g. fine limestone powder, rely on a more
physical approach.
• They provide nucleation sites i.e. serve as ideal sites for the
precipitation and growth of early-age cement hydration products.
• The nucleation sites eventually get incorporated into the C-S-H gel
structure. 46
 Retarders
•Retardants are used to retard the initial setting time. They
are useful when mixes have to be transported/pumped over
large distances.
•Retardants are also used to compensate for the
accelerating effect of high temperature towards initial set
•Retardants can be organic (e.g. hydrocarboxalic acid,
carbohydrates) or inorganic (e.g. oxides of lead or zinc).
•Two natural materials, readily available in India, sugarcane
juice and sugarcane bagasse, are known to act as very
effective retarders in concrete.
•However it is difficult to quantify their retarding effect, since
it varies with the source i.e. the type of sugarcane.
47
 Retarders
•Retarders work by temporarily interrupting the hydration
reactions, thereby creating a longer incubation period.
•Some retarders create a blocking mechanism whereby the
retarder adsorbs strongly on the surface of the cement particle.
•This creates a diffusion barrier around cement particles, and
prevents water from reaching the unhydrated cement particles.
•Other retarders delay the hydration reaction by tending to
retain the calcium ions longer in the solution.
•Depending on the retarder, one or both of the above processes
may be involved.
•The second process is probably the more important for most
retarder types, since it delays setting but does not cause loss
48
of
workability.
 Superplasticizers
•To increase workability without increasing the water content –
pozzolanic materials such as fly ash can be used as a partial
replacement of cement.
•The use of fly ash also decreases the heat of hydration.
•However superplasticizers are the most widely used admixtures
to reduce the water requirement.
•These are chemicals which can produce concrete of a desired
workability at a lower water cement ratio than ordinary concrete.
•They therefore result in concretes with higher compressive
strength.
•Most superplasticizers in current use are polycarboxylate-ether
based (PCEs) chemicals. 49
 Superplasticizers
• Superplasticizers change the rheology of plastic concrete: they
reduce the yield stress 𝜏𝑦 of plastic concrete. Their effect on
the viscosity 𝜇 is not fully understood.
Rate of gain of
shear stress
• These properties describe a fluid's
increases with
shear strain rate
internal resistance to flow, and are Shear
thickening

Rate of gain of
shear stress
the main macroscopic parameters decreases with
shear strain rate
which can be monitored to quantify
the effect of superplasticizers.
Shear
thinning
• How do superplasticizers improve μ
the workability of concrete? 𝜏𝑦 Bingham fluid
• The addition of PCE superplasticizers delays the flocculation of
the cement particles.
50
 Flocculation and Dispersion
•Delay of flocculation releases trapped water. The released
water facilitates flow. It also is a much more effective lubricant
51
than trapped water.
 Electrostatic Repulsion
• This is because PCE superplasticizers increase the electrostatic
and steric dispersion forces between the cement particles.
• The electrostatic repulsion force between particles occurs
because of their identically charged surfaces.
• Negatively charged polymer anions are adsorbed on the
surfaces of the positively charged cement particles. It results in
electrostatic repulsion between the particles.
• The adsorption of the negatively charged anions also results in
formation of a slipping layer i.e. a layer with low resistance to
flow on the surface of the cement particles. This facilitates flow.
• According to some authors (Darwin et al., 1994, Yoshioka et al.,
1997), electrostatic repulsion is not a major dispersion
mechanism – since the magnitude of the electrostatic repulsive
forces is comparatively small. 52
Electrostatic vs. Steric Action
53
 Steric Hindrance
• However the negative charge of the PCE anions is important
in ensuring that adsorbent layers form on the surface of the
cement particles.
• Instead of electrostatic repulsion, it is steric hindrance which
plays the main role in preventing flocculation.
• Steric hindrance is formally defined as the prevention or
retardation of inter-molecular or intra-molecular interactions
as a result of the spatial structure of a molecule.
• When spherical particles, even with zero surface charge, and
covered with a macromolecular adsorbed layer approach one
another, a repulsion force is induced when the layers overlap.
54
 Criterion for Steric Stabilization
• Work is required to push the particles together when the
distance between them (H) is less than 2t
55
 Role of PCE architecture
• Therefore, polymer architecture plays a major role in
determining the effectiveness of PCEs. In particular, the fact
that PCE molecules have side chains is crucial.
• In theory, longer side chains should exert higher steric
repulsion between two particle surfaces, thus improving
performance.
56
 Role of PCE architecture
• However, superplasticizers with long chains do not produce
the best performance in fresh mixtures.
• This is because of their lower charge density which results in
poor adsorption.
• PCEs with short side chains ensure high charge density. This
ensures better adsorption of PCE anions on the surface of
positively charged cement particles.
• If one compares two PCEs with the same side chain length but
higher charge density, the one with the higher charge density
yields a mixture with better rheology.
• Cement composition also plays an important role in
determining the effectiveness of superplasticizers. In
57
particular, the C3A content of the cement is important.
 Role of cement content
• Presence of significant amounts of C3A in cement lead to the
formation of ettringite.
• The needle shaped crystals of ettringite contribute to increase
in the effective surface area of the cement particles.
Needles of
ettringite
• Studies have shown that ettringite is the cement phase that
adsorbs the most superplasticizers.
• Hence increase in the C3A content facilitates adsorption of
PCEs and retards flocculation of cement particles.
• On the other hand, the presence of other negative ions in58the
solution may affect the efficiency of PCEs.
 Role of other ions
• For example if SO or SO are present in plastic concrete, they are
adsorbed on the surface of cement particles.
• They therefore prevent the adsorption of PCE anions with side
chains, hence adversely affecting the dispersibilty of the mix.
• This can result in unexpected incompatibilities between PCE
superplasticizers and certain types of cement.
• Ongoing experimental research has led to better understanding of
cement-superplasticizer interactions.
• For increasing workability, the typical dosage is 0.1%-0.3%, for
liquid superplasticizer with 40% of active material. To reduce the
water cement ratio, dosages typically range between 0.5%-2%.
• However, for each concrete mix the dosage of superplasticizer
needed is unique, and has to be determined through testing.
• If dosage is too high the spacing of cement particles is excessive:
results in reduced friction between aggregates, facilitates
segregation and water movement leading to increased bleeding. 59
 Properties of Concrete
A good concrete must have three basic properties:
• Strength
• Workability
• Durability
The purpose of any concrete mix design is to achieve
all three goals to the extent desired by the usage of the
concrete.
60
 Strength
•The concrete must be able to bear stresses arising from the
design loads
•It is uneconomical to design a concrete mix stronger than
required – however it must have the minimum strength
required.
•Factors influencing the strength of concrete are: cement
quality, water cement ratio, grading of aggregate, degree of
compaction, efficiency of curing, temperature during curing
etc.
•The age of concrete also influences the strength. With
increase in age, the degree of hydration generally increases
so strength also increases. However the rate of increase in
strength decreases with age.
•Water cement ratio is by far the most important factor
determining the strength of concrete. 61
Strength vs. water cement ratio
62
 Strength vs water cement ratio
•Compressive strength decreases with water cement ratio
•The reason is that the amount of water required for
hydration of cement is limited.
•The water in excess of that required for hydration of
cement improves workability of concrete.
•However over time the excess water may evaporate
leading to increased porosity in the paste. Thus higher
water cement ratios lead to lower strength.
•The strength of concrete will not increase by increasing the
cement content unless the water-cement ratio is decreased.
•Reduction of water cement ratio however adversely affects
the workability of concrete.
•Thus an optimum water cement ratio is required for
63
maximum workability as well as strength.
 Types of pores in concrete
•There are three types of pores in concrete: gel pores, capillary
pores and entrapped air. They together constitute the total void
volume in concrete.
•Gel pores: These are
interstitial spaces within the
C-S-H gel. The gel pores
occupy about 28% of the total
volume of gel.
•Gel pores are much smaller
in size than capillary pores,
with size normally ranging
between 0.5 and 2.5 nm.
•Size of the capillary pores is
of the order of 10 to 50 nm 64
 Capillary and Gel Pores
•Capillary pores: represent that part of the gross volume which has
not been filled by the products of hydration.
Segmentation
and reduction
in volume of
capillary
pores,
increase in
volume of gel
pores
•The volume of capillary pores decreases with hydration whereas the
volume of gel pores increases along with the volume of C-S-H gel as
hydration proceeds.
•Capillary pores affect strength and, when interconnected, influence
permeability and hence durability of concrete.
•Gel pores have a strong influence on the amount of shrinkage and
creep. 65
 Influence of entrapped air voids on strength
•Each percentage increase of air void by volume decreases strength by
as much as 5%.
•The total volume of voids depends on the water cement ratio – as
evaporation of excess water leads to void creation.
•To reduce the presence of air voids, one must (i) achieve the maximum
possible packing density (ii) optimize the water cement ratio. 66
 Workability of Concrete
•Workability refers to the amount of energy necessary for
compaction of concrete.
•In compacting concrete, energy is spent in three ways:
(i) to overcome internal friction between the particles of the mix
(ii) to overcome friction on the formwork surface
(iii)to overcome friction on the surface of the rebars.
•In more general terms, workability of freshly mixed concrete is
that property which determines the ease and homogeneity with
which it can be mixed, placed, compacted and finished.
•Workability of concrete is different from “consistency” of a
concrete mix.
•Consistency refers to the ease with which a concrete flows. 67
 Workability of Concrete
•A concrete that can easily flow, is not necessarily more workable.
Concretes of the same ‘consistency’ can vary in workability.
•Workable concretes should flow without segregation: i.e.
separation and local accumulation of coarse aggregates from
cement paste
•Usually however, wet concretes are not only more consistent i.e.
can flow easily but also, within limits, possess more workability.
•Workability increases with the maximum size of the aggregate,
because as the aggregates increase in size, the total surface area
of the aggregates reduces.
•This reduces the “wetting” surface, and the free water available
can act as a more effective lubricant to reduce friction between
aggregates, as well as between aggregates and formwork and
between aggregates and reinforcement. 68
 Role of aggregate texture and shape
• Workability also improves if the aggregates have smooth
texture – since this reduces frictional forces and ensures
easier compaction.
• This is because a smoother surface results in less specific
surface area. 69
 Rounded vs. Angular Aggregates
•Aggregate shape is important as well. Rounded aggregates
have smaller specific area than angular aggregates of the
same size. All particles of size d = 8 mm i
Particle is of size di if bounding box containing particle (in at
least one orientation) can pass through a sieve of size di
70
 Test for workability: slump test
•A mould, which is a frustum of a cone, is placed with its base
on a smooth surface.
•The frustum has a height of 300 mm and a base diameter of
200 mm.
•It is then filled with concrete in three layers.
•Each layer is hand tamped 25 times with a standard diameter
steel rod to ensure proper compaction.
•Immediately after filling the mould is slowly lifted.
•The unsupported concrete now slumps – hence the name of
the test.
71
Slump Test
spread
72
 Slump Test
•The decrease in the height of the center of the slumped concrete is
called the slump and is measured to the nearest 5 mm.
•The slump is sensitive to variations in workability, the extent of the
slump determines the degree of workability
•Following ranges are commonly adapted for normally compacted
concrete:
Degree of Workability Slump (mm)
Very Low 0-25
Low 25-50
Medium 50-100
High 100-175
•For flowable concretes, such as self-compacting concrete, the
emphasis is on spread rather than slump in determining the flowability.
•Spread in self compacting concrete must exceed 500 mm. 73
 Slump Test
•The results of the slump test have been used to calculate the yield
stress of concrete.
Journal of
Rheology,
May 2005
74
Relation between slump test output & yield stress
•For normally compacted concretes, with slump between 50 mm and
200 mm, an empirical relation was proposed by Roussel relating
slump 𝑆 to yield stress 𝜏 :
𝑆 25.5 17.6 𝜏 ⁄𝜌
•For even smaller values of slump, the following relation, where 𝐻 is
the initial height of the cone, was proposed:
𝜌𝑔 𝐻 𝑆 ⁄ 3 =𝜏
•For flowable concretes, for example, for self-compacting concrete
with spread 600 mm, Roussel and Coussot proposed the following
analytical expression linking spread with yield stress:
𝜏 225𝜌𝑔𝛺 ⁄ 128𝜋 𝑅
•This expression assumes flow under pure shear conditions. 𝛺 is the
sample volume and 𝑅 is the radius of the spread.
•The expression, however, is only valid when the “homogeneity
75
criterion” is met.
 Limitations of the slump test
•However, with increasing interest in concretes with high flowability,
i.e. with high spread, the slump test results for such concretes have
come under scrutiny.
•For very high flows, the spread values obtained from the slump test
may not be reliable, because of failure to satisfy the “homogeneity
criterion”.
•The homogeneity criterion requires the characteristic dimension of
the sample, 𝐷, being the maximum sample thickness at cessation of
flow, be at least equal to five times the maximum aggregate size
5𝑑 .
•Satisfaction of this criterion ensures that there is no loss of
homogeneity i.e. no segregation at the “tail” of the spread.
𝐷
76
 The LCPC box test
•To overcome this problem and satisfy the homogeneity criterion,
Roussel (2007) proposed an alternative experiment suitable for field
use: the LCPC box test.
•Unlike in the slump test, flow in the LCPC box is unidirectional.
•As a result, for the same sample volume the thickness of the sample
at stoppage, 𝐷, is higher in the LCPC box than in the slump test.
•This tends to ensure the satisfaction of the homogeneity criterion
(𝐷 5𝑑 ), prevents segregation at the “tail”, and hence results in
a more reliable indicator of the flowability of highly flowable concretes.
77
 Workability: Need for retempering
•Often in urban areas, the construction site is a significant
distance from the central batching plant, and traffic conditions
cause delay in transporting the mix to the work site.
•This can result in casting time delay (CDT), which causes loss
of workability of concrete.
•Loss of workability may lead to inadequate compaction,
resulting in loss of strength.
•Hence retempering is often performed in order to restore the
initial slump and keep the concrete workable at the construction
site
•Retempering of concrete with water, superplasticizers or a
combination of both, is the most common remedy for restoring
78
slump loss in concrete
 Effect of retempering
• It is possible that retempering water added at the construction site to
restore workability to acceptable levels, may cause a reduction in
concrete strength. However this is not always true.
•If water is added to compensate for (i) insufficient water batched
initially (ii) water lost due to evaporation (iii) water absorped by the
aggregates during CDT, then the retempering water will not cause
reduction in strength.
• On the other hand, if retempering water is added to compensate for
loss of free water on account of hydration, then the additional water will
lead to increase in water-cement ratio and possible loss of strength.
•It is also possible that retempering may yield acceptable workability
and adequate strength but cause a reduction in durability of concrete.
•Therefore the effect of retempering on durability is of concern as well.
79
Retempering with superplasticizers
•In this method, concrete with an unacceptably small slump is
retempered by addition of appropriate amounts of
superplasticizer.
•This retempering compensates for the loss of slump without
increasing the water-cement ratio.
•The assumption is that the available pore water is adequate
for the formation of the additional hydration products.
•Retempering with superplasticizers generally leads to an
increase in compressive strength as compared to the “un-
restored” concrete, i.e. concrete with low workability.
•Retempering with superplasticizers has also been found to
lead to a reduction in the permeability, and hence lead to more
durable concrete. Improved flowability – leading to better compaction – greater
strength & lower permeability 80
 Retempering with withheld water
•In this method, during initial mixing only a fraction (say 70%)
of the entire water requirement as per mix design is added.
The remaining water is added during the retempering process.
• The gain in compressive strength is reported to be even
higher than the gain in compressive strength on retempering
with superplasticizers. Note: Here wewater
do not make the assumption that available
is adequate for hydration
•However the increase in workability is comparatively less than
in case of retempering with superplasticizers.
•Also unlike in case of retempering with superplasticizers,
retempering with withheld water is reported to have no
influence, positive or negative, on the permeability, and hence
on the durability of the concrete. 81
 Retempering with water
•In this method, slump is restored by adding the requisite
amount of additional water to the mix.
• This method can lead to significant reduction in compressive
strength even though workability can be restored to desired
levels.
•It has been reported that if CDT is small (< 30 mins),
retempering with water may not adversely affect strength.
•This is because in this case the retempered water
compensates for water absorbed by the aggregates or lost due
to evaporation.
•On the other hand, if the CDT is longer, the water required for
restoring workability is considerably higher.Because some of the water required
for lubrication has been lost due to
hydration
•This increases the water-cement ratio and results in concrete
82
with low strength and increased permeability.
 Retempering: some figures
•Suppose we have a mix with 𝑤𝑎𝑡𝑒𝑟: 𝑐𝑒𝑚𝑒𝑛𝑡 𝑟𝑎𝑡𝑖𝑜 0.4
•If 𝑤 is the mass of cement used, water required for hydration 0.25𝑤
•Suppose there has been CDT less than 10 hrs (Final setting time)
•At the time the mix reaches the site, max. hydration 30% 𝑜𝑓 𝑡𝑜𝑡𝑎𝑙
•Water used for hydration .30 .25 .075𝑤
•Water available (for hydration & lubrication) .4𝑤 .075𝑤 .325𝑤
•Water necessary for hydration .7 .25𝑤 .175𝑤
•Water necessary just for lubrication .325𝑤 .175𝑤 .15𝑤
•Suppose weight of water lost due to evaporation & hydration 𝛼𝑤
•Then if: 𝛼 .175𝑤 Hydration is affected:
Cannot be addressed only by retempering with superplasticizers
𝛼 .15𝑤 Lubrication severely affected:
Retempering with superplasticizers may not be enough
𝛼 .15𝑤 Lubrication affected:
Retempering with superplasticizers may be adequate 83
 Compaction of concrete
•Compaction aims to minimize bubbles of entrapped air in concrete.
•Immediately upon placing concrete in the form work, the concrete is
compacted by hand tools or vibrators.
•Hand compaction by tamping rods requires the concrete to flow
readily around the reinforcement bars – thus it usually requires the
concrete to be sufficiently wet i.e. possess higher water cement ratio.
•Compaction by high frequency power driven vibrators allows
compaction to occur without having to increase the water cement ratio
– thus they allow the use of stiffer mixes.
•Compaction using power driven vibrators ensures more impenetrable
and dense concrete, as well as a higher bond between concrete and
reinforcement
•Power vibrators include internal needle vibrators which need to be
immersed in the concrete, as well as external vibrators that act on the
form work. 84