LECTURES NO.

9
ADMIXTURES-II

Objectives:

 To introduce the set-controlling chemicals

 To introduce the mineral admixtures

 Set-Controlling Chemicals
• There are a large number of chemicals that can be used
as retarding admixtures. In addition, there are
chemicals that can accelerate the setting time and the
rate of strength development at early ages.

• Interestingly, some chemicals act as retarders when

used in small amounts (e.g., 0.3% by weight of
cement), but in large dosage (e.g., 1% by weight of
cement) they behave as accelerators.
 Set-Controlling Chemicals

• The retarders can be divided into several groups

according to the type of curve obtained when initial
setting time was plotted against the concentration of
the retarder in the cement-water system.

• Another classification was developed covering both

retarders and accelerators is shown in Fig. 8-5. The
composition of the commonly used chemicals under
each class is also shown in the figure.
• Classification covering both retarders and
accelerators according to the type of curve obtained
when initial setting time was plotted against the
concentration
 Set-Controlling Chemicals
Mechanism of Action
• It is generally accepted that the early reactions of Portland cement
compounds with water occur through solution; that is, the
anhydrous compounds first ionize and then the hydration products
form in the solution.

• Due to their limited solubility, the hydration products crystallize

out and the stiffening, setting, and hardening phenomena with
Portland cement pastes are directly related to different stages of
the progressive crystallization process.

• By adding certain soluble chemicals to the Portland cement-water

system, one can influence either the rate of ionization of cement
compounds or the rate of crystallization of the hydration products.
 Set-Controlling Chemicals
Mechanism of Action
•  The action of set-controlling chemicals on Portland cement can be
attributed mainly to dissolving of the anhydrous constituents rather
than to the crystallization of the hydrates.

• To understand the mechanism of acceleration or retardation, consider a

hydrating Portland cement paste as being composed of calcium cations
and silicate and aluminate anions, the solubility of each being
dependent on the type and concentration of the acid and base ions
present in the solution.

• Because most chemical admixtures readily ionize in water, it is

possible to alter the type and concentration of the ionic constituents in
the solution phase by adding these admixtures to the cement-water
system.
 Set-Controlling Chemicals
Mechanism of Action
Therefore, the chemical admixtures expected to influence the dissolution
of the cement compounds according to the following guidelines:

1.An accelerating admixture must promote the dissolution of the

cement cations or anions from the cement. As there are two
predominant anions to dissolve, the accelerator should promote the
dissolving of that constituent which has the lowest dissolving rate
during the early hydration period (such as the silicate).

2.A retarding admixture must impede the dissolution of the cement

cations or anions, preferably that anion which has the highest
dissolving rate during the early hydration period (such as the
aluminate).
 Set-Controlling Chemicals
Mechanism of Action
The influence on the dissolution of the cement compounds according to
the following guidelines (con’t):

3.The presence of monovalent cations in solution (i.e., K+ or Na+)

reduces the solubility of Ca2+ ions but tends to promote the solubility of
silicate and aluminate ions. In small concentrations, the former effect is
dominant; in large concentrations, the latter effect becomes dominant.

3.The presence of certain monovalent anions in solution (i.e., Cl−, NO-3

or SO42- ) reduces the solubility of silicates and aluminates but tends to
promote the solubility of calcium ions. In small concentrations, the
former effect is dominant; in large concentrations, the latter effect
becomes dominant.
 Set-Controlling Chemicals
Mechanism of Action
• The overall outcome when a chemical admixture is added to a
Portland cement-water system will be determined by the type
and concentration of ions contributed to the solution by the
admixture.

• When used in small concentration (e.g., 0.1 to 0.3% by mass of

cement), the salts of weak bases and strong acids (e.g., CaCl2) or
strong bases and weak acids (e.g., K2CO3), the retardation
effect on the solubility of calcium and aluminate ions from the
cement is the more dominant effect than the acceleration of
solubility of silicate ions; hence the overall result is
retardation.
 Set-Controlling Chemicals
Mechanism of Action
• With larger concentrations (e.g., 1% or more) of these salts, the
accelerating effect of the ions in solution on the solubility of the
silicate and the aluminate ions of cement become the more
dominant effect than the retarding effects; thus, it is possible
for the same salt to change its role and become an accelerator
instead of a retarder.

• It should be noted that CaCl2 (with 1 to 3% by mass of cement),

is the most commonly used accelerator for unreinforced
concrete.
 Applications

Accelerating admixtures. Accelerating admixtures are useful for

modifying the properties of Portland cement concrete, particularly in
cold weather, to:

(a) expedite the start of finishing operations and, when necessary, the
application of insulation for protection;
(b) reduce the time required for proper curing and protection;
(c) increase the rate of early strength development so as to permit earlier
removal of forms and earlier opening of the construction for service; and
(d) permit more efficient plugging of leaks against hydraulic pressures.
 Applications
Retarding admixtures. the following applications of retardation of setting are
particularly important in the construction practice:

a) Adverse ambient temperature conditions such as hot weather concreting.

Extensive use is made of retarding admixtures to permit proper placement and
finishing, and to overcome the damaging and accelerating effects of high
temperature.
b) Control of setting in large structural units to keep concrete workable
throughout the entire placing period. This is particularly important for the
elimination of cold joints and discontinuities in large structural units. Also,
control of setting may prevent cracking of concrete beams, bridge decks, and
composite construction due to form deflection associated with the placement of
adjacent units.
 Mineral Admixtures
INTRODUCTION
• Nowadays it is a normal practice to use blended cements for
producing a durable and economical concrete and to save
the energy and to reduce the environmental pollution.

• These blended cements are obtained by intergrinding or

blending Portland cement with particular mineral
admixtures.

• Pozzolanic materials (i.e., natural pozzolana or artificial

pozzolana such as fly ash, silica fume) and ground
granulated blast furnace slag (GGBS) are among the most
widely used mineral admixtures for manufacturing the
blended cements.
 SOURCES AND CHARACTERISTICS
Natural pozzolana:
• Obtained by grinding the sediments of volcanic eruptions
• Contains mainly silica
• Example: Italian pozzolana, which was used by the Romans.

Fly ash (FA) also called as pulverized fly ash (PFA):

• Obtained from thermoelectric power plants
• Contains mainly the silica and a small percentage of alumina with a negligible amount of
lime
• Fineness in the range of 300 to 600 m2/kg, which is about same as the fineness range of
Portland cements

Silica fume (SF) also called as microsilica, etc:

• Obtained from the industries manufacturing ferro-silicon alloys
• Contains mainly the silica
• Has fineness very high, about 100 times more finer than common Portland cements

Ground granulated blast furnace slag (GGBS):

• Obtained in huge quantities from the blast furnaces used for production of pig iron in the
iron industries
• Contains all the main components of Portland cement (i.e., lime, silica, and alumina), thus
behaves like a cement
 DIFFERENCE BETWEEN POZZOLANA AND GGBS

• A pozzolanic material is defined as a siliceous or

siliceous and aluminous material without
considerable lime, which in itself possesses little or
no cementing property
whereas
• A GGBS, containing lime, silica, and alumina, has a
similar behavior as a Portland cement.
therefore,
• Pozzolanic materials may only be used as admixtures
for cement
• GGBS having self-cementing charecteirstics and
thus, may either be used alone as a binder or may be
used as admixture for cement.
 Composition of cement and mineral admixtures
plotted on a C-S-A ternary diagram
(Classification of mineral admixtures by RILEM, source: the concrete portal)
 Source:
www.ce.memphis.edu/1101/notes/concrete/PCA_manual/Chap03.pdf
CHAPTER 3 Fly Ash, Slag, Silica Fume, and Natural Pozzolans
EFFECTS OF MINERAL ADMIXTURES ON DURABILITY
Effect on Microstructure of Hydrated Concrete
 The reaction between silica (from a mineral admixture) and
lime (from a Portland cement) results into the formation of a
secondary C-S-H, as follows:
C3S (of Portland cement) + H → C-S-H (primary) + CH (lime)

S (present in Pozzolana or GGBS) + CH (lime liberated from PC) +H

→ C-S-H (secondary)

 The additional C-S-H gel, produced as a result of above

secondary hydration reaction, makes the pore structure of
concrete denser, as shown in the following figure, thereby
reducing the penetration and diffusion of concrete by the
aggressive agents.
EFFECTS OF MINERAL ADMIXTURES ON DURABILITY
Effect on Microstructure of Hydrated Concrete
 EFFECTS OF MINERAL ADMIXTURES ON DURABILITY
Effect on Resistivity of Concrete

 The resistivity of concrete

made using the mineral
admixtures is found to be
significantly higher than
that of ordinary Portland
cement concrete, thereby
reducing the rate of
reinforcement corrosion.
 This is due to the
achievement of a dense
microstructure of concrete
made using a mineral Effect using the mineral admixtures on
admixture. resistivity of concrete
w/c = 0.45, 2% chloride mixed-in
CEM I: OPC; CEM II/B-V: PFA cement; CEM
III/B: GGBS cement
 EFFECTS OF MINERAL ADMIXTURES ON DURABILITY
Effect on Chloride Diffusivity of Concrete

 Diffusivity of chloride ions in PFA concrete is reported to

be about 2 times lesser and in GGBS concrete 8 times
lesser as compared to the OPC concrete, at a typical w/c
ratio of 0.5.

 10% addition of silica fume is reported to reduce the

coefficient of chloride diffusion from 227×10-13 m2/s to
22×10-13 m2/s
 EFFECTS OF MINERAL ADMIXTURES ON DURABILITY
Effect on Resisting Reinforcement Corrosion

Time to initiation of reinforcement Corrosion current density on steel in

corrosion in plain and blended cement plain and blended cement concretes,
concrete specimens after 425 days.
PRACTICAL DOSAGES OF THE MINERAL ADMIXTURES

 The activities of pozzolanic materials depend on the silica

content and fineness of a mineral admixture.
 The amount of a mineral admixture should be proportioned
to the amount of CH (lime) produced in the hydration of
Portland cement. Any excess addition of the mineral
admixture will not react and thus will behave as an inert
material.
 The amount of fly ash addition to Portland cement
generally ranges from 20 to 40% (very commonly 20%) of
the total cement content.
 Silica fume is usually added in the range of 5 to 10% (very
commonly 7%) of the total cement content.
 In order to achieve an optimal densification of concrete the
GGBS content should be higher than 65%.