4 Admixtures and Additions

4.1 Admixtures
Admixtures are compounds added in small quantities at the mixing stage of concrete, with the aim of
modifying or improving certain properties of fresh and/or hardened concrete. Admixtures, while
imparting beneficial effects may have harmful effects as well. Therefore, the selection and use of
admixtures have to be done cautiously.
Nowadays, mostly admixtures are available as proprietary formulations. The behaviour of an
admixture in concrete depends on the properties of cementitious material, aggregate, other
admixtures, temperature and mixing methods. Therefore, the properties given in
manufactures’ trade literature cannot be treated no more than an approximate guide. The real
behaviour can be observed only by making trial mixes under the proposed condition, viz.,
batching/mixing method, temperature, and with the intended ingredients.
Admixtures can be categorized in different ways. One such division is based on the water – solubility
of the compound. Another division is based on whether the compounds are active, interactive or
passive. By definition, active admixtures react with the soluble components of cement to produce a
compound imparting the effect; interactive admixtures are surface-active compounds associating
with liquid-air and solid-liquid interfaces; passive admixtures do not change their form and give only
a physical contribution. During early days, admixtures were classified as chemical admixtures.
Chemical admixtures are mainly liquids, either in solution or in suspension form. They may also be in
the form of water-soluble solids.

4.2 Types of Admixtures and Their Applications

Some types of admixtures and their applications are briefly outlined in Table 4.1.
Table 4.1 - Some types of admixtures
Category of Admixture
Air – entraining admixture
Set – retarding admixture
Set – accelerating admixture
Very fast set –accelerating admixture
Hardening- accelerating admixture
Brief Description of Application
Air – entraining admixture is primarily used where freeze –
thaw resistance of the resulting concrete needs to be
enhanced. Besides, it helps to improve cohesiveness, reduce
bleeding, and plastic settlement of fresh concrete, where the
mix is lean and lacks fine particles, or the fine aggregate lacks
particles toward fine end. Mere addition of air-entrainer to an
existing mix enhances workability, it but reduces strength.
Offsets the acceleration of setting of concrete in hot weather,
and thereby to maintain the normal setting time (Figure 4.1).
Slows down the falling of consistence, and the formation of
unintentional joints called cold joints. May be used as a
surface spray in making exposed aggregate finish. Slip forming.
Offsets the delay in setting of concrete in cold weather, and
thereby to maintain the normal setting time (Figure 4.1). Also
used to shorten the finishing time. Reduces the chance of early
frost attack.
Used in sprayed concrete or shotcrete, and also in water
plugging (not to be confused with under-water concreting).
Suitable for applications where rapid early strength gain is
required (Figure 4.2). Early formwork side removal.
26

Table 4.1 – Some applications of admixtures (continued.)

Water-reducing/ plasticizing
admixture
Set-retarding/water-
reducing/plasticising admixture
Set-accelerating/water
reducing/plasticizing admixture
High-range water-
reducing/superplasticizing admixture
Set-retarding/high-range water-
reducing/ superplasticizing admixture
Water-retaining admixture
Water-resisting admixture
Viscosity-modifying admixture
Corrosion inhibiting admixture
Alkali-silica reaction mitigating
admixture
Shrinkage reducing admixtures
Polymer modifiers
Useful in achieving increased workability of a given mix
without an increase in water content, achieving high-strength
without increasing cement, or obtaining specified strength at
lower cement content. (Figure 4.3).
Useful for applications where set-retarding property
(secondary function) is needed in addition to that of water-
reducing property (primary function).
Useful for applications where set-accelerating property
(secondary function) is needed in addition to that of water-
reducing property (primary function).
Applicable for making high - strength and/or high-workable
concrete, including self – compacting concrete (SCC). Effective
in reducing permeation.
Applicable where combined effects of a high-range water-
reducing/ superplasticizing admixture (primary function) and a
set-retarding admixture (secondary function) is desired.
For minimizing bleeding, and thereby to reduce plastic
settlement, and permeability as a reduction of bleed channels.
For reducing capillary rise and damp - proofing.
In high-workable concrete, under-water concreting.
For prolonging the service life by delaying the onset of steel
corrosion.
For slowing down alkali-silica reaction (ASR), where non-
reactive aggregates are not practically available.
For mitigating shrinkage induced cracking.
For bonding overlays, and repair works, and to reduce
permeability.

Increasing temperature or
Decreasing temperature or
adding accelerator
adding retarder

27.6
Penetration resistance

3.5

Final setting time

Initial setting time
(Vibration limit)
Time lapsed
Figure 4.1 – Effects of temperature, accelerating admixture and retarding admixtures on setting time
27 CE 592 – Concrete
Technology

With accelerator

Compressive Without accelerator

1-d 7-d 28-d

Age

Figure 4.2 – Effect of accelerating admixture on strength

Strength > A + WRA Strength > A

Workability = B Less water Workability = B

More cement
Strength = A Workability = B Strength = A Workability = B
+ WRA
Less water
More cement Less cement
More water
Strength = A Workability > B Strength = A Workability > B
+ WRA

Figure 4.3 – Role of water – reducing admixtures

4.3 Active Ingredients and Effectiveness

The following section briefly outlines the types of active ingredients of certain types of admixtures.
4.3.1 Air – Entraining Admixture
Certain cements are incorporated with air-entrainers at the stage of production, e.g., ASTM Type IA,
IIA, etc. When added at the production of cement, the compound is called an additive. Admixtures
are the ones added to the mix at the mixing stage of concrete, mortar, grout or paste. This
description is true not only for air-entrainers, but for all other chemicals as well.
Air-entrainers are surface active chemicals, reducing surface tension of water. Some of the liquid or
water-soluble powdered air-entraining agents are composed of: wood resins; synthetic detergents;
salts of sulphonated lignin; salts of petroleum acids; fatty and resinous acids and their salts; and
organic salts of sulphonated hydrocarbons. However, every material listed will not produce a
desirable size of air bubbles and dispersions.
Gas-forming admixtures like, hydrogen peroxide, aluminium powder, and modified-protein foaming
agents are NOT fitting to the air-entraining category.
28

The amount of air-entraining admixture necessary to obtain a required air-content depends on many
factors. Particle shape and grading of aggregate in concrete or mortar are among them. Demand for
dosage of air-entrainer, for a required air-entrainment is increased where: the cement content in the
mix or the fineness of cement is increased; the amount of fine materials like fly-ash and carbon in
the mix is increased; and the temperature of the fresh mix is increased. Within limits, the increase in
dosage of the air-entrainer, increases the amount of air entrained.
It is highly important to measure the air content and to compare it with the expected value.
Unnoticed increase in air content will lead to have concrete with reduced strength.
4.3.2 Set-Retarding Admixture and Water-Reducing Admixture
Set-retarding admixtures are used primarily for offsetting the set-acceleration and fast loss of
workability, and associated problems such as the increased tendency to form cold-joints, caused by
rapid hydration in hot-weather. Besides, deliberate retardation is effected to minimize cracking of
concrete beams and slabs, caused by formwork deflection during continuous concreting; in slip-
forming and underwater concreting; lowering the early rate of temperature rise due to hydration;
and obtaining architectural exposed aggregate finish.
The extent of retardation can be increased by increasing the dosage of the admixture. The dosage is
expressed in proportion to a mass of cement, say x mL/100 kg of cement. However, with increasing
dosage, air content is also increased as an unintentional side effect.
Some of the categories of chemicals used for the purpose, singly or in combination with other
compounds are:
1. Lignosulfonic acid or modifications, and derivatives of lignosulfonic acid and its salts
2. Hydroxylated carboxylic acid or modifications, and derivatives of hydroxylated acid and its
salts
3. Carbohydrates, polysaccharides and sugar acids
4. Inorganic salts such as borates and phosphates
In many instances, chemical compounds giving set-retarding effect also impart water-reducing
properties, and vice-versa. Reduction of water demand for a given workability, or in other words, the
increase of workability by adding the admixture without increasing water content is caused by the
deflocculation of cement particles accommodating a layer of water in between, and entrainment of
air. Water-reducing admixtures also help to reduce bleeding and segregation in fresh concrete,
partly due to the air-entrainment.
The effect of increasing workability without addition of water helps to get increased strength
without increasing the content of cement. Also, the same strength can be achieved with lesser
amount of cement (Figure 4.3). This allows reducing the total heat generated by the mix.
The extent of water reduction or increase in workability depends on the admixture dosage.
However, very high degree of water reduction or increase in workability cannot be achieved by
extreme dosages of water-reducing admixtures, due to the prominence of adverse side effects, such
as excessive retardation and air-entrainment at such dosages.
For applications where very high degree of water-reduction is needed, a different class of
admixtures called high-range water-reducing or superplasticizing admixtures are to be used.
29 CE 592 – Concrete
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4.3.3 High-Range Water-Reducing or Super plasticizing Admixture

Whenever a water-reducing effect greater than that is possible with water-reducing admixtures,
high-range water-reducing or superplasticizing admixtures are needed. Chemicals used as high-range
water-reducing admixtures are of large molecular weight, and not by-products as water-reducing
admixtures. Hence, they are more expensive. Some of the chemicals used for the purpose are:
1. Sulfonated naphthalene formaldehyde (SNF)
2. Sulfonated melamine formaldehyde (SMF)
3. Polycarboxylate ester
4. Copolymer of carboxylic acrylic acid with acrylic ester
5. Cross – linked acrylic polymer
Superplasticizers enhance the mobility of cement paste as a result of electrostatic repulsion of
cement particles with adsorbed admixture molecules. Rheological behaviour of superplasticized
cement paste is shown in Figure 4.4.

Without admixture

Superplasticizer
Shear stress,

dosage

Shearing rate ,𝛾̇

Figure 4.4 – Effect of superplasticizer on rheological properties of paste

Unlike water-reducing admixture, high-range water-reducing admixture does not entrain air. In fact,
with this type of admixture it becomes difficult to entrain air, when air-entrainment is a
requirement.
When choosing a high-range water-reducing admixture, compatibility of that with the cement used
has to be checked. Otherwise, the effectiveness in water reduction will be less prominent, and short
lived.
Marsh cone and mini - slump tests can be used to judge the compatibility. Typical Marsh cone
behaviour patterns are shown in Figure 4.5.
30

Flow
Flow

60 min
60 min
5 min
Saturation point 5 min

Superplasticizer dosage Superplasticizer dosage

(a) (b)
Figure 4.5 – Compatibility test by Marsh flow time (a) compatible (b) incompatible
Finer cements have a larger specific surface area than the coarser ones. Since the admixture is
adsorbed to the surface of particles, higher dosage of admixture is needed for finer cement than for
coarser ones to get the same effect of water reduction. Cements with high C 3A content reduce the
effectiveness of superplasticizer. On the other hand, cements with very low content of C 3A may
result in excessive retardation.
Consumption of admixture by cement with the commencement of the hydration reaction leads to
rapid loss of flowability achieved with the admixture. Therefore, in order to retain the effect of
water reduction for a longer period, superplasticizers except polycarboxylate type, have to be added
as the last ingredient, with a smaller fraction of mixing water, toward the latter part of mixing.
Retarder added at the beginning of mixing may also help to prolong the water reducing effect of
superplasticizer. Redosing of the admixture is helpful in restoring the lost workability with time.
However, multiple re-dosing is less effective.
Because of the effective deflocculating action, superplasticizers are beneficial where very fine
additions like silica fume or pigments are to be effectively dispersed in a cementitious mix.
Even though the direct benefit of superplasticizer is to get desired workability with much less water
content, concrete mixes can be designed by making use this characteristic to obtain:
(1) high-strength concrete;
(2) reduced cement content;
(3) reduced heat of hydration;
(4) reduced diffusivity and water permeability even under pressure; and
(5) increased strength at early age such as at 3-7 days without increasing cement content.
All those benefits are obtainable as a result of the possibility of reducing water in the mix at
proportioning stage, causing reduction of water-cement ratio. These benefits can be achieved to a
lesser degree with water-reducing or plasticizing admixture. The benefit (5) is illustrated in
Figure 4.6.
31 CE 592 – Concrete
Technology

With admixture,
reducing w/c ratio
while maintaining
workability

Compressive Without admixture

1-d 3-d 7-d 28-d

Age

Figure 4.6 – Utilization of water reduction to gain high early as well as late strength
It is to be emphasised that mere addition of water-reducing or high-range water-reducing admixture
to a mix without keeping the water content reduced does not give those benefits listed under (1)
through (5).
4.5.4 Accelerating Admixture
It was mentioned earlier, the existence of two types of accelerating admixtures: one is specifically
for advancing the time of setting; and the other is for increasing the early strength gain. In general,
there is some acceleration of setting even with the later type.
Very fast set acceleration is useful for pneumatic placing of concrete, commonly called shotcreting.
There are two methods involved: one is dry method, where blended dry ingredients are carried to
the spray nozzle by compressed air, and water with admixture is fed to the nozzle. In the other
method, which is called wet-method, concrete of pumpable consistency is directed to the spray
nozzle, where admixture and compressed air are fed. Concrete should stiffen upon reaching the
surface where it is to be applied, in order to minimize rebouncing and sloughing. The quick setting or
stiffening is highly necessary in overhead applications.
Chemicals such as sodium aluminate, sodium fluoride, potassium carbonate, and those based on
sodium and potassium silicates can impart fast set-accelerating properties.
Hardening accelerators find application mainly in cold weather to compensate the retardation of
hydration reaction at low temperature. It reduces the setting time so that finishing operations can
proceed without undue delay. In this way, shutter and mould stripping, lifting and handling of
precast items and finishing of flatwork can proceed normally. In addition, liability to damage by early
age freezing can also be eliminated. However, these admixtures do not lower the freezing point of
water.
Calcium chloride is a simple set and hardening accelerator. However, due to the risk of corrosion of
embedded steel due to chlorides, that compound should always be avoided in reinforced and
prestressed concrete, where only chloride-free accelerators (CFA) to be used. Chloride-free
hardening accelerators include: calcium nitrite and calcium nitrate; calcium formate and
triethanolamine. Calcium nitrite and calcium nitrate have corrosion inhibition properties as well.
Triethanolamine, an accelerator, is not used alone, but with others to compensate the retarding
effect of those. An example is making normal water-reducing admixtures.
32

4.5.5 Water-Resisting or Damp-Proofing Admixture

Water-resisting admixture is sometimes called incorrectly as water-proofing admixture. Actually, this
category is effective in reducing sorptivity of concrete. Sorptivity is the property of sucking water into
capillaries due to surface tension effect.
Hydrophobic layer

(a) (b)

Figure 4.7 – Contact angles (a) without water-resisting admixture (b) with admixture
The admixture alters the concrete surface by forming a thin hydrophobic layer, so that the surface
becomes water-repellent. This action is illustrated in Figure 4.7. The repellence so given to concrete
is only effective in preventing water from entering the capillaries when the applied water pressure is
small. That is why this type of admixture is called damp-proofer. Not only high hydraulic pressure in
water-retaining structures, even raindrops blown at high wind speeds and hitting a concrete surface
may cause pressure sufficient to overcome the benefits of water repellents.
Damp-proofers are mainly based on fatty acids, such as oleic (C 17H33COOH), caprylic (C7H15COOH),
capric (C9H19COOH), and stearic acid (C17H35COOH). However, the effectiveness of some products is
enhanced by combining those with tiny globules of polymers which joined forming a kind of plug in
pores under pressure. Still, they are not effective for the purpose of water proofing at high pressure.
4.6 Specifications for Admixtures
The essential properties of admixtures should satisfy the limits given in appropriate standards.
Among the many standards available, only limited examples are cited herein from the European and
ASTM standards.
4.6.1 European Specifications
The standard – Admixtures for concrete, mortar and grout–part 2: Concrete admixtures–Definitions,
requirements, conformity, marking and labelling (EN 934 – 2: 2009 + A1:2012) deals with commonly
used admixtures. The specific requirements given in Tables 4.3 to 4.8 are given in that standard.
Tests shall be performed on reference mortar of composition used for cement testing (EN 196 -1) or
reference concrete as specified in EN 480-1:2006 + A1:2011. The reference concrete and mortar
shall be made with a CEM I cement of strength class 42.5 or 52.5 conforming to EN 197-1. The
cement used shall have a C3A content of 7 % to 11 % by mass calculated from chemical analysis
according to EN 196-2, and a specific surface area of 360 to 460 m²/kg determined according
to EN196-6. Natural normal-weight aggregate conforming to EN 12620 with low water absorption
(less than 2 % by mass) and falling within a range of grading is specified for the mixes.
There are 4 types reference concrete described in EN 480 – 1, and the requirements are shown in
Table 4.2.
33 CE 592 – Concrete
Technology

Table 4.2 – Requirements for reference concrete a

Reference concrete Cement content c Consistence at required test temperature
kg/m³ Slump b Flow d
(mm) (mm)
I 350 ± 5 70 ± 10 400 ± 20
II 300 ± 5 120 ± 20 450 ± 20
III 350 ± 5 50 ± 10 350 ± 10
IV 350 ± 5 30 ± 10 350 ± 20
a
When testing at equal w/c ratio the requirements for consistence shall only apply to the control mix.
b
These tests are alternatives and have to be chosen before starting the test. Slump shall be determined in
accordance with EN 12350-2 or flow in accordance with EN 12350-5 respectively.
c
Control mix only: The resulting cement content of the test mix may change as a result of volume change to
concrete caused by water reducing or air entraining effects of the admixture under test.
d
For high range water reducing/superplasticising admixture the consistence of the test mix shall be not less
than the consistence of the control mix with no upper limit on consistence of the test mix .
Control mix is the one without admixture, and test mix is the one with admixture at compliance
dosage, which is within the range of recommended dosage stated by the manufacturer. Setting time
is determined on mortar by procedure described in EN 480 -2, using Vicat apparatus. Instead, in the
former British method and ASTM method, penetration resistance is measured with a plunger. So,
those results are not comparable, and hence cannot be applied on EN specifications.
Table 4.3 - Specific requirements for set-retarding admixtures (at equal consistence) [8]*
Property Reference Test method Requirements
mortar/concrete
Setting time EN 480 – 1 EN 480 - 2 Initial: test mix ≥ control mix + 90 min
MortarA Final: test mix ≤ control mix +360 min
Compressive EN 480 - 1 EN 12390 - 3 At 7 days:
strength reference Test mix ≥ 80 % of control
concrete I mix At 28 days:
Test mix ≥ 90 % of control mix
Air content in EN 480 – 1 EN 12350 - 7 Test mix ≤ 2 % by volume above control
fresh concrete reference mix
concrete I unless stated otherwise by the manufacturer
*
Shown in square brackets are the Table numbers in EN 934-2: 2009
A
The composition of reference mortar is by mass shall be one part of the cement, three parts of
CEN standard sand, and one half part of water (water/cement ratio 0.50).
Table 4.4 – Specific requirements for water-reducing/plasticizing admixtures (at equal consistence) [2] *
Property Reference Test method Requirements
concrete
Water EN 480 – 1 slump EN In test mix ≥ 5 % compared with control
reduction reference 12350 – 2 or mix
concrete I flow EN
12350 5
Compressive EN 480 – 1 EN 12390 - 3 At 7 and 28 days:
strength reference Test mix ≥ 110 % of control mix
concrete I
Air content in EN 480 – 1 EN 12350 - 7 Test mix ≤ 2 % by volume above control
fresh concrete reference mix
concrete I unless stated otherwise by the manufacturer
34

Table 4.5 – Specific requirements for high-range water-reducing/ superplasticizing admixtures (at
equal consistence) [3.1]*
Property Reference Test method Requirements
concrete
Water EN 480 – 1 slump EN In test mix ≥ 12 % compared with control
reduction reference 12350 – 2 or mix
concrete I flow EN
12350 -5
Compressive EN 480 – 1 EN 12390 - 3 At 1 day:
strength reference Test mix ≥ 140 % of control mix
concrete I At 28 days:
Test mix ≥ 115 % of control mix
Air content in EN 480 – 1 EN 12350 - 7 Test mix ≤ 2 % by volume above control
fresh concrete reference mix
concrete I unless stated otherwise by the manufacturer

Table 4.6 - Specific requirements for high-range water-reducing/ superplasticizing admixtures ( at

equal w/c ratio)a [3.2]*
Property Reference Test method Requirements
concrete
Increase in EN 480 - 1 slump EN Increase in slump ≥ 120 mm from initial
consistence reference 12350 – 2 or (30 ±
concrete IV flow EN 10) mm
12350 - 5 Increase in flow ≥ 160 mm from initial (350
±
20) mm
Retention of EN 480 – 1 slump EN 30 min after the addition, the consistence of
consistence reference 12350 -2 or the test mix shall not fall below the value of
concrete IV flow EN the initial consistence of the control mix
12350 - 5
Compressive EN 480 – 1 EN 12390 - 3 At 28 days:
strength reference test mix ≥ 90 % of control mix
concrete IV
Air content in EN 480 – 1 EN 12350 - 7 Test mix ≤ 2 % by volume above control
fresh concrete reference mix
concrete IV unless stated otherwise by the manufacturer
a
The compliance dosage for admixtures used to meet the requirement of Table 4.7 does not have
to be the same as that used to meet the requirements of Table 4.6.

Table 4.7 – Specific requirements for set-accelerating admixture (at equal consistence) [6] *
Property Reference Test method Requirements
mortar/concrete
Initial setting EN 480 – 1 EN 480 - 2 At 20 °C: test mix ≥ 30 min
time mortar At 5 °C: test mix ≤ 60 % of control mix
Compressive EN 480 – 1 EN 12390 - 3 At 28 days:
strength reference Test mix ≥ 80 % control mix
concrete I At 90 days:
Test mix ≥ test mix at 28 days
Air content in EN 480 – 1 EN 12350 - 7 Test mix ≤ 2 % by volume above control
fresh concrete reference mix
concrete unless stated otherwise by the manufacturer
35 CE 592 – Concrete
Technology

Table 4.8 - Specific requirements for hardening-accelerating admixture (at equal consistence) [7] *

Property Reference Test method Requirements

concrete
Compressive EN 480 – 1 EN 12390 - 3 At 20 °C and 24 h: test mix ≥ 120 % of
strength reference control
concrete I mix
At 20 °C and 28 days: test mix ≥ 90 % of
control mix
At 5 °C and 48 h: test mix ≥130 % of
control
mix
Air content EN 480 – 1 EN 12350 - 7 Test mix ≤ 2 % by volume above control
reference mix
*
Shown in square brackets are the Table numbers in EN 934-2: 2009

Designation of admixtures according to EN 934-2:2009

EN 934-2: Table Number1 & Table Number2
Example of designation of high range water reducing/super plasticizing admixture for concrete
EN 934-2:T3.1 & T3.2
4.6.2 ASTM Specifications
ASTM classification is widely used in product descriptions. Some of the products may qualify for
more than one type.
ASTM C494/C494M – 17, covers 8 types of admixtures, and their performance requirements are
shown in Table 4.9:
Type A – Water - reducing
Type B – Retarding
Type C – Accelerating
Type D – Water-reducing and retarding
Type E – Water- reducing and accelerating
Type F – Water-reducing, high range
Type G – Water-reducing, high range, and retarding
Type S – Specific performance

Testing of admixtures for non-specific applications is done on concrete mixes having 307 ± 3 kg/m3 of
ASTM Type I or Type II cement or blend of cements in equal parts , aggregate of grading specified in
ASTM C494/C494M, and slump of 90 ± 15 mm.

It is to be noted that for the purpose of ASTM C494/C494M, setting time is to be determined on
screened mortar, using the penetrometer following the procedure of ASTM C403/C403M.
36

Table 4.9 – Physical requirements for admixturesA (Table 1 of ASTM C494/C494M – 17)
Type A, Type B, Type C, Type D, Type E, Type F, Type G, Type S,
Water Retarding Accelera Water Water Water Water Specific
Reducing -ting Reducing Reducing Reducing Reducing Performa
and and High High -nce
Retarding Accelerating Range Range and
Retarding
Water content, max % of
95 … … 95 95 88 88 …
control
Time of setting, allowable
deviation from control,
h:min:
Initial: at least … 1:00 1:00 1:00 1:00 … 1:00
later earlier later earlier later
not more than 1:00 3:30 3:30 3:30 3:30 1:00 3:30 1:00
earlier later earlier later earlier earlier later earlier
nor 1:30 nor 1:30 nor
later later 1:30
later
Final: at least … … 1:00 … 1:00 … …
earlier earlier
not more than 1:00 3:30 … 3:30 … 1:00 3:30 1:000
earlier later later earlier later earlier
nor 1:30 nor 1:30 nor
later later 1:30
later
Compressive strength, min, %
of control:B
1 day … … … … … 140 125 …
3 days 110 90 125 110 125 125 125 90
7 days 110 90 100 110 110 115 115 90
28 days 110 110 110 110
90 100 110 90
(120)C (120)C (120)C (120)C
90 days (117)C n/a n/a (117)C n/a (117)C (117)C n/a
6 months 100 90 90 100 100 100 100 90
(113)C (113)C (113)C (113)C
1 year 100 90 90 100 100 100 100 90
Flexural strength, min, %
control:B
3 days 100 90 110 100 110 110 110 90
7 days 100 90 100 100 100 100 100 90
28 days 100 90 90 100 100 100 100 90
Length change, max
shrinkage (alternative
requirements):D
Percent of control 135 135 135 135 135 135 135 135
Increase over control 0.010 0.010 0.010 0.010 0.010 0.010 0.010 0.010
Relative durability factor,
80 80 80 80 80 80 80 80
minE
A
The values in the table include allowance for normal variation in test results. The objective of the 90 % compressive strength
requirement for a Type B and Type S admixture is to require a level of performance comparable to that of the reference concrete.
B
The compressive and flexural strength of the concrete containing the admixture under test at any test age shall be not less than 90 %
of that attained at any previous test age. The objective of this limit is to require that the compressive or flexural strength of the concrete
containing the admixture under test shall not decrease with age.
C
Alternative requirement. If the physical requirements are met and any of the measured relative strengths are greater than the
requirement in parenthesis, the admixture shall be considered provisionally qualified until the 1-year strength test results are obtained.
D
Alternative requirements, see 17.1.4, % of control limit applies when length change of control is 0.030 % or greater; increase over
control limit applies when length change of control is less than 0.030 %.
E
This requirement is applicable only when the admixture is to be used in air-entrained concrete which may be exposed to freezing and
thawing while wet.
37 CE 592 – Concrete
Technology

Specific performance (ASTM Type S) is defined as an admixture that provides a desired

performance characteristic(s) other reducing water content, or changing the time of setting of
concrete, or both, without any adverse effects on fresh, hardened and durability properties of
concrete as specified.
Those specific performance characteristics include, but are not limited to, shrinkage reduction,
mitigation of alkali-silica reaction, and viscosity modification. In the context of the aforementioned
specification, water-repellent, and efflorescence-controlling admixtures are not falling within Type S.

There are five more ASTM specifications other than ASTM C494/C494M – 17, on chemical
admixtures:
 Standard Specification for Cold-Weather Admixture Systems (ASTM C1622/C1622M-10
(2016) e1)
 Standard Specification for Admixtures to Inhibit Chloride-Induced Corrosion of
Reinforcing Steel in Concrete (ASTM C1582/C1582M-11 (2017) e1)
 Standard Specification for the use of Chemical Admixtures for use in Producing Flowing
Concrete (ASTM C1017/C1017M – 13e1)
 Specification for Air-entraining Admixtures for Concrete (ASTM C260/C260M – 10a
(2016))
 Standard Specification for Admixtures for Shotcrete (ASTM C1141/C1141M-15)

Cold-weather admixture is defined as an admixture or group of admixtures that depress

and in concrete. These
the freezing point of mixing water increases the hydration rate of cement
admixtures are to be added to hydraulic-cement concrete to when the
avoid early frost
temperature of the concrete immediately after placement is as low as -5.0

4.7 Mineral Admixtures or Additions

When are needed for a job but are not available on the the
some of the types of
quality of the required type of cement may be achieved
by incorporating suitable additions to
readily available general - purpose cements at the of concrete or mortar.
mixing
The standard - Concrete — Part 1: Specification, performance, production and conformity (EN 206 -
1:2000 + A1:2004 +A2: 2005) defines addition as, finely divided material used in concrete in order to
improve certain properties or to achieve special properties.
This standard deals with two types of inorganic
— and
Type nearly inert
Type — pozzolan or latent additions.
For an example, instead of using pigmented cement, the character of it can be achieved by adding
pigments to the grey coloured or white Portland cement at the mixing stage of concrete or mortar.
Here, the pigment is an inert or nearly inert addition, since there is no significant reaction between
cement and the pigment.
Another example is, say, CEM II/B – V is needed for a concrete construction to ensure durability. But
that type is not available in the locality. Then, the required character can be achieved by mixing
CEM I with siliceous fly ash at the dosage of 21-35 % of the mass of CEM I at the concrete mixing
stage. The cementitious material so is called a combination according to BS and is
designated in this particular instance as CIIB – V. In that example, the causing
addition is
The additions,
additional in the form of powders finer than
cementitious also act as nucleation sites for C- H and
involves in reducing porosity of the transitional or interfacial between aggregate and
38

cement paste. This

strengthens the weak region where micro-cracks are leading to failure are
originated.
4.7.1 Supplementary Cementitious Material
The term, supplementary cementitious material (SCM), refers to a group of inorganic
that
contributes to the properties of a cementitious mixture through hydraulic or pozzolanic activity, or
both.

Pozzolanic is the reaction of silicon and aluminium compounds of SCM with the Ca(OH)2
liberated from hydration reaction. Latent hydraulic refers to the slow reaction between
calcium and silicon/aluminium compounds of a material and formation of substance that is capable

0 100
of hardening under water. Blast furnace slag and some types of fly ash possess latent hydraulic
property. Under normal temperature, silica only in amorphous or non-crystalline form can react with
Ca(OH)2.

Figure 4.8 – Tri-linear composition diagram of some cementitious materials

There are different types of supplementary cementitious materials, and are waste
most of
materials of industries. Typical calcium, aluminium and silicon compositions of some commonly used
cementitious materials are shown in Figure 4.8.
Natural Pozzolan
The use of natural pozzolana in construction has a long history. The common materials of the kind
are: volcanic ash, pumicite, opaline shales and cherts. Some of the materials do not occur naturally
in pozzolanic form, but can be made pozzolanic through calcining. Some examples are calcined clays
and shales. Rice husk is a highly pozzolanic, silica rich material, which requires burning of rice
husk under controlled temperature.
Fly ash

Powdered or pulverised is fed as fuel in the coal-fired power Burning results in two
types of ashes. One consists of very fine particles, which are transported by flue gasses to the stacks.
Those fine particles are prevented from leaving the chimneys to avoid air pollution, by collecting at
39 CE 592 – Concrete
Technology

electrostatic precipitators. This type is called fly ash or (pfa) which is a mineral
pulverised fuel
rich substance that cools and solidifies into consisting of amorphous
rounded glassy
The finest of fly ash is called ultra-fine fly The product of burning and consisting of somewhat
large particles settled to the bottom of the furnace. This type is called bottom ash. Bottom ash is not
used as an SCM, but has the potential of using as an aggregate.
The chemical composition of pfa depends on that of coal from which it is originated. There are
types: siliceous, silico-calcareous, and calcareous. Siliceous fly ash is produced typically by burning
anthracite or bituminous coal, and calcareous fly ash is by lignite or sub-bituminous coal. Siliceous fly
ash is called Class F and calcareous fly ash is called Class C. Siliceous fly ash has a higher percentage
of SiO2 and a little CaO, whereas calcareous fly ash comparatively has a lesser amount of SiO 2 and a
higher amount of CaO (Figure 4.8). Even though somewhat weaker in pozzolanic activity due to low
SiO2 content, the presence of SiO2 and CaO together, makes Class C fly ash showing some latent
hydraulic cement properties. Ash formed by incineration of municipal and industrial is called
incinerator ash, and does not qualify to be classified as fly ash.
Apart from economic benefits, adding fly ash to concrete as an ingredient results in environmental
benefits including conserving raw materials for cement production and
reducing carbon
emissio by substituting for part of Portland cement, while at the same time delivering enhanced
performance benefits. Improving cohesiveness, long – term strength gain, reduction of permeability
and heat of hydration, mitigating sulphate attack and alkali-silica reaction are among those benefits.
Composition and hence the quality of fly ash tends to vary as it depends on the properties of coal.
Traces of normally present in fly ash causes some undesirable effects.

Silicafume is a by-product of silicon extraction and ferro-silicon alloy industries. It is collected by

Silica
filters of the smelting process. Silica fume is extremely rich in amorphous SiO 2 spherical particles
smaller than 10-6 m and is highly pozzolanic.
It is supplied in three forms: as collected from the filters (undensified); after treatment to increase
its bulk density (densified); or as slurry.
Silica fume helps to produce concrete with improved properties in both the fresh and hardened
states. Silica fume in a concrete mix leads to some reduction in flowability. In order to facilitate
uniform dispersion of particles, and to compensate for the reduction of flowabilty, silica fume is
normally used in combination with a plasticizer and/or superplasticizer. Inadequate deflocculation of
densified particles causes adverse alkali-silica reaction and associated disruptive expansion.
Presence of carbon gives darker colour to the material and causes adverse effects.

Metakaol is a highly efficient supplementary cementitious material. It is formed when china clay,
Metakaolin
composed of mineral kaolinite, is heated to the temperature range 600 – 800 °C. The efficiency is so
high that the Ca(OH)2 released from cement hydration can be virtually eliminated by its
incorporation. Among the benefits of its use in concrete include: reduced permeability and
diffusivity; improved freeze-thaw resistance; reduced shrinkage; improved sulphate resistance;
improved strength; reduced efflorescence; and mitigation of ASR expansion.
Ground granulated blastfurnace slag (ggbs)
Blastfurnace slag is a by-product of iron making process. Slag is formed from fusion of limestone or
dolomite with siliceous aluminous residues from the iron ore, and coke ash. Being a lighter material,
molten slag floats on molten iron. Granulation is through rapid quenching of molten slag as it passes
40

through water sprays, followed by water granulation. The granulated material is largely glassy, and is
powdered to the fineness similar to that of cement to use as an addition in concrete, or interground
with cement clinker. The latter results in such like Portland slag cement, blastfurnace cement, and
supersulfated cement, which may contain very little quantity of clinker.
The benefits of using in concrete include: reduced cost; reduced temperature in large pours;
improved sulphate resistance; and mitigation of ASR expansion.

Ricehusks
Rice husk slowly burnt in the range of 500 to 700 °C and powdered have a very high amorphous
silica content.
4.7.2 Nearly Inert Material
Nearly inert materials, may be pigments, ground calcium carbonate, or other fine mineral fillers.
Those fine particulate materials have been shown to be effective in improving the packing density of
solid materials in the concrete and enhancing hydration reaction of the cementitious paste by
providing nucleation sites. In addition, ground calcium carbonate also enters into chemical reaction
with C3A and C4AF.
This kind of additions is a common ingredient in self-compacting concrete to improve cohesiveness
and flow characteristics of the mix.

4.8 Specifications for Supplementary Cementitious Material

4.8.1 European Specifications
Specifications on three supplementary cementitious materials are:
(1) Fly ash for concrete - Part 1: Definition, specifications and conformity criteria
(EN 450 -1:2012)
(2) Silica fume for concrete — Part 1: Definitions, requirements and conformity criteria
(EN 13263  1:2005 + A1:2009)
(3) Ground granulated blast furnace slag for use in concrete, mortar and
grout - Part 1: Definitions, specifications and conformity criteria. (EN 15167-1:2006)
Some definitions and properties specified in (1) and (2) are listed in the following section.
Fly ash
In clause 3.2 of EN 450 – 1, fly ash is defined as:
“A of mainly derived from burning of pulverised with or
fine spherical, glassy particles,
without co-combustion materials, which has pozzolanic properties and consists essentially of SiO 2 and
Al2O3 and which:
 is obtained by electrostatic or mechanical precipitation of dust-like particles from the flue gasses
of the power stations; and
 may be processed, for example by classification, selection, sieving, drying, blending, grinding or
carbon reduction, or by combination of these processes, in adequate production plants, in which
case it may consist of fly ashes from different sources, each conforming to the definition given in
this clause.”
In that specification, municipal and industrial waste incineration ashes are exclud from the
category of fly ash.
41 CE 592 – Concrete
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Table 4.10 – Requirements specified for fly ash as characteristic values in EN 450-1: 2012

Property Test method Requirements

Chemical requirements
Loss on ignition EN 196-2 Category A: ≤ 5.0 % by
mass Category B: ≤ 7.0 %
by mass Category C: ≤ 9.0
% by mass
Note: The purpose of this requirement is to limit
the residue of unburnt carbon in the fly ash.
Chloride EN 196-2 Cl - ≤ 0.10 % by mass
Sulphate (SO3) EN 196-2 SO3 ≤ 3.0 % by mass
Free calcium oxide EN 451-1 If the content > 1.5 % by mass, requirement is
based on the soundness.
Reactive calcium oxide EN 197-1 ≤ 10.0 % by mass
Reactive silicon dioxide EN 197-1 ≥ 25 % by mass
Fly ash obtained from combustion of pulverised
coal only shall be deemed to satisfy this
requirement.
Sum of SiO2, Al2O3, and EN 196-2 ≥ 70 % by mass
Fe2O3 Fly ash obtained from combustion of pulverised
coal only shall be deemed to satisfy this
requirement.
Total content of alkalis, EN 196-2 ≤ 5.0 % by mass
Na2Oeq Fly ash obtained from combustion of pulverised
coal only shall be deemed to satisfy this
requirement.
Magnesium oxide EN 196-2 ≤ 4.0 % by mass
Fly ash obtained from combustion of pulverised
coal only shall be considered to satisfy this
requirement.
Total Phosphate (P2O5) ISO 29581-2 ≤ 5.0 % by mass
Fly ash obtained from combustion of pulverised
coal only shall be deemed to satisfy this
requirement.
Physical requirements
Fineness (Percent EN 451-2 or Category N: ≤ 40
retained on 0.045 mm EN 933-10 % Category S: ≤
sieve)
12 %
Activity index a,b EN 196-1 At 28 days: ≥ 75 %
At 90 days: ≥ 85 %
42

Table 4.10 – Requirements specified as characteristic values in EN 450-1: 2012 (continued.)

Property Test method Requirements

Soundness a
EN 196-3 ≤ 10 mm
(Mix 30 % fly ash + Where free CaO ≤ 1.5 %, the requirement
70 % test cement, shall
both by mass) be considered to be satisfied.
Particle density EN 1097-7 Shall not deviate by more than 200 kg/m 3 from
the value declared by the producer.
Initial setting time a EN 196-3 (Mix 25 % ≤ Initial setting time of test cement alone
fly ash + 75 % test Fly ash obtained from combustion of pulverised
cement, both by coal only shall be deemed to satisfy this
mass) requirement.
Water requirement a Annex B of EN 450-1 Category S: ≤ 95 % of that for test cement
alone
Category N: No requirement
a
Test cement:
CEM I, strength class 42.5 or higher
Fineness (Blaine): at least 300 m2/kg
Tricalcium aluminate (C3A): (6 – 12) % by mass
Alkalis (Na2Oeq): (0.5 – 1.2) % by mass
b
Activity index is defined as the ratio (in percent) of the compressive strength of standard mortar
bars, prepared with 75 % test cement plus 25 % fly ash by mass, to the compressive strength of
standard mortar bars prepared with 100 % test cement and tested at the same age.

Silica fume
In Clause 3.24 of EN 13263-1:2005+A1:2009, silica fume is defined as:
“Very fine particles of amorphous silicon dioxide collected as a by-product of the smelting process used
to produce silicon metal and ferro-silicon alloys.
Silica fume may be processed, for example by classification, selection, blending, densifying, or
slurrifying, or by a combination of these processes, in adequate production plants. Such processed silica
fume may consist of silica fumes from different sources, each conforming to the definition given in this
subclause.
Other names used for silica fume are condensed silica fume and microsilica.”

Undensified silica fume - Silica fume taken directly from the collection filter, the bulk density typically
being in the range 150 kg/m³ to 350 kg/m 3.

Silica fume - A homogeneous, pH regulated liquid suspension of silica fume in water, typically
with a dry content of 50 % by mass, corresponding to about 700 kg of silica fume per 1 m³ of slurry.

Densified silica - Silica fume that has been treated to increase the bulk density by particle
agglomeration; the bulk density is typically above 500 kg/m 3.
43 CE 592 – Concrete
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Table 4.11 – Requirements specified as characteristic values in EN 13263-1:2005+A1:2009

Property Test method Requirements
Chemical requirements
Silicon dioxide EN 196-2 Class 1: ≥ 85 % by mass
Class 2: ≥ 80 % by mass
Elemental silicon ISO 9286 ≤ 0.4 % by mass
Free calcium oxide EN 451-1 ≤ 1.0 %
Sulphate (SO3) EN 196-2 ≤ 2.0 %
Total content of alkalis EN 196-2 Declare
(Na2Oeq)
Chloride EN 196-2 ≤ 0.3 % by mass

Loss on ignition EN 196-2 ≤ 4.0 % by mass

(but ignition
time 1 hour)
Physical requirement
Specific surface (Nitrogen ISO 9277 Lower limit: ≥ 15.0 m2/g
adsorption) Upper limit: ≤ 35.0 m2/g
Dry mass content in slurry EN 13263-1 Deviation from the value declared by the supplier:
≤ ± 2 % by mass of the slurry
Activity index a EN 196 -1 At 28 ≥ 100 %
days:
a
The activity index is determined as the ratio (in percent) of the compressive strength of standard
mortar bars, prepared with 90 % test cement plus 10 % silica fume per mass of total binder, to
the compressive strength of standard mortar bars prepared with 100 % test cement, when tested
at the same age.
Preparation of standard mortar bars and determination of the compressive strength shall be
carried out in accordance with the method described in EN 196-1. The mortar containing silica
fume shall be mixed with an amount of superplasticizer (conforming to EN 934-2) so that the
mortar has a consistency equivalent to the reference mortar when tested by the flow table
method given in EN 413-2.
4.8.2 ASTM Specifications
Some of the relevant specifications are:
(1) Standard Specification for Coal Fly Ash and Raw or Calcined Natural Pozzolan for Use in
Concrete (ASTM C618 -17a)
(2) Standard Specification for Silica Fume Used in Cementitious Mixtures (ASTM C1240-15)
(3) Standard Specification for Blended Supplementary Cementitious Materials (ASTM 1697-
16)
(4) Standard Specification for Slag Cement for Use in Concrete and Mortars (C989/C989M –
17)

Fly classification
The ash and raw or calcinedto ASTM C618 is as follows:
according
Class N: Raw or calcined natural pozzolans that comply with the applicable requirements for the
class as given in the standard, such as some diatomaceous earths; opaline cherts and shales; tuffs
and volcanic ashes or pumicites, calcined or uncalcined; and various materials requiring calcination
to induce satisfactory properties, such as some clays and shales.

Class Fly ash that meets the applicable requirements for this class as given in the standard. This
class of fly ash has pozzolanic properties.
Class C: Fly ash that meets the applicable requirements for this class as given in the standard. This
class of fly ash, in addition to having pozzolanic properties, also has some cementitious properties.
44

This definition of fly ash given in the standard excludes, among other things, the residue resulting
from: (1) the burning of municipal garbage or any other refuse with coal; (2) the injection of lime
directly into the boiler for sulfur removal. Ash from the burning of industrial or municipal garbage in
incinerators is commonly known as “incinerator ash.”
According to ASTM specification, pozzolan satisfying the appropriate requirements given Table 4.12
are considered suitable for use in making concrete.
Table 4.12 – Requirements for Class N, F and C pozzolan (ASTM C618 – 17a)
Class
Property
N F C
Chemical requirements (ASTM C618-Table 1)
Silicon dioxide (SiO2) plus aluminum oxide (Al2O3) plus iron oxide (Fe2O3), min, % 70 70 50
Sulfur trioxide (SO3), max, % 4.0 5.0 5.0
Moisture content, max, % 3.0 3.0 3.0
Loss on ignition, max, % 10 6.0A 6.0
A
The use of class F pozzolan having up to 12.0 % loss on ignition may be approved by the user if either acceptable
performance records or laboratory test results are made available.
Physical requirements (ASTM C618-Table 2)
Fineness:
Amount retained when wet-sieved on 45 μm (No. 325) sieve, max, % 34 34 34
Strength activity index:
With Portland cement, at 7 days, min, percent of control 75 75 75
With Portland cement, at 28 days, min, percent of control 75 75 75
Water requirement, max, percent of control 115 105 105
Soundness:
Autoclave expansion or contraction, max, % 0.8 0.8 0.8
Uniformity requirements:
The density and fineness of individual samples shall not vary from the average
established by the ten preceding tests, or by all preceding tests if the number is
less than ten, by more than:
Density, max variation from average, %
5 5 5
Percent retained on 45-μm (No. 325), max variation,
percentage points from average 5 5 5
Optional physical requirements (ASTM C618-Table 3)
Increase of drying shrinkage of mortar bars at 28 days, max, difference, in %, over
control 0.03 0.03 0.03
Uniformity Requirements:
In addition, when air-entraining concrete is specified, the quantity of air-
entraining agent required to produce an air content of 18.0 vol % of mortar shall
not vary from the average established by the ten preceding tests or by all
preceding tests if less than ten, by more than, % 20 20 20
Effectiveness in controlling alkali-silica reaction:
Expansion of test mixture as percentage of low-alkali cement control, at 14 days,
max, % 100 100 100
Effectiveness in contributing to sulfate resistance:
Procedure A:
Expansion of test mixture:
For moderate sulfate exposure after 6 months exposure, max, % 0.10 0.10 0.10
For high sulfate exposure after 6 months exposure, max, % 0.05 0.05 0.05
Procedure B:
Expansion of test mixture as a percentage of sulfate resistant cement
control after at least 6 months exposure, max,% 100 100 100

Strength Activity with Portland cement is a measure of reactivity with a given cement and is
subject to variation depending on the source of both the fly ash or natural pozzolan and the cement.
45 CE 592 – Concrete
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Silica
Definition of silica fume according to ASTM C1240 – 15 is as follows:
Silica fume—very fine pozzolanic material, composed mostly of amorphous silica produced by
electric arc furnaces as a by-product of the production of elemental silicon or ferro-silicon alloys
(also known as condensed silica fume and microsilica).
Silica fume, densified—silica fume processed to increase bulk density to facilitate handling and
shipping.
Silica fume, undensified—silica fume in its raw, as produced or as collected, unprocessed
form. The requirements specified in ASTM C1240-15 are given in Table 4.13.
Table 4.13 – Requirements for silica fume (ASTM C1240 – 15)
Property Requirement
Chemical requirements (ASTM C1240-Table 1)
SiO2, min, % 85
Moisture content, max, % 3
Loss on ignition, max, % 6
Physical requirements (ASTM C1240-Table 2)
Oversize: 10
Percent retained on 45-μm (No. 325), max, %
Percent retained on 45-μm (No. 325), max variation from 5
average, percentage points
Accelerated pozzolanic strength activity index: 105
With Portland cement at 7 days, min percent of control
Specific surface, min, m2/g (Nitrogen adsorption) 15
Optional physical requirementsA (ASTM C1240-Table 3)
Uniformity requirements: 20
When air-entraining concrete is specified, the quantity of air-
entraining agent required to produce air content of 18.0 vol % of
mortar shall not vary from the average established by the ten
preceding tests or by all preceding tests if less than ten, by more than,
%
Reactivity with cement alkalis: 80
Reduction of mortar expansion at 14 days, min, %
Sulfate resistance expansion,
(moderate resistance) 6 months, max, % 0.10
(high resistance) 6 months, max, % 0.05
(very high resistance) 1 year, max, % 0.05
A
Will be made only at the request of the purchaser.

Colloidal silica and nano- are another extremely fine, amorphous forms of SiO 2, applicable in
making dense and high-strength concrete as well as self-compacting concrete. Colloidal is
normally in a suspension form whereas nano-silica may take powder form.