CV322: Concrete Technology

[Session: July – December 2018]

Lecture # 8: Admixtures
Prepared and presented based on Concrete: Microstructure, Properties, and Materials, Fourth
Edition by: P. Kumar Mehta, Ph.D., Paulo J. M. Monteiro, Ph.D.
by
Dr. Suresha S. N.
Department of Civil Engineering
National Institute of Technology Karnataka, Surathkal
Mangaluru – 575025, INDIA
 Nomenclature, Surface Active
specification and Chemicals
classification

Overview
Set Controlling Mineral Admixtures
Chemicals

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Composition • Admixtures vary widely in composition, from surfactants and
soluble salts to polymers and insoluble minerals.
• Generally, they are used in concrete to improve workability,
Uses
accelerate or retard setting time, control strength development, and
enhance the durability to frost action, thermal cracking,
alkali-aggregate expansion, sulfate attack, and resistance to
corrosion of the reinforcement.
Definition • ASTM C 125 defines an admixture as a material other than water,
aggregates, hydraulic cements, and fiber reinforcement that is used
as an ingredient of concrete or mortar and added to the batch
immediately before or during mixing.
Classification • Chemical admixtures (Surface active and set-controlling admixtures)
and Mineral admixtures.
Specifications • Specifications
– IS 9103
– ASTM C260, ASTM C494, ASTM C618, ASTM 989, ASTM
Date: 22/10/2018
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C1240
Also explore the commercially available concrete admixtures

Explore IS and ASTM Standards

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 Types of Admixtures and Physical Requirements as IS 9103
Types Characteristics/Requirements
1. Accelerating admixtures 1. Amount of reduction in water
2. Retarding admixtures 2. Slump
3. Water-reducing admixtures 3. Time of setting
4. Air-entraining admixtures, and 4. Compressive strength
5. Superplasticising admixtures 5. Flexural strength
6. Length change
7. Bleeding
8. Loss of workability
9. Air content

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Concrete Testing (IS 516 and IS 1199)
Date: 23/10/18
Makeup class

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 Let us explore commercially available admixtures
• Manufacturer/Supplier
• Manufacturer/Supplier

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In concrete technology, mostly anionic admixtures are used, either with a
nonpolar chain or with a chain containing some polar groups. The former
serves as air-entraining, and the latter as water-reducing, admixtures.

Mechanism of action and applications of

admixtures

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 Surface active chemicals: air-entraining surfactants
These generally consist
of salts of wood resins,
proteinaceous materials
and petroleum acids,
and some synthetic
detergents.
(a) Formula of a typical air-entraining surfactant derived from pine oil or tall oil processing;
(b) mechanism of air entrainment when an anionic surfactant with a nonpolar hydrocarbon chain is added to the cement paste.

• The chemical formula of typical air-entraining surfactant, which consists of a nonpolar

hydrocarbon chain with an anionic polar group.
• At the air-water interface the polar groups are oriented toward the water phase lowering the
surface tension, promoting bubble formation, and counteracting the tendency for the
dispersed bubbles to coalesce.
• At the solid-water interface where directive forces exist in the cement surface, the polar
groups become bound to the solid with the nonpolar groups oriented toward the water,
making the cement surface hydrophobic so that air can displace water and remain attached to
the solid particles as bubbles. 9
 Surface active chemicals: water-reducing/plasticizing surfactants
● These usually are salts and modifications, and
derivatives of lignosulfonic acid, hydroxylated
carboxylic acids, and polysaccharides or any
combinations of the foregoing three, with or
without other subsidiary constituents.
● The first generation of superplasticizers or high
range water-reducing admixtures consist of
sulfonated salts of melamine or naphthalene
formaldehyde condensates.
● However, the now more popular "new
generation" superplasticizers, polycarboxylic
ether-based superplasticizers have gained in
popularity due to certain advantages.

When a surfactant with a hydrophilic chain is added to the cement-water system, the polar chain is
adsorbed alongside the cement particle; in this case the surfactant directs a polar end, instead of a nonpolar
end toward the water, thus lowering the surface tension of water and making the cement particle
hydrophilic. 10
 Some
Examples

Superplasticizers
● In the case of ordinary water-reducing surfactants, surface adsorption of chemicals helps to induce
electrostatic repulsion that helps dispersion of cement particle.
● In the case of superplasticizer, due to steric repulsions, short-range physical barriers are created
between the cement particles. This help in inhibition of reactive sites. 11
Surface active chemicals: Shrinkage Reducing Admixtures (SRA)
Can you explain the phenomena of Concrete Shrinkage?
Glycol ether blends, propylene glycol ether mixtures, or as
polyoxyalkylene ethers are considered to be commercially
commonly available SRA.
Addition of SRAs reduces the surface tension (i.e., interfacial
energy) of the water-air (i.e., liquid-vapor) interface.

The most common use of SRA in concrete is through integral

mixing, wherein the admixture is first dissolved into the mixing
water prior to contact with the solids (cement, aggregates, etc.).
Autogenous shrinkage is the external (bulk) shrinkage
experienced by a cementitious paste, mortar, or concrete under
sealed, isothermal conditions.
Autogenous shrinkage is driven by internal drying that induces
a relative humidity (RH) decrease and the development of
capillary stresses that cause bulk shrinkage in a hydrating
cementitious material.
Date: 25/10/18 12

Classification and
composition of set-controlling chemicals:
Class I, CaSO4·2H2O;
Class II, CaCl2, Ca(NO3)2;
Class III, K2CO3, Na2CO3, Na2SiO3;
Class IV, (1) surfactants with polar groups in the
hydrocarbon chain (i.e., gluconates, lignosulfates,
and sugars), (2) sodium salts of phosphoric, boric,
oxalic, or hydrofluoric acid, and (3) zinc or lead
salts;
Class V, salts of formic acid and triethanolamine.
Set-Controlling Chemicals
Do you remember the mechanism of hydration?
● thorough-solution hydration
● solid-state hydration or topochemical of cement
An accelerating admixture must promote the dissolution of the
cations or anions from the cement. As there are two
predominant anions to dissolve, the accelerator should promote
the dissolution of that constituent which has the lowest
dissolution rate during the early hydration period (i.e., the
silicate).
Applications: Expedite start of finishing operation, reduction the
time for proper curing and protection, increase the rate of early
strength gain etc.
A retarding admixture must impede the dissolution of the
cement cations or anions, preferably that anion which has the
highest dissolution rate during the early hydration period (i.e.,
the aluminate).
Applications: hot weather conditions, large structural units, etc.
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Classification, chemical and mineralogical composition, particle
characteristics, applications

Mineral Admixtures

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 Mineral Admixtures
• Definition Mineral admixtures are often finely divided siliceous
• Classification materials that are added to concrete in relatively large
amounts, generally, in the range 20 to 70 percent by mass of
• Applications the total cementitious material.

Pozzolan: According to ACI Terminologies: It is a siliceous or silico-aluminous

material that will, in finely divided form and in the presence of moisture, chemically
react with calcium hydroxide at ordinary temperatures to form compounds having
cementitious properties (there are both natural and artificial pozzolans).

Major Sources: Power plants using coal as fuel, and metallurgical furnaces producing
cast iron, silicon metal, and ferrosilicon alloys are the major sources of by-products
being produced at the rate of millions of tons every year in many countries.

How to use: Low-value utilisation/High-value utilisation.

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• Definition • Cementitious (Granulated blast furnace slag)
• Cementitious and Pozzolanic (High-calcium fly ash)
• Classification • Highly Active Pozzolans (Silica fume and rice husk ash)
• Applications • Normal Pozzolans (Low-calcium fly ash, volcanic soils, Metakaolin)
• Weak Pozzolans (bottom ash, boiler slag)
Granulated blast furnace slag is mostly silicate glass containing mainly calcium, magnesium, aluminium,
and silica. Unprocessed material is of sand size and contains 10–15% moisture. Dried and ground
GBFS will have Blaine specific surface area of 500 m2/kg and particle size less than 45 𝛍m.
High-calcium fly ash is mostly silicate glass containing calcium, magnesium, aluminum, and alkalies.
Small quantities of quartz and C3A, free lime and periclase may also present. Most particles are solid
spheres less than 20 μm in diameter and Blaine specific surface area of 300 - 400 m2/kg.
Silica fume consist essentially of pure silica in noncrystalline form.Extremely fine powder consisting of
solid spheres of 0.1 μm average diameter (about 20 m2/g surface area by nitrogen adsorption).
Low-calcium fly ash is mostly silicate glass containing aluminum, iron, and alkalies. Powder
corresponding to 15–30% particles larger than 45 μm (usually 200–300 m2/kg Blaine).
Metakaolin is a Kaolinitic clay calcined at 650–800°C to enhance pozzolanic activity. These will be
grounded to a very fine particle size (surface area 12 m2/g by nitrogen adsorption).
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• Definition • Workability improvement
• Durability to thermal cracking
• Classification • Durability to chemical attack
• Applications • Production of high-strength and high-performance concrete

Workability improvement can be achieved with the use of fly ash or slag. Also, it is possible to reduce the
required water content. This is possible due to the small size and the glassy texture of fly ash and slag.
Assuming that due to heat of hydration the maximum temperature in a massive structure is reached within about
3 days of the concrete placement, the use of ordinary mineral admixtures (i.e., natural pozzolan, fly ash, or slag)
offers the possibility of reducing the temperature rise almost in direct proportion to the amount of portland
cement replaced by the admixture. Thus, durability to thermal cracking is ensured.
Durability to chemical attack co the pozzolanic reaction involving mineral admixtures causes pore refinement
that reduces the permeability of concrete, both field and laboratory studies have shown considerable
improvement in the chemical durability of concrete containing mineral admixtures.

Production of high-strength and high-performance concrete is that concrete which has i) high constructability, ii)
high resource productivity through high durability, iii) high ultimate strength and moderate early strength, iv)
high environmental friendliness, and iv) cost-effectiveness.

Date: 05/11/18 17
Any questions?

Give Your Feedback

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 Try to answer the following questions
1. When producing a certain type of portland cement it is important that the oxide composition remains uniform. Why?
2. Why are plasticizing admixtures called water reducing? What is the distinction between normal and high-range water-reducing admixtures
according to the ASTM Standard Specification?
3. Can you list and define the eight types of chemical admixtures, four classes of mineral admixtures, and three grades of iron blast-furnace
slag that are used as admixtures for concrete?
4. After reviewing the ASTM C 618 and C 989 Standard Specifications and other published literature, write a critical note comparing the two
standards.
5. What are the essential differences in composition and mode of action between the surfactants used for air entrainment and those used for
water reduction?
6. Some manufacturers claim that application of water-reducing admixtures can lower the cement content and increase the consistency and
strength of a reference concrete mixture. Explain why all three benefits may not be available at the same time.
7. Commercial lignin-based admixtures when used as water-reducing agents may exhibit certain side effects. Discuss the possible side effects
and explain how they are corrected.
8. In their composition and mechanism of action, how do the superplasticizers differ from the normal water-reducing admixtures? Addition of
1 to 2 percent of a normal water-reducing agent to a concrete mixture may cause segregation and severe retardation. These effects do not
take place in the superplasticized concrete. Explain why.
9. When added to portland cement paste in very small amounts, calcium chloride acts as a retarder, but in large amounts it behaves as an
accelerator. Can you explain the phenomenon?
10. Why doesn't calcium sulfate behave like an accelerator for portland cement similar to calcium chloride?
11. As an accelerator, why isn't sodium chloride as effective as calcium chloride?
12. Mineral acids are accelerators for portland cement, but organic acids do not show a consistent behavior. Explain why.
13. Formic acid is an accelerator, while gluconic acid is a retarder. Explain why.
14. What type of admixtures would you recommend for concreting in: (i) hot weather, (ii) cold weather.
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 Try to answer the following questions
15. When used as an accelerator, what effect would calcium chloride have on the mechanical properties, dimensional stability, and durability
of concrete?
16. State several important reasons why it is desirable to use pozzolanic admixtures in concrete.
17. Why are clays and shales heat treated to make them suitable for use as a pozzolan?
18. Name some of the commonly available industrial by-products that show pozzolanic or cementitious properties when used in combination
with portland cement.
19. What do you know about the origin and characteristics of the following mineral admixtures: pumice, zeolitic tuff, rice husk ash, and silica
fume?
20. Compare and contrast industrial fly ashes and ground iron blast-furnace slag with respect to mineralogical composition and particle
characteristics.
21. Explain the mechanism by which mineral admixtures are able to improve the pumpability and finishability of concrete mixtures. In the
amounts normally used, some mineral admixtures are water reducing whereas others are not. Discuss the subject with the help of examples.
22. Discuss the mechanisms by which mineral admixtures improve the durability of concrete to acidic waters. Why is that not all fly
ash-portland cement or slag-portland cement combinations may turn out to be sulfate-resisting?
23. What maximum strength levels have been attained in recently developed high-strength concrete mixtures? Explain the role played by
admixtures in the development of these concretes.
24. What is high-performance concrete?

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