Chapter Two, Cementing Materials Notes.

JU; FCEE; Civil Engineering; Construction Engineering and management stream; Construction Materials Lecture note
CHAPTER TWO
CEMENTING MATERIALS
Cementing materials
In a general sense of the word, cements are materials with adhesive and cohesive properties,
which make them capable of uniting or bonding together fragments or particles of solid
matter into a compact whole.
For engineering purposes the meaning is limited to those materials when mixed with water
form a paste, which is temporarily plastic and later on a rigid mass after setting and
hardening. Cements of this are known as calcareous cements whose principal constituents
are compounds of lime.
Calcareous cements are classified into Non - hydraulic cements and hydraulic cements.
 Non - hydraulic cements: either not able to set and harden in water (example: non-
Hydraulic lime or fat lime) or not stable in water (example: gypsum plasters)
 Hydraulic cements: able to set and harden in water and remain stable in water
(Example: Portland cement, hydraulic limes).
Lime, gypsum, Portland cement are used in the construction of buildings and engineering
works either as components for binding materials (example: mortar) or as constituents of
building materials (example: concrete).
LIME
Lime is made from calcium or magnesium carbonate, which are abundant minerals and
occur in limestone rocks. High - calcium limestone consists of more than 90 percent of
calcium carbonate while dolomitic limestone contains about 40 and 43 percent of magnesium
carbonate.
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Production and use of lime
Lime, also called quicklime, is calcium oxide (CaO), a white or grayish white, finely
crystalline substance that sometimes has a yellow or brown tint because of iron impurities.
The raw materials used for the production of lime are limestone (CaCo3), but sometimes
dolomites (a mineral form of calcium-magnesium carbonates) is used. The limestone used
should be of high calcium type containing more than 90% CaCO 3.
Lime is manufactured by crushing, grinding, and grading the raw material and then
calcining or burning it at about 900-1100oC in kilns to drive off carbon dioxide.
CaCo3 (+MgCO3) + heat CaO(+MgO) + CO2
Lime reacts vigorously with water to form calcium hydroxide [Ca(OH) 2] known as SLAKED
or HYDRATED lime. When lime is used as a cementing agent in mortar for masonry or
plaster, it is used in the hydrated form.
CaO + H2O Ca(OH)2 + Heat

This process is known as slaking or hydration. It requires about 7 to 15 days so that all the
particles will get enough time to be hydrated.
Slaking
During slaking considerable heat is evolved followed by sudden expansion which makes the
lime burst into pieces and finally becomes powder or pasty.
Depending on the amount of water added, there are two types of slaking: Wet-slaking and
Dry-slaking
Wet-slaking
Quicklime is mixed with excess water on sites. After sieving unslaked particles the hydrated
lime is left to mature for several days.
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Dry-slaking
Under carefully controlled operation (as it can be in a factory) just sufficient water is added
to hydrate the quicklime, the lumps break down into a dry powder known as dry hydrate or
hydrated lime. It is obtained by adding almost exactly the theoretical quantity of water
required to change the burnt lime into hydrated lime.
Quicklime must be kept in dry storage and carefully protected from dampness until used.
Setting and Hardening of Lime
Slaked lime hardens or sets by gradually losing its water through evaporation and absorbing
carbon dioxide from the air, thus reverting back to calcium Carbonate (CaCO3).
The cycle is completed in the chemical changes from the original limestone, through burning,
slaking, and setting, as shown below.
Drying CaCO3
+ Heating (around
CO2 10000c)
CaO
Ca(OH)2
Slaking
Lime mortar does not harden under water, (and for construction under water lime has to be
ground together with a volcanic ash or finely ground burnt clay tile: Silica + Alumina + lime
pozzolanic cement.) The process of hardening of lime mortar is so slow that nowadays-pure
lime mortar is not much used in the construction industry.
Uses
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In construction, slaked lime chiefly used to make mortar for building brick and stone
masonry and for plastering walls of buildings.
The following are the major uses of lime in the construction industry:
1. Bedding for laying masonry units (i.e. bricks, concrete blocks, stone units etc): lime
cement mortar is used for this purpose, usually in the ratio of C: L: S of 1:1:6 or
1:2:6. The 1:1:6 ratio gives/results in a stronger mortar while the 1:2:6 ratios are
more workable, because in mortar cement contributes to strength where as lime
improves workability of the fresh mortar.
2. Because lime reacts with siliceous materials under hydrothermal conditions, it is
employed in the manufacture of a number of calcium silicate products such as bricks,
blocks, tiles etc.
3. Stabilization of road surfaces bases and sub-bases. The use depends upon the
reaction of lime with particular constituent materials of the soil to give a cementing
effect. Slow & ineffective in cooler climates.
The presence of lime in a mortar contributes the following:
1. Plasticity and workability
2. High water retentivity (hardens slowly)
3. Improved bond strength
4. A lighter colour mortar
5. High sand carrying capacity
Typical mortar proportions and applications:
Mortar Application
Portland cement (C) : Lime (L) : Sand (S)
1 0.25 3 Highly stressed engineering applications
1 1 6 General purpose
1 2 9 General purpose but unsuitable where
dampness occurs
1 3 12 Interior use or where sheltered from sever
exposure; unsuitable where dampness occurs
Never attempt to use lime as plaster unmixed with other material, as wide cracks would occur
on account of the shrinkage of lime on hardening.
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Hydrated limes are often added to Portland cement mortars in proportions varying from 5 to
85 percent of the weight of cement (the product being compo mortar) to increase the plasticity
and workability.
Lime has been used in the hydrated form although calcium oxide (quicklime) may be more
effective in some cases (e.g. application in stabilization). Quicklime will corrosively attack
equipment and there is a risk of severe skin burns to personnel. Even when working with
slaked lime, prolonged exposure of the skin can result in irritation, and occasionally, rashes.
The average compressive strength of lime mortar is less than that of cement-and gypsum-
mortars. It varies from 5 kgf/cm2 to 20 kgf/cm2. Its tensile strength is about 3 to 5 kgf/cm 2.
Usually adding Portland cement to the mixture improves the mechanical properties of lime-
mortar.
Hydraulic lime-this a special type of lime containing 10 to 17% each of aluminum oxide,
silicon, and iron oxide with 40 to 45% lime and some magnesium oxide, and can set under
water. It is used where slow under water setting is required.
Production and use of gypsum

Gypsum is a hydrated calcium sulphate with the chemical formula CaSO4. 2H2O. It is widely
found in nature in ore bodies of sedimentary origin sometimes covered by deposits of NaCl
or clay and lime rocks. It is rarely found in the pure form.
Production Process
Gypsum has a unique property that makes it valuable in construction. When the raw gypsum,
CaSO4.2H2O, is heated to a temperature of about 160-2000C, it loses about three-fourths
(3/4) of its water of crystallization, giving a calcined substance commonly called PLASTER
OF PARIS, or hemihydrates.
2[CaSO4.2H2O] + Heat 2[CaSO4. ½H2O + 3/2 H2O]

2CaSO4. 2H2O + Heat (CaSO4)2.H2O + 3H2O
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By burning gypsum to a considerably higher temperature anhydrous sulphate may be

produced (high temperature gypsum derivative)
(CaSO4.2H2O) + High heat * CaSO 4 + 2H2O
*Plaster too slow in setting action (reluctant to absorb water)
When water is added to 2[CaSO 4.1/2 H2O], it hydrates into felted (fibers matted together)
crystals cemented together and resets in any desired shape to its original rocklike form,
CaSO4. 2H2O.
A wide variety of setting accelerators and retardants (retarders) are used in the technology
of gypsum. Accelerations include such substances as potassium alum and calcium. The most
used retarders are generally organic substances of high molecular weight, which act as
protective colloids and improve the stiffness and mechanical strength of the materials.
Commonly used retarders are keratin, aligimate, sodium silicate, glycerol, bentonite, glue,
sawdust etc.
Properties of Gypsum as a Construction Material

A serious limitation in the use of gypsum derives from the inherent characteristics of the
structure of gypsum to absorb moisture. Owing to this phenomenon, the mechanical strength
greatly decreases.
Gypsum has low coefficient of thermal conductivity and therefore, it is a very good material
for thermal (fire) proofing. A great deal of heat is required to remove the water of hydration
of gypsum and as the evaporation takes place, the gypsum (plaster) doesn’t crack or spal but
its surface is converted to anhydrous powder which acts as an excellent heat insulator
retarding the further evaporation of water of crystallization of the inside layers of gypsum.
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The strength of gypsum is, however, destroyed by prolonged exposure to extreme heat after
the water of hydration is finally removed or driven off.
Gypsum is also used for sound-absorbing constructions as in acoustical plaster, plasters

boards, partition tile, roof tile and reinforced plaster decking. Uncalcined gypsum is an
effective, economical retarder in cement.
Strength of Structural Gypsum
The ultimate strength of gypsum has been found to vary from 5 kgf/cm 2 to 200 kgf/cm2,
depending upon the amount of H 2O used in mixing the gypsum paste, the completeness of
drying out of H2O after the gypsum paste has set, the amount of foreign materials mixed with
the gypsum to retard or accelerate its rate of setting and the temperature used in calcining
the gypsum rock.
For highest strength, least possible amount of water should be added or used in preparing
the gypsum plaster. To make gypsum sufficiently plastic or workable 33-38% water is
required. With care in mixing and drying out, gypsum can be produced regularly with an
average compressive strength of 100 kgf/cm 2. Gypsum gains it full strength in a few hours if
carefully kiln-dried, and air-cured gypsum gains strength so rapidly that forms may be
removed the day the gypsum is poured.
Gypsum is weakened by prolonged exposure to water and should not be used where it will be
kept wet for a long period of time.
The modulus of elasticity of structural gypsum is about 70,000-kgf/cm2 and 2,100,000

kgf/cm2 for steel. The unit weight of structural gypsum is about 1280 kg/m 3, whereas that of
concrete is 2,400 kg/m3.
PORTLAND CEMENT
Portland cement is a cementing material which is obtained by thoroughly mixing together

calcareous or other lime bearing material with argillaceous and/or other silica, alumina or
iron oxide bearing materials, burning them at a clinkering temperature and grinding the
resulting clinker.
Manufacture
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The process of manufacture of cement consists of grinding the raw materials, mixing them
intimately in certain proportions depending upon their purity and composition and burning
them in a kiln at a temperature of about 1300 to 15000c, at which temperature the material
sinters and partially fuses to form a nodular shaped clinker. The clinker is cooled and
ground to a fine powder with addition of about 2 to 3% of gypsum.
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Mixing may be in dry (dry or semi-dry process) or wet (wet process) state depending on the
hardness of the available rock.
The wet process is used, in general for the softer materials such as chalk or clay. Water is
added to the proportion mixture of crushed chalk and clay to produce slurry, which is
eventually led to a kiln.
The dry or semi-dry process is used for the harder rocks such as limestone and shale. The
constituent materials are crushed into powder form and, with a minimum amount of water,
passed into an inclined rotating nodulising pan where nodules are formed (known as raw
meal). This is fed into a kiln and thereafter the manufacturing process is similar to the wet
process although a much shorter length of kiln is used. Dry and semi-dry processes are more
energy efficient than the wet process.
Proportioning of Raw Materials
In order to fix the proportions accurately, chemical analysis should be made on the raw
materials. The results are usually reported in terms of the oxides of the principal
constituent elements.
The raw materials used for the manufacture of cement consist mainly of lime, silica, alumina
and iron oxide. These oxides interact with one another in the kiln to form more complex
compounds. The relative proportions of these oxide compositions are responsible for
influencing the various properties of cement; in addition to rate of cooling and fineness of
grinding.
Approximate Oxide Composition Limits of Raw Materials.
Oxide Content (Wt. %)
Lime (CaO) 60 – 67
Silica (SiO2) 17 – 25
Alumina (Al2O3) 3–8
Iron Oxide (Fe2O3) 0.5 - 6.0
Magnesia (MgO) 0.5 – 4.0
Sulphur trioxide (SO3) 1–3
Alkalis - Soda (Na2O)
- Potash (K2O) 0.3 - 1.2
Titanium Oxide (TiO2) 0.1 - 0.4
Phosphorous Pent-oxide (P2O5) 0.1 - 0.2
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Carbon dioxide (CO2) 1–3

Manganese Oxide (Mn 2O3) 0 - 0.1
Basic Characteristics
1. Chemical Composition
Generally four principal compounds are considered to be important.
Name of compounds Chemical Composition Usual abbreviation
Tricalcium silicate 3CaO.SiO2 C3S
Dicalcium silicate 2CaO.SiO2 C2S
Tricalcium aluminate 3CaO.Al2O3 C3A
Tetracalcium aluminoferrite 4CaO.Al2O3.Fe2O3 C4AF
It is more usual to calculate the proportions of these compounds from the proportions of their
oxide constituents using Bogue’s method.
C3S = 4.07 (CaO) - (7.60SiO2 + 6.72Al2O3 + 1.43Fe2O3 + 2.85SO3)

C2S = 2.87SiO2 - 0.754C3S
C3A = 2.65Al2O3 - 1.69Fe2O3
C4AF = 3.04Fe2O3
The two silicates, C3S and C2S together form 70 to 80 per cent of the constituents in the
cement and contribute most to the physical properties of concrete. During hydration C3S
hydrates rapidly, generating a considerable amount of heat and making a significant
contribution to the development of the early strength (initial setting), particularly during the
first 14 days. C2S hydrates slowly and is mainly responsible for the development in strength
after about 7 days. Cements rich in C2S result a greater resistance to chemical attack and a
smaller drying shrinkage.
The hydration of C3A is extremely exothermic and takes place very quickly, producing little
increase in strength after about 24 hours. It is the least stable and concrete of a cement rich
in C3A are susceptible to sulphate attack. Sulphate combines with C3A to produce an
expanding compound which could result in disintegration of the concrete.
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C4AF reacts slowly. Its main purpose in Portland cement is to reduce the temperature
required during burning in the kiln.
While there can be of large differences in the early strength of concretes made with different
Portland cements, their final strengths will generally be very much the same.
2. Fineness
The greater the surface area of a given volume of cement the greater the hydration.
Therefore fine cement will develop strength and generate heat more quickly than coarse
cement.
Fine cements, in general, improve the cohesiveness of fresh concrete and can be effective in
reducing the risk of bleeding, but they increase the tendency for shrinkage cracking.
Measured fineness is an overall value known as specific surface and is expressed in square
metres per kilogram (m2 /kg).
3. Hydration
Particles of cement take up water, forming a gel, which cements the individual particles
together. This chemical process is called hydration. It continues for months or years as long
as water is present. The total amount of water required to complete the hydration of the
cement is about 25% of the mass of the cement.
The rate of hydration depends on the relative proportion of silicate and aluminate
compounds, the cement fineness and the ambient conditions (particularly temperature and
moisture).
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Time taken to achieve 80 per cent hydration of the main compounds of Portland cement
Chemical compound Time, days Heat of hydration
Cal/g J/g
C3 S 10 120 502
C2 S 100 62 251
C3 A 6 207 837
C4AF 50 100 419
It is the rate at which heat is generated and not the total liberated heat, which in practice
affects the rise in temperature. As concrete is a poor conductor of heat generated during
hydration can develop micro-crack on the binding medium (affects the durability of
concrete).
The progress of hydration in cement can be determined by different means, such as
measurement of:
1. The amount of Ca(OH)2 in the paste

2. The heat evolved by hydration
3. The specific gravity of the paste
4. The amount of chemically combined water
5. The amount of unhydrated cement paste
6. Also indirectly from the strength of the hydrated paste
The final product of hydration may approximately be written as follows:
2C3S + 6H C3S2H3 + 3Ca(OH)2

2C2S + 4H C3S2H3 + Ca(OH)2
The initial hydration involves very high heat of hydration which due to C 3A at the surface of
cement particles. The duration of this high heat of hydration is very short, and there follows a
so-called dormant period, sometimes called also an induction period, during which the rate
is very high. This period lasts one or two hours during which the cement paste is workable.
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4. Setting and Hardening

The cement paste begins to lose its fluidity when the layers of gel, formed around each of the
cement particles during hydration, grow to the extent that they come into contact with each
other.
The beginning of noticeable stiffening in the cement paste is known as the initial set.
The stage at which increment in the volume of gel is completed followed by commencement of
final hardening process is responsible for cement strength is known as final set. The times
from the addition of the water to the initial and final set are known as the setting times. Vicat
apparatus measures the setting times of the cement by using different penetration
attachments.
For the determination of the initial set, a round needle with a diameter of 1.13 0.05 mm is
used. This needle, acting under a prescribed weight, is used to penetrate a paste of standard
consistency placed in a special mould.
Final set is determined by similar needle fitted with a metal attachment hollowed out so as to
leave a circular cutting age 5 mm in diameter and set 0.5 mm behind the tip of the needle .
Final set is said to have taken place when the needle, gently lowered to the surface of the
paste, penetrates it to a depth of 0.5 mm but the circular cutting age fails to make an
impression on the surface of the paste.
Stiffening of cement within a few minutes after mixing due to insufficient gypsum to control
rapid reaction of C3A with water is known as the flash set. A false set also produces a rapid
stiffening of the paste that can regain its plasticity by re-mixing. False set is thought to be the
result of inter-grinding gypsum with a very hot clinker in the final stages of the manufacture
of cement.
5. Strength
The cement paste alone is not used for the strength test because of the unacceptably large
variation of strength thus obtained. Standard aggregates are used for making prescribed
mortar or concrete test mixes.
6. Soundness
It is essential that cement paste, once it has set, does not undergo a large change in volume.
Excessive change in volume of cement is known as unsoundness. Expansion of hydrated
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cement paste may take place due to the delayed or slow hydration, or other reaction, of some
compounds present in the hardened cement, namely free lime, magnesia and calcium
sulphate.
7. Loss on ignition
The loss of ignition shows the extent of carbonation and hydration of free lime and free
magnesia due to the exposure of cement to the atmosphere. The maximum loss on ignition (at
1000oC) permitted by ASTM is 3 % (4% is acceptable for cements in tropics). Because
hydrated free lime is innocuous, for a given free lime content of cement, a greater loss on
ignition is advantageous.
Types Cement (ASTM Classification)

Varying the principal compounds, which can be adjusted in raw material composition of
oxides, can develop cements having specific properties. Small change in oxide composition
induces large influence on compound composition of cement. Accordingly, the following
major types of commercial cements can be produced:
Type I (Ordinary Portland Cement)

For use in general concrete construction, where the special properties specified for Types II,
III, IV & V are not required.
Type II (Modified cement)

For use in general concrete construction exposed to moderate sulphate action, or where
moderate heat of hydration is required.
Type III (Rapid Hardening cement)
Develops strength rapidly (3 days strength = 7 days strength of ordinary Portland cement).
The rapid rate of development of strength is attributed to the higher fineness of grinding
(specific surface not less than 3250 sq. cm per gram) and higher C3S and lower C2S content.
The use of rapid hardening cement is recommended in the following situations:
1. In pre-fabricated concrete construction.
2. Where formwork is required to be removed early for re-use elsewhere.
3. Road repair works.
4. In cold weather concrete, where the rapid rate of development of strength reduces the
vulnerability of concrete to the frost damage.
Type IV (Low Heat cement)
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For use when low heat of hydration is required. Reducing the contents of C 3S and C3A, and
increasing C2S achieve a low-heat evolution. Used in mass concrete works, such as dam,
where cracks can be formed due to the rapid rate of hydration.
Type V (Sulphate Resisting cement)
For use when high sulphate resistance is required. It has a higher content of C 2S and a lower
content of C3A.
The use is recommended under the following conditions.
1. Concrete to be used in marine (structure nearby sea water) condition.
2. Concrete to be used in foundation and basement, where soil is infested with sulphates.
3. Concrete used for fabrication of pipes, which are likely to be buried in marshy region
or sulphate bearing soils.
4. Concrete to be used in the construction of sewage treatment works.
Type IP (Portland Pozzolana cement)
A pozzolana is essentially a siliceous material, which, while in itself possessing no or little
cementitious properties, will in finely divided and in the presence of water, react with calcium
hydroxide at ordinary temperature to form compounds possessing cementitious properties.
It may include such natural materials as diatomaceous earth, opaline cherts and shales, tuffs,
volcanic ashes and pumicites.
It produces less heat of hydration and offers greater resistance to the attack of aggressive
waters than ordinary Portland cement. Moreover, it reduces the leaching of calcium
hydroxide when used in hydraulic structures.
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Typical Compound Composition and Fineness of Portland Cements

Type of cement Designation Compound comp.% Fineness*,cm2/g
ASTM
C3S C2S C3A C4AF
Ordinary Type I 50 24 11 8 1800
Modified Type II 42 33 5 13 1800
Rapid Hardening Type III 60 13 9 8 2600
Low Heat Type IV 26 50 5 12 1900
Sulphate Resisting Type V 40 40 4 9 1900
* Fineness as determined by Wagner turbidimeter test.
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Chapter Two, Cementing Materials Notes.

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Chapter Two, Cementing Materials Notes.

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JU; FCEE; Civil Engineering; Construction Engineering and management stream; Construction Materials Lecture note

Production and use of lime

CaCo3 (+MgCO3) + heat CaO(+MgO) + CO2

CaO + H2O Ca(OH)2 + Heat

Setting and Hardening of Lime

Production and use of gypsum

2[CaSO4.2H2O] + Heat 2[CaSO4. ½H2O + 3/2 H2O]

By burning gypsum to a considerably higher temperature anhydrous sulphate may be

(CaSO4.2H2O) + High heat * CaSO 4 + 2H2O

*Plaster too slow in setting action (reluctant to absorb water)

Properties of Gypsum as a Construction Material

Gypsum is also used for sound-absorbing constructions as in acoustical plaster, plasters

Strength of Structural Gypsum

The modulus of elasticity of structural gypsum is about 70,000-kgf/cm2 and 2,100,000

Portland cement is a cementing material which is obtained by thoroughly mixing together

Carbon dioxide (CO2) 1–3

C3S = 4.07 (CaO) - (7.60SiO2 + 6.72Al2O3 + 1.43Fe2O3 + 2.85SO3)

1. The amount of Ca(OH)2 in the paste

The final product of hydration may approximately be written as follows:

2C3S + 6H C3S2H3 + 3Ca(OH)2

4. Setting and Hardening

Types Cement (ASTM Classification)

Type I (Ordinary Portland Cement)

Type II (Modified cement)

Typical Compound Composition and Fineness of Portland Cements

* Fineness as determined by Wagner turbidimeter test.

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