CEMENT

Building Materials
 Introduction
• Ancient Romans were first to use concrete -
word of Latin origin- based on hydraulic cement,
that is a material which hardens under water.
• The properties of not undergoing chemical
changes by water have contributed to the
widespread use of concrete as a building
material.
• Only in 1824 modern cement “Portland Cement”
was patented by Joseph Aspdin.
 Portland Cement
• Portland Cement: Name given to a cement obtained by
intimately mixing together:
▫ Calcareous materials (Lime stone CaO, chalk)
▫ Argillaceous materials (Silica (SiO2) from sand,
alumina (Al2O3) from clay or shale)
▫ and iron oxide (Fe2O3)
burning them at a clinkering temperature, and grinding
the resulting clinker.
• No materials other than Gypsum (CaSO4.4H2O), water,
and grinding aids may be added after burning.
 Manufacture of Portland Cement
• Crushing the raw material.
• Grinding raw materials into a very fine powder.
• proportioning.
• Mixing.
• Burning in a large rotary kiln (7m diameter and 230 m
long, slightly inclined) at temperature of 1400oC.
• Product is called clinker which is cooled down and
ground to a very fine powder (1.1x1012 particles/kg).
• Some gypsum added (to prevent flash-setting of cement)
and the resulting product is the commercial Portland
cement.
 Manufacture of Portland Cement
• The mixing & grinding of the raw materials can be done
either in water or in a dry condition (thus the process are
called wet and dry accordingly).
• Various chemical changes take place along the kiln and
the lime, silica, and alumina recombine. The mass then
fuses into balls (3 to 25 mm diameter) known as clinker.
• Modern kilns using dry process can produce 6200
tonnes of clinker/day.
• Iron Oxide is responsible for the dark color of the normal
Portland cement. White cement contains no or little Iron
Oxide.
Cement Microstructure
 Chemistry of Cement
• Raw materials [Lime (CaO), Silica (SiO2), Alumina (Al2O3), and Iron
Oxide (Fe2O3)] interact in the kiln to form a series of more complex
products where a state of chemical equilibrium is reached.
• During cooling the equilibrium is not maintained, and rate of cooling
will affect the degree of crystallization.
• Thus cement can be considered as being in frozen equilibrium (i.e. the
cooled products are assumed to reproduce the equilibrium existing at the
clinkering temperature).
• This assumption made in the calculation of the compound composition
of cement.
• The compound composition is calculated from the measured quantities
of oxides present in the clinker as if full crystallization of equilibrium
products had taken place.
Clinker
 Chemistry of Cement Cont.

• Main Compounds in Portland Cement

Compound Oxide Composition Abbreviation
Tricalcium Silicate 3CaO.SiO2 C3S
Dicalcium Silicate 2CaO.SiO2 C2S
Tricalcium Aluminate 3CaO.Al2O3 C3A
Tetracalcium 4CaO.Al2O3. Fe2O3 C4AF
Aluminoferrite

C= CaO S= SiO2 A = Al2O3, F = Fe2O3

H = H2O,
 Bogue’s Equation
• Bogue’s equations are used to find the
percentage of main compounds in cement.

C3S= 4.07(CaO) – 7.60(SiO2) – 6.72(Al2O3) -1.43(Fe2O3) – 2.85(SO 3)

C2S= 2.87(SiO2) – 0.754(3CaO.SiO2)

C3A= 2.65(Al2O3) -1.69(Fe2O3)

C4AF= 3.04(Fe2O3)
⚫ The terms in brackets represent the percentage of the given
oxide in the total mass of the cement.
 Example: Bogue’s Equation

C3S= 4.07C – 7.60 S – 6.72 A -1.43 F – 2.85(SO 3)

C2S= 2.87 S – 0.754 C3S

C3A= 2.65 A -1.69 F

C4AF= 3.04 F

⚫ Find the oxide composition for the cement with percentage of

main compounds of C3S = 60%, C2S = 18%, C3A = 6%,
C4AF = 6 %, and SO3 = 3%
 General Properties of Cement
Compounds
• C3S and C2S are the most important compounds which are
responsible for the strength of hydrated cement paste.
• C3S
Hydrates & harden rapidly & is largely responsible for initial setting &
early strength.
• C 2S
Hydrates & harden slowly and contribute largely to strength increase at
ages beyond one week.
• C3A
Undesirable, it contribute slightly to early strength, liberate large amount
of heat which helps in the hydration of C3S and C2S.
C3A is beneficial in the manufacture of cement in that it facilitate the
combination of lime and silica.
• C4AF
Doesn’t affect the behavior significantly, its presence may accelerate the
hydration of the silicates, it reacts with gypsum.
 Minor Cement Compounds
• In addition to the major compound, there exist minor
compounds such as :
MgO, TiO2, MnO3, K2O, and Na2O
Their amount is not more than few % of the mass of cement.
• Oxide of Sodium (Na2O) & Potassium (K2O) (Known as
Alkalis) are of interest since they react with some
aggregates (Alkali-Aggregate reaction) that cause
disintegration of concrete and affect the rate of gain of
strength of cement.
• Minor compounds refer to their quantity and not
necessarily their importance.
• See Table 2.2 for approximate composition limits of
Portland cement.
 Hydration of Cement
• Cement paste = cement + water.
• In presence of water, silicates and aluminates of Portland cement
form products of hydration or hydrates, which in time produce a
firm and hard mass, the hardened cement paste.
• C3S and C2S ( main cementitious compounds)
2C3S + 6H → C3S2H3 + 3Ca(OH)2
[100] [24] [75] [49]

2C2S + 4H → C3S2H3 + Ca(OH)2

[100] [21] [99] [22]
C 3A + 6H → C3AH6
[100] [40] [140]

⚫ The numbers in the square brackets are the corresponding

masses.
 Hydration of Cement
• Both silicates require approximately the same
amount of water for hydration, but C3S
produce more than twice as much as Ca(OH)2
as is formed by the hydration of C2S.
• The reaction of C3A with water is very rapid
and would lead to a flash set, which is
prevented by the addition of Gypsum to the
cement clinker.
• C3A requires more water for hydration than the
silicates.
 Heat of Hydration & Strength
• Heat of hydration: the quantity of heat (in
joules) per gram of unhydrated cement evolved
upon complete hydration at a given temperature.
• The temperature at which the hydration occurs
greatly affect the rate of heat development.
• About one-half of the total heat is liberated
between 1 & 3 days.
• About 3/4 of total heat is liberated in 7 days.
• Nearly 90% of total heat is liberated in 6
months.
 Heat of Hydration & Strength
• Heat of hydration depends on the chemical composition of the
cement. Approximately = SUM (Heat of hydrations of individual
pure compounds).
• Highest (C3A, C3S, C4AF, C2S) lowest
• Heat of hydration can be reduced by reducing the proportions of
C3A, C3S.
• Fineness of cement affect the rate of heat development but not the
total amount of heat liberated, which can be controlled by the
quantity of cement (Richness).
• Figure 2.2 shows development of strength of pure compounds.
• C3S contributes the most to strength development during first 4
weeks, while C2S influence the later gain.
• At the age of 1 year both (C3S & C2S) contribute approximately
equal.
 Heat of Hydration & Strength
• Rate of heat of hydration depends on:
1. Mixtures added
2. Temperature
3. Degree of fineness
4. Amount of water
5. Cement type
 Tests on Cement
• Quality of cement is vital for production of good
concrete.
• Quality control is achieved by performing some tests in
the cement plant LAB.
• Tests are also needed to conform to requirements of
national standards.
• Cement tests are also necessary for periodic acceptance
tests.
• Tests for chemical composition will not be covered in
this course.
• Fineness tests, setting times, soundness tests, an
• strength tests will be briefly covered.
 Fineness of Cement
• Hydration starts at the surface of cement
particle, thus the total surface area of cement
represent the material available for hydration.
• Rate of hydration depends of the fineness of
cement particle. Thus for rapid development of
strength a high fineness is necessary.
• Test: Determination of Specific Surface (m2/kg)
see page 16 in Text (Wagner turbidimeter, air
permeability methods, & Nitrogen adsorption).
Consistence of Standard Paste
• To determine the initial and final setting times and
soundness tests, neat cement paste of standard
consistence has to be used.
• It is necessary to determine for any given cement the
water content which will produce a paste of standard
consistence Normal Consistency.
• Normal Consistency is determined by the Vicat
apparatus:
• Vicat apparatus: Measures the depth of penetration of
a 10mm diameter plunger under its own weight.
• When a depth of penetration reaches a certain value
(10 +-1mm), the water content required gives a
standard consistence (Normal Consistency) (between
26 and 33) % by mass of dry cement.
Vicat Consistency Apparatus
 Setting Time
• Term used to describe the stiffness of the cement
paste.
• Setting refers to a change from liquid to rigid state.
• Setting is caused by a selective hydration of C3A and
C3S and is accompanied by rise in temperature of the
cement paste.
• Initial set (corresponds to rapid rise) & final set
(correspond to the peak temperature).
• False set: Some times occurs within few minutes of
mixing with water. No heat is evolved and concrete
can be remixed with no addition of water.
• Flash set: Occurs when C3A reacts with water rapidly
which would lead to a flash set. Characterized by the
liberation of heat.
 Initial Setting Time
• Initial setting time: Time required for the paste to
change from liquid state to plastic state.
• Using Vicat apparatus
The time in which a1mm diameter needle acting under prescribed
weight on Normal consistency paste penetrates to a point (5mm)
from the bottom of special mold.
(BS: Min. of 45 min. and higher for lower strength class)
• Using ASTM C191-92
The time in which a1mm diameter needle acting under prescribed
weight on Normal consistency paste penetrates (25mm).
(smaller depth of penetration than Vicat in BS)
(ASTM: Min. of 60 min.)
 Final Setting Time
• It occurs when the paste harden.
• Final setting = time when the needle doesn’t sink
visibly in the paste or when the needle makes an
impression on the paste surface.
• BS: Max of 10 hrs
Final time (min.) = 90 + 1.2 [Initial time
(min)]
 Setting Time using Gillmore Test
• Gillmore Test (ASTM C266-89)
• The initial setting time is the time required for
the test specimen to bear the initial Gillmore
needle (113.4 g and a tip diameter of 2.126 mm)
without appreciable indentation, while the time
required for the test specimen to bear the final
Gillmore needle (453.6 g and a tip diameter of
1.066 mm) without appreciable indentation is
the final setting time.
Gillmore Test Apparatus
 Factors Affecting Setting
• Fineness of the cement: finer cement accelerates
setting.
• Chemical composition of cement: Tricalcium
Aluminate (C3A) and tricalcium silicate (C3S)
decrease the setting time.
• Amount of Water: High water content increase
the setting time
• Ambient Temperature: High ambient
temperature decreases the setting time.
 Soundness Test
• Cement Paste after setting may under go a large
change in volume (expansion) which cause disruption
of the hardened concrete.
• Expansion can be due to reaction of CaO, MgO, &
Ca(SO4)
• Cements exhibit this type of expansion are classified as
unsound.
• Le Chatelier accelerated test (BS EN 196-3:1995) for
detecting unsoundness due to free lime
• Autoclave test (ASTM C151-89) for detecting
unsoundness due to Magnesia (MgO) and lime.
• No test is available to detect soundness due to excess
of Calcium Sulphate but may be done by chemical
analysis.
 Strength of Cement
• Strength tests are not conducted on neat cement
paste because its difficult to obtain good
specimen and the variability in test results due
to that.
• Cement-sand mortar (cement + sand + water)
specimens are used to determine the strength of
cement.
• Strength tests:
▫ Direct tension
▫ Compression
▫ Flexural
Compressive Strength of Cement
• BS EN 196-1:1995 Mortar prism test.
▫ Strength classes
 N: Normal
 R: Rapid hardening properties
• ASTM C109-92 (Compressive Strength of Hydraulic Cement
Mortars using 2-in. or [50-mm] Cube Specimens)
▫ Cement-sand mix (1: 2.75)
▫ Water/cement ratio = 0.485
▫ Ottawa sand
▫ 50 mm cubes
▫ Cube samples are cured in saturated lime water at 23oC
▫ Compressive strength = load @ failure/ cross section area.
• ASTM C349-82 (Compressive Strength of Hydraulic-
Cement Mortars using Portions of Prisms Broken in
Flexure).
 Flexural Test
• ASTM C348-93 (Flexural Strength of Hydraulic-
Cement Mortars).
▫ Mortar prism (40 x 40 x 160 mm) loaded at mid span.
▫ Mix proportions, storage, and curing are same as compressive
strength test.

Sf = 0.0028 P
where:
S f = flexural strength, MPa, and
P = total maximum load, N.

▫ Sf = (M/I) y ………. Y =h/2, M=Pl/4, I= bh3/12

Cube & Prism Molds
 Direct tension
• Briquette mold samples of cement mortar.
• Fixed and pulled apart at specified rate.
• Tensile strength = T/A
• A = 1 in2