D28MA Civil Engineering Materials: Lecture 4 - Cement

D28MA
Civil Engineering Materials
Lecture 4 – Cement
Course delivery team
Dr. ‘Nwendu Ogwuda Dr. Chu, May Yen Dr. Ceren Ince
e: o.i.ogwuda@hw.ac.uk e: c.may_yen@hw.ac.uk e: c.ince@hw.ac.uk
D28MA Civil Engineering Materials

Cement: Content
4.1 Introduction
4.2 Historical development
4.3 Cement manufacture
4.4 Oxide and compound composition of Portland cement
4.5 Cement hydration
4.6 Structure of hydrated cement
4.7 Portland pozzolan cement (Blended cement)
4.8 Embodied energy/carbon
4.9 Test on cement

4.1 Introduction
Portland cement is a binding material produced by pulverising a small amount of

gypsum, along with the Portland cement clinker that is obtained by burning an
appropriate combination of calcareous and clayey materials.
The finished product (the Portland cement) is in powdered form and has grayish colour.
This colour is from the small amount of iron oxide in the raw material.
The mixture of cement and water is called cement paste.
When Portland cement is mixed with water, a plastic paste is formed that can be
moulded into any shape. However, as time goes by, paste sets (gains rigidity) and
hardens (gain strength) due to the chemical reaction between water and compounds in
Portland cement. Since Portland cement can set and harden under water, it is a
hydraulic binder.
The proportions of compounds and the fineness of cement particles influence the setting
and hardening of Portland cement.
The development of strength and other properties depend on the degree of occurrence
of the chemical reaction between water and cement, in other word, degree of hydration.
4.1 Introduction
Clinker Cement
Types of cement
4.1 Introduction
Portland cement is used in making mortars and concrete.

Mortar = Cement + water + fine aggregate (sand)
Concrete = Cement + water + fine aggregate (sand) + coarse aggregate (gravel)
Joseph Aspdin (1824, England) was the person who first produced Portland
cement by burning finely divided limestone and clay in a furnace and pulverising
the burnt product.
Cement produced by Aspdin was quite different than the what may be called
modern cement - because the burning temperatures were not sufficiently high
and the cement particles were not fine enough. Englishman, Isaac Charles
Johnson was the inventor of the modern Portland cement (1872).
Apart from the Portland cement, Portland-pozzolan type of cements are also
widely used in making mortars and concrete.
4.1 Introduction
Mortar - Masonry Concrete
Concrete placing Formworks

2nd / 1st Century BC : Greeks and Romans

▪ Extensive use of lime mortars (non-hydraulic)
▪ Hardened by reaction with atmospheric carbon dioxide
▪ Reaction (hence strength development) is very slow and summarised by:
For production of lime:

CaCO3 (heat 850ºC) → CaO (quicklime) + CO2
CaO + H2O → Ca(OH)2 (slaked lime)
For hardening:
Ca(OH)2 + CO2 → CaCO3 + H2O
Limestone
CO2 CO2
H 2O
Non-hydraulic Moderately hydraulic Very hydraulic
Carbonation Carbonation + Hydration Hydration
LIME NATURAL HYDRAULIC CEMENT

LIMES
Non-hydraulic lime NHL 2
Calcium lime
Hydrated lime NHL 3.5
CL 90
CL 80 NHL 5
CL 70
Min. compressive strength

Calcium Min. CaO in MPa at 91 days
lime content
18th / 19th Century

▪ 1793: John Smeaton found that the calcination of limestone
containing clay gave a lime which hardened under water (hydraulic
lime). He used hydraulic lime to rebuild Eddystone Lighthouse in
Cornwall, England which he had been commissioned to build in
1756, but had to first invent a material that would not be affected by
water.
▪ 1812: Louis Vicat in France prepared artificial hydraulic lime by
calcining synthetic mixtures of limestone and clay.
▪ 1822: James Frost prepared artificial hydraulic lime like Vicat's and
called it ‘British Cement’.
19th Century
▪ 1824: Joseph Aspdin of England invented Portland cement by burning
finely ground chalk with finely divided clay in a lime kiln until carbon
dioxide was driven off. The sintered product was then ground and he
called it Portland cement named after the high quality building stones
quarried at Portland, England.
▪ 1828: I. K. Brunel is credited with the first engineering application of
Portland cement, which was used to fill a breach in the Thames Tunnel.
▪ 1845: Isaac Johnson claims to have burned the raw materials of Portland
cement to clinkering temperatures.
▪ 1860: The beginning of the era of Portland cements of modern
composition.
4.3 Cement Manufacture
Over one billion tonnes of Portland cement used annually.
Limestone (CaCO3) and clay are the

two main raw materials used for the
manufacturing Portland cement
clinker. Clay is composed of SiO2
and Al2O3. Pure clay is composed
of Al2O3.2SiO2.2H2O.
The same raw materials are used for both: Two processes:
▪ Calcareous - limestone, chalk (calcium) ▪ Wet process
▪ Argillaceous – clay, marl (silica, alumina) ▪ Dry process
• Chalk/limestone crushed to a fine powder and dispersed in water

• Clay is broken up and mixed with water
• These two mixtures are added together in predetermined proportions to form a slurry
• Slurry fed into a kiln and heated to 1500°C
• Materials fuse together to form a clinker
• Clinker ground to a fine powder and a small amount of gypsum added (CaSO4.2H2O)
Quarried limestone Quarried clay/shale
Grinding Grinding
Schematic diagram
of Portland cement Blending
production • Water driven off
Preheating • CO2 given off
100°C 850°C 1450°C • Fusion of clinker
Burning in kiln Up to 3.5m
Up to 150m
Addition of gypsum
Final grinding
Distribution
rotary kiln
Sketch of a rotary
kiln for burning
Portland cement
The Kiln
Manufacturing process consists of grinding the raw materials (for uniform mixing),
mixing them in appropriate proportions, burning the raw materials in a kiln at 1400-
1500°C until the materials sinters (becomes coherent mass) or partially fuses into small
balls known as clinker.
The mixing the raw materials are done either in the dry state “dry process” or in water
“wet process”.
The mixture of raw materials is burned in a rotary kiln. Sketch of a rotary kiln for
burning Portland cement is shown in the figure below.
The Kiln
Rotary kiln is along steel cylinder (6m in diameter and 180m in length) with a
production capacity of ~1000 tons a day. The kiln is inclined a few degrees from the
horizontal. It rotates about its axis. Pulverised coal or gas is used as the source of heat.
The heat is supplied from the lower end and the maximum temperatures occur at the
lower end are in the range of 1400-1500°C. The temperature is lower towards the upper
end (150°C) of the kiln.
The mixture of raw materials is fed from the upper end of the kiln and are subjected to
several distinct processes as they move downward.
1. Drying of the material takes place. Free water is evaporated. Loosely bound water is
lost from the clay in the range of 150-350°C.
2. Decomposition of clay minerals occurs at 350-650°C. Thus SiO2 and Al2O are
obtained.
3. Decomposition of any magnesite (MgCO3) occurs at 700°C. CO2 is lost and MgO is
obtained.
4. Decomposition of limestone (CaCO3) occurs at 900°C. CO2 is lost and CaO is
obtained.
5. At about 1250-1280°C someThe liquid
Kilnformation (melting) begins and compound
formation takes place.
6. Clinkering begins at 1280°C and continues to

about 1400°C. Liquid that forms during burning
process causes the charge to agglomerate into
nodules of various sizes, characteristically dark gray
and hard. This product is known as “Portland cement
clinker”.Once the material reaches the lower end of
the kiln, it enters a short cooling zone and drops off Clinker Cement
in temperature.
Manufacture of Portland cement: The clinker that is already cooled is conveyed to ball mills to
be interground with gypsum (3-6%) to prevent quick setting of the cement. After the grinding
process is completed, cement is ready for packing .
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Manufacture of Portland-pozzolan cement: This type of cement is produced by intergrinding a
combination of Portland cement clinker, some pozzolan, and small amount of gypsum.
4.4 Oxide and compound composition
Portland cement is mainly composed of lime (CaO), silica (SiO2), alumina (Al2O3) and iron
(Fe2O3). These four oxides are named as major oxides.
CaO is the highest amount of oxide in cement (from limestone).

SiO2 and Al2O3 are obtained from clay.
Fe2O3 is found as an impurity in clay.
In addition to the major oxides, cement also contains small quantities of “minor oxides”.
These are magnesia (MgO), alkalies (Na2O and K2O) and sulfuric anhydride (SO3).
All the oxides other than sulfuric anhydrate are obtained by burning a mixture of raw
materials (that take place in the clinker). The sulfuric anhydrate comes from the gypsum.
The major oxides play a significant role in the formation of calcium-silicate compounds that
are the strength giving compounds and other main compounds such as calcium aluminates
and calcium alumino ferrites.
The minor oxides do not make a significant contribution to the strength development but if
The
they are present in excessive amounts, theyKiln
lead harmful expansions.
In cement chemistry each oxide is abbreviated by a single letter and the number
of oxides in a compound is written as a subscript after the letter. These common
notations are shown in table below.
The Kiln
Compound composition of cement

Portland cement clinker has four major compounds as a result of the chemical
reactions among the major oxides. The names, chemical formulas and shorthand
notations of these compounds are given in Table below.
Since Portland cement is the ground form of clinker with some little amount of
gypsum rock, the major compounds of clinker are also the major compounds of
Portland cement.
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The main chemical compounds present in Portland cement:

o Tricalcium silicate 3CaO.SiO2
o Dicalcium silicate 2CaO.SiO2
o Tricalcium aluminate 3CaO.Al2O3
o Tetracalcium aluminoferrite 4CaO.Al2O3Fe2O3
Simplified terminology:
Compounds become:
CaO = C (not carbon ! )
C3S also known as alite
SiO2 = S (not sulphur ! )
C2S as known as belite
Al2O3 =A
C3A
Fe2O3 =F
C4AF
H2O = H (not hydrogen!)
Chemical composition of Portland cement
▪ Ordinary Portland Cement contains, typically (by weight) :

C3S : 50-55%
C2S : 20-25%
C3A : 10-12%
C4AF : 5-10%
▪ OPC now covered by BS EN-197-1 (CEM I) (formerly BS 12)

Suggested structure of a cement grain
10-20mm
C4AF
C2S
C3A
C3S
Influence of compound composition upon the characteristics of Portland cement
When Portland cement is mixed with water, the compounds in the cement undergo chemical
reactions with water independently, and different products result from these reactions. The
characteristics of each major compound of cement are shown in table below.
The combined effect

of chemical reactions
with water determines
the behaviour of
Portland cement.
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Strength gain of pure compounds
C3S
80
Compressive strength
60 C2S
(N/mm2)
40
20 C3A
C4AF
0
7 28 90 180 360
Age (days) – log scale

Strength gain of pure compounds
Compounds in cement hydrate (hence gain strength) at different rates:
• C3S contributes to initial strength - within 24-hours and over the first
few weeks
• C2S contributes to strength development in the longer term – two
weeks and beyond.
• C3A and C4AF - contribute little overall strength
In Portland cement, strength increases only gradually after 4 weeks due to
relative proportions of components.

Different types of Portland

Ordinary Portland cement cements can be produced by
Portland Blast furnace
cement
adjusting the proportions of the
raw materials to give desired
Rapid hardening Portland
cement
compound compositions. For
instance, the typical compound
Low heat Portland cement

compositions of the five main
types of Portland cements are
Sulphate Resisting Portland

present in Table.
cement
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Composition of Portland Cements
Proportions of compounds define properties of cement:
C3 S C2 S C3 A C4 AF
OPC 54 20 12 8
RHPC* 62 9 12 8
SRPC 30 46 5 13
Low heat PC 43 36 4 12
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Range of Euro-cements
BS EN 197-1
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Types of Portland Cement
• Ordinary Portland cement – BS EN 197-1 (replaces BS 12)

• Rapid hardening Portland cement – BS EN 197-1
• Sulphate Resisting Portland cement – BS 4027 now BS EN 197-1
• White Portland cement - BS EN 197-1
• Portland Blast furnace cement – BS EN 197-4 (replaced BS146) further replaced by
BS EN 197-1
• High Alumina cement – BS EN 14647: 2005 (replaces BS 915)
• Low heat Portland cement – BS EN 197-1 (replaces BS 1370)
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Significance of the oxide composition of Portland cement

Amount of oxides depends on the proportioning of raw materials and the performance of
burning in the kiln. Oxide composition of cement is found by chemical analysis and this is
shown in table below for ordinary Portland cement (Type1).
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• CaO, SiO2, Al2O3 and Fe2O3 are the major oxides and form the major compounds.
Therefore the proportions of these oxides determines the proportions of the
compounds and hence affect the performance of the cement.
• The amount of gypsum (SO3) prevent quick setting of cement. However, too much
of gypsum results in disruptive expansions.
• High content of MgO and free CaO (that is not participated in the formation of major
compounds) reacts very slowly with water and usually take place after the cement is
set and hardened. Later reaction of these oxides with water cause expansion in the
hardened state and results in cracking.
• The presence of alkalies (Na2O+K2O) together with a cement that has reactive
aggregates might result in a aggressive reaction between the alkaline hydroxide
(from alkalies) and silica (from aggregates) and hence form a alkali-silica gel which
can imbibe a lot of water and swell. This cause disintegration and cracking in the
hardened state of paste, mortar and concrete.
• Insoluble residue is the fraction of cement which is not soluble in hydrochloric acid.
This indicates the completeness of the reactions in the kiln. (Max. of 0.75% is
allowed).
• Loss on ignition is the loss inThe Kilnof a one gram of cement sample after being
weight
heated to 1000°C. (Max. of 3% is allowed).
Methods determining the compound composition of Portland cement
The compound composition of Portland cement or clinkers can be determined by three
different methods:
Microscopy
X-ray diffraction
Computation (using Bogue’s equations)
The computational method is the simplest and most popular for determining the
approximate compound composition of Portland cement or clinker. In this method, it is
necessary to know the oxide composition of the cement or the clinker to determine the
compound composition.
Bogue’s equations are given below:
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Hydration of Portland cement
• Chemical reactions with water are designated as “hydration” and starts as soon as the
cement is mixed with water.
• Each compound in the cement is assumed to react with water independently.
• Thus the rate of hydration and the heat liberated by the reaction of each compound is
different.
• In other words, each compound produces different products following hydration.
• Different characteristics of these compounds are already shown in the lecture.
• So the characteristics of a cement depend on its compound composition and the
degree of hydration.
The chemical reactions of the major compounds with water are explained here.
Hydration of C2S and C3S: The chemical reactions of the calcium silicate compounds
with water are shown by the following equations:
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The overall chemical reactions are:
C3S and C2S
2C3S + 6H → C3S2H3 + 3Ca(OH)2 (fairly fast + heat)
2C2S + 4H → C3S2H3 + Ca(OH)2 (slow)
 
calcium-silicate-hydrate calcium hydroxide
41
• Hydration reactions of both of the calcium silicate compounds (C2S and C3S) result
in two principal products: C3S2H3 and CH.
• C3S2H3 is called tobermorite gel (because of its similarity to a naturally occurring
mineral with this name). The calcium-silicate-hydrate gels are simply called C-S-H
gels. (The term gel designates a rigid aggregation of colloidal materials.
• When Table 7.4 is studied, it can be seen that C2S and C3S are the two compounds
that contribute to the ultimate strength as they hydrate.
• It is known that the production of calcium hydroxide (CH) does not contribute very
much to the development of strength.
• It can be concluded that calcium-silicate-hydrate gels are the major products of
hydration that provide the ultimate binding characteristics of cement.
Hydration of C3A: The reaction of C3A is very rapid, leading to the formation of
crystalline alumino hydrates. The rapid hydration of C3A causes immediate stiffening of
the cement paste known as “quick set” or “flash set”. To prevent this, small amount of
gypsum is added to the clinker.
On the other hand, when cement that contain C3A and gypsum react with water, either
one or both of the products are formed:
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C3A
• Straight reaction to form calcium-aluminate-hydrate:
C3A + 6H → C3AH6
• This reaction is both rapid and violent and would cause flash set of the
cement
• In the presence of gypsum (calcium sulphate: CaSO4.2H20), the reaction
is suppressed and ettringite (AFt) is formed:
C3A + Water + Gypsum → Ettringite (AFt)
• As the gypsum is consumed, there is a phase transition and the AFt
converts to monosulpho-aluminate (AFm)
AFt → AFm (monosulpho-aluminate)
This reaction is reversible (and expansive) – sulphate attack
is the calcium-alumino-monosulfohydrate. It causes great expansion and it is

not stable. If it finds the possibility of reacting with more gypsum, it can lead to the
formation of .
is the calcium-alumino-trisulfohydrate. It is commonly called “ettringite”

which is a stable product with needle-like crystals having hexagonal cross-section. When
ettringite forms, a very great expansion is produced.
No or little amount of gypsum ~ flash set

Too much gypsum ~ ettringite formation = expansion and cracking
The C3A compound does not significantly contribute to strength and therefore the amount
of C3A should not be high.
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ettringite
Hydration of C4AF: When C4AF hydrates in the presence of gypsum, similar sequence of
events and hydration products occurs as C3A. Here, the Al ions are partly replaced by Fe
ions. The reactions of C4AF causes expansion and heat liberation, too. C4AF does not
cause flash set as C3A.
Heat of hydration
The hydration reactions of the compounds of Portland cement are all “exothermic”; heat
is liberated by these reactions. This heat is called “heat of hydration”.
Heat of hydration of pure compounds is given in table below. Heat of hydration is
affected by the compounds in the cement. Heat of hydration of cement is of the order of
85-100cal/g.
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During the setting and hardening process of cement, heat is generated due to the
reactions that leads to the temperature rise in the concrete.
The rate of heat of hydration has great importance for practical purposes:
• Concrete, in itself, is a fair insulator. In a large mass, such as concrete used for a dam,
heat generation is not readily dissipated. High rise in temperature results in expansion
of concrete mass. Following cooling to a normal temperature, contraction takes place
and this results in the development of serious cracks.
• On the other hand, high heat of hydration might be advantageous when concreting
during cold weather. (High heat of hydration compensate the negative effect of cold
weather during hydration).
• One-half of the total heat of hydration is liberated in 1-3 days and three-quarters in 7
days.
Higher rate of heat evolution results:

(a) When C2S and C3S contents are high
(b) When hydration takes place at high temperatures
The Kilnare high
(c) When the fineness of cement particles
Stage I
• Initial 5 minutes or so
• Alkalinity (pH) of water rises to 12-13
• Some crystal growth (C3A)
• Generally an amorphous coating on the
cement grains (C3S) which slows down
reactions
• Leads into a dormant period (Stage II)
where there is little chemical activity
within the paste.
End of Stage II – Stage III
• End of Stage II (dormant period) after 2

hours and marks the change from fluid to
solid sate i.e. setting
• Reactions mainly on the C3S phase and more

crystalline microstructure
• Temperature within the paste increases

• Leads to Stage IV
Stage IV
• Temperature within paste begins to

decrease
• Reactions become slower

• Continued crystal growth (on C3S
phase).
• Start of the period of hardening

Unhydrated core
Capillary pores filled

with water
Products of hydration
Calcium hydroxide
Hydration continues until: At any stage in the hydration process, the

cement paste will comprise:
• All unreacted (i.e. unhydrated) • unreacted cement
cement is used up. • products of hydration
• Products of hydration fill all
• calcium hydroxide
the space.
• water (different types)
• All the water within the paste
• an interconnected capillary
is used up.
pore network
Even in very mature cements, some Capillary pores are the void spaces
unreacted cement will be present between the hydrating cement grains which
are filled with water and/or air.
Stage I Stage II Stage III Stage IV

Dormant Setting Hardening
period
Rate of heat liberation
C3A C3S
C3S
and
C2S
10 2 10 hours 24 hours

minutes hours
Time
Calcium Silicates: Products of Hydration
C-S-H
2mm
Calcium Silicates: products of Hydration
CH
C-S-H
Setting
The term setting means stiffening of cement paste. Setting is different than hardening as
this refers to the strength gain of cement paste.
The two compounds that react with water first are the C3A and C3S. The quick reaction of
C3A is retarded with gypsum. As the chemical reactions proceeds, cement paste starts to
loose its plasticity; it gains rigidity and hardness.
The length of time starting from the mixing of cement and water until the cement paste
sets is called “setting time”. Setting time is important as the cement paste is only
shapeable during this time.
The Kiln
Setting time of cement should neither be too short nor too long. (According to ASTM C
150, setting time of ordinary Portland cement should not be shorter than 45 minutes, and
should not be longer than 375 minutes.
Very quick setting time of cement may take place as either “flash set” or “false set”.
The Kiln
Flash set (quick set) occurs when there is an insufficient amount or no gypsum in cement.
In this case, C3A reacts with water very fast, and paste becomes rigid in a very short time.
False set is the abnormal premature stiffening of the paste after a few minutes of mixing.
This is different than flash set and that re-mixing the cement paste restores it plasticity.
Some of the causes of flash set are:
(a) When gypsum rock is interground with too hot a clinker – gypsum rock loses its
water and becomes plaster or Paris or gypsum anhydride. This product react with
water too quickly and result in stiffening.
(b) If the alkali in cement has carbonated during storage, alkali carbonate reacts with
calcium hydroxide and leads to the formation of CaCO3 increase the rate of rigidity
in the paste.
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Fineness
The term “fineness” refers to the average size of the cement particles obtained by
intergrinding the clinker with a small amount of gypsum rock. A higher fineness means a
more finely ground cement where the particles are smaller.
Fineness (cm2/g) is usually determined by conducting test with the so-called Blaine
apparatus. ASTM C 150, min. value of fineness of cement is 2800 cm2/g.
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Fineness of cement is a vital parameter that affects the several properties of cement and
concrete:
• Increase in fineness leads to the increase in the rate of hydration (since total surface
area of the particles are greater).
• Increase in the rate of hydration results in the increased rate of strength gain.
• However if the particles are too fine, pre-hydration during storage might occur, leading
to the low binding capacity of cement.
• When the cement particle are coarse, hydration starts on the surface of the particles but
further hydration is prevented (or delayed) due to the formation of reaction products.
Therefore, the coarse particles may not be completely hydrated and result in low
strength and low durability.
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Soundness
Soundness is the property of being strong, safe, secure and free from injury or defects.
Soundness of the hardened cement paste is referred to the property of this paste not to
undergo a large change in volume that will cause disruption and cracking.
Unsoundness in a hardened cement paste may take place due to the delayed or slow
hydration or other reactions of oxides and sulfates present in the hardened cement paste,
namely free lime, magnesia and calcuim sulfate.
Free lime – as a result of the use of excessive amount of lime is used in the kiln – excess
calcium oxide shows slow hydration – expansion of calcium oxide takes place in the
hardened cement causes crack.
Magnesia – if the kiln contains some magnesia (magnesium oxide) – hydration is slow-
causes cracking since expansion takes place after the cement is hardened.
Calcium sulfate – if too much gypsum added to the clinker – it reacts with C3A and
The isKiln
expansion takes place.
Structure of hydrated cement
As soon as cement and water are mixed, the major compounds start to produce calcium-
silicate-hydrate gels, calcium hydroxide and calcium-alumino-sulfohydrates. There are
also some minor components in cement. All of these hydration products are referred to
collectively as “cement gel”.
At the beginning of the mixing operation of cement and water, the paste has a structure
which consists of cement particles with water-filled space between them. As the hydration
proceeds, the gels are formed and they occupy some of this space.
At any stage of hydration, the structure of the cement paste consists of:
• Hydration products, referred collectively as gel
• Some cement that has not hydrated yet
• Water-filled spaces, which are called capillary pores.
Figure (next page) shows a simplified model of a hardened paste structure. Gels are
represented as solid dots in this model; interstitial space are gel pores; spaces such as
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those marked “C” are capillary pores. (Sizes of the gel pores are exaggerated in this
model.
Gel pores: Gel pores are interconnected interstitial spaces within the gel itself;
they constitute a part of the gel structure. Gel pores occupy about 28% of the
total volume of gel. Because the size of the pores is very small, the loss of water
from the gel pores by evaporation or the gain of water by the gel pores from an
outside source is not easy. The water in the gel pores may only be gained or lost
under the effect of some forces.The
GainKilnor loss of gel water causes expansion or
contraction of the paste. The water in the gel pores freezes at -78°C.
Capillary pores: Capillary pores are relatively large pores in the hardened cement paste.
These pores have varying sizes and shapes and are randomly distributed.
When the cement paste is first prepared, the voids between the cement particles are full of
water, and these voids are interconnected. Following hydration, gels occupy some of the
capillary spaces.
Capillary porosity mainly depends on the following factors:

1. Water / cement ratio: High water / cement ratio results in high void spaces in the
cement paste. Although hydration products occupy some of these void spaces, there
still remains a lot of void spaces as a result of high water/cement ratio.
2. Degree of hydration: As more hydration takes place and therefore more amount of
hydration products occupy the void spaces, higher amount of decrease takes place in
the capillary pores.
The water in the capillary pores is mobile (water can get in and out of pores).
Interconnected capillary pores are mainly responsible for the permeability of the
hardened paste. If the water in the capillary pores freeze (volume expansion), formation
TheHigh
of ice leads to high internal stresses. Kilnstrength and durability of hardened paste is
only obtained when the total number of capillary pores is low.
4.7 Pozzolans
Portland-pozzolan cements (Blended cements)

Portland-pozzolan type of cements (blended cements) are usually produced by
intergrinding a mixture of Portland cement clinker, pozzolans and 3-6% of gypsum.
The amount of pozzolanic material replacing clinker varies between 6-94%.
The pozzolanic materials used in producing Portland-pozzolan type of cements may be
volcanic tuff, volcanic ash, fly ash, silica fume, granulated blast furnace slag or a
combination of two or more of these.
The cement produced is more specifically named with the type of pozzolan used in the
production. For example: fly-ash cement or slag cement.
Pozzolanic materials do not possess binding properties in themselves; however, when they
are in a finely divided state, and combine with calcium hydroxide in the presence of
moisture, they possess hydraulic binding properties.
When a Portland-pozzolan cement is mixed with water, the calcium silicate compounds in
the Portland cement portion of the cement start to produce C-S-H gel and calcium
hydroxide; calcium hydroxide thus The react Kiln
with pozzolanic material to produce new C-S-H
gels and contribute to the strength of cement.
4.7 Pozzolans
What is ‘Pozzolan’?
Pozzolan is siliceous or siliceous and aluminous material. It has little or no cementitious

value in itself. However, pozzolans chemically react with calcium hydroxide and form
compounds possessing hydraulic cementitious properties in the case of
a) the presence of moisture

b) pozzolans powdered in fine form
Q. Where does the calcium hydroxide come from?
A. Calcium hydroxide (also known as portlandite) is one of the hydration

products. Calcium hydroxide contributes slightly to the strength and impermeability of
the paste, because it reduces the total pore volume by converting some of the liquid
water into solid form. (Calcium hydroxide is also obtained when Calcium Oxide, CaO, is
The Kiln
slaked with water).
4.7 Pozzolans
Where does the name ‘Pozzolans’ come from?
The name ‘pozzolan’ comes from the town Pozzuoli, Naples, Italy. The ancient Romans
produced a hydraulic binder by mixing hydrated lime with soil which composed of
volcanic ash. Later on, this name was given to all those materials.
Pozzolans, when in a finely divided form and it the presence of moisture, could chemically
react with calcium hydroxide to form a compounds that have hydraulic binding properties.
Q. What were the other pozzolanic materials used in ancient times?
A. Sticky rice soup, vegetable and fruit juices, leaves of plants, egg whites and animal
blood as well as fish oil and lime were used as pozzolanic materials in ancient time.
The Kilnthe compressive strength of a mortar by 30

(For example: Sticky rice soup increased
times)!
4.7 Pozzolans
Classification of pozzolans: a) Natural Pozzolans

The most common naturally occurring pozzolans are the volcanic ash, volcanic tuff,
pumice, crushed ceramic waste and diatomaceous earth.
Volcanic ash Pumice Diatomaceous earth Crushed ceramic waste
What is common among them?
Natural pozzolans have high amounts of silica (SiO2) and alumina (Al2O3) as well as
small amounts of iron oxide (Fe2O3), calcium oxide (CaO), magnesium oxide (MgO)
usually as an impurity. The Kiln
4.7 Pozzolans
Classification of pozzolans: b) Artificial Pozzolans

Fly ash, silica fume, granulated blast furnace slag (GGBS), rice husk ash and metakaolin
are the most commonly used artificial pozzolans in construction practice.
Fly ash is obtained as GGBS is obtained by rapid Metakaolin is

a by-product from cooling of the slag that is a dehydroxylated
burning of pulverized produced as a by-product form of the clay
coal in power plants. material. mineral kaolinite.
Apart from the high amounts ofThe

SiO2Kiln
and Al2O3, artificial pozzolans also have some
amounts of carbon too.
4.7 Pozzolans
History of pozzolans:
Q. When was the invention of cement?
A. 1824 (Joseph Aspdin)
Q. What type of binder was used before then?

A. lime + natural pozzolans as hydraulic binders were used.
• Extensive use of ‘lime + natural pozzolan’ mixtures as hydraulic binders in large construction
started with Romans (100 BC).
• In the absence of natural pozzolans, finely crushed burned bricks instead of volcanic ash
were used.
• So, until 1824 all the hydraulic binders used in obtaining pozzolanic concrete were either
‘lime + natural pozzolans’ or ‘lime + finely crushed brick’.
• The construction of many ancient structures that still exist was accomplished by using
pozzolanic materials. The Kiln
4.7 Pozzolans
History of pozzolans:
Pont du Gard is constructed using pozzolan-

lime mortars and concrete.
Rome's Pantheon is made using
pozzolan lime mortars.
Also Horosan mortar, a mixture made from
lime and finely divided burned clay was used
extensively in the Ottoman time of Turkey.
The Kiln
4.7 Pozzolans
Pozzolanic Reaction
The main chemical reaction takes place between the silica (from the finely divided pozzolan)
and calcium hydroxide (hydration product of cement and/or slaked lime).
The chemical reaction that takes place in the presence of moisture is as follows:
Calcium hydroxide + silica + water ‘Calcium – Silicate – Hydrate’ + ……..

C-S-H is the hydration product in
From cement From the finely very fine state. It has an
hydration or divided extraordinarily high surface area.
directly from lime pozzolanic This product provides the hydraulic
(slaked lime) materials binding property of the material.
The Kiln
An image taken from the Scanning Electron Microscopy,

showing the needles like crystals, C-S-H crystals.
4.7 Pozzolans
Pozzolanic Activity
Q. What is pozzolanic activity?
Pozzolanic activity refers to the capacity of the pozzolans to form alumino-silicates with lime
to form cementitous materials.
Q. What are the factors that affect the pozzolanic activity?

Pozzolanic activity depends on the following factors:
a)The content of ‘SiO2 + Al2O3 + Fe2O3’ in its composition

b) The degree of amorphousness of its structure
c)The fineness of its particles
The Kiln
4.7 Pozzolans
Pozzolanic reaction
Q. What type of reactions take place ?
A. First of all, cement hydration takes place: (hydration reaction)
Cement + water Calcium silicate compounds
Calcium-silicate-hydrate gel Calcium hydroxide, Ca(OH)2
Pozzolans + Calcium hydroxide Calcium-silicate-hydrate gel
Hydraulic
binding property The Kiln
Responsible from They further contribute in strength gain
the strength gain
4.7 Pozzolans
Pozzolanic reaction
Formation of Calcium-silicate-hydrate gel - Scanning Electron Microscopy
Lime mortars – No crystals are detected! Lime mortars with GGBS
The Kiln
large hexagonals needles like crystals
Calcim hydroxide crystals C-S-H crystals
4.7 Pozzolans
Compressive Strength (short-term)

Increase in the pozzolanic replacement levels decreased the short-term compressive
strength!
WHY ?
1. Pozzolanic reaction can only take

place following the hydration
reaction of cement!
2. This is beacuse silica (from the

pozzolans) reacts with calcium
hydroxide (product of cement
hydration).
3. So the pozzolanic reaction is much

slower than that of hydration.
4. Hence, higher the % replacement

Short-term compressive strength of cement levels of pozzolans, lower the short-
term compressive strength.
mortars with % replacement levels of silica fume.
The Kiln Initial rate of reaction of pozzolans is
slower than cement.
4.7 Pozzolans
Compressive Strength (long-term)

Initial rate of reaction of pozzolans is slower than cement. BUT this only means that pozzolans
gain the equivalent compressive strength of cement at a relatively longer period of time!
So the long-term compressive strength of pozzolan-concrete is either equivalent or higher than
that of the control speciment (concrete made with cement alone). Greater proportion of C-S-H
gels are produced.
Uses
Pozzolanic concrete can be used in any type of structures.
Important point: Concrete with a high percentage of GGBS used in cold weather will have a low
The
short-term compressive strength and may Kiln formwork to be in place longer.
require
4.7 Pozzolans
Permeability
As the reaction between the silica and calcium hydroxide proceeds, C-S-H gels are produced.
These C-H-S gels fill the voids in concrete and results in a much less permeable concrete.
Decrease in permeability results in an increase in durability such as high resistance to sulphate
attack, high resistance to carbonation, etc...
voids
C-S-H gels fill

the voids of
concrete
GGBS concrete – 28th days GGBS concrete – 1 year

4.7 Pozzolans
Heat of hydration
Pozzolans have low heat of hydration and therefore, higher the % pozzolanic materials in
cement, lower the heat of hydration. Low heat of hydration avoids the presence of
thermal cracking especially in mass concrete. This property is important particularly for
water retaining structures such as dams, tunnels etc...
Thermal cracking should be avoided in

dams as the cracking is detrimental to the
Thermal cracking in concrete due performance of water retaining structures.
to high heat of hydration
The Kiln
4.7 Pozzolans
The use of pozzolans in concrete provides:
1. High compressive strength

2. Enhanced durability characteristics
Enhanced durability
a) Higher resistance to sulphate and acid attacks
b) Higher resistance to alkali-aggregate reaction
c) Higher resistance to carbonation
3. Low permeability
4. Low heat of hydration High compressive strength
5. Enhanced architectural appearance

6. Increased sustainability
The Kiln
Increased sustainability Increased permeability
4.7 Pozzolans
Sustainability
Cement will remain the key material to satisfy global housing and modern infrastructure needs.
As a result, the cement industry is working towards to conserve materials and energy resources,
as well as to reduce CO2 emissions.
Two important aspects:

1. To reduce the amount of clinker (reduce the volume proportion of cement).
2. Re-introduce the pozzolans in cement either as an additive or an admixture.
The Kiln
Construction Materials and their Carbon Footprint
In order to reduce the carbon footprint of civil infrastructure it is important to

consider the energy that is embodied in the materials we use.
Every developed country has an obligation to reduce its greenhouse gas emissions in
the transition to a low carbon economy.
The Kiln
Source: www.globalissues.org
Construction Materials and their Carbon Footprint
Embodied Energy
The energy consumed in all the processes associated with the production of a building
material which includes raw material extraction, transportation and manufacturing
Embodied CO2 (CO2e)

The CO2 emitted in all the processes associated with the production of a building
material which includes raw material extraction, transportation and manufacturing
Operational CO2
Refers to CO2 emitted during the The
life ofKiln
a building, which includes the emissions from
heating, cooling, lighting etc.
Embodied energy for common building materials
Galvanised steel 38
Copper 100
Aluminium 170
Steel 30
Stainless Steel 90
Glass 12.7
Autoclaved aerated concrete… 3.6
Concrete blocks 1.5
Clay bricks 2.5
Precast steam-cured concrete 2
In situ concrete 1.9
Cement 5.6
Plasterboard 4.4
Gypsum plaster 2.9
Synthetic rubber 110
Plastics 90
Glue-laminated timber 11
0
The Kiln
40 80 120 160 200
Embodied Energy (GJ/t)
Portland Cement and Climate Change
▪ Portland cement is an essential component

1 tonne
of concrete. 1 tonne
Portland
CO2
cement
▪ Global cement production is in excess of 3
billion tonnes.
▪ More than 1 m3 of concrete (2.4 tonnes) is

produced per year for every person on the
planet i.e. about 7.4 billion m3 !
▪ The production of Portland cement accounts for about 5% of

global emissions of anthropogenic (man-made) carbon
The Kiln
dioxide (CO2).
Plywood
Timber
Steel (42% recycled content)
Stainless Steel
Steel
Glass
Concrete: Non Structural
Concrete: High Strength
Cement
Brick
0 1000 2000 3000 4000 5000 6000 7000
The Kiln
Embodied CO2e (kgCO2e/tonne)
CO2e (kgCO2e/m3) CO2e (kgCO2e/tonne)

30% 50% 30% 50%
Concrete Application CEM I CEM I
Fly Ash GGBS Fly Ash GGBS
Blinding, mass fill, strip
footings, mass
177 128 101 77 55 44
foundations, trench
foundations
Reinforced Foundations 316 263 197 133 111 83
Ground floors 316 261 186 134 110 79
Structural: in situ floors,

superstructure, walls, 369 313 231 154 131 96
basements
High strength concrete 432The Kiln

351 269 178 146 111
Source: http://www.concretecentre.com/
4.9 Test on cement
Most cement standards state the maximum amounts of SO3, MgO, Cl, insoluble residue
and loss on ignition that may be allowed to ocur in each cement type. These properties can
be determined by chemical analysis.
Setting time, soundness, strength, and fineness are the physical requirements for cement
and cement paste. (BS EN 196-1, BS EN 196-3, BS EN 196-5, BS EN 196-6).
Normal Consistency (Standard Consistency): The time of setting and soundness of a

cement paste depend on the water content of the paste. Therefore, it is necessary to define
a water content at which these tests should be conducted. This is defined in terms of
‘normal or standard consistency’.
Normal or standard consistency for a cement paste is found by conducting a test. Vicat
apparatus shown in figure (next page) is used for this purpose and the following procedure
is applied:
4.9 Test on cement
Consistency
A trial paste obtained by mixing dry cement and water is placed in a mold having an
inside diameter of 70mm at the base and 60mm at the top and a height of 40mm. The
plunger (having 10mm diameter) is then brought into contact with the top surface of the
paste and released. Under the action of its weight the plunger will penetrate the paste, the
depth depending on the water content of the paste. A paste with a water content that will
allow the plunger penetration 5-7mm from the bottom of the mold is seeked. Therefore,
different trials on pastes having different water content are tried. When the plunger
penetrates the paste to a point 5-7 mm from the bottom of the moldi that paste is
considered to be at ‘normal consistency’.
The water content of the paste is expressed as a percentage by weight of dry cement, the
The Kiln
usual range of values being between 26 to 33%.
4.9 Test on cement
The Kiln
Vicat apparatus: front and side views (shown with needle used for determining setting time).
4.9 Test on cement
Setting Time:
The setting time is conducted by using the Vicat apparatus shown in figure above. The
plunger is removed and a 1 mm diameter needle is attached to the apparatus to be used for
penetration. The test is started about 15 minutes after placing the cement paste (that has
normal consistency) into the mold. Trials for penetration of the needle are made.
The inital setting time is defined as the length of time between the preparation of the paste
and the time when the needle penetrates 25mm into the cement paste.
The final setting time is defined as the length of time between the preparation of the paste
and the time when the needle no longer sinks visibly into the paste.
The Kiln
4.9 Test on cement
Setting and Hardening of cement paste
Portland cement + water
Plastic / workable paste
Initial set
Stiff / unworkable paste
Final set
Strength
Rigid solid gaining strength
with time
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Time
4.9 Test on cement
Setting time of cement paste
▪ Defined in BS EN 196-3 and

Total mass:
300g determined using the Vicat
apparatus
▪ Arbitrary definition and related to
Scale
the penetration of different needles
into a sample of cement paste
Initial-set under a standard weight
needle Final set needle ▪ Two setting times: initial set and
final set – determined by different
Cement paste needles
▪ Typically, for OPC, initial set 100
minutes; final set  200 minutes
Side elevation The Kiln
4.9 Test on cement
Soundness:
The cement paste should not undergo large changes in volume after it has set. However,
when excessive amounts of free CaO or MgO are present in the cement, these oxides can
slowly hydrate (because of being overburned in the kiln) and cause expansion of the
hardened cement paste.
Soundess is defined as the volume stability of the cement paste. The Turkish and European
standards prescribe a soundness test conducted uisng the Le Chatelier apparatus shown in
figure
The Kiln
4.9 Test on cement
The apparatus consists of small brass cylinder split along its generatrix. Two indicators with
pointed ends are attached to the cylinder on either side of the split. The cylinder (which is open
on both ends) is placed on a glass plate. It is filled with cement paste of normal consistency and
covered with another glass plate. The whole assembly is then immersed in water at 20±1˚C for
24 hours. At the end of that period, the distance between the indicator points is measured. The
mold is then immersed in water again and brought to a boil. After boiling for one hour, the mold
is removed from the water; after cooling, the distance between the indicator points is measured
again. This increase of distance between the indicator points represents the expansion of the
cement paste. For Portland cements, expansion is limited to 10mm.
The Le Chatelier test detects unsoundness due to the

presence of relatively high amountsThe Kilnlime and
of free
magnesia in the cement.
4.9 Test on cement
Compressive strength: Compressive strength of Portland cement is determined according
to the BS EN 196-1.
The cement paste/mortar (consisting of 1 part of cement + 3 parts of standard sand +1/2
part of water, by weight) is placed in three steel molds that have 4 cm width, 4 cm height
and 16 cm length. The mortar bar specimens taken out of the molds are first subjected to
bending on the day the strength is tested (such as the 7th and 28th days).
To conduct the bending test, each mortar bar is placed on two supports that are 12 cm
apart and a load P (kgf) is applied until the bar breaks more or less at the middle.
Flexural (bending) strength in kgf/cm2 of each bar can be found using the relation σf=1.5
Pmax L/b3 where b is the width of the bar and L is the length between the supports. The
average of the flexural strength values found on three bars is expressed as the flexural
strength of the cement mortar. The flexural strength shows the tensile resistance of the
bar specimen to bending.
The compressive strength test is conducted on the broken halves of the mortar bars.
Since three specimens are broken in flexure, six specimens of 4 cm * 4 cm *
approximately 8 cm are available The Kiln
for this purpose. A piece of metal plate
(4cm*4cm*1cm) is placed on top and bottom of the specimen.
4.9 Test on cement
When a compressive force is applied, the mortar specimen behaves as if it were a

4cm*4cm*4cm cube. Following finding the breaking load in compression, Pmax,
compressive strength in terms of kgf/cm2 is calculated by the relation σc= Pmax/A, where
A=16cm2. The average of the results found by testing six specimens is the compressive
strength of the mortar bars.
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4.9 Test on cement
Fineness:
There are various methods for determining the fineness of cement particles. The Blaine air
permeability method is the most commonly used method.
In the Blaine air permeability method, a given volume of air is passed through a prepared
sample of definite density. The number and size of pores in a sample of given density is a
function of the size of the particles and their size distribution, and determines the rate of air
flow through the sample.
Calculations are made and the specific surface area of the particles present in the sample is
found. This value is the Blaine fineness value of the cement and it is expressed in terms of
cm2/g.
The Kiln

D28MA Civil Engineering Materials: Lecture 4 - Cement

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D28MA Civil Engineering Materials: Lecture 4 - Cement

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D28MA

Civil Engineering Materials

Course delivery team

D28MA Civil Engineering Materials

4.2 Historical development

4.3 Cement manufacture

4.4 Oxide and compound composition of Portland cement

4.5 Cement hydration

4.6 Structure of hydrated cement

4.7 Portland pozzolan cement (Blended cement)

4.8 Embodied energy/carbon

4.9 Test on cement

Portland cement is a binding material produced by pulverising a small amount of

Portland cement is used in making mortars and concrete.

Mortar - Masonry Concrete

Concrete placing Formworks

2nd / 1st Century BC : Greeks and Romans

For production of lime:

Non-hydraulic Moderately hydraulic Very hydraulic

Carbonation Carbonation + Hydration Hydration

LIME NATURAL HYDRAULIC CEMENT

Min. compressive strength

18th / 19th Century

Over one billion tonnes of Portland cement used annually.

Limestone (CaCO3) and clay are the

• Chalk/limestone crushed to a fine powder and dispersed in water

Quarried limestone Quarried clay/shale

Burning in kiln Up to 3.5m

6. Clinkering begins at 1280°C and continues to

CaO is the highest amount of oxide in cement (from limestone).

Compound composition of cement

The main chemical compounds present in Portland cement:

Chemical composition of Portland cement

▪ Ordinary Portland Cement contains, typically (by weight) :

▪ OPC now covered by BS EN-197-1 (CEM I) (formerly BS 12)

Suggested structure of a cement grain

Influence of compound composition upon the characteristics of Portland cement

The combined effect

Strength gain of pure compounds

Age (days) – log scale

Strength gain of pure compounds

Compounds in cement hydrate (hence gain strength) at different rates:

• C2S contributes to strength development in the longer term – two

weeks and beyond.

• C3A and C4AF - contribute little overall strength

In Portland cement, strength increases only gradually after 4 weeks due to

relative proportions of components.

Different types of Portland

Low heat Portland cement

Sulphate Resisting Portland

Composition of Portland Cements

Proportions of compounds define properties of cement:

Types of Portland Cement

• Ordinary Portland cement – BS EN 197-1 (replaces BS 12)

Significance of the oxide composition of Portland cement

is the calcium-alumino-monosulfohydrate. It causes great expansion and it is

is the calcium-alumino-trisulfohydrate. It is commonly called “ettringite”

No or little amount of gypsum ~ flash set

Higher rate of heat evolution results:

End of Stage II – Stage III

• End of Stage II (dormant period) after 2

• Reactions mainly on the C3S phase and more

• Temperature within the paste increases