CEMENT

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There are three distinct purposes:

Cement: The binding element in both concrete and

mortar.

Concrete: A product composed of cement, sand (fine

aggregate) and gravel (coarse aggregate). When water is
mixed in with this product, it activates the cement,
which is the element responsible for binding the mix
together to form one solid object.

Mortar: A product composed of cement and sand.

When water is mixed in with this product, the cement is
activated. Whereas concrete can stand alone, mortar is
used to hold together bricks, stones or other such
components
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History of cement
Different forms of cementitious materials were used by
Egyptians, Greek, Romans and Indians in their old architectures,
mainly consist of gypsum and lime.
Greeks and Romans became aware of using volcanic ash and tuff
in lime mixture to enhance strength and durability properties.
The added ground material was named Pozzolana referring to
Pozzuoli village- Italy.

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Modern cement
John Smeaton in 1756 was the first one reported that limestone
which contained a considerable amount of clayey matter
yielded better lime possessing superior hydraulic properties.
In 1800 the product was named Roman cement and was in use
till 1850 after which this was outdated by Portland cement.
Vicat was the leader worked on calcining an intimate mixture
of limestone and clay.
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James Frost was established a small factory in London district

in 1811.

However, the story of invention of Portland cement is

attributed to Joseph Aspdin on 21st October 1824.

In Iraq, Babil cement factory is the first cement factory

established in 1955 by KRUPP- Germany.

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Manufacture of Portland cement

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The raw materials are
- Calcareous materials such as limestone or chalk
- Argillaceous materials such as shale or clay.

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The process of manufacturing consists of:
-grinding the raw materials, mixing them intimately in
certain proportions

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- burning them in rotary kiln at a temperature of about 1300 to
1500oC.
As a result, materials sinters and partially fuses to form clinker.

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- Clinker cools down and ground with addition 3% to
5% gypsum.

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There are two processes depending on grinding raw materials in dry or
wet condition, called
- dry process and
-wet process.
- semi-dry with the addition of 10-14% water.
Nowadays, dry process is used widely since grinding material could be
done well without water addition.
Dry process:
- Requires much less fuel for burning. Because in wet process there is a
slurry contains 35-50% water to be dried.
- Size of rotary kiln in wet process is larger.

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Rotary kiln:

It is a thick cylinder of 3-8 m diameter, lined with

refractory brick, capable of rotating about its

longitudinal axis. The length varies from 30 m to 200 m.

Slurry being sprayed into the upper end and slowly

moves don to the lower end accompanying with

temperature increase.
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Changes:

With increasing temperature, the material undergoes a series of

chemical reaction and finally at about 1500oC about 20 to 30%

get fused.

Lime, silica and alumina (exist in raw materials) get

combined.

The fused mass has a nodular form of 3 mm to 20 mm size

known as clinker.
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Schematic diagram of rotary kiln
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CHEMICAL COMPOSITION OF PORTLAND CEMENT
Generally speaking, lime, silica, alumina, iron oxide
react to form more complex product. Different cement
types may be obtained by changing the proportioning of
the oxides present in the raw material.

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Bogue's Equation

The calculation of the composition of P.C is based on Bogue's works and

others which relates the percentage of oxides and compounds in the product
such that

C3S = 4.07 (CaO – free CaO) – (7.6 (SiO2) + 6.72 (Al2O3) + 1.43 (Fe2O3) + 2.85 (SO3))
C2S = 2.87 (SiO2) - 0.753 C3S
C3A = 2.65 (Al2O3) - 1.69 (Fe2O3)
C4AF = 3.04 (Fe2O3)

Minor compounds such as MgO, Mn2O3, K2O and Na2O usually amount to
not more than few percent of wt. of cement

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H.W
Sulphate resisting Portland cement (type IV) contain

C3S = 43%, C2S = 36%

Find the percentage of these oxides SO3, Fe2O3, Al2O3,

SiO2
If you know that
CaO/SiO2 = 3& 2C3A + C4AF = 20%
Using Bogue's equation

Note: Assume any necessary values you find it important (type

IV, C3A = 1-5 %)

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Development of Strength of pure compound of cement

Rate of hydration of pure compounds 30

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4- Free SiO2
SiO2 is another oxide which may be free in cement, it is not desirable oxide
in cement but it is not harmful such as CaO, due to not complete
combination of oxide during cement manufacturing. The amount of free
SiO2 is a measure of cement manufacture efficiency and known as Insoluble
Residue (IR). Insoluble Residue (IR) can be determine by treating with
hydrochloric acid, is a measure of adulteration of cement. Iraqi and British
Standard limits the IR to 1.5% of the mass of cement and ASTM limited it to
about 0.75%.

5- Alkalis Na2O,K2O
It was found that alkalis can react with some aggregate causing
disintegration of concrete. Cement used under such circumstances often
has their alkali content limited to 0.6%. It also affects the rate of gain in
strength of the paste. Alkalis should not exceed 1.3%.

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8. Sulphur trioxide (SO3)
The sources of SO3 are:
raw material (limestone & clay)
firing (some SO3 come from fuel during manufacturing
of cement)
gypsum added at the grinding stage.

Iraqi specification (No. 5) & British Standard (No. 12)

limited the amount of SO3 according the percentage of
C3A
SO3 ≤ 2.5% C3A<5% for S.R.P.C
SO3 ≤ 2.8% C3A > 5 for O.P.C.

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Gypsum for Retardation of Setting
If water added to clinker it will set very quickly. In order to
retard its set (sufficiently to enable it to meet commercial
requirements), gypsum is added to cement clinker.
Gypsum and C3A react to form insoluble calcium
sulphoaluminate (called ettringite)
(3CaO.Al2O3.3CaSO4.31H2O)
As more C3A comes into solution, the sulphate content
decreasing continuously and monosulphate
(3CaO.Al2O3.CaSO4.12H2O) produces.

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In hardened cement, the formation of these products may lead
to an expansion and consequence disruption of concrete.
Thus, the amount of gypsum added to the cement clinker has
to be very careful watched. The optimum gypsum content
(OGC), that gives maximum strength, minimum shrinkage
and low expansion when submerged in water, depend on:
C3A content (increase with increasing C3A)
A- fineness of cement (increasing with increasing in cement
fineness)
B- alkali content (increase)
C-curing temperature (increase)
D-curing time (increase)
E- free lime and MgO (decrease)
F- chloride content (decrease)

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Hydration of cement
The reaction of dry cement takes place in the presence of water
and also called hydration. As a result, the cement gains the
ability of binding and harden with time.
- The products of hydration have a low solubility.
- The rate of hydration decreases continuously so that even
after long time there remains appreciable amount of
unhydrated cement.
Hydration proceeds by a gradual reduction in the size of
cement particles.
The main hydrates can be broadly classified as calcium silicate
hydrates and tricalcium aluminate hydrate.
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The progress of hydration of cement can be determined by
the amount of Ca(OH)2 in the paste
the heat evolved by hydration
the specific gravity of the paste
the amount of chemically combined water
the amount of unhydrated cement present
Also indirectly from the strength of hydrated paste.

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Calcium silicate hydrate
Upon the addition of water, calcium silicate reacts to release
calcium ions, hydroxide ions, and a large amount of heat.
The pH quickly raises to over 12 because of the release of
alkaline hydroxide (OH-) ions. This initial hydrolysis slows
down quickly after it starts resulting in a decrease in heat
evolved.
The C-S-H produced is the principal binding phase in Portland
cements and is quantitatively the most significant hydration
product.

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Note that C3S produces more than twice as much Ca(OH)2 as is
formed by the hydration of C2S.
C3S & C2S Consists about 70±1 % of cement therefore, the
physical properties of the calcium silicate hydrate are of
interest in connection with the setting and hardening
properties of cement.
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Tri Calcium Aluminate hydrate
The C3A present is comparatively small but its effect and
behavior is importance.

The stable form of the calcium aluminate hydrate is probably

the cubic crystal C3AH6, but it is possible that hexagonal
C4AH12 crystallizes out first and later changes to cubic form.
Pure C3A reaction with water is very violent and leads to
immediate stiffening of the paste known as flash set. Gypsum
(CaSO4.2H2O) is added to cement clinker, thus, to retard the
reaction. Hydration of C3A occurs with sulfate ions supplied
by dissolved gypsum. The result of the reaction is calcium
sulfoaluminate hydrate, called "ettringite" after a naturally
occurring mineral. 43
A= Thin layer of ettringite is formed around C3A.
B= Formation of ettringite directly on C3A grains producing crystallization
pressure.
C= Bursting of ettringite
D= Burst section is seald by newly formed etteringite
E= Insufficient sulphate ions to allow formation of ettringite, on further hydration
of C3A, attringite converts to monosulphate.
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If all gypsum is consumed before all the C3A, the direct
hydrate, C3AH6 is formed.
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Disadvantages and advantage of C3A

It contributes little or nothing to the strength of cement

except at early age (see P.21).

When hardened cement paste is attacked by sulphate,

expansion due to the formation of calcium
sulphoaluminate from C3A may result in a disruption of
the hardened paste.

However, C3A acts as a flux and thus reduces the

temperature of burning of clinker and facilitates the
combination of lime and silica.

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Tertra Calcium Alumino Ferrite
Ferrite Phase (C4AF) act as a flux and during hydration forms
Calcium Sulphoferrite and calcium sulphoalominate, and its
presence may accelerate the hydration of silicates.

Development of hydration
The rate of hydration of C3A, C3S, C4AF & C2S in a pure state
differ considerably as shown in the figure. Reactions for even
identical compounds may vary due to:
1) fineness,
2) rate of cooling of clinker
3) impurities.

Development of hydration of pure compounds 47

Physical Properties of Portland Cement
Most specification for Portland cement place limits on both its chemical
composition and physical properties.

Setting and hardening

Setting and hardening of cement paste are related to the hydration of cement.
Setting refers to a change from a fluid to a rigid state without much gain of
strength. Hardening refers to the gain of strength of a set cement paste.
Initial set: Occurs when the paste begins to stiffen considerably. (min 45 min)
Final set: Occurs when the cement has hardened to the point at which it can
sustain some load. (< 10 hrs)
For construction purposes, the initial set must not be too soon and the final set
must not be too late.
Setting time is affected by
- cement composition
- cement fineness,
- humidity of the surrounding air.
- ambient temperature (cold weather retard setting and temperature rise
decreases the setting time.
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Cement hydration does not proceed at a fixed rate. The
evolution of hydrating cement can be qualitatively
characterized by the heat evolution curve sketched in Figure
below:

Stages in the hydration of Portland cement

Stage I: Rapid heat generation.
Stage II: Dormant period - causes cement to remain plastic.
Stage III: Acceleration period -Final set has passed and early hardening begins
(4-8 hours).
Stage IV: Deceleration
Stage V: Steady state -
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Flash set:
Takes place in cement with insufficient gypsum to
control the rapid reaction of C3A with water. This
reaction generates a considerable amount of heat causes
the cement to stiffen within a few minutes after mixing.
This can only be overcome by adding more water and
re-agitating the mix.

False set:
Also produces a rapid stiffening of the paste but is not
accompanied by excessive heat. In this case remixing the
paste without further addition of water causes it to
regain its plasticity and its subsequent setting and
hardening.

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Causes:
-Dehydration of gypsum when enter ground with too hot
clinker; hemihydrates (CaSO4.1/2H2O) or anhydrate (CaSO4)
gypsum are formed and when the cement is mixed with
water these hydrate to form gypsum. Thus plaster set takes
place with a resulting stiffening of the paste.

- Bad storage: alkali in cement may causes false set. During

storage they may carbonate, and alkali carbonate react with
Ca(OH)2 liberated by the hydrolysis of C3S to form CaCO3.
This precipitates and induces a rigidity of the paste.

- Activation of C3S by aeration at high humidity. Water is

absorbed on the grain cement, and these freshly activated
surface can combine very rapidly with more water during
mixing produce false set.
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Heat of Hydration

The heat of hydration is the heat generated when water and Portland
cement react.
Influenced by:
- the proportion of C3S and C3A in the cement,
- water-cement ratio,
- fineness and
- curing temperature.
As each one of these factors is increased, heat of hydration increases.
Note: In large mass concrete structures such as gravity dams, hydration
heat is produced significantly faster than it can be dissipated
(especially in the center of large concrete masses), which can create
high temperatures in the center of these large concrete masses that, in
turn, may cause undesirable stresses as the concrete cools to ambient
temperature.
Conversely, the heat of hydration may prevent freezing of the water in
the capillaries of freshly placed concrete in cold weather.

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The heat of hydration is the quantity of heat, in joules per gram of
unhydrated cement, evolved upon complete hydration at a given
temperature.
The most common method of determining the heat of hydration is by
measuring the heats of solution of unhydrated and hydrated cement in
a mixture of nitric and hydrofluoric acids: the difference between the
two values represents the heat of hydration.
The heat of hydration of 1 gm of cement can also be estimated by
Heat of hydration of 1 gm = 136 (C3S) + 62 (C2S) + 200 (C3A) + 30 (C4AF)
Where: the terms in brackets denote the percentage by mass of the
individual compounds in cement.

The rate of heat evolution depends on:

- Temperature at which hydration take place.
- Cement composition, as different compounds hydrates at different
rate, the rate and the total heat will be composition dependent (C3A &
C3S particularly), Fig 1.
- Types of cement, Fig 2.

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Fig 1: influence of C3S & C3A content on heat evolution
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Fig 2: development of heat of hydration of different cements cured at 21 oC

- Fineness speeds up hydration reactions and consequently the

rate evolution but does not affect the total amount of heat.
- Richness of the mix affects the total heat developing.
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Fineness
Grinding of the clinker is the last step in Portland cement
production. The degree that the Rate of hydration increases
with fineness, leads to high strengths and heat generation.

Hydration takes place on the cement particle surface. Finer

particles will be more completely hydrated.

Action of fineness
Increasing fineness decreases the amount of bleeding but also
requires more water for workability which can result in an
increase in dry shrinkage.
High fineness reduces the durable to freeze-thaw cycles & to
alkali-reactive aggregate.
Increased fineness requires more gypsum to control setting.

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Specific surface (Wagner) m2/kg

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The most important properties are: specific surface of the
particles, and particle-size distribution.
Fineness was originally measured using a sieve analysis,
Retained on 75 micron sieve (No. 200) is allowed to be
10%, while on 90 micron (No. 170) it will be 22%.
However, this method is very awkward and really gives
no information about the distribution of fine particles.

Modern standards tests are:

Wagner Turbidimeter: ASTM C115-93
Air permeability apparatus: BS 12-1971
Blain: ASTM C204-94

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Soundness
Is the characteristic of excessive volume change after setting. It may
appear many months or years after setting. Cement paste once
hardened should not undergo a large volume change, expansion or
contraction.
This excessive change in volume indicates that the cement is unsound
and not suitable for the manufacture of concrete.
The methods for testing the soundness of cement are Autoclave test and
that developed by Le Chatelier as described in BS 4550: part 3. After
testing maximum spacing between indicators is limited to 10 mm. On
failure, the test is repeated of cement sprayed and aerated for 7 days
aeration. Maximum spacing is limited to 5 mm. Maximum expansion in
length is limited to 0.8% in autoclave test.

Le Chatelier Autoclave expansion 59

Minor constituents causing volume change are
1- Free lime CaO: free CaO during hydration produce Ca(OH)2,
the formation of Ca(OH)2 cause increase in the solid volume
(volume of hydrated lime > volume of CaO) which cause
expansion of the product that lead to internal stresses and possible
crack.

2- Magnesium oxide (MgO): MgO in cement comes from raw

materials which react similar to CaO and lead to unsound cement.

3- Calcium sulphates, gypsum (CaSO4): This is intentionally added

to cement to prevent flash set. Excess of SO3- causes expansion and
cement unsoundness.

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Strength of Cement Paste
The cement composition controls the rate of hydration, heat
evolution, total evolved temperature and resistance to chemical
attack. The affects of major compounds on strength
development are as follows:

C3S + C2S primarily responsible for strength of cement

Approximately C3S contributes most of the strength during the
first 4 weeks (see Fig. P. 21).
C2S influences the gain of strength beyond 4 weeks
After 1 year they contribute equally to the ultimate strength.
Impurities may strongly affect the rate of reaction

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C3A contributes to early strength of the paste i.e. within
1-3 days but causes retrogression at an advance age
particularly in cement of high C3A or high C3S+C4AF.

C4AF given no appreciable positive contribution but it

may cause delay in the hydration of other compounds (due
to deposition of CaO.Fe2O3 on cement grains).

The mechanical strength of hardened cement is the

property of the material that is perhaps most obviously
required for structural use.
Cement-sand mortar is used for the purpose of determining
the strength of cement.

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Structure of Hydrated Cement

Mechanical properties depend so much on the chemical

composition of the hydrated cement as on the physical structure
of the product of hydration. Fresh cement is a plastic network of
particles of cement in water. When set the volume of the paste
remains approximately constant.
At any stage of hydration the hardened paste consists of:

a- Gel which is hydrates of various compounds insoluble with

cementing properties. The actual source of strength of gel is not
fully understood but it may be arise from two kinds of cohesive
bonds:
- Physical attraction between solid surfaces separated only
by small gel pores i.e. Van der Waal's force.
- Chemical bonds, as swelling is limited it seems that gel
particles are cross-linked by chemical forces.
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b- Unhydrated cement
c- Crystals of Ca(OH)2 & minor components

d-Pores:
Gel pores within the gel
Capillary pores (residue of water-filled spaces)

Water is absorbed and causes an increase in the surface area.

Water existed in several forms:
- Free water (pore water)
- Gel water (adsorbed water)
- Chemical ly combined water

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