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Cement: N-W.F.P UET, Peshawar 1

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INTRODUCTION

Definition: Cement is a crystalline compound of


calcium silicates and other calcium compounds
having hydraulic properties (Macfadyen, 2006).

CEMENT

History

History of cement and concrete

Lime and clay have been used as cementing


material on constructions through many
centuries.

The early days:


Setting stone blocks without cementing
them
Mud mixed with straw is the oldest
cementing material used to bind dried bricks
together
Pyramid of Cheops.

Romans are commonly given the credit for the


development of hydraulic cement, the most
significant incorporation of the Romans was
the use of pozzolan-lime cement by mixing
volcanic ash from the Mt. Vesuvius with lime.
Best know surviving example is the Pantheon
in Rome

In 1824 Joseph Aspdin


invented the Portland cement

from

England

Cheops, Giza
Stones were brought from Aswan and Tura
using the Nile river
Built around 2566 B.C.
It would have taken over 2,300,000 blocks of
stone with an average weight of 2.5 tons each
Total weight of 6 million tons
30 years and 100,000 slaves to build it
Has a height of 482 feet (140m)
It is the largest and the oldest of the Pyramids
of Giza
Mortars made by calcining impure gypsum

N-W.F.P UET, Peshawar

History of cement and concrete


Non-hydraulic cements
Gypsum and lime
Cements based on compounds of lime (calcareous
cements)

Gypsum
Calcining impure gypsum at 130 C

Add water calcined gypsum and water recombine


Cannot harden under water because gypsum is quite
soluble.
Pyramid of Cheops (3000 B.C.)
6

Hydraulic Limes

History of cement and concrete

Hydraulic Limes

Hydraulic Limes

10

11

12

History of Cement and Concrete

N-W.F.P UET, Peshawar

Types of Cement
Cements are considered hydraulic because of their ability to set and harden
under or with excess water through the hydration of the cements chemical
compounds or minerals.
There are two types:
Those that activate with the addition of water
And pozzolanic that develop hydraulic properties when the
interactwith hydrated lime Ca(OH)2
Pozzolanic: any siliceous material that develops hydraulic cementitious
properties when interacted with hydrated lime.
HYDRAULIC CEMENTS:
Hydraulic lime: Only used in specialized mortars. Made from calcination of
clay-rich limestones.
Natural cements: Misleadingly called Roman. It is made from argillaceous
limestones or interbedded limestone and clay or shale, with few raw materials.
Because they were found to be inferior to Portland, most plants switched.

Portland cement: Artificial cement. Made by the mixing clinker with


gypsum in a 95:5 ratio.
Portland-limestone cements: Large amounts (6% to 35%) of ground
limestone have been added as a filler to a Portland cement base.
Blended cements: Mix of Portland cement with one or more SCM
(supplementary cemetitious materials) like pozzolanic additives.
Pozzolan-lime cements: Original Roman cements. Only a small
quantity is manufactured in the U.S. Mix of pozzolans with lime.
Masonry cements: Portland cement where other materials have been
added primarily to impart plasticity.
Aluminous cements: Limestone and bauxite are the main raw
materials. Used for refractory applications (such as cementing furnace bricks)
and certain applications where rapid hardening is required. It is more
expensive than Portland. There is only one producing facility in the U.S.

GEOLOGY (RAW MATERIALS)

Clinker compounds in Type I portland cement

The fundamental chemical compounds to produce cement clinker are:


Lime (CaO)
Silica (SiO2)
Alumina (Al2O3)
Iron Oxide (Fe2O3)
Raw materials used in the production of clinker cement

Fly ash: by-product of burning finely grounded coal either for industrial application or in
the production of electricity
(Macfadyen, 2006)
www.recycleworks.org/images/flyash_concrete.gif

SOURCES OF CaCO3
Sedimentary deposits of marine origin (limestone)
Marble (metamorphosed limestone)
Chalk
Marl
Coral
Aragonite
Oyster and clam shells
Travertine
Tuff
LIMESTONES
Originate from the biological deposition of shells and skeletons of plants and animals.

SOURCES OF ARGILLACEOUS
MINERALS
Argillaceous mineral resources:
Clay and shale for alumina and silica
Iron ore for iron

Other natural sources of silica are and alumina are:


Loess, silt, sandstone, volcanic ash, diaspore, diatomite, bauxite

Massive beds accumulated over millions of years.


In the cement industry limestone includes calcium carbonate and magnesium carbonate.
Most industrial quality limestones is of biological origin.

The ideal cement rock 77 to 78% CaCO3, 14% SiO2, 2.5% Al2O3, and 1.75% FeO3.
Limestone with lower content of CaCO3 and higher content of alkalis and magnesia
requires blending with high grade limestone
(Macfadyen, 2006)
(Kussmaul, 2003)

Shales, mudstones, and sandstones are typically interbedded with the


limestone and were deposited as the inland waters and oceans covered the
land masses. Clays are typically younger surface deposits

(Macfadyen, 2006)
http://en.wikipedia.org/wiki/Image:ShaleUSGOV.jpg

http://en.wikipedia.org/wiki/Image:Limestoneshale7342.jpg

N-W.F.P UET, Peshawar

USES
Uses

SUBSTITUTES

Main use is in the fabrication of concrete and mortars


Modern uses
Building (floors, beams, columns, roofing, piles, bricks, mortar, panels, plaster)
Transport (roads, pathways, crossings, bridges, viaducts, tunnels, parking, etc.)
Water (pipes, drains, canals, dams, tanks, pools, etc.)
Civil (piers, docks, retaining walls, silos, warehousing, poles, pylons, fencing)
Agriculture (buildings, processing, housing, irrigation)

It competes in the construction industry with concrete substitutes:


Alumina
Asphalt
Clay brick
Fiberglass
Glass
Steel
Stone Wood

Some materials like fly ash and ground granulated furnace slugs have
good hydraulic properties and are being used as partial substitutes for
Portland cement in some concrete applications

PRODUCTION

Data in thousand metric


tons

World production of hydraulic cement by region

(http://pubs.usgs.gov/of/2005/1152/2005-1152.pdf).

N-W.F.P UET, Peshawar

http://minerals.usgs.gov/minerals/pubs/commodity/cement/cemenmcs07.pdf

U.S production and consumption of portland cement


(http://pubs.usgs.gov/of/2005/1152/2005-1152.pdf)

PORTLAND CEMENT
 Chemical composition of Portland Cement:
a) Tricalcium Silicate (50%)
b) Dicalcium Silicate (25%)
c) Tricalcium Aluminate (10%)
d) Tetracalcium Aluminoferrite (10%)
e) Gypsum (5%)

FUNCTION :DICALCIUM SILICATE


 Hardens slowly
 It effects on strength increases occurs at ages
beyond one week .
 Responsible for long term strength

Cements with low Tricalcium Aluminate


contents usually generate less heat, develop
higher strengths and show greater
resistance to sulfate attacks.
 It has high heat generation and reactive
with soils and water containing moderate
to high sulfate concentrations so its least
desirable.

N-W.F.P UET, Peshawar

FUNCTION :TRICALCIUM SILICATE


 Hardens rapidly and largely responsible for
initial set & early strength
 The increase in percentage of this compound
will cause the early strength of Portland
Cement to be higher.
A bigger percentage of this compound will
produces higher heat of hydration and
accounts for faster gain in strength.

FUNCTION :TRICALCIUM ALUMINATE


 Contributes to strength development in the
first few days because it is the first compound
to hydrate .
 It turns out higher heat of hydration and
contributes to faster gain in strength.
 But it results in poor sulfate resitance and
increases the volumetric shrinkage upon drying.

FUNCTION : TETRACALCIUM
ALUMINOFERRITE
Assist in the manufacture of Portland Cement
by allowing lower clinkering temperature.
 Also act as a filler
 Contributes very little strength of concrete
eventhough it hydrates very rapidly.
 Also responsible for grey colour of Ordinary
Portland Cement

Manufacture of Portland cement


Raw materials
Manufacture of Portland cement

Limestone (calcium carbonate) is a common source of


calcium oxide.
Iron-bearing aluminosilicates are the most common
source of silica.
Aluminum and iron oxides act as fluxing agents i.e.
lower fusion temperature of part of the raw mix to a
practical firing temperature

Raw materials
Preparation of materials
Burning
Final processing
Quality control

31

32

WET PROCESS

Preparation of Materials

 Raw materials are homogenized by crushing,


grinding and blending so that approximately
80% of the raw material pass a No.200 sieve.
 The mix will be turned into form of slurry by
adding 30 - 40% of water.
 It is then heated to about 2750F (1510C) in
horizontal revolving kilns (76-153m length
and 3.6-4.8m in diameter.

Crush the materials and store them


Blend the materials and grind them
Store them and do final blending
Blending assure constant composition and
predictable properties.
Wet, dry, and semi-dry processes
Burn the materials
Grind, blend, and store the materials

33

 Natural gas, petroluem or coal are used for


burning. High fuel requirement may make it
uneconomical compared to dry process.
Wet process is obsolete

N-W.F.P UET, Peshawar

DRY PROCESS
 Raw materials are homogenized by crushing,
grinding and blending so that approximately
80% of the raw material pass a No.200 sieve.
 Mixture is fed into kiln & burned in a dry state
 This process provides considerable savings in
fuel consumption and water usage but the
process is dustier compared to wet process
that is more efficient than grinding.

DRY PROCES & WET PROCESS


 In the kiln, water from the raw material is
driven off and limestone is decomposed into
lime and Carbon Dioxide.
limestone
lime + Carbon Dioxide
 In the burning zone, portion of the kiln, silica
and alumina from the clay undergo a solid
state chemical reaction with lime to produce
calcium aluminate.
silica & alumina + lime
calcium aluminate

Burning process

Sintering (become a coherent mass with no melting)


Fusion (complete melting)
Clinkering only about of the charge is in the liquid state
Kiln
Long steel pipe
Lined with refractory brick
Inclined a few degrees
Rotated at 60 to 200 rev/h
Typically 6 m (20 ft) in diameter and 180 m (600 ft) long
Time in the kiln from 2 h (wet process) to 1 h (dry process) or even (20 min)
modern heat exchangers
Four processes take place in the kiln
Evaporation 240 to 450 C
38

Calcination 600 to 1100 C


Clay decomposes (600 C)
Limestone decomposes (700 C) CO2 driven off
Formation of initial compounds (1000 C)
Initial formation of C2S (1200 C), formation of calcium
aluminates and Ferrites
Formation of melt (flux compounds melt) (1350 C)
Clinkering charge temperature is 1400 to 1600 C
Formation of C3S
Cooling

Klinker

 The rotation and shape of kiln allow the


blend to flow down the kiln, submitting it to
gradually increasing temperature.
 As the material moves through hotter regions
in the kiln, calcium silicates are formed
 These products, that are black or greenish
black in color are in the form of small
pellets, called cement clinkers
 Cement clinkers are hard, irregular and ball
shaped particles about 18mm in diameter.

Rate of cooling significantly affects the reactivity of the final cement

39

CEMENT CLINKERS

N-W.F.P UET, Peshawar

 The cement clinkers are cooled to about


150F (51C) and stored in clinker silos.
 When needed, clinker are mixed with 2-5%
gypsum to retard the setting time of cement
when it is mixed with water.
 Then, it is grounded to a fine powder and
then the cement is stored in storage bins or
cement silos or bagged.
 Cement bags should be stored on pallets in
a dry place.

THE CEMENT MANUFACTURING PROCESS

THE CEMENT MANUFACTURING PROCESS

quarry

Raw grinding and burning


dumper

loader

storage at
the plant

Raw mill
conveyor

Raw mix

Quarry face
1. BLASTING

2. TRANSPORT

preheating

storage at
the plant

crushing

1. RAW GRINDING

kiln

conveyor

cooling
clinker

3. CRUSHING & TRANSPORTATION

2. BURNING

1. BLASTING : The raw materials that are used to manufacture cement (mainly limestone and clay) are blasted
from the quarry.
2. TRANSPORT : The raw materials are loaded into a dumper.
3. CRUSHING AND TRANSPORTATION : The raw materials, after crushing, are
transported to the plant by conveyor. The plant stores the materials before they are
homogenized.

1. RAW GRINDING : The raw materials are very finely ground in order to produce the raw mix.
2. BURNING : The raw mix is preheated before it goes into the kiln, which is heated by a flame that can
be as hot as 2000 C. The raw mix burns at 1500 C producing clinker which, when it leaves the kiln,
is rapidly cooled with air fans. So, the raw mix is burnt to produce clinker : the basic material needed to
make cement.

THE CEMENT MANUFACTURING PROCESS


Grinding, storage, packing, dispatch
Gypsum and the secondary additives are added
to the clinker.
clinker
storage

Oxides composition of cement

Finish grinding

1. GRINDING

silos

dispatch
bags

2. STORAGE, PACKING, DISPATCH


1.GRINDING : The clinker and the gypsum are very finely ground giving a pure cement. Other secondary
additives and cementitious materials can also be added to make a blended cement.
2. STORAGE, PACKING, DISPATCH :The cement is stored in silos before being dispatched either in
bulk or in bags to its final destination.

46

KILN

N-W.F.P UET, Peshawar

CEMENT SILO

Properties of cement and tests


1. Fineness
95% of cement particles are smaller than 45 micrometer,
with the average particle around 15 micrometer.
Fineness of cement affects heat released and the rate of
hydration.
More is the fineness of cement more will be the rate of
hydration.
Thus the fineness accelerates strength development
principally during the first seven days.

Fineness Testing
On left, Blaine
test apparatus.

Continue on Fineness
Fineness tests indirectly measures the surface
area of the cement particles per unit mass :
Wagner turbidimeter test

(ASTM C 115)
Blaine air-permeability test

(ASTM C 204)
Sieving using No. 325 (45 m) sieve (ASTM C
430)

Particle size distribution of Portland


Cement

On right, agner
turbidmeter

2. Soundness
Soundness is the ability of a hardened paste to
retain its volume after setting.
A cement is said to be unsound (i.e. having lack of
soundness) if it is subjected to delayed destructive
expansion.
Unsoundness of cement is due to presence of
excessive amount of hard-burned free lime or
magnesia

N-W.F.P UET, Peshawar

Cont. on Soundness
Unsoundness of a cement is determined by
the following tests:
Le-Chatelier accelerated test
(BS 4550: Part 3)
Autoclave-expansion test
(ASTM C 151)

Autoclave-expansion test
(ASTM C 151)

3. Consistency
Consistency refers to the relative mobility of a
freshly mixed cement paste or mortar or its ability
to flow.
Normal or Standard consistency of cement is
determined using the Vicats Apparatus. It is
defined as that percentage of water added to form
the paste which allows a penetration of 10 1 mm
of the Vicat plunger.

Vicat Plunger Consistency Test

4. Setting Time

Consistency Test for mortar using


the flow table

Cont. on Setting Time

This is the term used to describe the stiffening of the cement


paste.

ASTM C 150 prescribes a minimum initial setting time of 60


minutes for Portland cements.

Setting time is to determine if a cement sets according to the


time limits specified in ASTM C 150.

Final setting time the time required for the paste to acquire
certain degree of hardness. This corresponds to the time at
which the Viacts final set needle makes an impression on the
paste surface but the cutting edge fails to do so.

Setting time is determined using either the Vicat apparatus


(ASTM C 191) or a Gillmore needle (ASTM C 266).
Initial setting time is the time from the instant at which
water is added to the cement until the paste ceases to be fluid
and plastic which corresponds to the time at which the Vicats
initial set needle penetrate to a point 5 mm from the bottom of
a special mould.

N-W.F.P UET, Peshawar

ASTM C 150 prescribes a maximum final setting time of 10


hours for Portland cements.
Gypsum in the cement regulates setting time. Setting time is
also affected by cement fineness, w/c ratio, and admixtures.

10

Vicat Needle

Time of Set for Portland Cements

5. Early Stiffening (False Set and Flash Set)

False Set

Early stiffening is the early development of


stiffening in the working plasticity of cement
paste, mortar or concrete. This includes both
false set and flash set.

False set is evidenced by a significant loss of plasticity, i.e.


stiffening, without the evolution of much heat shortly after
mixing.
Stiffening caused by rapid crystallization of interlocking
needle-like secondary gypsum.
False set cause no difficulty in placing and handling of
concrete if the concrete is mixed for a longer time than
usual or if it is remixed without additional water before it
is transported or placed.

6. Compressive Strength
Flash Set (quick set)
Evidence by a quick and early loss of workability
and it is usually accompanied by evolution of
considerable heat from the hydration of
aluminates.
The workability can not be regained without the
addition of water.

N-W.F.P UET, Peshawar

Compressive strength of cement is the most important


property.
It is determined by ducting compression tests on standard 50
mm mortar cubes in accordance with ASTM C 109.
In general, cement strength (based on mortar-cube tests) can
not be used to predict concrete compressive strength with great
degree of accuracy because of many variables in aggregate
characteristics, concrete mixtures, construction procedures,
and environmental conditions in the field.
Rates of compressive strength development for concrete, made
with various types of cement, are shown in Fig. 2-42.

11

Compressive Strength Test

7. Heat of Hydration

Strength Development of Portland


Cement mortar cubes

Heat of Hydration determined by ASTM C 186 (left)


or by a conduction calorimeter (right).

It is the quantity of heat (in joules) per gram of unhydrated cement evolved upon complete hydration at a
given temperature.
The heat of hydration can be determined by ASTM C
186 or by a conduction calorimeter.
The temperature at which hydration occurs greatly
affects the rate of heat development.
Fineness of cement also affects the rate of heat
development but not the total amount of heat librated.

Type

Name

Normal

Heat of
hydration
(kj/kg)
349

II

Moderate

263

III

High early
strength
Low heat of
hydration
Sulfate
resistant

370

Cont. on Heat of Hydration


The amount of heat generated depends upon the chemical
composition of cement. Following are the heat of hydration
generated on hydration of the four compounds of cement.
Compound Heat of hydration Remarks C3S 502 j/g--C2S
260 j/gMinimumC3A 867 j/g MaximumC4AF 419 j/g--C3S
and C3A are the compounds responsible for the high heat
evolution.
The approximate amount of heat generated using ASTM C
186, during the first 7 days (based on limited data) are as
follows:

N-W.F.P UET, Peshawar

IV
V

233
310

12

Cont. on Heat of Hydration

Stage 1:heat of wetting or initial hydrolysis


C3A and C3S Hydration. 7 min after mixing.
Stage 2: dormant period related to initial set.

Cements do not
generate heat at
constant rate as
illustrated in Figure
2-45 for a typical
type I Portland
cement

Stage 3. accelerated reaction of the hydration


products.
That determine the rate of
hardening and final set.
Stage 4: decelerates formation of hydration products
determines the rate of early strength gain.

and

Stage 5: is a slow, steady formation of hydration products.

8. Loss on Ignition (LOI)

Loss on Ignition Test of cement

The test for loss on ignition is performed in


accordance with ASTM C 114.
A high weight loss on ignition of a cement sample
(between 900 to 1000C) is an indication of prehydration and carbonation, which may be caused
by:
Improper and prolonged storage
Adulteration during transport and transfer

Loss on ignition values range between 0 to 3%

9. Density and Specific Gravity


(ASTM C 188)
Density is the mass of a unit volume of the solids or particles,
excluding air between particles. The particle density of
Portland cement ranges from 3.10 to 3.25 Mg/m3, averaging
3.15 Mg/ m3.
It is used in concrete mixture proportioning calculations.
For mixture proportioning, it may be more useful to express
the density as relative density (specific gravity). On an average
the specific gravity of cement is 3.15.

N-W.F.P UET, Peshawar

Storage of Cement
Cement is moisture-sensitive material; if
kept dry it will retain its quality indefinitely.
When exposed to moisture, cement will set
more slowly and will have less strength
compared to cement that kept dray.
At the time of use cement should be freeflowing and free of lumps.

13

Storage of Cement

N-W.F.P UET, Peshawar

14

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