Académique Documents
Professionnel Documents
Culture Documents
by
Hassan Z. Harraz
hharraz2006@yahoo.com
13 March 2014
OUTLINE OF TOPIC 5:
CEMENT
TYPES OF CEMENTS
PORTLAND CEMENT
TYPES OF PORTLAND CEMENT
GENERAL FEATURES OF THE MAIN TYPES OF PORTLAND CEMENT
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CEMENT
DEFINATION:
Cement is the mixture of calcareous, siliceous, argillaceous and other substances.
Cement is a hydraulic binder and is defined as a finely ground inorganic material
which, when mixed with water, forms a paste which sets and hardens by means of
hydration reactions and processes which, after hardening retains it's strength and
stability even under water.
Cement used in construction is characterized as hydraulic or non-hydraulic.
1) Hydraulic cements (e.g., Portland cement) harden because of hydration, chemical
reactions that occur independently of the mixture's water content; they can harden even
underwater or when constantly exposed to wet weather. The chemical reaction that results
when the anhydrous cement powder is mixed with water produces hydrates that are not
water-soluble.
2) Non-hydraulic cements (e.g. Gypsum plaster) must be kept dry in order to retain their
strength.
TYPES OF CEMENTS:
1)Portland cements
2)Natural cements
3)Expansive cements
4)High-alumina cements
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PORTLAND CEMENT
Portland Cement
is a hydraulic cement that hardens in water to form a waterresistant compound.
The hydration products act as binder to hold the aggregates
together to form concrete.
A hydraulic cement made by finely pulverizing the clinker
produced by calcining to incipient fusion a mixture of
argillaceous and calcareous materials
Portland cement is the fine gray powder that is the active
ingredient in concrete
Limestone + Shale/Clay + Heat = Clinker +CKD + Exit Gas
Material Temperatures Exceed 2700 oF
Pulverized Clinker + Gypsum = Portland Cement
Cement is powder so fine that one pound contains 150 billion
grains
The name Portland Cement comes from the fact that the colour
and quality of the resulting concrete are similar to Portland
stone, a kind of limestone found in England.
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Note:
sulphates can react with C4ASH18 to from an expansive product. By reducing the C3A
Cement
The oxide and mineral compositions of a typical Type I Portland cement were given in Tables.
Classification
General purpose
Type V
Moderate sulfate
resistance (Modified
cement)
High early strength
(Rapid-hardening)
Low heat of hydration
(slow reacting)
High sulfate
resistance
White
White color
Type II
Type III
Type IV
Characteristics
Fairly high C3S content for
good early strength
development
Low C3A content (<8%)
Ground more finely, may have
slightly more C3S
Low content of C3S (<50%)
and C3A
Very low C3A content (<5%)
No C4AF, low MgO
Applications
General construction (most
buildings, bridges,
pavements, precast units,
etc)
Structures exposed to soil or
water containing sulfate ions
Rapid construction, cold
weather concreting
Massive structures such as
dams. Now rare.
Structures exposed to high
levels of sulfate ions
Decorative (otherwise has
properties similar to Type I)
Chemical composition of
the main types of
Portland cement
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This type of cement use in constructions when there is no exposure to sulfates in the soil or
groundwater.
The chemical composition requirements are listed as shown below:
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Chemical Name
Oxide Formula
Cement
Notation
Mineral
Name
Weight
(%)
Tricalcium Silicate
3CaO.SiO2
C3S
Alite
50
Dicalcium Silicate
2CaO.SiO2
C2S
Belite
25
Tricalcium Aluminate
3CaO.Al2O3
C3A
Aluminate
12
C4AF
Ferrite
CSH2
Gypsum
3.5
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CaO.SO3.2H2O
The differences between these cement types are rather subtle. All five types contain about 75 wt% calcium silicate
minerals, and the properties of mature concretes made with all five are quite similar. Thus these five types are
often described by the term Ordinary Portland Cement, or OPC.
Types II and V OPC are designed to be resistant to sulfate attack. Sulfate attack is an important phenomenon that
can cause severe damage to concrete structures. It is a chemical reaction between the hydration products of C3A
and sulfate ions that enter the concrete from the outside environment. The products generated by this reaction
have a larger volume than the reactants, and this creates stresses which force the concrete to expand and crack.
Although hydration products of C4AF are similar to those of C3A, they are less vulnerable to expansion, so the
designations for Type II and Type V cement focus on keeping the C3A content low. There is actually little difference
between a Type I and Type II cement, and it is common to see cements meeting both designations labeled as
Type I/II. The phenomenon of sulfate attack will be discussed in much more detail in Sections 5.3 and 12.3, but it
should be noted here that the most effective way to prevent sulfate attack is to keep the sulfate ions from entering
the concrete in the first place. This can be done by using mix designs that give a low permeability (mainly by
keeping the w/c ratio low) and, if practical, by putting physical barriers such as sheets of plastic between the
concrete and the soil.
Type III cement is designed to develop early strength more quickly than a Type I cement. This is useful for
maintaining a rapid pace of construction, since it allows cast-in-place concrete to bear loads sooner and it reduces
the time that precast concrete elements must remain in their forms. These advantages are particularly important in
cold weather, which significantly reduces the rate of hydration (and thus strength gain) of all Portland cements.
The downsides of rapid-reacting cements are a shorter period of workability, greater heat of hydration, and a
slightly lower ultimate strength.
Type IV cement is designed to release heat more slowly than a Type I cement, meaning of course that it also
gains strength more slowly. A slower rate of heat release limits the increase in the core temperature of a concrete
element. The maximum temperature scales with the size of the structure, and Type III concrete was developed
because of the problem of excessive temperature rise in the interior of very large concrete structures such as
dams. Type IV cement is rarely used today, because similar properties can be obtained by using a blended
cement.
White Portland cement (WPC) is made with raw ingredients that are low in iron and magnesium, the elements
that give cement its grey color. These elements contribute essentially nothing to the properties of cement paste, so
WPC actually has quite good properties. It tends to be significantly more expensive than OPC, however, so it is
typically confined to architectural applications. WPC is sometimes used for basic cements research because the
lack of iron improves the resolution of nuclear magnetic resonance (NMR) measurements.
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Uses
a)The uses of this cement is indicated where a rapid strength development is desired (to develop
high early strength, i.e. its 3 days strength equal that of 7 days ordinary Portland cement), for
example:
i) When formwork is to be removed for re-use
ii) Where sufficient strength for further construction is wanted as quickly as practicable, such
as concrete blocks manufacturing, sidewalks and the places that can not be closed for a
long time, and repair works needed to construct quickly.
b) For construction at low temperatures, to prevent the frost damage of the capillary water.
c) This type of cement does not use at mass concrete constructions.
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MANUFACTURING OF CEMENT
1) Quarry
2) Raw Material
3) Mixing and crushing of raw
materials:
a) Dry process
b) Wet process
4) Burning
5) Grinding
6) Storage
7) Packing
8) Dispatch
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Quarry face
1. BLASTING
2. TRANSPORT
storage at
the plant
crushing
conveyor
storage at
the plant
Raw mill
conveyor
preheating
Raw mix
1. RAW GRINDING
kiln
cooling
clinker
2. BURNING
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.
Finish grinding
1. GRINDING
silos
dispatch
bags
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19
As coal is used as a fuel the coal ash, a combustion product of the coal, has to
be treated as an individual raw material component and the appropriate
corrections made at the weigh-feeder stage.
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The raw materials used for manufacturing Portland Cement are limestone, clay and
Iron ore.
a) Limestone (CaCO3) is mainly providing calcium in the form of calcium oxide
(CaO)
CaCO3 (1000oC) CaO + CO2
b) Clay is mainly providing silicates (SiO2) together with small amounts of Al2O3 +
Fe2O3
Clay (1450oC) SiO2 + Al2O3 + Fe2O3 + H2O
c) Iron ore and Bauxite are providing additional aluminum and iron oxide (Fe2O3)
which help the formation of calcium silicates at low temperature. They are
incorporated into the raw mix.
d) The clinker is pulverized to small sizes (< 75 m). 3-5% of gypsum (calcium sulphate)
is added to control setting and hardening.
The majority particle size of cement is from 2 to 50 m.
(Note: Blaine refers to a test to measure particle size in terms of surface area/mass)
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a) Dry process:
In this process calcareous material such
as lime stone (calcium carbonate) and
argillaceous material such as clay are
ground separately to fine powder in the
absence of water and then are mixed
together in the desired proportions.
Water is then added to it for getting
thick paste and then its cakes are
formed, dried and burnt in kilns. This
process is usually used when raw
materials are very strong and hard.
In this process, the raw materials are
changed to powdered form in the
absence of water.
Dehydration zone requires a somewhat
shorter distance than wet process.
74% of cement produced.
kilns less fuel requirements
b) Wet process:
In this process, the raw materials are changed to powdered
form in the presence of water.
In this process, raw materials are pulverized by using a
Ball mill, which is a rotary steel cylinder with hardened
steel balls. When the mill rotates, steel balls pulverize the
raw materials which form slurry (liquid mixture). The
slurry is then passed into storage tanks, where correct
proportioning is done. Proper composition of raw
materials can be ensured by using wet process than dry
process. Corrected slurry is then fed into rotary kiln for
burning.
This process is generally used when raw materials are soft
because complete mixing is not possible unless water is
added.
Actually the purpose of both processes is to change the
raw materials to fine powder.
dehydration zone would require up to half the length of
the kiln
easiest to control chemistry & better for moist raw
materials
high fuel requirements - fuel needed to evaporate 30+%
slurry water
The kiln is a continuous stream process vessel in which
feed and fuel are held in dynamic balance
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AM ~2
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CEMENT KILNS
the Largest Moving Equipment in any Manufacturing Operation
High temperature
Long residence time
Natural alkaline environment
CKD is only by-product of the process
Thermal stability
Kiln Process
Temperature (oC)
20 - <100
Reactions
Chemical Transformation
100 - 300
400 - 750
Pre-heat
600 - 900
Calcining
600 - 1000
Sintering
Clinkering
Al4Si4O10(OH)8
2(Al2O3.2SiO2) + 4H2O
Al2O3.2SiO2 Al2O3.+ 2SiO2
Cooling
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Clinker Burning
For the production of cement clinker, the raw meal which is known as kiln feed at this stage
has to be heated to a temperature of about 1550 oC in the long cylindrical rotating kiln.
The kiln feed enters the system at the top of the pre-heater and fall until the lower end of
the kiln.
The heat exchange occurs during this process when the hot gases from the kiln end rise up
to the top of the pre-heater.
The clinker formation process is divided into four parts: drying, calcining, sintering and
cooling.
As the kiln feed moves towards the lower end of the kiln it undergoes successive reactions
as shown in the table:
CLINKER
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Clinker Microstructure
Dark, Rounded C2S
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Burning Process
This description refers to a standard dry-process kiln. Such a kiln is typically about 180 m
long and 6 m in diameter, has a downward slope of 3-4%, and rotates at 1-2 revolutions
per minute.
The raw mix enters at the upper end of the kiln and slowly works its way downward to
the hottest area at the bottom over a period of 60-90 minutes, undergoing several
different reactions as the temperature increases. It is important that the mix move
slowly enough to allow each reaction to be completed at the appropriate temperature.
Because the initial reactions are endothermic (energy absorbing), it is difficult to heat the
mix up to a higher temperature until a given reaction is complete.
The general reaction zones are as follows:
1) Dehydration zone (up to ~ 450C)
2) Calcination zone (>450C 900C)
3) Solid-state reaction zone (>900 - 1300C)
4) Clinkering zone (>1300C 1550C)
5) Cooling zone
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Dehydration
up to ~ 450
Calcination
450C 900
Solid-state
reaction
>900 - 1300
Characteristics
This is simply the evaporation and removal of the free water
Even in the dry process there is some adsorbed moisture in the raw mix.
Although the temperatures required to do this are not high, this requires significant time and
energy.
In the wet process, the dehydration zone would require up to half the length of the kiln, while
the dry process requires a somewhat shorter distance.
The term calcination refers to the process of decomposing a solid material so that one of its
constituents is driven off as a gas.
At about 600C the bound water is driven out of the clays,
and by 900C the calcium carbonate is decomposed, releasing carbon dioxide.
By the end of the calcination zone, the mix consists of oxides of the four main elements which
are ready to undergo further reaction into cement minerals.
Because calcination does not involve melting, the mix is still a free-flowing powder at this
point.
This zone slightly overlaps, and is sometimes included with, the calcination zone.
As the temperature continues to increase above ~ 900C there is still no melting, but solidstate reactions begin to occur.
CaO and reactive silica combine to form small crystals of C2S (dicalcium silicate; Belite), one of
the four main cement minerals.
In addition, intermediate calcium aluminates (C3A) and calcium ferrite (C4AF) compounds form.
These play an important role in the clinkering process as fluxing agents, in that they melt at a
relatively low temperature of ~1300C, allowing a significant increase in the rate of reaction.
Without these fluxing agents, the formation of the calcium silicate cement minerals would be
slow and difficult.
In fact, the formation of fluxing agents is the primary reason that Portland (calcium silicate)
Cements contain aluminum and iron at all.
The final aluminum- and iron-containing cement minerals (C3A and C4AF) in a Portland Cement
contribute little to the final properties.
As the mix passes through solid-state reaction zone it becomes sticky due to the tendency
Clinkering
Cooling
>1300 1550
Characteristics
This is the hottest zone where the formation of the most important cement mineral, Alite
(C3S), occurs.
The zone begins as soon as the intermediate calcium aluminate (C3A) and ferrite (C4AF) phases
melt.
The presence of the melt phase causes the mix to agglomerate into relatively large nodules
about the size of marbles consisting of many small solid particles bound together by a thin
layer of liquid.
Inside the liquid phase, Alite (C3S) forms by reaction between Belite (C2S) crystals and CaO.
(C2S + C C3S)
Crystals of solid Alite (C3S) grow within the liquid, while crystals of Belite (C2S) formed earlier
decrease in number but grow in size.
The clinkering process is complete when all of silica is in the C3S and C2S crystals and the
amount of free lime (CaO) is reduced to a minimal level (<1%).
As the clinker moves past the bottom of the kiln the temperature drops rapidly and the liquid
phase solidifies, forming the other two cement minerals C3A (aluminate) and C4AF (ferrite).
In addition, alkalis (primarily K) and sulfate dissolved in the liquid combine to form K2SO4 and
Na2SO4.
The nodules formed in the clinkering zone are now hard, and the resulting product is called
cement clinker.
The rate of cooling from the maximum temperature down to about 1100C is important, with
rapid cooling giving a more reactive cement.
This occurs because in this temperature range the C3S can decompose back into C2S and CaO,
among other reasons.
It is thus typical to blow air or spray water onto the clinker to cool it more rapidly as it exits the
kiln.
Rapid cooling of the clinker is essential as this hampers the formation of crystals, causing
part of the liquid phase to solidify as glass.
The faster the clinker cooling the smaller the crystals will be when emerging from the liquid
phase.
Planetary Cooler
Exhaust
Gases
Raw
Feed
Zone
Gas
Temperature
Material
Temperature
Clinker Out
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temperature.
Grinding of clinker is done in large tube mills.
After proper grinding gypsum (Calcium sulphate CaSO4) in the ratio of 01-04 % is added for
controlling the setting time of cement.
Finally, fine ground cement is stored in storage tanks from where it is drawn for packing.
Once the nodules of cement clinker have cooled, they are ground back into a fine powder in a
large grinding mill. At the same time, a small amount of calcium sulfate such as gypsum (calcium
sulfate) is blended into the cement. The calcium sulfate is added to control the rate of early
reaction of the cement
Cement is produced by grinding clinker with gypsum (calcium sulfate) in the finish-grinding mill to
a required fineness.
A small quantity of gypsum, about 3 to 5 %, is needed to control the setting time of cement
produced.
The amount of gypsum being used is determined by the Sulphuric anhydride (SO3) contents in
cement.
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Schematic of a
Grinding Mill
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CEMENT CHEMISTRY
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CHEMICAL COMPOSITIONS
1) Cement chemistry notation based on oxides
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Oxide
CaO
SiO2
Al2O3
Fe2O3
SO3
Notation
C
S
A
F
H2O
MgO
Na2
O
H
M
N
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Compound Composition of
Clinker / Cement
Chemical
Formula
Oxide Formula
Cement
Notation
Mineral Name
Ca3SiO5
3CaO.SiO2
C3S(40-60%)
Alite
Dicalcium Silicate
Ca2SiO4
2CaO.SiO2
C2S(16-30%)
Belite
Tricalcium Aluminate
Ca3Al2O6
3CaO.Al2O3
C3A(7-15%)
Aluminate
Tetracalcium
Aluminoferrite
Ca2AlFeO5
4CaO.Al2O3.Fe2O3
C4AF(7-12%)
Ferrite
Calcium hydroxide
Ca(OH)2
CaO.H2O
CH
Portlandite
Calcium sulfate
dihydrate
CaSO4.2H2O
CaO.SO3.2H2O
CSH2
Gypsum
Calcium oxide
CaO
CaO
Lime
Chemical Name
Tricalcium Silicate
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Phase Diagram
Tricalcium Silicate
Tricalcium Aluminate
CaO
CaO
SiO2
Al2O3
CaO
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CaO
CaO
CaO
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Case 1 : If
A/F >=0.64
C3S = 4.071C - 7.6S - 6.718A - 1.43F - 2.852S
C2S = 2.867S - 0.7544C3S
C3A = 2.65A - 1.692F
C4AF = 3.043F
Case 2 : If
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Fineness of cement
Grinding is the last step in
processing
Measures of fineness
Specific surface
Particle size
distribution
Blaines fineness
Measure of air
permeability
Typical surface areas
350m2 / kg (Normal
cements)
~ 500 m2 / kg (High early
strength cements)
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Significance of fineness
Finer cement = Faster reaction
Finer cement = Higher heat of
hydration
Large particles do not react
with water completely
Higher fineness
Higher shrinkage
Reduced bleeding
Reduced durability
More gypsum needed
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