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Portland Cements

“Your dreams are like the cement. If you water it with


actions, it becomes a hard concrete mass. But if you leave
it exposed and unwatered, the air will easily blow it away!”
― Israel Ayivor

Major Reference/s:
Austin, G. (1984). Shreve's Chemical Process Industries.
McGrawHill.
Salah, D. B. (n.d.). Portland Cement.

CHE150 – B01 CHEMICAL PROCESS INDUSTRIES


© 2017
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History of Portland Cement

• Used by Egyptians in constructing


Pyramids.
• Greeks and romans used volcanic tuff
mixed with lime for cement.

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Origin of Portland Cement

• In 1756, an Engineer named John


Smeaton gave serious attention to the
principle of setting lime under water.
• Smeaton found that by mixing lime and
pozzolana, a substance was produced
which became hard and solid, with the
addition of water.

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Origin of Portland Cement
• Aspdin (1824) found that by mixing finely
pulverized clay in specified proportions, burning
them to a high temperature and then grinding the
resultant clinker, he was able to produce a
hydraulic binding material far superior to any
product known at the time.
• It was Aspdin who named it “Portland Cement”
because when set it looked like “Portland Stone.”

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Origin of Portland Cement

• Before 1900, manufacturing of


concrete was an expensive process.
• Thanks to the invention of labor
saving machinery, cement is now low
in cost and is applied everywhere.

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Portland Cement
• It is the product by pulverizing clinker
consisting essentially of hydraulic calcium
silicates, usually containing one or more
forms of calcium sulfate as an interground
addition.
• Hydraulic calcium silicates possess ability to
harden without drying or reaction with
atmospheric CO2.
• Reactions involved in hardening of cement
are hydration and hydrolysis.
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Cements - Function
 To bind the sand and coarse
aggregate together
 To fill voids in between sand
and coarse aggregate
particle
 To form a compact mass

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Concrete vs. Cement
Concrete and cement are NOT synonymous
terms.

Concrete – is an artificial stone made from a


carefully controlled mixture of cement, water,
and fine aggregate (usually sand).

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Types of Cement
• Hydraulic Cement - sets and hardens by
action of water. Such as Portland Cement
In other words it means that hydraulic
cement are:
“ Any cements that turns into a solid product
in the presence of water (as well as air)
resulting in a material that does not
disintegrate in water.”

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Types of Cement
• Nonhydraulic Cement - any cement that does
not require water to transform it into a solid
product.
2 common Non-hydraulic Cement are
a) Lime- derived from limestone / chalk
b) Gypsum
(CaSO. 4· 2H2O)

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Types of Portland Cement

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Retrieved from https: http://iti.northwestern.edu/cement/monograph/Monograph3_8.html/
Type I

• Regular Portland cements


• For general construction
• Includes: White cement (less ferric oxide)
Oil well cement
Quick setting cement

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Type II

• Moderate heat hardening and sulfate resisting


• Moderate heat of hydration is required.
• For general concrete construction exposed to
moderate sulfate action.

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Type III

• High early strength (HES) cements


• Made from materials with lime to silica ratio
higher than that of type I.
• Ground finer than type I.
• Contains high proportion of tricalcium silicate
(C3S) than regular cements.
• Used in roads

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Type IV

• Low heat Portland cements


• Lower percentage of C3S and tricalcium
aluminate (C3A), thus lower heat evolution.
• The percentage of tetracalcium aluminate
(C4AF) is then increased because of the addition
of Fe2O3 to reduce the amount of C3A.
• Has a heat of hydration that is 15 to 35% lower
than of regular or HES.

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Type V

• Sulfate resisting Portland cements


• Resist sulfate better than the other four types.
• Used when high sulfate resistance is required.
• Lower in C3A content, thus C4AF is higher.

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Use of Air Entertaining Agents

• Use of minute quantities of resinous materials,


tallow, and greases.
• Increase the resistance of the hardened
concrete to scaling from alternate freezing and
thawing.
• Federal specifications permit the addition of an
air-entertaining material to each of the three
types designated as (IA, IIA, IIIA).

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Chemical composition of Portland Cements:

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Raw Materials

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Raw Materials
• Two types of materials are necessary: rich in
calcium (calcareous) such as limestone and rich
in silica such (argillaceous) as clay.
• Formerly, large amount of cement was made
from argillaceous limestone known as cement
rock.
• Some plant use blast furnace slag and
precipitated calcium carbonate obtained from
as by product in alkali and synthetic
ammonium sulfate industry.

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Raw Materials
• Sand, waste bauxite (Al(OH)3), and iron ore are
used in small amounts to adjust the
composition of the mix.
• Gypsum (4 to 5%) is added to regulate
(slowing) the setting time of the cement.
• These raw materials are finely ground, mixed
and heated in a rotary kiln to form cement
clinker.

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Clinker Compounds
• Common abbreviations used for the clinker
compounds:
CaO - C
SiO2 - S
Al2O3 - A
Fe2O3 - F
MgO - M
SO3 - S
Na2O – N
K2O - K
CO2 - C
H2O - H
Ca3SiO5 (3CaO SiO2) – C3S
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Methods of Manufacturing

• Wet process grinding and mixing of the raw


materials in the existence of water.
• Dry process grinding and mixing of the raw
materials in their dry state.

The process to be chosen, depend on the


nature of the used raw materials.

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Wet Process

• When percentage of the moisture in the raw


materials is high.
• Size of the kiln needed to manufacture the
cement is bigger.
• The amount of heat required is higher, so the
required fuel amount is higher.
• Less economically

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Kiln

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Dry Process

• Size of the kiln needed to manufacture the


cement is smaller.
• The amount of heat required is lower, so the
required fuel amount is lower.
• More economically.
• The machinery and equipment need more
maintenance.

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Rotary
Kiln
1450 deg C

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Process

• Wet Process. Slurry is filtered in a continuous rotary filter and fed into the
kiln.

• Dry process. Applicable for natural cement rock and to mixtures of


limestone and clay, shale, or slate.
• In this process, materials may be roughly crushed and passed through
ball mills.

• Heat is provided by burning oil, gas, or pulverized coal.


• Dry process kilns may be 45 m while wet process may be up to 90 to
180m.
• The internal diameter of the kiln are usually 2.5 to 6m rotating from 0.5 to
2 rpm. Kilns are slightly inclined so that materials fed in at upper end
travel slowly to the lowering firing end (1 to 3 h).
• Efficient pollution control equipment such as baghouses and precipitators
are also employed.

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Process

• The final product consist of hard granular masses from


3 to 20 mm in size called clinker.
• The clinker is discharged from the rotating kiln into the
coolers and bring down temperature up to 100 to 200
deg C. These coolers preheat the combustion air used
in the kiln.
• During the fine grinding after the kiln, setting retarders,
gypsum, plaster, air entraining, dispersing and
waterproofing agents are added.
• The entire cement process can be monitored by x –ray
machines.

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Clinker Compounds

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Reactions in the Kiln

1. Evaporation
2. Evolution of CO2
3. Reaction between lime and clay

• Most of these reactions proceed in the solid phase,


but, toward the end of the process, the important
fusion occurs.
• Liquid formation begins at 1250C and probably no
appreciable formation of C3S occurs below this
temperature.

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Reactions in the Kiln

• C3S is the chief strength producing


constituent of cement.
• Between 20 and 30% of the reactions take
place in the final fluid phase.

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Reactions in the Kiln

• The wet process, though the original one, is


being replaced by the dry process.
• Because of saving heat, more accurate
control, and the mixing of the raw materials
it affords.

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Reactions during the Clinker Formation

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Major Reactions in the Kiln

• Clay →SiO2 + Al2O3


• CaCO3→CaO + CO2
(Calcination)

Oxide Common Name Abbreviation Approx. Amount (%)


CaO Lime C 60-67
SiO2 Silica S 17-25

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Hardening of Cement and Function of
Compounds
• Hydration and hydrolysis are involved in the
setting and hardening of cement. Various
compounds contribute to the heat of
hardening as follows (equal wt, 28 days):
C3A>C3S>C4AF>C2S
• Function of compounds

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Other Cements

• Pozzolans – Material which is not cementitious in itself but which


becomes so upon admixture with lime. Resist corrosive action of saline
solutions and seawater.
• High Alumina Cements – a calcium aluminate cement. Manufactured
by fusing a mixture of limestone and bauxite. Characterized by very
rapid rate of strength development.
• Silicate Cements – Silica-filled. Not suitable at pH values above 7. Used
ofr joining bricks in chromic acid reaction tanks and in alum tanks.
• Sulfur Cements – Mixture of fillers. Standard material for joining bricks,
tile, and cast iron.
• Polymer Cements – Discovered by Sorel and sometimes called Sorel’s
cement. Used to adheres in thin layers of concrete and serves to seal
cracks therein.

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Lime (CaO)

• Cheap commodity because the limestone deposits are readily available.


• Is a calcium-containing inorganic material in which carbonates, oxides,
and hydroxides predominate.

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Gypsum

• Is a mineral that occurs in large deposits


throughout the world.

• Sulfate mineral composed of calcium sulfate


dihydrate, with the chemical formula CaSO. 4·
2H2O. It is widely mined and is for blackboard
chalk, wallboard, etc.

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HAZARDS

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Soda Ash – Manufacturers

VBV TRADING (Philippines)

CEMEX Philippines
Davao/Negros/Cebu/Manila,
Philippines
Holcim Philippines
La Union, Philippines

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GdMu. (n.d.). Retrieved from http://www.holcim.ph/

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