PRODUCTION

CHEMISTRY AND
TYPES OF CEMENT
By:Dr. Hana Aljewifi
 The cement

1. Historical reminder
2. Production of Cement
3. Chemical Composition of Cement
4. The types of cement

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 Introduction

• Cement is a finely pulverized, dry material that by itself is not a binder

but develops the binding property as a result of hydration (i.e., from
chemical reactions between cement minerals and water).

• A cement is called hydraulic when the hydration products are stable in

an aqueous environment. The most commonly used hydraulic cement for
making concrete is portland cement, which consists essentially of
reactive calcium silicates; the calcium silicate hydrates formed during the
hydration of portland cement are primarily responsible for its adhesive
characteristic, and are stable in aqueous environment.

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 Introduction

Hydraulic cements comprise about 20% by volume of most concretes:

their hydration products serve as a binder for the aggregate.

Cement composition and fineness, along with other concrete

constituents, influence fresh concrete properties such as rheology, heat
evolution, setting, rates of strength development, ultimate strength, and
color. The hydration products of cement affect concrete durability.

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 Historical reminder

John Smeaton
Properties study
hydraulic lime
James Parker
Louis Vicat
Joseph Aspedin
Discovered Portland cement
1800 - 1900 Isaac Johnson
Study of the composition Le Chatelier
chemical and mineralogical
Tönebolm
Standard proposal
for Cement Wilhelm Michaelis
Invention of the rotary oven Atlas Portland Cement

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 Historical reminder

Preheating the oven

1900 - 1950

Pre- calciner oven

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 Historical reminder

Innovation in Measuring Instruments

Reduced cost and quantity of energy

1950 - 2011 Essential development of information resources

Development of the computer-based control system

Progress in regulations and techniques to control pollution.

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 From limestone to cement

Limestone is the main source of CaCO3. Calcium

Limestone clay carbonate is the main constituent of the raw
material. It represents 75 to 83% of the raw material.

Clay is the main source of Si, Fe and Al

In 1756, Smeaton discovered that lime that presents
best "hydraulic" properties are those containing clay
materials.
Clinker is the product that comes out of the oven
of the cement plant
Gypsum is added to the clinker as a set retarder.
The percentage and 2 to 5%.
Cement
The Additives :pozzolana , fly ash, and slica fume
can be add to the clinker to improve the
characteristics of cement.

The cement is a gray powder obtained after grinding

the clinker, gypsum and additive.
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The three stages of cement manufacture
First step: Preparation of the raw
The cement is must bring for the material that he introduces
into the oven has a constant chemical composition. This part
covers the following substeps: Extraction of raw materials
(ex: limestone) Transportation, crushing, mixing, controlling,
storage, grinding, homogenization and storage of the raw.
This part is very important for detecting the type of cement
(eg resistant to sulphate) and chemical composition.
Second step: The manufacture of clinker
The cooking workshop has two parts:
Precalciner: a tower composed of several stages of cyclones for
promote heat change and ensure partial decarbonation.
Oven: it completes the decarbonation and ensures the
clinkerization.
Third step: the production of cement
This step involves grinding the clinker, gypsum and additive to
produce cement. This step and very important to detect the
class of resistance and the type cement (portland, modified or
compound). 9
Source: PCA, 2003 10
Traditional Manufacture of Portland Cement

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12
2. Raw materials are ground to powder and blended.

or Source: PCA, 2003

2. Raw materials are ground, mixed with water to form slurry, and blended.

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3. Burning changes raw mix chemically into cement clinker.

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Source: Mindess, Young, and Darwin, 2004 15
 Cement clinker
 Cement clinker is manufactured from a finely
ground, homogenized blend of limestone shale and
iron ore sintered in a rotary oven to temperatures
of approximately 1450 °C: clinker nodules 3-20 mm
in diameter are normally produced. The nodules
are subsequently ground with gypsum, which
serves to control setting, to a fine powder ˂ 45 µm)
to produce cement.
 Phase composition and texture (crystal size,
abundance, and distribution) of clinker result from
complex interactions of raw feed particle size, feed
homogenization, and the heating and cooling
Nodule of portland cement regime.
clinker with a cut and polished
face.
 Mil grinding affects the cement microstructure
through fracturing of the calcium silicates and
interstitial phase crystals and, depending
conditions, it may modify the form of calcium
sulfate added at this stage to control cement setting.
These features in turn influence the cement's
hydration characteristics. 16
Clinker Gypsum

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 Grinding

 Clinker is ground with gypsum

(calcium sulfate) to produce
portland cement

 Fine grinding is necessary for high

early strength:

 85-95% -325 mesh (45 microns)

 ~ 7 trillion particles per pound

 Gypsum absorbs water and prevents

setting of C3A during hydration.

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Chemical Reactions

In the preheating
The temperature is less than 700 °C. Free and combined
water evaporates.

At the entrance of the oven

The temperature is between 700 and 900 °C. Calcium carbonate
CaCO3 is decomposes to give CaO and CO2 according to the
equation: CaCO3 → CaO + CO2

In the first section of the oven

The temperature is between 900 and 1200 ° C. Decarbonation

becomes complete. There is formation of small round crystals
of C2S according to the equation: 2CaO + SiO2 → Ca2SiO4.

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Chemical Reactions
In the second section of the oven
The temperature is between 1200 and 1350 °C. The material is
divided in two phases; the liquid phase (Al, Fe, P, S) and the
solid phase (Si, Ca). The liquid phase plays an important role
in minimizing the distance between particles of the solid phase
which accelerates the reaction between the constituents of the
solid phase.
The percentage of C2S increases and one part of this phase
reacts with free lime to produce C3S (hexagonal crystals)
according to the equation: CaO + Ca2SiO4 → Ca3SiO5

At the exit of the oven (the cooking zone)

The temperature is between 1350 and 1450 ° C.
The percentage of free lime becomes negligible.
The percentage of C2S decreases and their dimension increases.
The percentage and dimension of C3S increases.

In the Cooler
The liquid phase crystallizes to give C3A and C4AF
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 Cement Chemistry
 During the burning operation in the manufacture of portland cement
clinker, calcium oxide combines with the acidic components of the raw
mix to form four principal compounds that make up 90% of cement by
weight. Gypsum and other materials are also present.
 The primary compounds, their chemical formulas, and abbreviations
used by cement chemists:

 Tricalcium silicate 3CaO•SiO2 = C3S

 Dicalcium silicate 2CaO•SiO2 = C2S
 Tricalcium aluminate 3CaO•Al2O3 = C3A
 Tetracalcium aluminoferrite 4CaO•Al2O3•Fe2O3 = C4AF

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 COMPOSITION CHIMIQUE DU CIMENT PORTLAND
COMPOSITION DU CLINKER

Clinker image in optical microscopy (polished section)

Liquid
Phase
C3A
C4AF

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 CHEMICAL COMPOSITION OF PORTLAND CEMENT
General considerations

Principal crystallochemical phases of clinker

Ca3 SiO5 Ca2 SiO4 Ca3 Al2O6 Ca4AI2 Fe2Olo

3CaO - SiO2 2CaO - SiO2 3 CaO Al2O3 4CaO Al2O3Fe2O3

C3S C2S C3A C4AF

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CHEMICAL COMPOSITION OF CEMENT PORTLAND
COMPOSITION OF CLINKER

constituents
clinker

Domain - - - -
Content
in %
Average

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COMPOSITION CHIMIQUE DU CIMENT PORTLAND
COMPOSITION DU CLINKER

CaO LIBRE
C2S
C3S
100 C3A
microns

C4 AF
MgO

Image of a clinker under an optical microscope

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Portland Cement Compound Transformations

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 Alite and Belite
 Alite (tricalcium silicate, Ca3SiOs):
forms the bulk of a clinker (40-70%, by mass) with crystal sizes up to about 150 µm.
Alite generally displays a hexagonal crystal habit in cross section, with forms
ranging from euhedral (clearly-defined crystal faces), to subhedral (poorly-defined
crystal faces), to anhedral (no crystal faces). Minor oxide contents may range from
about 3% to 4% by mass. Alite reacts rapidly with water and is responsible for much
of the early-age (28 d) strength development
 Belite (dicalcium silicate, CazSiO4):
forms 15-45% of a clinker, and displays a rounded habit with crystal sizes ranging
from 5 to 40 µm. Light microscopy of lamellar structures on etched specimens and
X-ray powder diffraction data are useful for distinguishing the belite forms. Belite is
less reactive than alite but does contribute to later-age strengths (>28 d). Upon
hydration, both alite and belite form a poorly-crystallized calcium silicate hydrate
(C-S-H) and well-crystallized calcium hydroxide.

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 Clinker Phases
Alite or 3CaO•SiO2 or Tricalcium silicate, C3S:

 Hydrates & hardens quickly

 High early strength
 Higher heat of hydration (setting)

Belite or 2CaO• SiO2 or Dicalcium silicate, C2S:

Alite (C3S) as light, angular crystals. The
darker, rounded crystals are belite (C2S).
 Hydrates & hardens slower than alite
Magnification 400X.  Gives off less heat
 High late strength (> 7 days)
Modern cements are manufactured to be higher
in alite for early strength
C3S and C2S require approximately the same
amount of water for hydration, but C3S produces
more than twice as much Ca(OH)2 as is formed by
the hydration of C2S,
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 COMPOSITION CHIMIQUE DU CIMENT PORTLAND
Microstructure of clinker DU CLINKER

Clinker image in optical microscopy (polished section)

Alite C3S Belite C2S

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 CHEMICAL COMPOSITION OF CEMENT PORTLAND
COMPOSITION OF CLINKER

 Minor elements of clinker (from 0.1 to some%)

SO3: present in the form of CaSO4 or alkaline sulfates or in clinker phases (C2S): from 0.5 to ~
3.0%.
 Alkaline :
- Content expressed as Na2O (% Na2O + 0.658 K2O)
- Predominantly in the phases C3A (Na), C2S (K)
- No specification for clinker, but low alkali cements (<0.6% Na2O) often requested 0.2 to 1.5%.

 The alkali content of cement (mostly chloride) is reflected in the amounts of potassium
oxide (K2O) and sodium oxide (Na2O). Large amounts can cause certain difficulties in
regulating set times of cement. Low alkali cements, when used with calcium chloride
in concrete can cause discoloration in trowelled flatwork surfaces. ASTM has an
optional limit in total alkalies of 0.60%, calculated by the equation Na2O + 0.658 K2O.
 Alkali sulfates and calcium sulfates may also occur in clinker and are of interest since
they have been found to affect hydration rates and strength development. Increased
alkali levels in clinker are considered potentially deleterious if alkali-susceptible
aggregates are used in the concrete.
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 CHEMICAL COMPOSITION OF CEMENT PORTLAND
COMPOSITION OF CLINKER

 Other phases
Phases in lesser quantities, but still influential to performance, include
periclase (MgO) and free lime (CaO).
 FREE LIME

- CaO
- Acceptable between 0.5 and 1.5
- No specification but effective limitation

 Periclase: may exhibit a dendritic or equant crystal habit both within and
between the other clinker constituents, ranging in size up to 30 µm. Free lime
may occur as isolated rounded crystals or in masses with variable crystal size.

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CHEMICAL COMPOSITION OF CEMENT PORTLAND PRICIPALES
PROPERTIES OF PHASES OF CLINKER

MAIN PROPERTIES OF THE CLINKER PHASES AND THEIR EFFECTS:

 Heat of hydration: heat emitted
development of thermal cracks in massive structures.
increase in resistance
 Hydration speed:
increase in resistance
properties of fresh concrete: rheology ...
Linking capacity:
long-term resistance
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CHEMICAL COMPOSITION OF CEMENT PORTLAND PRINCIPAL
PROPERTIES OF PHASES OF CLINKER
Hydration heats

Heats of hydration typical of the different phases of the clinker

PHASE Joule/g

C3S 500
C2S 250
C3A 1340
C4AF 420
Free lime 1150

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 CHEMICAL COMPOSITION OF CEMENT PORTLAND
PRINCIPAL PROPERTIES OF PHASES OF CLINKER

Compressive strength of the

main constituents of clinker
(according to Bogue and
Lerch).

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 CHEMICAL COMPOSITION OF CEMENT PORTLAND
PRINCIPAL PROPERTIES OF PHASES OF CLINKER

COMPOUND ALITE BELITE CELITE

Aluminoferrite
Chemical Tricalcium silicate Dicalcium silicate Tricalcium aluminate
4CaO - Fe2O3 - Al2O3
composition 3CaO - SiO2 (C3S) 2CaO - SiO2 (C2S) 3CaO - Al2O3 (C3A)
(C4AF)

Hydration Speed Fast (hours) Slow (days) Instant Very fast (minutes)

Resistance
Fast (days) Slow (week) Very fast (1 day) Very fast (1 day)
Development

Final resistance Strong Probably strong: ≈ 10 Low: Low:

(≈ 10 N / mm²) N / mm² a few N / mm² a few N / mm²

hydration heat Average Low: Very high: Average:

(~ 500 J/g) ~ 250 J/g ~ 1340 J/g ~ 420 J/g

Characteristic Unstable with water,

Gives cement its gray
Note component of susceptible to attack
color
Portland cements by sulphates

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 Types of portland cement

these five types are often described by the term “ordinary portland cement”, or
OPC. 36
 References

 http://iti.northwestern.edu/cement/index.html
 Microstructral of concrete
 Concrete techenolgy

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