GL - 204 Fundamentals of Geology

MINERALOGY
Portland-Cement minerals

Dr. Mulugheta Tewelde

University of Zimbabwe
Department of Geology
What is Portland Cement?

 Portland cement is defined as a “hydraulic cement”

that is produced by pulverizing a mixture of raw
materials (calcium silicates and calcium carbonates) that
also contain some aluminum and iron oxides.

 And these raw materials are obtained by heating a

mixture of limestone and clay at very high temperature
(next slide).

 Portland cement is a type of binder that glue

individual filler particles together to form concrete.
Manufacture of
Portland-Cement
The Manufacture of Portland Cement

(1) Mixing of raw materials (see next slides): Rocks and

soils that are rich in clay minerals (containing
aluminum, iron, magnesium, silicon, and potassium)
and rich in calcium (such as limestone and chalk) are
mixed.

(2) Grinding of the mixture: The rocks and soils are then
ground up into particles finer in size than 75μm.
Manufacture of Portland Cement (Contd.)

(3) Heating of the ground mix: The ground material is

then slowly heated in a rotating kiln to T=1500°C. Along
the way, a number of important reactions occur:

Reactions that takes place at this stage:

- At T= about 900°C – 1000°C the calcium carbonate

(CaCO3) in limestone separates into lime (CaO) and
carbon dioxide (CO2).

- At T=1200°C the formation of silicates and

aluminates begin, and continues up through T=1500°C.
Manufacture of Portland-Cement (Contd.)

Idealised Formulas
Manufacture of Portland Cement (Contd.)

(4) Cooling of the material: The material (at this stage it is

called clinker) that emerges from the kiln in roughly
millimeter-sized particles is then allowed to cool.

(5) Adding of gypsum to the clinker: 5% gypsum or chalk

in the form of calcium sulfate hydrate (CaSO4·2H2O) is
then added to the clinker particles.

(6) Grinding of the mixture: The mixture is then ground

down to particles sizes in the range of 2-80μm. The
resulting portland cement powder has a specific surface
area of roughly 300 m2/kg.

Note: producing cement produces also CO2!!!!!

Manufacture of Portland Cement (Contd.):
Manufacture of Portland Cement (Contd.):

Clay Limestone

Mill Gypsum
Kil n
1400°C
Portland-
Clinker Mill Cement
The four main minerals of portland cement:

- Alite (C3S): approximately tricalcium silicate (typically

about 65% of the total)

- Belite (C2S): approximately dicalcium silicate

(typically about 15% of the total)

- Aluminate (C3A): very approximately tricalcium

aluminate (typically about 7% of the total)

- Ferrite (C4AF): very approximately tetracalcium

aluminoferrite (typically about 8% of the total)
Hydration Reaction of
Portland-Cement
 Hydration Reaction of Portland-Cement (Contd.)
Hydration of Ordinary Portland Cement
Hydration starts as soon as the cement and water are mixed.
- The rate of hydration and the heat liberated by the reaction
of each compound is different.
- Each compound produces different products when it
hydrates.
- Tricalcium silicate (C3S): Hydrates and hardens rapidly and
is largely responsible for initial set and early strength.
Portland cements with higher percentages of C3S will exhibit
higher early strength.
- Tricalcium aluminate (C3A): Hydrates and hardens the
quickest. Liberates a large amount of heat almost
immediately and contributes somewhat to early strength.
 Hydration Reaction of Portland-Cement (Contd.)
Hydration of Ordinary Portland Cement
- Gypsum is added to Portland cement to retard C3A
hydration. Without gypsum, C3A hydration would cause
Portland cement to set almost immediately after adding
water.

- Dicalcium silicate (C2S): Hydrates and hardens slowly and

is largely responsible for strength increases beyond one
week.

- Tetracalcium aluminoferrite (C4AF): Hydrates rapidly but

contributes very little to strength. Its use allows lower kiln
temperatures in Portland cement manufacturing. Most
Portland cement color effects are due to C4AF.
 Hydration Reaction of Portland-Cement
Hydration Reactions of Principal Clinker Phases

- C3S + H2O  C-S-H* + Ca(OH)2

- C2S + H2O  C-S-H* + Ca(OH)2

- 2C3A + 18H2O  C2AH8 + C4AH10

- 2C3A + 32H2O + 3(Ca2+(aq) + SO42-(aq))  C6AS3H32

- C6AS3H32 + 2C3A  3C4ASH12

- C4AF has analogous reactions to C3A,
i.e. produces e.g. C6(A,F)S3H32
*C-S-H is an amorphous hydrogel having variable composition in
terms of Ca/Si ratio and H2O/SiO2 ratios
 Hydration Reaction of Portland-Cement (Contd.)

- When Portland cement is mixed with water its chemical

compound constituents undergo a series of chemical reactions
that cause it to harden.
- This chemical reaction with water is called "hydration". Each
one of these reactions occurs at a different time and rate.
- Together, the results of these reactions determine how Portland
cement hardens and gains strength.
END
The chemistry of portland cement:

- Shorthand notations that are used in cement chemistry

are the following:
Types of Portland-Cement:
a cement with different characteristics can be obtained
by changing the fineness and the relative proportions of
the chemical compounds in portland cement.

For example, there exist six relatively standard types of

portland cement with the compositions shown below.
Types of Portland-Cement (Contd.):
- Type I portland cement:
is a general-purpose cement suitable for all uses where
the special properties of other types are not required.
E.g.: pavements, floors, concrete buildings, bridge.

- Type II portland cement:

is used where precaution against moderate sulfate attack
is important. E.g.: drainage structures where sulfate
concentrations in groundwaters are higher than normal.

- Type III portland cement:

Is similar to Type I cement but is finer and gives high
strengths at an early period (a week or less).
It is applied in areas where the structure must be put into
service quickly.
Types of Portland-Cement (Contd.):
- Type IV portland cement:
is used in fields where the rate and amount of heat
generated from hydration must be minimized.
E.g.: massive concrete structures (big dams) where the
temperature rise that results from heat generated during
hardening must be minimum.

- Type V portland cement:

is used only in concrete (cement + aggregate + water)
exposed to areas where severe sulfate is a concern; e.g:
soils or groundwaters which have a high sulfate content.
Types of Portland-Cement (Contd.):
- White portland cement:
is a portland cement that differs from gray cement only in
color.
It is made of raw materials that contain negligible amounts
of iron and magnesium oxides (those substances that give
cement its gray color).

Note: Generally all portland cements are not resistant to

acids.
Hydration Reaction of
Portland-Cement
 Hydration Reaction of Portland-Cement
Hydration Reactions of Principal Clinker Phases

- C3S + H2O  C-S-H* + Ca(OH)2

- C2S + H2O  C-S-H* + Ca(OH)2

- 2C3A + 18H2O  C2AH8 + C4AH10

- 2C3A + 32H2O + 3(Ca2+(aq) + SO42-(aq))  C6AS3H32

- C6AS3H32 + 2C3A  3C4ASH12

- C4AF has analogous reactions to C3A,
i.e. produces e.g. C6(A,F)S3H32
*C-S-H is an amorphous hydrogel having variable composition in
terms of Ca/Si ratio and H2O/SiO2 ratios
 Hydration Reaction of Portland-Cement (Contd.)

- When Portland cement is mixed with water its chemical

compound constituents undergo a series of chemical reactions
that cause it to harden.
- This chemical reaction with water is called "hydration". Each
one of these reactions occurs at a different time and rate.
- Together, the results of these reactions determine how Portland
cement hardens and gains strength.
 Hydration Reaction of Portland-Cement (Contd.)
Hydration of Ordinary Portland Cement
Hydration starts as soon as the cement and water are mixed.
- The rate of hydration and the heat liberated by the reaction
of each compound is different.
- Each compound produces different products when it
hydrates.
- Tricalcium silicate (C3S): Hydrates and hardens rapidly and
is largely responsible for initial set and early strength.
Portland cements with higher percentages of C3S will exhibit
higher early strength.
- Tricalcium aluminate (C3A): Hydrates and hardens the
quickest. Liberates a large amount of heat almost
immediately and contributes somewhat to early strength.
 Hydration Reaction of Portland-Cement (Contd.)
Hydration of Ordinary Portland Cement
- Gypsum is added to Portland cement to retard C3A
hydration. Without gypsum, C3A hydration would cause
Portland cement to set almost immediately after adding
water.

- Dicalcium silicate (C2S): Hydrates and hardens slowly and

is largely responsible for strength increases beyond one
week.

- Tetracalcium aluminoferrite (C4AF): Hydrates rapidly but

contributes very little to strength. Its use allows lower kiln
temperatures in Portland cement manufacturing. Most
Portland cement color effects are due to C4AF.
 Hydration Reaction of Portland-Cement (Contd.)
Properties of Cement Hydration Products

 Ca(OH)2 :
crystalline, isostructural with the natural mineral
Portlandite.

 C-S-H :
poorly crystalline product of variable composition.
Considered to be based on a crumpled layer structure
(analogous to a distorted clay sequence) which traps
regions of porosity - pore size distribution from nm to
m. Simplified composition given by:

CaxH6-2xSi2O7.zCa(OH)2.nH2O where CaO/SiO2 = (x+z)/2

 Hydration Reaction of Portland-Cement (Contd.)
Properties of Cement Hydration Products (Contd.)

 AFt - or ettringite, or aluminoferrite trisulphate (C6AS3H32):

Crystalline - trigonal. Forms columnar type structure

consisting of (Al,Fe)(OH)6 octahedra alternating with
triangular groups of edge sharing CaO8 polyhedra with
which they share OH- ions
Electron microprobe
Tests of Portland cement
 Basic tests of Portland cement:
1) Fineness (surface area / weight):
- Controls hydration
- is the average size of cement
- value = 350m² / Kg
- measured using the Blaine method (air
permeability method)

2) Normal consistency test: 10 mm-diameter needle

under 300g weight sink into 10 mm in30s (next slide).
Basic tests of Portland cement (Contd.):
Basic tests of Portland cement (Contd.):
3) Time of setting:

Initial setting:
- The paste starts to stiffen and lose the
consistency after the mixing with water

- Initial setting time for (ordinary) Portland

cement: not earlier than 45min

- If the initial setting time is not qualified, the

cement can not be used in engineering

- 1mm-diameter needle penetrate 25 mm

Basic tests of Portland cement (Contd.):
3) Time of setting:

Final setting:
- The paste loses completely its consistency
and begins to gain strength
- No obvious penetration of a 1mm-diameter
needle
- Final setting time : not longer than 6.5h for
Portland cement
Basic tests of Portland cement (Contd.):
4) Unsoundness:
- Unsoundness results from excessive or
- unstable volume change after setting
- Unsoundness may cause cracking of the
paste
- Unsoundness can be caused by slow
hydration of MgO, free lime or later formation
of ettringite due to their crystal growth
pressure
Basic tests of Portland cement (Contd.):
5) Strength:
Basic tests of Portland cement (Contd.):
6) Heat of hydration test:
- hydration is a heat release process.
- temperature of concrete is higher in the
interior and lower at the surface.
- Temperature difference between surface and
the interior should not be greater than 25 °C.
1) Extraction of raw materials
2) Grinding and storage of raw materials
3) The firing of raw materials
4) Storage and grinding of cement
5) Packaging and shipment
Difraction pattern of portland-cement klnker
Manufacture of Portland Cement:

 In a cement factory limestone and clay are mixed and

then milled for better reactivity and subsequently heated
in a rotating kiln to a temperature of 1450°C to 1550°C.

 The reaction then produces nodules (5-30 mm) in

diameter that are called clinker.

 About 5% gypsum is added to the clinker to control

the early setting and hardening reactions of the cement.
The composite is then ground to <75 μm in diameter.
Manufacture of Portland Cement (Contd.):

 During the manufacturing (burning and decomposition

of carbonates) of cement a relatively large amount of CO2
is released.

 The cement industry is responsible for 8% of the

world’s industrial production of CO2
Manufacture of Portland Cement (Contd.):
Manufacture of Portland Cement (Contd.):

Approximate Composition Limits of Oxides in Portland

Cement