CEMENT

BACKGROUND

Cement is the essential component of concrete which, when hydrated, binds the aggregates together
to form the hard, strong and monolithic whole that is so useful. Well over 95% of the cement used in
concrete throughout the world is Portland cement in its various forms. It is by no means a simple
material, and its complexities have an impact on the properties and behaviour of concrete from mixing
right through to the end of its life. It is therefore important to have some understanding of its
manufacture, its composition, the processes involved in its hydration and of its final hardened structure
if it is to be used effectively

Cement consists of the four compounds in different proportions, together with some lime. When it comes
out of the kiln, it is called clinker, and must be ground to make the final product. The fineness of grinding
affects the rate at which the cement hydrates. It is measured as the total surface area of the particles,
in m2/kg, and is calculated from a measurement of the permeability to air of a compacted bed of cement,
of standard thickness (the air will flow more easily through a bed of coarser particles because the gaps
between them will be larger).

Gypsum is used to slow down the setting of the C 3A, and is added during grinding. The gypsum may
be in the form of anhydrite or dihydrate. A mixture of equal parts of the two may be used.

Portland cement world consumption is reaching 1.6 billion tones and each ton of Portland cement clinker
is accompanied by the release of 1 ton of carbon dioxide. This is why it is estimated that about 7% of
the world carbon dioxide emission is attributed to the Portland cement industry.

The word “cement” is used to cover a wide variety of materials that, when mixed, may be formed into
shapes, and then set to become solid

When cement is mixed with water, the mixture is known as cement paste (or unsanded grout).
When cement is mixed with sand and water, the mixture is known as mortar (or sanded grout). Mortar
is used to lay bricks. When cement is mixed with larger stones, sand, and water, the mixture is known
as concrete. The term concrete is also sometimes used to describe a mixture of other binders and
aggregate, for example, asphaltic concrete.

CEMENTS PRODUCTION
THE STAGES OF CEMENT PRODUCTION
The production and hydration of cement may be considered in five stages that take it from a raw material
in the quarry to a hydrated mix in a structure as follows:
1. Component elements – these are in the raw materials.
2. Component oxides – these are produced in the kiln.
3. Cement compounds – these are formed from the oxides.
4. Portland cements – the properties of these are determined by the compounds.
5. Hydration products – produced when the cements react with water.
These different stages are discussed below.

COMPONENT ELEMENTS
Traditionally, the raw materials for cement manufacture were clay and chalk but, with the industry
working at a vast scale of production for over 100 years, a very wide range of different source materials
have been used. These materials need to have the correct proportions of the different chemical
elements in them to make the required type of cement. The proportions of the elements will not change,
so a chemical analysis of concrete in a structure, that may be many years old, will reveal the type of
cement that was used.

Production of Portland cement starts with two basic raw ingredients: a calcareous material and an
argillaceous material. The calcareous material is a calcium oxide, such as limestone, chalk, or oyster
shells. The argillaceous material is a combination of silica and alumina that can be obtained from clay,
shale, and blast furnace slag. These materials are crushed and then stored in silos. The raw materials,
in the desired proportions, are passed through a grinding mill, using either a wet or dry process. The
ground material is stored until it can be sent to the kiln. Modern dry process cement plants use a heat
recovery cycle to preheat the ground material, or feed stock, with the exhaust gas from the kiln. In
addition, some plants use a flash furnace to further heat the feed stock. Both the preheater and flash
furnace improve the energy efficiency of cement production. In the kiln, the raw materials are melted at
temperatures of 1400°C to 1650°C (2500°F to 3000°F), changing the raw materials into cement clinker.
The clinker is cooled and stored. The final process involves grinding the clinker into a fine powder.
During grinding, a small amount of gypsum is added to regulate the setting time of the cement in the
concrete. The finished product may be stored and transported in either bulk or sacks (bags). In Nigeria,
a standard sack (bag) of cement is 50 kg. The cement can be stored for long periods of time, provided
it is kept dry.
Calcareous material DRY PROCESS Argillaceous material Calcareous material
WET PROCESS Argillaceous material
Lime stone Clay Lime stone Clay

Crushing Crushing Crushing Wash mill

Fine grinding in ball Fine grinding in ball Storage basin Storage basin
mills and tube mills mills and tube mills

Storage basin Storage basin Wet grinding mill

to make slurry

Blending of slurry into

Mixing in correct correct composition
proportion
Storage of
Preheat at 800oC corrected slurry
by gases
Corrected slurry fed
Storage tank for into rotary kiln
raw mix
Slurry converted
Fed to rotary kiln into clinkers

Clinkers are
Clinker are grinded in ball mill
grounded in ball mill
Clinkers are
Cement silos grinded in ball mill

Packing Plant
Packing Plant

Figure 1: Diagram of Wet Process and Dry Process

Comparison of Wet process and Dry process

- The chief advantages of wet process are the low cost of excavating and grinding raw materials, the
accurate control of composition and homogeneity of the slurry and the economical utilization of fuel
through the elimination of separate drying operations.
- On the other hand, the longer kilns, essential in the wet process, cost more and are less responsive
to a variable clinker demand than the short kilns which can be used in the dry process.
Cement Kiln
COMPONENT OXIDES

The raw materials are mixed together, and ground and fed into a kiln where they combine with oxygen.
The component oxides of cement each have single letter abbreviations in cement chemistry.

Table 1: Component oxides of Cement

Names Chemical constituents Proportions (%)

Lime CaO 60 – 70
Silica SiO2 17 – 25
Alumina Al2O3 3–8
Iron Fe2O3 0.5 – 6
Sulphuric anhydride SO3 1
Magnesia MgO 0.1 – 1
Soda Na2O 0.1 – 1.3
Potassa K2O 0.2 – 1.3

CEMENT COMPOUNDS

As the cement progresses along the kiln, it is heated to higher temperatures; and, before reaching the
maximum of around 1400°C, the oxides combine to form four different compounds.
The four major cement compounds are:

Table 2: Compounds formed during Cement Production

Tricalcium silicate C3S

Dicalcium silicate C2S

Tricalcium aluminate C3A

Tetracalcium aluminoferrite C4AF

The approximate proportions of these in the cement may be calculated from the Bogue equations:

TYPES OF PORTLAND CEMENTS

Most Portland cement is used in making concrete, required for buildings, pavements, roads,
bridges, and dams. Other uses of Portland cement are in masonry mortar, plaster, stucco,
siding, and flooring. Because the requirements for various concretes and other mixes vary,
Portland cement is manufactured in five different types—Types I, II, III, IV, and V. These
types are distinguished from each other by small changes in their chemical composition,
giving them different properties
Table 3: Types of Cement

Type I Ordinary Portland Cement

Type II Mderate Sulphate Resistance Portland cement
Type III High early strength Portland cement
Type IV Low heat of hydration (slow reacting) cement
Type V High sulphate resistance
White White colour

By varying the proportions of different compounds, cements for different applications may be produced:

• Type I - Ordinary Portland cement (OPC).

This is the cheapest and most commonly used cement. The name “Portland” was given to it by its
inventor (John Aspadin of Leeds, UK, in 1824) because he wished to imply that the cast material had
the properties of Portland stone. It is used for general purposes at no severe exposure

• Type II - Moderate Portland cement

This type of cement is used for general purposes where moderate sulphate and heat resistance is
required. For example: massive structures, abutments. Piers, retaining walls etc.

•Type III - High early strength Portland cement (Rapid hardening cement.)

This has a fineness of not less than 350 m2/kg (compared with 275 m 2/kg for OPC), and a high C3S
content. It has a strength approximately 50% higher than OPC at 3 days, but similar long-term strength.
Heat evolution rates are high. It is generally used in making precast concrete elements, such as hollow-
core slabs, double-tees, and concrete pipes. Economic considerations require that the formwork for
precast elements be used as frequently as possible. Generally, precast concrete elements are cast one
morning and stripped off the form the following morning, giving a 24-hr turnover cycle

• Type IV - Low heat of hydration Portland cement.

This contains relatively small percentages of C3S and C3A, and it is meant for use in massive concrete
structures (dam walls or bridge piers), where the temperature rise due to heat generated from hydration
must be minimized. Due to its limited use, Type IV cement is produced by manufacturers only on special
request.

•Type V is sulphate-resistant Portland cement. Portland cement can be affected adversely by the
presence of sulphur. In fact, concrete made out of Type I Portland cement will decompose into small
fragments (spall) after just a few years in the presence of high-sulphur-containing environments. Some
soils and groundwater have a high sulphur content. The use of Type V Portland cement is
recommended in such environments.

• White cement.

This has a low C4AF content to give white cement for architectural purposes.

Other Cements

There are some other cements that are different from Portland cement.

• High alumina cement (HAC).

• Super-sulphated cement.

• Expansive cements.
Hydration of Portland cement

Hydration is the chemical reaction between the cement particles and water. The features of this reaction
are the change in matter, the change in energy level, and the rate of reaction. The primary chemical
reactions are shown in Table 4. Since Portland cement is composed of several compounds, many
reactions are occurring concurrently.

The hydration process occurs through two mechanisms: through-solution and topochemical. The
through-solution process involves the following steps (Mehta and Monteiro, 2005):

1. Dissolution of anhydrous compounds into constituents

2. Formation of hydrates in solution
3. Precipitation of hydrates from the supersaturated solution

The through-solution mechanism dominates the early stages of hydration. topochemical hydration is a
solid-state chemical reaction occurring at the surface of the cement particles.

The aluminates hydrate much faster than the silicates. The reaction of tricalcium aluminate with water
is immediate and liberates large amounts of heat. Gypsum is used to slow down the rate of aluminate
hydration. The gypsum goes into the solution quickly, producing sulphate ions that suppress the
solubility of the aluminates.

The balance of aluminate to sulphate determines the rate of setting (solidification). Cement paste that
sets at a normal rate requires low concentrations of both aluminate and sulphate ions. The cement
paste will remain workable for about 45 minutes; thereafter, the paste starts to stiffen as crystals
displace the water in the pores. The paste begins to solidify within 2 to 4 hours after the water is added
to the cement. If there is an excess of both aluminate and sulphate ions, the workability stage may only
last for

Table 4

10 minutes and setting may occur in 1 to 2 hours. If the availability of aluminate ions is high, and
sulphates are low, either a quick set (10 to 45 minutes) or flash set (less than 10 minutes) can occur.
Finally, if the aluminate ions availability is low and the sulphate ions availability is high, the gypsum can
recrystalize in the pores within 10 minutes, producing a flash set. Flash set is associated with large heat
evolution and poor ultimate strength (Mehta and Monteiro, 2005). Calcium silicates combine with water
to form calcium-silicate-hydrate, C-S-H.

The crystals begin to form a few hours after the water and cement are mixed and can be developed
continuously as long as there are unreacted cement particles and free water. C-S-H is not a well-defined
compound. The calcium-to-silicate ratio varies between 1.5 and 2.0, and the structurally combined water
content is more variable. As shown in Table 4, the silicate hydration produces both C-S-H and calcium
hydroxide. Complete hydration of produces 61% C-S-H and 39% calcium hydroxide; hydration of C2S
results in 82% C-S-H and 18% calcium hydroxide. Since C-S-H is what makes the hydrated cement
paste strong, the ultimate strength of the concrete is enhanced by increasing the content of C2S relative
to the amount of Furthermore, calcium hydroxide is susceptible to attack by sulphate and acidic waters.
C3S hydrates more rapidly than C2S contributing to the final set time and early strength gain of the
cement paste. The rate of hydration is accelerated by sulphate ions in solution. Thus, a secondary effect
of the addition of gypsum to cement is to increase the rate of development of the C-S-H

SETTING OF CEMENT

When Portland cement is mixed with water to make a soft paste, it becomes gradually less plastic, and
finally rigid to withstand a definite amount of pressure. The tine at which the cement paste loses its
plasticity after the addition of water is known as initial setting time, while the time corresponding to the
paste becoming a hard mass is known as final setting time.

At the time of the initial set, the temperature rises rapidly and at final setting, the temperature reaches
a peak value.

Flash Set

If the gypsum content is not enough to react with C3A, then the excess C3A would react with water too
rapidly, forming calcium aluminates which causes the flash setting of cement paste within few minutes.
A high rise in temperature is accompanying it, without any possibility to regain the plastic nature of set
paste upon mixing.

False Set

It is an unusual set that takes place within few minutes after the addition of water. It differs from the
flash set by the very low evolved heat. This set is controllable and the plastic nature of the set paste
can be retained by its remixing without any necessity for water addition, where it will reset normally with
no adverse effect on the compressive strength.

Possible Causes

- The drying out of gypsum water, so that it is absorbed from mixing water
- Poor storage conditions cause the alkalis to react with CO2 forming carbonates which react with
water and Ca(OH)2 to form CaCO3
- During long time storage, the surfaces of cement particles might have come in contact with
water.

Gypsum Added To Cement

Gypsum is added in a specified percentage, so that it may react with the aluminates (C 3A) upon early
hydration to form calcium sulphur aluminates which are of low solubility and help in retarding the rapid
reaction of C3A

Optimum Gypsum Content: it is that content that provides higher compressive strength, less dying
shrinkage, and low expansion in water.