Cement – An Insight View

Doc. No: QMD/2018-04-2/23

No. of Pages: 7 of A4 Size
DOI: Apr 2018

{The Input data is based upon IS: 269-2015, IS: 1489 -1 - 1999, and personal experience}

The term cement derives from the Latin word caementum, which means
stone chippings (such as were used in Roman mortar—not the binding
material itself). Cement is a chemical. Portland cement gets its strength
from an exothermic chemical reaction between the cement and water. The
process is known as hydration. This is a complex process and the detailed
chemical properties of different constituents are not yet, full understood and
is still the object of research.
Cement is a binder, a substance used for construction that sets, hardens
and adheres to other materials, binding them together. Cement is seldom
used on its own (except under special circumstances like cement filling in
fine joints, cement + chemical grouting etc.), but rather to bind sand and
gravel (aggregate) together. Cement is used with fine aggregate to
produce mortar for masonry, or with sand and aggregates to
produce concrete.
Cements used in construction are usually inorganic, often lime or calcium
silicate based, and can be characterized as being either hydraulic or non-
hydraulic, depending upon the ability of the cement to set in the presence of
water.

History of Cement
The origin of hydraulic cements goes back to ancient Greece and Rome as
they were able to make mortars and concretes about 2000 years ago. The
materials used were lime and a volcanic ash (mined near what is now the
city of Pozzuoli, Italy) that slowly reacted with it in the presence of water to
form a hard mass. Volcanic ash was particularly rich in essential alumino-
silicate minerals, giving rise to the classic pozzolana cement of the Roman
era and today’s term pozzolana, or pozzolan, refers either to the cement
itself or to any finely divided alumino-silicate that reacts with lime in water
to form cement.

Portland cement is a successor to a hydraulic lime that was first developed

by John Smeaton in 1756 when he was called in to erect the Eddystone
Lighthouse off the coast of Plymouth, Devon, England. The next
development, taking place about 1800 in England and France, was a
material obtained by burning nodules of clayey limestone.

The invention of portland cement usually is attributed to Joseph

Aspdin of Leeds, Yorkshire, England, who in 1824 took out a patent for a
material that was produced from a synthetic mixture of limestone and clay.
He called the product “portland cement” because of a fancied resemblance of
the material, when set, to portland stone, a limestone used for building in

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England. Aspdin’s product was improved by Isaac Charles Johnson of south
eastern England in about 1850.

During the 20th century, cement manufacture spread worldwide. By the

early 21st century, China and India had become the world leaders in cement
production, followed by the United States, Brazil, Turkey, and Iran.

Manufacture of cement
Portland cement is manufactured by crushing, milling and proportioning the
following materials:

 Lime or calcium oxide (CaO): from limestone, chalk, shells, shale or

Calcareous materials
 Silica (SiO2): from sand, clays, shales, slates, and estuarine muds or
Argillaceous materials
 Industrial wastes (for Pozzalona Cements only) such as blast-
furnace slag, Fly Ash, Calcium Carbonate. (Kaolin, a white clay for
white portland cement only)
 Alumina (Al2O3): from bauxite, recycled aluminium, clay
 Iron (Fe2O3): from clay, iron ore, scrap iron
 Gypsum (CaSO4.2H20): found together with limestone

The materials, without the gypsum, are proportioned to produce a mixture

with the desired chemical composition and then ground and blended either
by dry process or wet process. The materials are then fed through a kiln at
1,450°C (2,640ºF) to produce grayish-black pellets known as clinker. The
alumina and iron act as fluxing agents which lower the melting point of
silica from 1,650 to 1,450°C (3,000 to 2600ºF). After this stage, the clinker
is cooled, pulverized and gypsum added to regulate setting time. It is then
ground extremely fine to produce cement.

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Composition of Raw Materials

The percentage compositions of some of the typical raw materials used for
the manufacture of portland cement are shown in the table.
Raw materials used in the manufacture of portland cement
(percentage composition)
loss on
raw material CaO SiO2 Al2O3 Fe2O3 MgO
ignition
limestone 52 3 1 0.5 0.5 42
chalk 54 1 0.5 0.2 0.3 43
cement rock 43 11 3 1 2 36
clay 1 57 16 7 1 14
slag 42 34 15 1 4 0

Cement rock contain both the calcareous and argillaceous components in

proportions that sometimes approximate cement compositions, thus the
name.
The magnesia (magnesium oxide, MgO) content of raw materials must be
low because the permissible limit in portland cement is 4 to 5 percent.
Other impurities in raw materials that must be strictly limited are fluorine
compounds, phosphates, metal oxides and sulphides, and excessive
alkalies.
Another essential raw material is gypsum, some 5% of which is added to the
burned cement clinker during grinding to control the setting time of the
cement.

Chemical shorthand

Because of the complex chemical nature of cement, a shorthand form is

used to denote the chemical compounds. The shorthand for the basic
compounds is:

Compound Formula Shorthand form

Calcium oxide (lime) Ca0 C
Silicon dioxide (silica) SiO2 S
Aluminium oxide (alumina) Al2O3 A
Iron oxide Fe2O3 F
Water H2O H
Sulphate SO3 S

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Chemical composition of clinker
The cement clinker formed has the following typical composition:

Compound Formula Shorthand % by

Source: Mindess & Young form weight#
Tri-calcium aluminate Ca3Al2O6 C3A 10
Tetra-calcium aluminoferrite Ca4Al2Fe2O10 C4AF 8
Belite or di-calcium silicate Ca2SiO5 C2S 20
Alite or tri-calcium silicate Ca3SiO4 C3S 55
Sodium oxide Na2O N Up to 2
Potassium oxide K2O K
Gypsum CaSO4.2H2O CSH2 5
# Representative weights only. Actual weight varies with type of cement.

Properties of cement compounds

These compounds contribute to the properties of cement in different ways:

1. Tri-calcium aluminate, C3A:-

It liberates a lot of heat during the early stages of hydration, but has
little strength contribution. Gypsum slows down the hydration rate of
C3A. Cement low in C3A is sulphate resistant.
2. Tri-calcium silicate, C3S:-
This compound hydrates and hardens rapidly. It is largely responsible
for portland cement’s initial set and early strength gain.
3. Di-calcium silicate, C2S:
C2S hydrates and hardens slowly. It is largely responsible for strength
gain after one week.
4. Tetra-calcium aluminoferrite, C4AF:
This is a fluxing agent which reduces the melting temperature of the raw
materials in the kiln from 1,650 to 1,450°C (from 3,000 o F to 2,600o F). It
hydrates rapidly, but does not contribute much to strength of the
cement paste.

By mixing these compounds appropriately, manufacturers can produce

different types of cement to suit several construction environments.

Considering the peculiar characteristics of cement – a chemical, chemical

reaction not fully understood, composition of raw materials, very high
sintering temperature, fine grinding – it is always recommended to use only
branded cements, durability of those are time tested.

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ENVIRONMENTAL IMPACTS
Cement manufacture causes environmental impacts at all stages of the
process. These include emissions of airborne pollution in the form of dust,
gases, noise and vibration when operating machinery and during blasting
in quarries, and damage to countryside from quarrying. Equipment to
reduce dust emissions during quarrying and manufacture of cement is
widely used, and equipment to trap and separate exhaust gases are coming
into increased use. Environmental protection also includes the re-
integration of quarries into the countryside after they have been closed
down by returning them to nature or re-cultivating them.
CO2 emissions
Carbon concentration in cement spans from ≈5% in cement structures to
≈8% in the case of cement roads. Cement manufacturing releases CO2 in the
atmosphere both directly when calcium carbonate is heated,
producing lime and carbon dioxide, and also indirectly through the use of
energy if its production involves the emission of CO2. The cement industry
produces about 10% of global man-made CO2 emissions, of which 60% is
from the chemical process, and 40% from burning fuel.
Nearly 900 kg of CO2 are emitted for every 1000 kg of OPC produced. In the
European Union the specific energy consumption for the production of
cement clinker has been reduced by approximately 30% since the 1970s.
This reduction in primary energy requirements is equivalent to
approximately 11 million tonnes of coal per year with corresponding benefits
in reduction of CO2 emissions. This accounts for approximately 5% of
anthropogenic CO2.
The majority of carbon dioxide emissions in the manufacture of OPC
(approximately 60%) are produced from the chemical decomposition of
limestone to lime, an ingredient in Portland cement clinker. These emissions
may be reduced by lowering the clinker content of cement.
To reduce the transport of heavier raw materials and to minimize the
associated costs, it is more economical for cement plants to be closer to the
limestone quarries rather than to the consumer centers.
Newly developed cement types from Novacem and Eco-cement can
absorb carbon dioxide from ambient air during hardening. Use of the Kalina
cycle during production can also increase energy efficiency.
Heavy metal emissions in the air
In some circumstances, mainly depending on the origin and the composition
of the raw materials used, the high-temperature calcination process of
limestone and clay minerals can release in the atmosphere gases and dust
rich in volatile heavy metals, a.o, thallium, cadmium and mercury are the
most toxic. Heavy metals (Tl, Cd, Hg, ...) and also selenium are often found
as trace elements in common metal sulphides (pyrite (FeS2), zinc blende
(ZnS), galena (PbS), ...) present as secondary minerals in most of the raw
materials. Environmental regulations exist to limit these emissions.

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Heavy metals present in the clinker
The presence of heavy metals in the clinker arises both from the natural raw
materials and from the use of recycled by-products or alternative fuels. The
high pH prevailing in the cement porewater (12.5 < pH < 13.5) limits the
mobility of many heavy metals by decreasing their solubility and increasing
their sorption onto the cement mineral phases. Nickel, zinc and lead are
commonly found in cement in negligibly small
concentrations. Chromium may also directly arise as natural impurity from
the raw materials or as secondary contamination from the abrasion of hard
chromium steel alloys used in the ball mills when the clinker is ground.
As chromate (CrO42−) is toxic and may cause severe skin allergies at trace
concentration, it is sometimes reduced into trivalent Cr (III) by addition
of ferrous sulphate (FeSO4).
Use of alternative fuels and by-products materials
A cement plant consumes 3 to 6 GJ of fuel per tonne of clinker produced,
depending on the raw materials and the process used. Most cement kilns
today use coal and petroleum coke as primary fuels, and to a lesser extent
natural gas and fuel oil. Selected waste and by-products with recoverable
calorific value can be used as fuels in a cement kiln, replacing a portion of
conventional fossil fuels, like coal, if they meet strict specifications. Selected
waste and by-products containing useful minerals such as calcium, silica,
alumina, and iron can be used as raw materials in the kiln, replacing raw
materials such as clay, shale, and limestone. Because some materials have
both useful mineral content and recoverable calorific value, the distinction
between alternative fuels and raw materials is not always clear. For
example, sewage sludge has a low but significant calorific value, and burns
to give ash containing minerals useful in the clinker matrix.
Normal operation of cement kilns provides combustion conditions which are
more than adequate for the destruction of even the most difficult to destroy
organic substances. This is primarily due to the very high temperatures of
the kiln gases (2000 °C in the combustion gas from the main burners and
1100 °C in the gas from the burners in the pre-calciner). The gas residence
time at high temperature in the rotary kiln is of the order of 5–10 seconds
and in the pre-calciner more than 3 seconds.

The Air Pollution caused by cement plants near Srinagar in Khonmoh-Shar

belt may cause the extinction of Saffron from just at outskirts of Srinangar
and Dist. Pulwama

Green cement
Green cement is a cementitious material that meets or exceeds the
functional performance capabilities of ordinary Portland cement by
incorporating and optimizing recycled materials, thereby reducing
consumption of natural raw materials, water, and energy, resulting in a
more sustainable construction material.

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New manufacturing processes for producing green cement are being
researched with the goal to reduce, or even eliminate, the production and
release of damaging pollutants and greenhouse gasses, particularly CO 2.
Growing environmental concerns and increasing cost of fuels of fossil origin
have resulted in many countries in sharp reduction of the resources needed
to produce cement and effluents (dust and exhaust gases).
Peter Trimble, a design student at the University of Edinburgh (UK) has
proposed 'DUPE' based on Sporosarcina pasteurii, a bacterium with binding
qualities which, when mixed with sand and urea through the process
of microbiologically induced calcite precipitation or biological cementation
may produce a product with binding properties about 70% as strong as
conventional cement.

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