Cement – An Insight View

Doc. No: QMD/2018-11-2/23

No. of Pages: 12 of A4 Size
DOI: Nov 2018

{The Input data is based upon IS: 269 - 2015, IS: 1489_1&2 - 2015, and 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 fully 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.

CEMENT MANUFACTURING
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 FORM FOR CEMENT

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 as per
Mindess & Young :

Compound Formula Shorthand % by

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 3,000o 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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CEMENT – AS PER INDIAN STANDARDS:
Chemical characteristics of various types of cement as per IS: 269-2015 and
IS:1489 Part 1- 2015 & IS: 1489 Part 2- 2015 are as under:
Sr Type of Lime Alumina Insoluble Magnesia Sulphuric Loss
cement saturation Iron ratio residue (%) anhydride on
factor (%) Min (%) Max Max (%) Max ignition
(%) (%)
Max

1 OPC - 33 0.66Min 0.66 5.0 6.0 3.5 5.0

1.02Max
2 OPC - 43 0.66 Min 0.66 5.0 6.0 3.5 5.0
1.02Max
3 OPC -43S 0.8 Min 0.66 2.0 5.0 3.5 4.0
1.02Max
4 OPC- 53 0.8 Min 0.66 5.0 6.0 3.5 4.0
1.02Max
5 OPC -53S 0.8 Min 0.66 2.0 5.0 3.5 4.0
1.02Max
6 PPC- -- -- 6.0 3.5 5
X + 4 (100 - X ) /100
Fly Ash (or Min. is 06 X, where
7 PPC – -- -- X is %age of Flyash) 6.0 3.0 5
CCB

1. Chloride content in all the above said cement grades (including

PPC) in % Max is 0.1 when used for RCC Works and % Max is 0.05
for Pre-stressed Concrete.

2. Cement used for railway Sleepers shall additionally satisfy the

following requirements:
a. Tri-calcium aluminate content % by mass Max 10.0
b. Tri-calcium Silicate content % by mass Min 45.0

Physical properties of various types of cement as per IS: 269-2015 and

IS:1489 Part 1- 2015 & IS: 1489 Part 2- 2015 are as under:

Sr Type of Cement Fineness Soundness Setting Time Compressive Strength

M²/Kg MPa (Min)
(Min) Le-Chatelier Autoclave Initial Final 72±1Hr 168±2 672±4
Method mm Test Method
Min Min . Hr. Hr.
(Max) % (Max)
(Min) (Max)
1 OPC - 33 225 10 0.8 30 600 16 22 33
48 Max
2 OPC - 43 225 10 0.8 30 600 23 33 43
58 Max

3 OPC – 43S 370 5 0.8 60 600 23 37.5 43

4 OPC- 53 225 10 0.8 30 600 27 37 53
5 OPC – 53S 370 5 0.8 60 600 27 37.5 53
6 PPC- 300 10 0.8 30 600 16 22 33
Fly Ash
7 PPC – CCB 300 10 0.8 30 600 16 22 33
(CALCINED CLAY
BASED)

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Notwithstanding the compressive strength requirements specified above, the
cement shall show a progressive increase in strength from the strength at
72 hours.

As evident from above, the Fineness of OPC is at least 225M²/Kg and is

lower than of PPC having Minimum Fineness of 300M²/Kg. Hence OPC has
higher permeability and as a result it has lower durability. PPC having
higher fineness, hence has lower permeability and as a result it has high
durability and better workability.
Fineness of OPC: IS code provides for a minimum specific surface of
225M²/Kg. Most of the Indian cement manufacturers resort to producing
cement with increased fineness even higher than 300 presumably to
improve the compressive strength of cement. This is not desirable in hot
weather concreting. It is, therefore, necessary to lay down upper limit of
fineness while ordering cement or framing contract conditions for concrete
works. The upper limit should be around 280 M²/Kg.

CEMENT COMPOSITION
OPC generally composed of 95% clinker products and 5% gypsum. PPC
contains about 60 - 65% clinker products, upto 30 - 35% mineral additives
like Fly Ash, GGBS, Calcinated Clay and 5% gypsum and other additives.

TYPES OF CEMENT AS PER INDIAN MARKET

As per the availability of Cement in Indian market, Cement is of two types:
Trade Cement and Non-trade Cement.

Trade Cement: The manufacturer directly sells trade cement to the dealers
and retailers, who alternately sell to the end consumers. The dealers get
incentives to sell the product. In India, only PPC Cement is sold in trade,
and the credit goes to the efforts made by NTPC to use flyash, since 1997.
Non- Trade Cement: Under non-trade cement mechanism, the manufacturer
directly sells to the consumer - like a construction company for self-usages
in project. Here, the cement can not re-sold to any third party. Here, the
dealer is not involved. For the project requirements, the construction
companies generally order OPC Cement.
The cost of trade cement is higher compared to non-trade.

WHEN SHOULD CEMENT BE REJECTED:

IS does not specify anything analytically when the cement is to be rejected
except mentioning that:
Cement may be rejected, if it does not comply with any of the requirements
of the specifications. Further, the codes reads, Cement remaining in bulk
storage at the factory, prior to shipment, for more than six months, or
cement in bags in local storage for more than 3 months after completion of
tests, may be retested before use and may be rejected if it fails to conform to
any of the requirements in specification.

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But IRS has more rational criteria of rejection and is as under:

Sr. Property Deviation from the

requirements
1 Strength lower limit:
7 days -2.0 N/mm²
28 days -2.5N/mm²
2 Strength- Upper limit 28days Not specified

3 Setting time -15 minutes

4 Soundness +1mm

5 Sulphate Content +0.5%

6 Chloride Content +0.01%

OPC v/s PPC: HOW TO MAKE THE RIGHT CHOICE

The most confusing thing is how to make the correct choice: OPC v/s PPC.
There is no need to blindly follow the trend. Knowing their properties,
recommended uses, cost benefits, knowledge of very basic fundamental - the
ultimate strength of concrete depends on the Mix Design (and other factors
like method of placing, compaction, curing) and not on the cement strength
alone, etc. will give you a better idea about which cement should be used
and where it should be used.
Property OPC PPC
Strength Its initial strength is higher than Its Initial strength is lower than OPC.
PPC. Hence props cannot be removed early.

Setting Time Its setting time is less than PPC so it Its setting time is more than OPC It is
is recommended in projects where the best choice for mass concreting,
props are to be removed early plaster and masonry

Curing Period Its curing period is less than PPC. Its curing period is a little higher than
Hence curing cost reduces, hence OPC
recommended where curing cost are
prohibitive.

Durability It is less durable when compared to It has high durability, means the
PPC structure will last longer.

Chemical Its resistance to aggressive chemicals It is resistant to attack against various

Resistance is lower than PPC. chemicals.

Concrete It produces comparatively less It produces more cohesive concrete

Quality cohesive concrete than PPC; hence which can be easily pumped.
concrete pumping becomes a little
difficult.

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 Property OPC PPC
Environment It is known to emit CO2 which is It is a green material, hence eco-
Friendly harmful to the environment. friendly and helpful in achieving green
rating.
Cost It is (slightly) costlier than PPC It is (slightly) less costly as compared
to OPC
Use 1. It cannot be used for mass It can be used at any and every place.
concreting as it has high heat of It has high durability, means the
hydration as compared to PPC structure will last longer.
2. Higher grade like grade 53 is not It has higher fineness, hence has
recommended to be used for lower permeability and as a result it
plastering as it is known to develop has high durability. But it is difficult
shrinkage cracks due to its high to handle.
strength
3. Use of OPC is highly recommended It can be used in all type of
where fast pace of construction is construction work Example: RCC work
required. in residential and commercial work,
Plaster and masonry, where high
strength is not so important, Marine
Works, In mass concrete work, Road,
Runway.
4. It’s also not required to use it in It’s recommended for all non-
masonry as mortar strength in initial structural concreting like wall mortar.
period is not that critical.
Types The different grades of OPC cement No specific grades of this cement are
available in India are: available.
 OPC 33 Grade It is classified into different types
 OPC 43 Grade depending on the type of Pozzolanic
 OPC 53 Grade material used; The different pozzolanic
materials used are:
 Fly ash
 GGBS
 Clay & Shale
 Rice Husk ash
 Volcanic tuffs and Pumicites
Fly ash is the most commonly used
Pozzolanic material followed by
Calcinated Clay, GGBS.

The above said merits / de-merits of OPC and PPC are more prominent for
general building works and ordinary construction works where the grade of
concrete is usually limited to M-25. For producing concrete of M-30 and
higher grades, the use of OPC + Flyash is far more technically feasible than
using PPC. In fact, PPC is equivalent to OPC-33 and where higher strength
of concrete is required, the obvious choice will be OPC- 43 or OPC – 53.
OPC-43S and OPC-53S are invariably used for casting of Railway PSC
Sleepers.

Apart from above said facts, based upon experience it is recommended that
for concrete grade up to and including M-20, PPC may be more suitable
considering the general structural requirements. For M-25 concrete, the
various options like strength requirements, time of removal of forms, w/c
ratio, curing regime etc. should be weighted for use of OPC or PPC. For the
concrete of grade M-30 and higher, based upon the experience, it is
solemnly advised to use OPC – 43 or OPC – 53 with the addition of mineral
additives that may be of the order of 100Kg FA or 80Kg GGBS and / or 5Kg

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SF per cubic meter of concrete. This will improve the workability, increase
strength, ensure uniform texture and reduce the permeability thus, enhance
to concrete durability and hence the service life of structure.

It may please be noted that since 2015, there is only one code for OPC
including Railway Sleeper Grade Cement and that is IS: 269 -2015.
Now IS: 8112, IS: 10269 and RDSO’s IRS T-40 -1985 are obsolete. (RDSO’s
Code for Sleeper Grade Cement is obsolete by the directives of Ministry of Consumer Affairs, Govt. of
India in June 2000)

REMOVAL OF FORM WORK (STRIPPING TIME) : In normal circumstance

the forms, may generally be removed after the expiry of the following
periods, as per CPWD Sepcs:
Minimum period Before Striking
Form work for
Sr. Type of Form work
OPC 33 OPC 43 PPC
grade grade
a Vertical form work to columns, walls, beams 16-24 h 16-24 h 24-36 h
b Soffit form work to slabs (Props to be refixed 3d 3d 4d
immediately after removal of formwork)
c Soffit form work to beams (Props to be refixed 7d 7d 10d
immediately after removal of formwork
d Props to slabs:
1 Spanning upto 4.5m 7d 7d 10d
2 Spanning over 4.5m 14d 14d 20d
e Props to beams and arches:
1 Spanning upto 6m 14d 14d 20d
2 Spanning over 6m 21d 21d 30d

In case of concrete with OPC+ FA, the stripping time will be 10/7 of the
period stated for OPC - 43.

The above said stripping time is applicable from academic view point and
codal provisions but practically the stripping time depends upon many other
factors like quantity & type of cement used, heat of hydration of the cement
used, w/c ratio of mix, method of placing of concrete, method of concrete
compaction, temperature of concrete at time of placing, ambient
temperature, type of formworks used (un-insulated steel or insulated
wooden), shape of structure e.g., flat, round, circular, square edges,
chamfered edges and formwork system as CNC shutters can be stripped
early etc.

TESTS ON CEMENT AT CONSTRUCTION SITES

1. Colour Test of Cement

The colour of the cement should be uniform. It should be grey colour
with a light greenish shade.
2. Presence of Lumps
The cement should be free from any hard lumps. Such lumps are formed
by the absorption of moisture from the atmosphere. Any bag of cement
containing such lumps should be rejected.

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3. Cement Adulteration Test
The cement should feel smooth when touched or rubbed in between
fingers. If it is felt rough, it indicates adulteration with sand.
4. Temperature Test of Cement
If hand is inserted in a bag of cement or heap of cement, it should feel
cool and not warm.
5. Float Test
If a small quantity of cement is thrown in a bucket of water, the particles
should float for some time before it sinks.
6. Setting Test
A thick paste of cement with water is made on a piece of glass plate and
it is kept under water for 24 hours. It should set and not crack.
7. Strength of Cement Test
A block of cement 25 mm ×25 mm and 200 mm long is prepared and it is
immersed for 7 days in water. It is then placed on supports 15cm apart
and it is loaded with a weight of about 34 kg. The block should not show
signs of failure.
The briquettes of a lean mortar (1:6) are made. The size of briquette may
be about 75 mm ×25 mm ×12 mm. They are immersed in water for a
period of 3 days after drying. If cement is of sound quality such
briquettes will not be broken easily.
8. Date of Packing:
Strength of cement reduces with time, so it is important to check the
manufacturing date of the cement. Generally, the cement should be used
before 90 days from the date of manufacturing.

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.
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 CO2.
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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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 the cement plant near Srinagar (J&K) in
Khonmoh-Shar belt may cause the extinction of Saffron from just at
outskirts of Srinangar and Dist. Pulwama!!!

*** End of Doc. ***

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