CHAPTER ONE

1.0 Introduction

A cement is a binder, a chemical substance used for construction that sets, hardens, and adheres

to other materials to bind them together. Cement is seldom used on its own, but rather to bind

sand and gravel (aggregate) together. Cement mixed with fine aggregate produces mortar for

masonry, or with sand and gravel, produces concrete. Concrete is the most widely used material

in existence and is behind only water as the planet's most-consumed resource (Rodgers, 2018).

Cement, one of the most important building materials, is a binding agent that sets and hardens to

adhere to building units such as stones, bricks, tiles, etc. Cement generally refers to a very fine

powdery substance chiefly made up of limestone (calcium), sand or clay (silicon), bauxite

(aluminum), and iron ore, and may include shells, chalk, marl, shale, clay, blast furnace slag,

slate. The raw ingredients are processed in cement manufacturing plants and heated to form a

rock-hard substance, which is then ground into a fine powder to be sold (Rodgers, 2018). Cement

mixed with water causes a chemical reaction and forms a paste that sets and hardens to bind

individual structures of building materials. Cement is an integral part of the urban infrastructure.

It is used to make concrete as well as mortar, and to secure the infrastructure by binding the

building blocks. Concrete is made of cement, water, sand, and gravel mixed in definite

proportions, whereas mortar consists of cement, water, and lime aggregate. These are both used

to bind rocks, stones, bricks, and other building units, fill or seal any gaps, and make decorative

patterns. Cement mixed with water silicates and aluminates makes a water-repellant hardened

mass that is used for water-proofing.

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Cement materials can be classified into two distinct categories: hydraulic cements and non-

hydraulic cements according to their respective setting and hardening mechanisms. Hydraulic

cement setting and hardening involves hydration reactions and therefore requires water, while

non-hydraulic cements only react with a gas and can directly set under air (Brehm, 2009).

Non-hydraulic cement is produced through the following steps (lime cycle):

1. Calcination: Lime is produced from limestone at over 825°C for about 10 hours.

(CaCO3 → CaO + CO2)

2. Slaking: Calcium oxide is mixed with water to make slaked lime. (CaO + H2O →

Ca(OH)2)

3. Setting: Water is completely evaporated.

4. The cement is exposed to dry air and it hardens after time-consuming reactions.

(Ca(OH)2 + CO2 → CaCO3 + H2O)

On the other hand, hydraulic cement is mainly made up of silicates and oxides:

1. Belite (2CaO·SiO2);

2. Alite (3CaO·SiO2);

3. Tricalcium aluminate/ Celite (3CaO·Al2O3)

4. Brownmillerite (4CaO·Al2O3·Fe2O3)

1.1 History of Cement

Cement, though different from the refined product found nowadays, has been used in many

forms since the advent of human civilization. From volcanic ashes, crushed pottery, burnt

gypsum, and hydrated lime to the first hydraulic cement used by the Romans in the middle-ages,

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the development of cement continued to the 18th century, when James Parker patented Roman

cement, which gained popularity but was replaced by Portland cement in the 1850s (Hill, 2013).

In the 19th century, Frenchman Louis Vicat laid the foundation for the chemical composition of

Portland cement and in Russia, Egor Cheliev published the methods of making cement, uses of

cement, and advantages. Joseph Aspdin brought Portland cement to the market in England and

his son, William Aspdin, developed the “modern” Portland cement, which was soon in quite high

demand. But the real father of Portland cement is considered to be Isaac Charles Johnson, who

contributed immensely by publishing the process of developing meso-Portland cement in the kiln

(Blezard, 1998).

In the 19th century, Rosendale cement was discovered in New York. Though its rigidity made it

quite popular at first, the market demand soon declined because of its long curing time and

Portland cement was again the favorite. However, a new blend of Rosendale-Portland cement,

which is both highly durable and needs less curing time, was synthesized by Catskill Aqueduct

and is now often used for highway or bridge construction (Sparavigna, 2011).

Cement, chemically speaking, is a product that includes lime as the primary binding ingredient,

but is far from the first material used for cementation. The Babylonians and Assyrians used

bitumen to bind together burnt brick or alabaster slabs. In Ancient Egypt, stone blocks were

cemented together with a mortar made of sand and roughly burnt gypsum (CaSO4 · 2H2O),

which is Plaster of Paris, which often contained calcium carbonate (CaCO3), (Blezard, 1998).

The cement used today has undergone experimentation, testing and significant improvements to

meet the needs of the present world, such as developing strong concretes for roads and highways,

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hydraulic mortars that endure sea water, and stucco for wet climates. Different kinds of modern

cement, most of them known as Portland cement or blends, including blast furnace cement,

Portland fly-ash cement, Portland pozzolan cement, pozzolan-lime cement, slag-lime cement,

etc.

1.2 Modern cements

The top three cement producers in the world as recorded in 2010 are the USA, China, and India.

Among these countries, China alone manufactures about 45% of the total worldwide production

of cement. Global consumption of cement continues to rise since it is a non-recyclable product

and so every new construction or repair needs new cement. Especially in the economies of Asia

and Eastern Europe, cement production is an important element of progress (Rodgers, 2018).

According to the global cement directory, there are about 2273 active cement production plants

in the world. Some of the leading cement manufacturers are Lafarge Holcim, Anhui Conch,

China National Building Materials, Heidelberg Cement, Cemex, Italcementi, China Resources

Cement, Taiwan Cement, Eurocement, and Votorantim. The total global consumption of cement,

as indicated by statistics in 2015, measures up to 18 million metric tons, most of which is

attributed to the rising national economy of North America.Among the developed capitalist

countries, the leading producers of cement are the USA, France, Italy, and Germany. Iran, now

the top producer in the Middle East, occupies the third position in the world for cement

manufacture. Asian and African countries are also progressive in the production of cement.

Modern cements are often Portland cement or Portland cement blends, but other cement blends

are used in some industrial settings. Portland cement, a form of hydraulic cement, is by far the

most common type of cement in general use around the world. This cement is made by heating

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limestone (calcium carbonate) with other materials (such as clay) to 1,450 °C (2,640 °F) in a

kiln, in a process known as calcination that liberates a molecule of carbon dioxide from the

calcium carbonate to form calcium oxide, or quicklime, which then chemically combines with

the other materials in the mix to form calcium silicates and other cementitious compounds

(Rodgers, 2018). The resulting hard substance, called 'clinker', is then ground with a small

amount of gypsum (CaSO4·2H2O) into a powder to make ordinary Portland cement, the most

commonly used type of cement (often referred to as OPC). Portland cement is a basic ingredient

of concrete, mortar, and most non-specialty grout. The most common use for Portland cement is

to make concrete. Portland cement may be grey or white.

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 CHAPTER TWO

Literature Review

2.1 Portland Cement

Portland cement is the most common type of cement in general use around the world as a basic

ingredient of concrete, mortar, stucco, and non-specialty grout. It was developed from other

types of hydraulic lime in England in the early 19th century by Joseph Aspdin, and is usually

made from limestone. It is a fine powder, produced by heating limestone and clay minerals in a

kiln to form clinker, grinding the clinker, and adding 2 to 3 percent of gypsum. Several types of

Portland cement are available. The most common, called ordinary Portland cement (OPC), is

grey, but white Portland cement is also available. Its name is derived from its resemblance to

Portland stone which is quarried on the Isle of Portland in Dorset, England. It was named by

Joseph Aspdin who obtained a patent for it in 1824. His son William Aspdin is regarded as the

inventor of "modern" Portland cement due to his developments in the 1840s (Courland, 2002).

Portland cement was developed from natural cements made in Britain beginning in the middle of

the 18th century. Its name is derived from its similarity to Portland stone, a type of building

stone quarried on the Isle of Portland in Dorset, England (Gillberg et al., 1999).

The development of modern portland cement (sometimes called ordinary or normal portland

cement) began in 1756, when John Smeaton experimented with combinations of different

limestones and additives, including trass and pozzolanas, intended for the construction of a

lighthouse, now known as Smeaton's Tower. ( Blezard, 1998). In the late 18th century, Roman

cement was developed and patented in 1796 by James Parker (Saikia et al., 2010). Roman

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cement quickly became popular, but was largely replaced by portland cement in the 1850s. In

1811, James Frost produced a cement he called British cement (Saikia et al., 2010). James Frost

is reported to have erected a manufactory for making of an artificial cement in 1826. In 1811

Edgar Dobbs of Southwark patented a cement of the kind invented 7 years later by the French

engineer Louis Vicat. Vicat's cement is an artificial hydraulic lime, and is considered the

"principal forerunner" of Portland cement.

The most commonly used cement nowadays is hydraulic cement (i.e. hardens when water is

added) known as Portland cement or Portland cement blends. These are usually the basic

ingredient in making concrete, which is a construction material used as a load-bearing element.

Portland cement is suitable for wet climates and can be used underwater. Different types or

blends of Portland cement include Portland blast furnace slag cement, Portland fly-ash cement,

Portland pozzolan cement, Portland-silica fume cement, masonry cement, expansive cement,

white blended cement, colored cement, and very finely ground cement (Saikia et al., 2010). In a

cement production plant, limestone and other raw materials such as silicate, bauxite, iron ore,

etc. are heated so that molecules of carbon dioxide are liberated from the limestone to form

quicklime, which combines with the other ingredients, resulting in the formation of calcium

silicates and other products. Thus clinker, a rock-hard substance, is made. Gypsum is added to

the clinker and then ground into a fine powder, which is the final product known as Portland

cement.

2.2 Composition

hydraulic cement (cement that not only hardens by reacting with water but also forms a water-

resistant product) produced by pulverizing clinkers which consist essentially of hydraulic

calcium silicates, usually containing one or more of the forms of calcium sulfate as an inter

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ground addition (Ugama et al., 2014). Portland cement clinker is a hydraulic material which shall

consist of at least two-thirds by mass of calcium silicates, (3 CaO·SiO2, and 2 CaO·SiO2), the

remainder consisting of aluminium- and iron-containing clinker phases and other compounds.

The ratio of CaO to SiO2 shall not be less than 2.0. The magnesium oxide content (MgO) shall

not exceed 5.0% by mass. Clinkers make up more than 85% Portland cement clinker (37-72% of

3CaO.SiO2; 6-47% 2CaO.SiO2; 2-20% 2CaO.Al2O3; 2-19% 4CaO. Al2O3.Fe2O3), 1.5-3.5%

gypsum by SO3 content, up to 15% admixtures (Kamel, et al., 2020).

2.3 Types of Portland Cement

2.3.1 Type I- General Use Cement

Portland cement type 1 or general purpose is the most used of all cements and is suitable for all

uses where special properties of other types are not required, with an average rate of heat

evolution and strength development (Ugama et al., 2014). The typical compound compositions of

this type are: 55% (C3S), 19% (C2S), 10% (C3A), 7% (C4AF), 2.8% MgO, 2.9% (SO3),

1.0% ignition loss, and 1.0% free CaO (utilizing cement chemist notation). It is used where

cement or concrete are not subject to specific exposures, such as sulfate attack from soil or water,

or an objectionable temperature increase due to the heat generated by hydration. Its uses include

sidewalks and pavements, reinforced concrete buildings, bridges, railway structures, tanks,

deposits, sewers, water pipes and masonry units (Baba et al., 2023).

2.3.2 Type II – Resistant To Moderate Sulfate Action

Portland cement is used when it is important to take precautions against moderate sulfate attack,

such as in drainage structures where sulfate concentrations in groundwater are higher than

normal but not unusually severe. Its typical compound composition is: 51% (C 3S), 24% (C2S),

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6% (C3A), 11% (C4AF), 2.9% MgO, 2.5% (SO3), 0.8% ignition loss, and 1.0% free CaO. Type

II cement will generally generate less heat at a slower rate than Type I. With this moderate heat

of hydration (an optional requirement), Type II cement can be used in large-mass structures, such

as large piers, heavy pillars and retaining wall. Its use will reduce the temperature rise, especially

important when the concrete is placed in a warm climate. A limitation on the composition is that

the (C3A) shall not exceed 8%, which reduces its vulnerability to sulfates (Baba et al., 2023).

This type is for general construction exposed to moderate sulfate attack, and is meant for use

when concrete is in contact with soils and ground water, especially in the western United States

due to the high sulfur content of the soils. Because of similar price to that of type I, type II is

much used as a general purpose cement, and the majority of portland cement sold in North

America meets this specification.

2.3.3 Type III – High Early Strength

The fast-hardening Portland cement is similar in chemical composition to ordinary cement, but

physically differs in the finest grinding during manufacturing. Type III has relatively high early

strength. Its typical compound composition is: 57% (C 3S), 19% (C2S), 10% (C3A), 7% (C4AF),

3.0% MgO, 3.1% (SO3), 0.9% ignition loss, and 1.3% free CaO. This cement is similar to type

I, but ground finer. Some manufacturers make a separate clinker with higher C 3S and/or C3A

content, but this is increasingly rare, and the general purpose clinker is usually used, ground to

a specific surface area typically 50–80% higher. The gypsum level may also be increased a small

amount. This gives the concrete using this type of cement a three-day compressive strength equal

to the seven-day compressive strength of types I and II. (Glavinich, 2008).

Although it is not “fast setting” and concretes made with it remain viable for similar periods of

time, the greater specific surface area provided by the finer particle size increases the rate of

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early hydration, which provides higher early resistances that are important in concrete work

where the economy requires the early removal of formwork or the rapid change of precast

concrete units in a mold. In cold weather, its use allows a reduction in the controlled curing

period. Although richer mixtures of Type I cement can be used to obtain high early strength,

Portland Type III cement, high-early-strength, can provide it more satisfactorily

and economically.

2.3.4 Type IV – Low Heat Of Hydration

Type IV is a low heat hydration cement for use where the speed and amount of heat generated

must be minimized. It develops strength at a slower rate than type I cement. Its typical

compound composition is: 28% (C3S), 49% (C2S), 4% (C3A), 12% (C4AF), 1.8% MgO, 1.9%

(SO3), 0.9% ignition loss, and 0.8% free CaO. The percentages of (C 2S) and (C4AF) are

relatively high and (C3S) and (C3A) are relatively low (Baba et al., 2023). A limitation on this

type is that the maximum percentage of (C3A) is seven, and the maximum percentage of (C3S) is

thirty-five. This causes the heat given off by the hydration reaction to develop at a slower rate.

Consequently, the strength of the concrete develops slowly. After one or two years the strength is

higher than the other types after full curing.

Portland cement type IV is designed for use in massive concrete, structures such as large gravity

dams, where the temperature rise resulting from the heat generated during curing represents a

critical factor. This type of cement is generally not stocked by manufacturers, but some might

consider a large special order.

2.3.5 Type V – High Resistance to Sulfate

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Type V is a sulfate-resistant cement that is used only in concrete exposed to a severe sulfate

action, mainly where soils or groundwater have a high sulfate content. Its typical compound

composition is: 38% (C3S), 43% (C2S), 4% (C3A), 9% (C4AF), 1.9% MgO, 1.8% (SO3), 0.9%

ignition loss, and 0.8% free CaO. This cement has a very low (C 3A) composition which accounts

for its high sulfate resistance (Glavinich, 2008). A low content of tricalcium aluminate (C 3A),

generally 5 % or less, is required when high sulfate resistance is required. Another limitation is

that the (C4AF) + 2(C3A) composition cannot exceed 20%. This type is used in concrete to be

exposed to alkali soil and ground water sulfates which react with (C3A) causing disruptive

expansion. It is unavailable in many places, although its use is common in the western United

States and Canada. As with type IV, type V portland cement has mainly been supplanted by the

use of ordinary cement with added ground granulated blast furnace slag or tertiary blended

cements containing slag and fly ash.

2.3.6 White Portland Cement

White Portland cement is widely used for visual effects in white or colored concrete that should

be left exposed, and also in white or colored mortars for masonry and rendering. It has the same

properties as type I, but it is manufactured from special raw materials that are substantially free

of color-forming compounds, such as iron oxides, which give other cements their characteristic

gray or gray-brown color. Obtaining this colour requires high purity raw materials (low

Fe2O3 content), and some modification to the method of manufacture, among others a higher kiln

temperature required to sinter the clinker in the absence of ferric oxides acting as a flux in

normal clinker. As Fe2O3 contributes to decrease the melting point of the clinker (normally

1450 °C), the white cement requires a higher sintering temperature (around 1600 °C). Because of

this, it is somewhat more expensive than the grey product (Glavinich, 2008). The main

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requirement is to have a low iron content which should be less than 0.5 wt.% expressed as

Fe2O3 for white cement, and less than 0.9 wt.% for off-white cement. It also helps to have the

iron oxide as ferrous oxide (FeO) which is obtained via slightly reducing conditions in the kiln,

i.e., operating with zero excess oxygen at the kiln exit.

2.4 Chemistry of Portland cement

Cement materials can be classified into two distinct categories: hydraulic cements and non-

hydraulic cements according to their respective setting and hardening mechanisms. Hydraulic

cement setting and hardening involves hydration reactions and therefore requires water, while

non-hydraulic cements only react with a gas and can directly set under air.

2.4.1 Hydraulic cement

By far the most common type of cement is hydraulic cement, which hardens by hydration of the

clinker minerals when water is added. Hydraulic cements (such as Portland cement) are made of

a mixture of silicates and oxides, the four main mineral phases of the clinker, abbreviated in the

cement chemist notation, being:

C3S: alite (3CaO·SiO2);

C2S: belite (2CaO·SiO2);

C3A: tricalcium aluminate (3CaO·Al2O3) (historically, and still occasionally, called celite);

C4AF: brownmillerite (4CaO·Al2O3·Fe2O3).

The silicates are responsible for the cement's mechanical properties — the tricalcium aluminate

and brownmillerite are essential for the formation of the liquid phase during the sintering (firing)

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process of clinker at high temperature in the kiln. The chemistry of these reactions is not

completely clear and is still the object of research (Brehm, 2009).

First, the limestone (calcium carbonate) is burned to remove its carbon, producing lime (calcium

oxide) in what is known as a calcination reaction. This single chemical reaction is a major

emitter of global carbon dioxide emissions (McCarthy, 2013).

The lime reacts with silicon dioxide to produce dicalcium silicate and tricalcium silicate.

The lime also reacts with aluminium oxide to form tricalcium aluminate.

In the last step, calcium oxide, aluminium oxide, and ferric oxide react together to form

brownmillerite.

2.4.2 Non-hydraulic cement

Calcium oxide obtained by thermal decomposition of calcium carbonate at high temperature

(above 825 °C). A less common form of cement is non-hydraulic cement, such as slaked lime

(calcium oxide mixed with water), which hardens by carbonation in contact with carbon dioxide,

which is present in the air (~ 412 vol. ppm ≃ 0.04 vol. %). First calcium oxide (lime) is produced

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from calcium carbonate (limestone or chalk) by calcination at temperatures above 825 °C (1,517

°F) for about 10 hours at atmospheric pressure:

The calcium oxide is then spent (slaked) by mixing it with water to make slaked lime (calcium

hydroxide):

Once the excess water is completely evaporated (this process is technically called setting), the

carbonation starts:

This reaction is slow, because the partial pressure of carbon dioxide in the air is low

(~ 0.4 millibar). The carbonation reaction requires that the dry cement be exposed to air, so the

slaked lime is a non-hydraulic cement and cannot be used under water (Brehm, 2009).

This process is called the lime cycle.

2.5 Properties of cement

Setting and hardening, compressive strength, soundness, fineness, water-cement ratio, heat of

hydration etc. are some of the main properties of the cement (Taylor, 1997).

 Setting: Stiffening of the cement paste after addition of water is called setting. It depends

on a number of factors such as : (i) percentage of the clinker present, mainly C3A, (ii)

percent of gypsum ground with the clinker, (iii) particle size of solids, (iv) ratio of water-

to-cement, (v) temperature, (vi) presence of alkalis. Hardening starts soon after initial

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 stiffening and is mainly due to the hydration of the silicate phases, where crystalline

Ca(OH)2 and calcium silicate hydrates (C-S-H) are formed.

 Compressive strength: Portland cement is a product which gives good compressive

strength both at the early and late stages. Hydration of C 3S is responsible for early While

C2S hydration at later strengths (Taylor, 1997).

 Soundness : Cement is considered sound if it does not expand on hydration. Free lime

(CaOr) and free magnesia (MgOr) are responsible for soundness in cement. The

manufacturers have to control the burning process such that minimum quantity of CaOr

or MgOr is formed in the clinker.

 Fineness: The specific surface per unit area is important for a powdery material like

cement. Usually rate of reaction is proportional to the surface area and hence finer the

cement better the quality.

 Water-cement ratio: The amount of water required to form a paste of standard

consistency is known as the water cement ratio (w/c) which is generally 0.5. Lower the

ratio required, better the quality of the cement.

 Heat of hydration: The heat evolved during the hydration has an important role to play

especially when mass concreting is done as in the construction of dams. Higher heat of

hydration may lead to cracks in massive structures like dams.

In addition to the above mention properties, cements should not have more than 0.6% alkalis

(Na20 + K20) as it has been found that alkalis react with some reactive aggregates in the concrete

causing cracks due to expansion called the alkali - aggregate reaction. Similary, higher doses of

chloride (>0.05%) have been found to create corrosion in Reinforced Cement Concrete (RCC)

and resulting in failure of the concrete.

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2.6 Cement paste structure and concrete properties

When Portland cement is mixed with water, the chemical reactions which take place bring about

a change in structure of the plastic mass whereby it becomes rigid and hard, immediately after

the addition of water there is a short period of intense chemical reaction. Although immediately

after mixing the rate of hydration is very high, this initial period is so short that the products have

very little effect on the physical structure of the paste (Kurdowski, 2014). With continued

formation of a hydrate, the paste stiffens and attains rigidity, passing through the stages

arbitrarily defined as 'initial' and 'final' set. This reaction quickly subsides and is followed by a

period of one to three hours, depending on the temperature and characteristics of the cement,

during which the reaction rate is slow. At the end of the dormant period the reaction rate

increases rapidly to reach a maximum in about 6-8 hours. Thereafter the rate of reaction

decreases progressively, but provided the conditions are suitable, the hydration process will

continue for many years, although increasingly slowly (Potgieter et al., 1999). Many of the

properties of concrete depend on the proportions and nature of several compounds present in

cement. However, the methods of manufacture (e.g. wet or dry process) also have a considerable

influence on cement properties. Both the method of cooling of the clinker and fineness of

grinding are particularly important factors. Research has confirmed that cements of apparently

identical composition may show different characteristics (Taylor, 1997). The physical structure

of the products of hydration, viewed at a level of colloidal dimensions, exert the greater

influence on the hardened cement and concrete. The fresh paste consists of cement particles

fairly uniformly distributed throughout the water-filled space. Fresh cement paste is a plastic

network of particles of cement in water. The plastic viscosity ranges from 5000 to 500 CP as the

water/cement ratio increases from 0.4 to 0.7. The viscosity value can be greatly decreased by the

16
addition of organic water-reducing admixtures specially formulated for this purpose. The fresh

paste, even in the dormant period, is normally thixotropic or shear thinning, indicating that the

structure is being continuously broken down and reformed during mixing. It is evident that the

average distance between cement particles depends on the fineness of the cement and the water/

cement ratio

2.6.1 Hydration and setting process

In cement chemistry one has to differentiate between setting and hydration (Singha et al., 2003).

Hydration refers to the chemical reaction between cement and water while setting concerns the

early formation of the three-dimensional network and the first increase of the concrete strength.

In fact, hydration is not setting, indeed both may be independently observed. For example, the

chemical transformation of anhydrous binder into hydrates occurs as soon as it is mixed with

water. However, if excess water is added to the cement, making it a suspension which is

dispersed by stirring in order to prevent contracts between particles, the setting does not occur.

Thus, the hydrate formation is not a sufficient condition of setting. The setting can occur only

when water or cement ratio is low enough to form a paste of standard consistency, and the

hydrates formed have compact structures. The mechanism of hardening of cement is a very

complex process. Historically Le Chatelier considered that cement hydration occurred by the

dissolution of anhydrous phases followed by the crystallization of the hydrates in the

interlocking mass. Michaelis on the other hand thought that the solidification of a paste occurred

17
by the formation of a colloidal material which hardened as it lost water. This lost water further

hydrated the anhydrom cement.

When water is added to portland cement, exothermic complex reactions occur. As a result of this

cement sets and hardens. The development of strength of a cement paste is associated with the

precipitation of hydration products of very low solubility to form a cohesive matrix binding the

residual cement grains into a composite solid. The main source of strength is derived from the

hydration of two principal silicate phases, i.e. alite and belite. The aluminate phase (both C3A

and C4AF) because of rapid hydration, influences the setting but do not contribute significantly

to the final strength of the paste (Brunauer and Greenberg, 1962).

The chemistry of cement hydration is a very complex phenomenon. This is mainly due to a large

number of variables like crystalline structure of reactive phases, fineness, thermal history,

temperature, water-cement ratio etc. (Singha et al., 2003). It is therefore difficult to study the

hydration mechanism as a whole but study of the hydration of individual phases can give some

information of the overall hydration and it has been discussed briefly by Potgieter and Kaspar.

Tricalcium silicate, C3S (alite) and dicalcium silicate, β-C 2S (the dominant form of belite),

reacting independently with water yield the same products, namely, calcium hydroxide and

calcium silicate hydrates (Ca3Si2O5 normally written as C-S-H gels) (Taylor, 1964). Although

both the silicates hydrate in a similar way, the hydration of C 3S is exothermic and much faster

than that of C2S. The following equations may be used to describe the hydration reaction

2 C3S + 6 H20 ~ C-S-H + 3 CH (tobermorite)

2 C2S + 4 H20 ~ C-S-H + CH

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The above equations are over simplified. C3S produces three times as much Ca(OH) 2 as C2S.

Calcium silicate hydrates (C-S-H) comprise a range of phases of differing composition and Ca:

Si ratio depending on factors such as time, temperature and water-cement ratio (Kurdowski,

2014).

2.7 Manufacturing

Portland cement is a fine powder, gray or white in color that consists of a mixture of

Hydraulic cement materials comprising primarily calcium silicates, aluminates and

aluminoferrites. More than 30 raw materials are known to be used in the manufacture of portland

cement, and these materials can be divided into four distinct categories: calcareous, siliceous,

argillaceous, and ferrifrous. These materials are chemically combined through pyroprocessing

and subjected to subsequent mechanical processing operations to form gray and white portland

cement. Gray Portland cement is used for structural applications and is the more common type of

cement produced. White portland cement has lower iron and manganese contents than gray

portland cement and is used primarily for decorative purposes. Portland cement manufacturing

plants are part of hydraulic cement manufacturing, which also includes natural, masonry, and

pozzolanic cement. The materials in cement clinker are alite, belite, tricalcium aluminate, and

tetracalcium alumino ferrite. The aluminium, iron, and magnesium oxides are present as a flux

allowing the calcium silicates to form at a lower temperature, and contribute little to the strength.

For special cements, such as low heat (LH) and sulfate resistant (SR) types, it is necessary to

limit the amount of tricalcium aluminate (3 CaO·Al2O3) formed. (Trendacosta, 2014).

Portland cement accounts for 95 percent of the hydraulic cement production in the United States.

The balance of domestic cement production is primarily masonry cement. Both of these materials

19
are produced in portland cement manufacturing plants. (Davis and Buonicore, 2000). A diagram

of the process, which encompasses production of both portland and masonry cement, is shown in

Figure 2.1. As shown in the figure, the process can be divided into the following primary

components: raw materials acquisition and handling, kiln feed preparation, pyroprocessing, and

finished cement grinding.

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Figure 2.1 : Process Flow Diagram for Portland Cement Manufacturing.

21
The initial production step in portland cement manufacturing is raw materials acquisition.

Calcium, the element of highest concentration in portland cement, is obtained from a variety of

calcareous raw materials, including limestone, chalk, marl, sea shells, aragonite, and an impure

limestone known as "natural cement rock". Typically, these raw materials are obtained from

open-face quarries, but underground mines or dredging operations are also used. Raw materials

vary from facility to facility. Some quarries produce relatively pure limestone that requires the

use of additional raw materials to provide the correct chemical blend in the raw mix. In other

quarries, all or part of the noncalcarious constituents are found naturally in the limestone.

Occasionally, pockets of pyrite, which can significantly increase emissions of sulfur dioxide

(SO2), are found in deposits of limestone, clays, and shales used as raw materials for portland

cement (Davis and Buonicore, 2000).

These materials are obtained from ores and minerals such as sand, shale, clay, and iron ore.

Again, these materials are most commonly from open-pit quarries or mines, but they may be

dredged or excavated from underwater deposits (Portland Cement Association, 1994). The

portland cement manufacturing industry is relying increasingly on replacing virgin materials

with waste materials or byproducts from other manufacturing operations, to the extent that such

replacement can be implemented without adversely affecting plant operations, product quality or

the environment. Materials that have been used include fly ash, mill scale, and metal smelting

slags.

The second step in portland cement manufacture is preparing the raw mix, or kiln feed, for the

pyroprocessing operation. Raw material preparation includes a variety of blending and sizing

operations that are designed to provide a feed with appropriate chemical and physical properties.

22
Cement raw materials are received with an initial moisture content varying from 1 to more than

50 percent. If the facility uses dry process kilns, this moisture is usually reduced to less than 1

percent before or during grinding.

Materials transport associated with dry raw milling systems can be accomplished by a variety of

mechanisms, including screw conveyors, belt conveyors, drag conveyors, bucket elevators, air

slide conveyors, and pneumatic conveying systems. In the wet process, water is added to the raw

mill during the grinding of the raw materials in ball or tube mills, thereby producing a pumpable

slurry, or slip, of approximately 65 percent solids.

The slurry is agitated, blended, and stored in various kinds and sizes of cylindrical tanks or slurry

basins until it is fed to the pyroprocessing system.

The heart of the portland cement manufacturing process is the pyroprocessing system. This

system transforms the raw mix into clinkers, which are gray, glass-hard, spherically shaped

nodules that range from 0.32 to 5.1 centimeters (cm) (0.125 to 2.0 inches [in.]) in diameter.

The final step in portland cement manufacturing involves a sequence of blending and grinding

operations that transforms clinker to finished portland cement. Up to 5 percent gypsum or natural

anhydrite is added to the clinker during grinding to control the cement setting time, and other

specialty chemicals are added as needed to impart specific product properties. This finish milling

is accomplished almost exclusively in ball or tube mills.

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2.7.1 Emissions And Controls

Particulate matter (PM and PM-10), nitrogen oxides (NOx), sulfur dioxide (SO2), carbon

monoxide (CO), and CO2 are the primary emissions in the manufacture of portland cement.

Small

quantities of volatile organic compounds (VOC), ammonia (NH 3), chlorine, and hydrogen

chloride (HCl), also may be emitted (Scalenghe et al., 2011). Emissions may also include

residual materials from the fuel and raw materials or products of incomplete combustion that are

considered to be hazardous. Because some facilities burn waste fuels, particularly spent solvents

in the kiln, these systems also may emit small quantities of additional hazardous organic

pollutants. Also, raw material feeds and fuels typically contain trace amounts of heavy metals

that may be emitted as a particulate or vapor (Levine, 2019). Sources of PM at cement plants

include (1) quarrying and crushing, (2) raw material storage, (3) grinding and blending (in the

dry process only), (4) clinker production, (5) finish grinding, and (6) packaging and loading

(Scalenghe et al., 2011). The largest emission source of PM within cement plants is the

pyroprocessing system that includes the kiln and clinker cooler exhaust stacks. Often, dust from

the kiln is collected and recycled into the kiln, thereby producing clinker from the dust.

2.8 Environmental impacts

Cement manufacture causes environmental impacts at all stages of the process. 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 (Matar et al., 2017). The cement industry produces about 10% of

24
global human-made CO2 emissions, of which 60% is from the chemical process, and 40% from

burning fuel.

The majority of carbon dioxide emissions in the manufacture of Portland cement (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. They can also be reduced by alternative fabrication methods such as the intergrinding

cement with sand or with slag or other pozzolan type minerals to a very fine powder

(Mahasenan, et al., 2003).

Hydrated products of Portland cement, such as concrete and mortars, slowly reabsorb

atmospheric CO2 gas, which has been released during calcination in a kiln.

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 non-negligible concentrations.

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, e.g. thallium, cadmium and mercury are

the most toxic (Czaplicki, 2012).

2.9 Uses

The most common use for portland cement is in the production of concrete (US Geological

Survey, 2009). Concrete is a composite material consisting of aggregate (gravel and sand),

25
cement, and water. As a construction material, concrete can be cast in almost any shape desired,

and once hardened, can become a structural (load bearing) element. Concrete can be used in the

construction of structural elements like panels, beams, and street furniture, or may be cast-in situ

for superstructures like roads and dams (Dunuweera and Rajapakse, 2018). These may be

supplied with concrete mixed on site, or may be provided with 'ready-mixed' concrete made at

permanent mixing sites. Portland cement is also used in mortars (with sand and water only), for

plasters and screeds, and in grouts (cement/water mixes squeezed into gaps to consolidate

foundations and road-beds (US Geological Survey, 2009) It is used for making joints for drains

and pipes.

It is used for the water-tightness of the structure. It is used in concrete for laying floors, and

roofs and constructing lintels, beams, stairs, pillars, etc. Cement can also be used where a hard

surface is required for the protection of exposed surfaces of structures against the destructive

agents of the weather and certain organic or inorganic chemicals (Dunuweera and Rajapakse,

2018). It is used for precast pipes manufacturing, piles, fencing posts, etc. It is used in the

construction of important engineering structures such as bridges, culverts, dams, tunnels,

lighthouses, etc. It is used in the preparation of foundations, watertight floors and footpaths.

26
 CHAPTER THREE

3.0 Conclusion and Recommendation

3.1 Conclusion

In conclusion, the chemistry of Portland cement is a complex yet essential aspect of its properties

and performance. Through the hydration process, various chemical reactions occur, ultimately

resulting in the formation of hardened cement paste. The composition of Portland cement,

including its primary constituents like calcium silicates, aluminates, and ferrites, significantly

influences its strength, durability, and setting characteristics.

3.2 Recommendation

Engineers and concrete technologists should optimize mix designs based on the specific

requirements of construction projects. By understanding the chemical interactions within the

cement paste, tailored mixes can be developed to achieve desired strength, durability, and

workability. Implementing rigorous quality control measures during the production of Portland

cement is crucial to ensure consistency and reliability in its chemical composition. This includes

regular testing of raw materials, intermediate products, and final cement samples. Given the

environmental footprint of cement production, efforts should be made to minimize CO 2

emissions and energy consumption. Providing education and training programs on the chemistry

27
 of Portland cement is essential for professionals in the construction industry. Continued research

into the chemistry of Portland cement can lead to the development of more sustainable and

efficient cementitious materials. Exploring alternative raw materials and admixtures can help

reduce environmental impact and enhance performance.

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