CEMENT

The term cement, in its broader meaning, applies to any material that will bind two or more non-adhesive substances together. The
cements to be considered here are those which have a one, oyster-shell, coquina shell of similar lime base and are used to form
concrete.

BRIEF HISTORY OF CEMENT

 Pre-historic Age – Egyptians, Greeks, Romans and other first civilization, were used stones, bricks and mud clay in
building early structures without using any material adhesion. Roman discovered the “red or purple volcanic tuff” located
near the bay of Naples. Later discovered the best variety of the earth materials in the neighborhood of “Pozzoli”, where
the materials acquired name of “Pozzolana”.
Romans structures were made mortar from mixtures of lime and natural pozzolana.
 1817 – A historical year
The year 1817 is considered to be the starting point for the revival of the construction industry. It was in the 1800’s that
Louis Vicat a young, 22-year old civil engineer conducted work on the hydraulicity of the “lime-volcanic ash” mixture. This
binder, which has been used since Roman times, remains the only materials known to set in contact with water.
 1824
The term “Portland Cement” was first used by Joseph Aspdin, a British cement maker, because of the resemblance
between concrete made from his cement and Portland stone, which was used in building England.
 1945
The first Portland cement, made from lime and clay or shale materials heated until they formed clinkers and then ground,
was produced in England.

DEFINITION OF TERMS

Hydraulic Cement – a material that sets and hardens by chemical interaction with water in air; a material that is capable of doing
under water.

Cement Clinker – a fused component of cement; a well-balanced, proportioned, homogenized raw material of certain fineness
fused by pyro-processing; a fused material consisting predominantly of crystalline hydraulic calcium silicates; a synthetically
produced rock.

Gypsum – a mineral composed essentially of hydrates calcium sulfate in various hydration states, CaSO 4.2H2O, CaSO4.1/2H2O
(Calcium Sulfate hemi-hydrate); a mineral added to clinker that retards setting of cement.

Pozzolan – a silicious or siliceous and aluminous material, which it itself possesses little or no cementitious value but which will, in
finely divided form and in the presence of moisture (H2O), chemically react with calcium hydroxide, Ca(OH)2 at ordinary
temperatures to form cementitious hydrates. Pozzolan exist in the natural or natural forms.

Blended Cement – a hydraulic cement consisting of two or more inorganic constituents (at least one of which is not Portland
cement or Portland cement clinker) which separately or in combination contribute to the strength gaining properties of the cement.

Masonry Cement – Hydraulic cement manufactured for use in mortars for masonry construction or in plasters, or both, which
contains a plastering materials and, possibly, other performance-enhancing addition(s).

Blast-furnace slag – a non-metallic product, consisting essentially of silicates and aluminosilicates of calcium and other bases, that
is developed in a molten condition simultaneously with iron in a blast furnace.

Blended Cement – a hydraulic cement consisting of two or more inorganic constituents ( at least one of which is not Portland
cement of Portland cement clinker) which separately or in combination contribute to the strength gaining properties of the cement.

Portland-Pozzolan Cement – a blended hydraulic cement consisting of an intimate and uniform blend of Portland cement or
portland blast-furnace slag cement and fine pozzolan produced by intergrinding portland-cement clinker and pozzolan, by blending
portland cement or portland blast-furnace slag cement finely divided pozzolan or a combination or integrinding and blending, in
which the amount of the pozzolan constituent is within specified limits.

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Portland Blast-furnace Slag Cement – a blended hydraulic cement consisting of an intimately interground mixture of portland
cement clinker and granulated blast-furnace slag or an intimate and uniform blend of portland cement and fine granulated blast-
furnace slag in which the amount of slag constituent is within specified limits.

Setting of Cement – a condition by which the cement paste, mortar or concrete mix starts to lose its plasticity and gain a certain
degree of rigidity.

Hardening of Cement – the condition by which the mortar or the concrete starts to develop and gain its strength.

PORTLAND CEMENT

- Is defined as the product obtained by burning (calcining) to incipient fusion a properly proportioned mixture of argillaceous
and calcareous materials and the burnt product which is called clinker is then mixed with Gypsum (CaSO 4.2H2O), and
pulverized to form Portland Cement.
o Incipient Fusion – Burning the material to make it liquid by heating it into a very high temperature, at about
1480°C. At this temperature, the initial melting stage of the materials is reached known as the point of incipient
fusion. Here sintering takes place and a clinker is formed.

HYDRAULIC CEMENT

- Portland Cement is a Hydraulic cement, that is, it reacts or combined chemically with water (hydrates), one that will
harden under water. The process is known as Hydration, and the heat generated in the reaction of cement and water is
called Heat of hydration. The reaction produce a substance that is durable, resists the effects of water, and continues to
gain strength as long as moisture is present. It will continue to gain strength even when completely submerged in water.

PORTLAND CEMENT HAS THE FF BASIC COMPOSITION

 Lime (CaO) – is one of the major raw material in cement manufacturing. It formed in different purity and in combination
with other minerals.
 Silica (SiO2)
 Iron Oxide (Fe2O3)
 Alumina (Al2O3)
 Gypsum (CaSO4.2H2O) – shall be added in small quantities to the other constituents of cement during its manufacture to
regulate the setting time that will be required for a particular cement
Typical sources of raw material used in the manufacture of Portland Cement

Components
Lime Silica Alumina Iron
Cement rock Sand Clay Iron ore
Limestone Traprock Shale Iron calcine
Marl Calcium Slag Iron dust
Alkali water Silicate Fly ash Iron pyrite
Oyster Shell Quartzite Copper slag Iron sinters
Coquina shell Fuller’s earth Aluminum ore Iron Oxide
Chalk Refuse Blast furnace
Marble Staurolite Flue dust
Diaspore Clay
Granodiorite
Kaolin

TYPES OF PORTLAND CEMENT

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  TYPE I (Normal Type) – Ordinary Portland;
o For use when special properties specified for any other type are not required.
o Uses: reinforced concrete buildings, bridges, pavement, and sidewalks (soil conditions are normal), concrete
masonry units, other uses where concrete is not subject to special sulfate hazard or where the heat generated by
the hydration of the cement is not objectionable.
 TYPE II (Moderate-Sulfate Resistant)
o Has lower heat of hydration than type 1 and generally sets more slowly
o For general use, more especially when moderate sulfate resistance or moderate heat of hydration is desired.
o Uses: drainage structures, foundations, floor slabs (soil contains a moderate amount of sulfates)
 TYPE III (High-Early Strength)
o Has approximately 190% of the strength of Type 1 at 3 days and 90-130% at 28days
o For general use when high early strength is desired.
o Uses: used where higher strengths are requires at early periods usually a week or less
 TYPE IV (Low-Heat of Hydration)
o It has slower setting time
o For general use when low heat of hydration is desired.
o Uses: intended for massive structures such as large dams
 TYPE V (Sulfate-Resistant)
o Used where the soil has high sulfate action or where water has high alkali content
o For general use when high sulfate resistance is desired.
o Uses: certain manufacturing plants or in ground water areas, resistant to action of seawater

Note: Some cement are designated with a combined type classification, such as Typed I/II, Indicating that cement meets the
requirements of the indicated types and is being offered as suitable for use when either type is desired.

PORTLAND CEMENT IS MANUFACTURED BY TWO BASIC PROCESSES:

 Wet Process
 Dry Process

MANUFACTURE OF HYDRAULIC CEMENT

The basic raw materials in the manufacture of Portland Cement are limestone, silica, shale and iron pyrite. These raw materials are
properly proportioned, pulverized and homogenized before being fed in a cement rotary klin up to a temperature of about 1,450
degrees centigrade to produce Portland cement clinker.

Clinker is a semi-finish cement product. It is fed into a pulverizing mill mixed with about 3 – 5 % gypsum to produce the final
product, Portland cement. The Portland cement is then stored at cement silos until they are either bagged or released in bulk
through bulk lorries.

In the manufacture of blended cements, clinker are fed to the finish pulverizing mill and blended or mixed with gypsum and either
pozzolan or blast furnace slag materials to produce blended cement either Portland-Pozzolan Cement or Portland Blast Furnace
Slag.

STEPS IN MANUFACTURING PORTLAND CEMENT

1. Raw materials is first reduced to 5 in. size (primary crusher), then 3/4 size (secondary crusher), and stored separately and
conveyed to grinding mill.
2. Raw materials are ground to powder and blended.
3. The burning of raw mix in a kiln to form a clinker.
4. The grinding or pulverizing the clinker with the addition of a small proportion of gypsum to a fine powder (Portland
cement).

PRINCIPAL COMPOUND PRESENT IN FINISHED CEMENT

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  Tricalcium Silicate 3Cao.SiO2 (C3S)
 Dicalcium Silicate 2CaO.SiO2 (C2S)
 Tricalcum Aluminate 3CaO.Al2O3 (C3A)
 Tetracalcium Aluminoferrite 4CaO.Al2O3.Fe2O3 (C4AF)

CHEMICAL ANALYSS OF HYDRAULIC CEMENT (ASTM C-114)

 Loss in ignition (LOI)

 Insoluble Residue (IR)
 Sulfur Trioxide (SO3)
 Magnesium Oxide (MgO)

Concentration of Reagents:

 Hydrochloric Acid (HCl) Sp. Gr. 1.19

 Hydroflouric Acid (HF) 48%
 Nitric Acid (HNO3) Sp. Gr. 1.42
 Phosphoric Acid (H3PO4) 85%
 Sulfuric Acid (H2SO4) Sp. Gr. 1.84
 Ammonium Hydroxide (NH4OH) Sp. Gr. 0.90

Indiacators: Methyl Red – 2 g methyl red per liter 95% ethyl alcohol

SIGNIFICANCE OF TEST METHODS

CHEMICAL PROPERTIES

 SILICA (SIO2)
Silica is one of the four major oxides found in clinker and cement.
This oxide is important in the formation of calcium silicates, C3S and C2S, the actual compound responsible for the
strength development of cement.
 ALUMINA (Al2O3)
Aluminum Oxide lower the sintering point during clinker burning.
It reacts with calcium oxide during burning to form calcium aluminate (C3A) compound which also contributes to early
strength of cement.
 FERRIC OXIDE (Fe2O3)
Iron (III) Oxide also lowers the sintering point of clinker burning. It reacts with lime and alumina to form tetra calcium
aluminoferrite, (C4AF).
The contribution of C4AF is not well-understood, but it may function similarly like C3A.
The cement color is influenced by the composition and amount of iron-containing phase. The more iron concentration, the
darker the color of cement.
The strength producing capabilities of C4AF can be enhanced with the use of chemical additives.
 CALCIUM OXIDE (CaO)
Lime is quantitatively one of the most important components of cement and is normally introduced during cement making
from limestone, principally calcite, CaCO3, which decarbonates from about 680oC.
It reacts with SiO2 during burning to form calcium silicate, the compound responsible for the strength of hardened cement.
 MAGNESIA (MgO)
Magnesia is a minor component of cement found as an impurity in the limestones source or in clay or shale raw feed.
MgO is being limited because of concern about expansion that can occur if free MgO as periclase hydrates to form
Mg(OH)2 at room temperature.
Periclase is undesirable due to its lower hydration kinetics and subsequent deleterious expansion in hardened paste
inducing unsoundness, volume instability (volume change) and cracking.
 LOSS ON IGNITION (LOI)

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 Loss on ignition is the weight percentage lost when Portland cement is heated at 950oC.
LOI was added in cement specification to prevent the addition of carbonate minerals such as limestone and dolomite.
The primary source of LOI is combined water of CaSO4.2H2O (Gypsum). Additional source of LOI is moisture picked up
from the clinker components during storage as well as during grinding.
 INSOLUBLE RESIDUE (IR)
IR is usually a silicate or alumino-silicate material.
IR comes from raw materials that did not combined completely in the burning process and from contamination during
retrieval of clinker.
All Portland cements contains IR from silicate impurities of gypsum (calcium sulfate) added during the final grinding
process.
The limit is set in order to prevent adulteration or contamination of cement with siliceous and argillaceous components.
 SULFUR TRIOXIDE (SO3)
Sulfur trioxide is the amount of sulfate in the cement in the form of calcium sulfate, hemihydrate, anhydrite, and many
other forms.
SO3 from clinker is included in the measured SO3 level and will reduce the amount of gypsum added.
SO3 regulates the initial setting and hardening reactions that take place during hydration.
The amount of SO3 allowed is directly related to the fineness and composition of the cement, particularly the C3A content.
SO3 above a certain optimum % causes a decrease in strength and an increase in expansion.

PHYSICAL PROPERTIES

 Density/Specific Gravity (ASTM C-188)

 Fineness by : No. 200 Sieve (ASTM c-184)
 Air Permeability Test (ASTM C-204)
 Normal Consistency (ASTM C-187)
 Time of Setting by:
o Vicat Needle (ASTM C-191)
o Gilmore Needle (ASTM C-266)
 Autoclave Expansion (ASTM C-151)
 Compressive Strength (ASTM C-109)

DENSITY/ SPECIFIC GRAVITY

The test method covers the determination of the density of hydraulic cement. The density of hydraulic cement is defined as the
mass of a unit volume of the solids. Its particular usefulness is in connection with the design and control of concrete mix.

The specific gravity of Portland cement is generally about 3.15. Specific gravity is not an indication of the quality of the cement. It is
used in calculating mix designs.

FINENESS

A very important physical property for cement because hydration rate of cement is a function of fineness

As fineness increases, the amount of water required for a constant slump concrete decreases, to the limits reached by the higher
ranges of fineness in high-early-strength cement. Greater fineness not only improves the strength but also water tightness,
workability, appearance and durability of concrete.

Both strength and permeability are influenced by fineness. Increasing the fineness substantially increases the rate of hydration.

Cement with particles larger than 45 mm are difficult to hydrate and those with particles larger than 75 mm may never hydrate
completely.

It is common practice in the industry to obtain a relative measure of the particle size distribution from specific surface area analysis
of the cement.

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Test Method Used:

 ASTM C204 – Standard Test Method for Fineness of Hydraulic Cement by Air Permeability
 ASTM C430 – Fineness of Hydraulic Cement by 45(325) sieve
 ASTM C786 – Fineness of Hydraulic Cement by 75(No.200) sieve by Wet Method

CONSISTENCY TEST

Refers to the flow behavior of a fresh mixture. The test method is intended to be used to determine the amount of water to prepare
hydraulic cement pastes for testing.

It determines the volume of water to be added in cement paste in order to reduce it in a certain state of plasticity. The amount of
water present in the mix that will give you the specified consistency required for normal setting and hardening.

There are two methods of test for consistency:

 Penetration resistance test – using Vicat Apparatus

 Flow test – using Flow Table

Consistency is affected by fineness and the rate of hydration of cement.

Cement consistency is generally assumed to affect concrete workability. Concrete Workability (slump) is assumed to correlate with
paste consistency at the same water-cement ratio and including the same mineral and chemical admixtures.

Strength (for some cements). Autoclave expansion, setting time, and premature stiffening tests are measured using stipulated
consistency.

Test Method Used:

 ASTM C187 - Standard Test for Normal Consistency

 ASTM C1437 - Standard Test for Flow of Cement

SETTING TIME

The time elapse when the cement paste gradually stiffens and loss its plasticity.

Setting time of concrete may be measured using cement paste or mortar because it is controlled by the reactions of cement and
water.

The test is used to insure that the cement does not produce abnormal setting times or to test the response of a particular
combination of cement and chemical admixture.

Types of Setting

 Initial Set - The time which elapses before the paste ceases to be fluid and plastic. Interval between the gauging and
partial loss of plasticity.
 Final Set - The time requires for the paste to harden to a certain degree. The time required for the gauged cement to
acquire sufficient firmness to resist a certain definite pressure.
 False set – conversion of gypsum to monohydrate during grinding and reconverted to gypsum when remixed during
testing; Grab set, Premature stiffening, hesitation set, is the rapid development of rigidity (hardness) in a mixed cement
paste, mortar or concrete without the evolution of much heat which rigidity can be dispelled and plasticity regained by
further mixing without the addition of water.
 Quick set (flash set) – insufficient amount of gypsum or calcium sulfate di-hydrate to retard hydration of C3A. Fluidity
cannot be regained on mixing; The rapid development of rigidity in a mixed cement paste, mortar or concrete, usually with
the evolution of considerable heat, which rigidity cannot be dispelled nor can the plasticity be regained by further addition
of water.

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The test s for setting time rely on measuring penetration resistance of cement paste or mortar. It is only affected by the percentage
and temperature of the mixing water used, and the amount of kneading the paste received, but also by the temperature and
humidity of the air.

Test Methods used:

 ASTM C 191: Vicat Needle Test

 ASTM C 266: Gillmore Needle Test
 ASTM C 451: Early Stiffening Test (Paste Method)

AUTOCLAVE EXPANSION

Determines potential delayed expansion caused by the hydration of Free CaO, or MgO, or both, when present in Portland Cement

Expansion may occur in Portland cement or in blended cement due to certain hydration reactions after the cement has set

Several reactions that cause expansion:

 Hydration for free lime (CaO) to form calcium hydroxide [Ca(OH)2]

 The hydration of periclase (MgO) to form magnesium hydroxide [Mg(OH)2]
 Formation of excess ettringite (C3A-3CS-H32) through reaction of C3A or of cacium aluminate hydrate (CA-CS-H12) with
CSH2

These reactions are slow, so they are accelerated in the laboratory by testing at an elevated pressure and temperature.

Test Method Used:

 ASTM C151 – Standard Test Method for Autoclave Expansion of Portland Cement

AIR CONTENT

Air content of freshly mixed mortar is the volume of air (or other gas) voids in freshly mixed cmenet mortar, usually expressed as a
percentage of total volume of the mortar. The purpose of the test method is to determine whether or not the hydraulic cement
under test meets the air-entraining or non-air-entraining requirements of the applicable hydraulic cement specification for which the
test is being made.

COMPRESSIVE STRENGTH

Strength is the property of cement that is probably the most important to engineers, both as general indicator of concrete quality
and to assure that concrete will perform as intended during design of the structure.

It also provides an excellent indication of the overall quality of hydrated cement .

The strength of cement developed either when tested as a mortar or a concrete is dependent on the following:

 Grading of the sand and aggregate

 The proportion of water used
 The degree of mixing
 The temperature and humidity of the atmosphere in which it is conducted
 The method by which the material is placed in the molds and the specimen made
 The curing condition
 The method of testing
 The age at which the tests are carried out

For testing purpose it is necessary to define all these conditions, and in all standards specifications this is done as closely as
possible.

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Test Method Used:

 ASTM C109/109M – Standard Test Method for Compressive Strength of Hydraulic Cement Mortars

HEAT OF HYDRATION

The quantity of heat that are liberated (exothermic) from the reaction of cement with water.

Concrete acts as an insulator due to low conductivity. When cement reacts with water, heat is liberated producing large rise in
temperature up to about 50oC. Because this temperature rise is contained in the concrete, this may cause cracking and
deterioration.

Ordinary Portland Cement (OPC) has a heat of hydration of about 90 cal/g at 28 days, T-II & IV at 60 – 70 cal/g and T-III has about
100 cal/g also after 28 days.

The rate at which the cement hydrates is the most important factor. The rate can be charge by:

 Adding Chemical Accelerators (increase Ca++ ion increase solubility of Aluminate ion) – accelerates hydration, setting &
hardening
 Adding chemical retarder (suppress Ca++ion by precipitating as insoluble compound) – retards hydration, setting and
hardening
 Changing the fineness of cement
 Changing the composition of the cement

Test Method Used:

 ASTM C186 – Standard Test Method for the Heat of Hydration of Hydraulic Cement

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POOLAN AND POZZOLANIC CEMENT

POZZOLAN

- A siliceous or siliceous and aluminous material, which in itself possesses little or no cementitious value but which will, in
finely divided form and in the presence of moisture, chemically react with calcium hydroxide (lime at ordinary temperature
to form compunds possessing cementitious properties.

TYPES OF POZZOLAN

 NATURAL POZZOLAN : Materials of volcanic origin ( volcanic ash), it includes a number of natural materials such as
diatomaceous earth, opaline cherts and shales, tuffs and pumicites, which is composed of a mixture silicates and contain
both glass and crystalline partciles.

 ARTIFICIAL POZZOLAN : Product obtain by heat treatment of natural materials such as clays and shales and certain
siliceous rocks and pulverized fuel ash.

o Pulverized Fuel Ash (Fly Ash) – most common artificial pozzolan, obtained by electrostatic or mechanical means
from the flue gases of furnace in coal-fired power stations. The fly ash particles are spherical and of at least the
same fineness as cement so that silica is readily available for reaction. A fly ash is a fine residue which results
from the combustion of powdered coal and may contain various amounts of carbon, silica, sulfur, alkalis and
other ingredients.

USES OF POZZOLAN

 use as substitute for a proportion of the portland cement in concrete, but in some cases it is prefereable to use it as an
addition (admixture). These pozzolanic materials are generally substituted for 10 to 35 percent of the cement. This
substitute produces concrete that is more permeable but much more resistance to the action of salt, sulfate, or and water.

BLENDED HYDRAULIC CEMENT

Hydraulic cement used for general construction and or some special application containing pozzolan or blast – furnace slag in
different proportions.

KINDS OF BLEND HYDRAULIC CEMENT

 Those made with blast – furnace slag

 Those containing a pozzolan

POZZOLANIC CEMENT (PORTLAND-POZZOLAN CEMENT)

Defined as a blend of ordinary portland cement and pozzolan. These cements are made by intergrinding or blending pozzolans
wiyth portland cement. A hydraulic cement consisting of an intimate and uniform blend of portland cement and fine pozzolan
produced by intergrinding portland cement clinker and finally divided pozzolan, or a combination of intergrinding and blending, in
which the amount of the pozzolan constituent is within specified limits, usually between 15 and 40 weight percent of the portland-
pozzolan cement.

TYPES OF PORTLAND – POZZOLAN CEMENT

 TYPE IP – Portland – Pozzolan cement for use in general concrete construction

 TYPE P – Portland – Pozzolan cement for use in concrete construction where high strengths at early ages are not
required.

USES OF PORTLAND – POZZOLAN CEMENT

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 particular useful in marine and hydraulic constructions and other mass concrete structures, use in large mass concrete
works because of reduction in heat evolution, examples are the constructions of dams and bridges.Portland-pozzolan
cement produces less heat of hydration and offers greater resistance to the attack of impurities in water than Normal
Portland Cement.
 The original reason for the use of pozzolanic portland cement was the improved durability combined with some economy
obtained marine, hydraulic and underground structures
 The portland-pozzolan cement can generally be used wherever ordinary portland cement is usable under normal condition
 Use in concrete with low-heat characteristics and in concrete requiring good chemical resistance.

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