CEMENT

Early History and Development of Portland Cement

Cement and concrete might be synonymous as household terms, but are by nature different: cement, an ultra-fine gray
powder, binds sand and rocks into a mass or matrix of concrete. Indeed, cement is the key ingredient of concrete.

Ever since civilizations first started to build were sought a material that would bind stones into a solid formed mass. The
Assyrians and Babylonians used clay for this purpose, and the Egyptians advanced to the discovery of lime and gypsum mortar as a
binding agent for building such structures as the Pyramids.The Greeks made further improvements and finally the Romans developed
cement that produced structures of remarkable durability.

Before Portland cement was discovered and for some years after its discovery, large quantities of natural cement were used.
Natural cement was produced by burning a naturally occurring mixture of lime and clay. Because the ingredients of natural
cement were mixed by nature, its properties varied as widely as the natural resources from which it was made.

In 1824, Joseph Aspdin, a bricklayer and mason in Leeds, England, took out a patent on hydraulic cement that he called
Portland cement because its hydration product resembled a building stone quarried on the Isle of Portland off the British coast.
Aspdin's method involved the careful proportioning of limestone and clay, pulverizing them, and burning the mixture into clinker, which
was then ground into finished cement.

HYDRAULIC CEMENT

A cement which possesses the property of hardening in combination with water.

3
The density of portland cement is 3.15 Mg/m .

Types of hydraulic cement:

I. Portland cement
II. Pozzolan

I. PORTLAND CEMENT

Portland cement is the product obtained by pulverizing clinker consisting of hydraulic calcium silicates to which some
calcium sulfate has usually been provided as an interground addition.

Main Constituents in a Typical Portland Cement

Chemical Name Chemical Formula Shorthand Notation Percent by Weight

Tricalcium Silicate 3CaO-SiO2 C3S 50

Dicalcium Silicate 2CaO-SiO2 C2S 25

Tricalcium Aluminate 3CaO-Al2O3 C3A 12

Tetracalcium Aluminoferrite 4CaO-Al2O3-Fe2O3 C4AF 8

Gypsum CaSO4-H2O CSH2 3.5

What causes hardening of HYDRAULIC CEMENT?

When Portland cement is mixed with water its chemical compound constituents undergo a series of chemical reactions that cause it to
harden (or set). These chemical reactions all involve the addition of water to the basic chemical compounds. This chemical reaction
with water is called "hydration". Each one of these reactions occurs at a different time and rate. Together, the results of these
reactions determine how Portland cement hardens and gains strength.

 Tricalcium silicate (C3S). Hydrates and hardens rapidly and is largely responsible for initial set and early strength. Portland
cements with higher percentages of C3S will exhibit higher early strength.
 Dicalcium silicate (C2S). Hydrates and hardens slowly and is largely responsible for strength increases beyond one week.
 Tricalcium aluminate (C3A). Hydrates and hardens the quickest. Liberates a large amount of heat almost immediately and
contributes somewhat to early strength. Gypsum is added to portland cement to retard C3A hydration. Without gypsum, C3A
hydration would cause portland cement to set almost immediately after adding water.
 Tetracalcium aluminoferrite (C4AF). Hydrates rapidly but contributes very little to strength. Its use allows lower kiln
temperatures in portland cement manufacturing. Most portland cement color effects are due to C4AF.

TYPES OF PORTLAND CEMENT

Knowing the basic characteristics of Portland cement's constituent chemical compounds, it is possible to modify its properties
by adjusting the amounts of each compound. ASTM C 150, Standard Specification for Portland Cement, recognize basic types of
Portland cement concrete.

ASTM Types of Portland Cement

Type Name Purpose

I Normal General-purpose cement suitable for most purposes.
Used as a precaution against moderate sulfate attack. It will usually generate less
heat at a slower rate than Type I cement. Type II cement gains strength a little more
Moderate Sulfate
slowly than Type I but ultimately will achieve equal strength. It is generally available in
II Resistance/Moderate Heat
most sections of the country and is preferred by some engineers over Type I for
Cement
general
construction.
Used when high early strength is needed. It is has more C3S than Type I cement and
has been ground finer to provide a higher surface-to-volume ratio, both of which
III High Early Strength speed hydration. Strength gain is double that of Type I cement in the first 24 hours. In
7 days, strength of concrete made with it is practically equal to that made with Type I
or Type II cement at 28 days.
Used when hydration heat must be minimized in large volume applications such as
IV Low Heat of Hydration
gravity dams. It has been developed for mass concrete construction. It contains about
 half the C3S and C3A and double the C2S of Type I cement.
Used as a precaution against severe sulfate action - principally where soils or
groundwaters have high sulfate content. It gains strength at a slower rate than Type I
cement. High sulfate resistance is attributable to low C3A content. It is particularly
V High Sulfate Resistance
suitable for structures subject to attack by liquors
containing sulfates, such as liquids in wastewater treatment plants, seawaters, and
some other natural waters.

In addition, portland cement can also be specified under ASTM C1157 (Standard Performance Specification for Hydraulic
Cement)

Type GU – General Use

Type HE – High Early strength

Type MS – Moderate Sulfate Resistance

Type HS – High Sulfate Resistance

Type MH – Moderate Heat of Hydration

Type LH – Low Heat of Hydration

What was the earliest use of Portland Cement?

The first use of Portland cement was in mortars. It was but a short step from its use with stone broken into small fragments and mixed
with cement.

CODES AND SPECIFICATIONS

• NSCP – National Structural Code of the Philippines

• ASTM – American Society of Testing and Materials
• AISC – American Institute of Steel Construction
• ACI – American Concrete Institute
• AREA – American Railway Engineering Association
• AASHTO – American Association of State Highway and Transportation Officials
• AWS – American Welded Society
• ASEP – Association of Structural Engineers of the Philippines

II. POZZOLAN

Pozzolan – a siliceous and aluminous material in finely divided form react with calcium hydroxide at ordinary temperatures to form
compounds having cementitious properties. There are both natural and artificial pozzolan.

What does POZZOLAN do in concrete?

As the definition implies, a pozzolan combines with calcium hydroxide to form calcium silicate similar to that produced by
hydration of portland cement. Most of the other pozzolans decrease the water demand. Pozzolans reduce bleeding because of
fineness, reduce the maximum rise in temperature when used in large amounts.

Bleeding – appearance of water on the surface of concrete after it has consolidated but before it is set. If the bleed water is remixed on
the top surface, a weak top surface will result. To avoid this, the finishing operations can be delayed until the bleed water has
evaporated.

CAUSES OF CONCRETE BLEEDING:

1. Lack of fines
2. Too much water content in the mix
PROBLEMS DUE TO CONCRETE BLEEDING:

1. It can delay in finishing

2. Cause high water cement ratio at the top
3. Result in poor bond between two layers
4. Result in poor pump ability

ASTM C595 – Specification for Pozzolan Cement as part of a blended hydraulic cement or as a separate ingredient added to the
concrete mixer.

Pozzolan are admixtures. Possibly, Class C fly ash (ASTM C618).

Natural Pozzolan – a raw or calcined pozzolan that is found in natural deposits. A material is referred as “calcined” when it has been
heated below the temperature of fusion to alter its composition or physical state. It is a natural material that has pozzolanic properties,
such as volcanic tuffs, opaline cherts and shales, clays, etc.

Natural Pozzolan: Fly Ash and Silica Fume (Microsilica)

Fly Ash is the finely divided residue that results from the combustion of ground or powdered coal and that is transported by flue gases.
ASTM C618 provides classifications for Class C and Class F. Fly ash meeting the requirements of ASTM C618, „„Specification for
Fly Ash and Raw or Calcined Natural Pozzolan for Use as a Mineral Admixture in Portland Cement Concrete,‟‟ is generally used
as a cementitious material as well as an admixture.

All fly ashes possess pozzolanic properties, the ability to react with calcium hydroxide at ordinary temperatures to form compounds with
cementitious properties. Type F ashes are the result of burning anthracite or bituminous coals and possess pozzolanic properties. They
have been shown by research and practice to provide usually increased sulfate resistance and to reduce alkali-aggregate expansions.
Type C fly ashes result from burning lignite or subbituminous coals. Because of the chemical properties of the coal, the Type C fly
ashes have some cementitious properties in addition to their pozzolanic properties.

Silica Fume – a by product resulting from the reduction of high purity quartz with coal or coke and wood chips in an electric arc furnace
during the production of pure silicon or ferrosilicon alloys.
It is a very fine material. The average size of silica fume particle is about 100 times smaller than an average portland cement particle.

Consistency - is the relative mobility or ability of freshly mixed concrete to flow. It includes the entire range of fluidity from the driest to
the wettest possible mixtures.

Plastic Consistency – indicates a condition where applied stress will result in continuous deformation without rupture. A plastic mixture
possesses cohesion and does not crumble. It flows sluggishly and without segregation.

Workability – the property of freshly mixed concrete that determines the ease with which it can be mixed, placed, consolidated and
finished to a homogeneous condition.

Setting Time

Cement paste setting time is affected by a number of items including: cement fineness, water-cement ratio, chemical content
(especially gypsum content) and admixtures. Setting tests are used to characterize how a particular cement paste sets. For
construction purposes, the initial set must not be too soon and the final set must not be too late. Additionally, setting times can give
some indication of whether or not cement is undergoing normal hydration (PCA, 1988). Normally, two setting times are defined.

1. Initial set. Occurs when the paste begins to stiffen considerably. Onset of rigidity occurs.
2. Final set. Occurs when the cement has hardened to the point at which it can sustain some load. It indicates that a useful and
measurable strength is developing.

Both common setting time tests, the Vicat needle and the Gillmore needle, define initial set and final set based on the time at which a
needle of particular size and weight either penetrates a cement paste sample to a given depth or fails to penetrate a cement paste
sample. The Vicat needle test is more common and tends to give shorter times than the Gillmore needle test.

ASTM C 150 Specified Set Times by Test Method

Test Method Set Type Time Specification

Initial 45 minutes
Vicat
Final 375 minutes
 Initial 60 minutes
Gillmore
Final 600 minutes

Major Factors that Affecting the Time of Setting

1. Cement composition
2. Water cementitious material ratio (w/cm)
3. Temperature
4. Admixture

When cement hydrates faster, the time of setting is reduced. Increases in w/cm result in increased time of setting. Time of
setting decreases as the temperature is increased. Admixtures may increase or decrease the time of setting depending on the
type.

False Set - the rapid development of rigidity in freshly mixed paste, mortar, or concrete without the evolution of much heat.
Plasticity can be regained by further mixing.

Flash Set – the rapid development of rigidity but with the evolution of considerable heat. Plasticity cannot be regained. Rapid
development of rigidity would interfere with delivery and placement operations. It would make concrete unusable, and concrete
hardened in the mixer could not be removed easily.

Strength

Cement paste strength is typically defined in three ways: compressive, tensile and flexural. These strengths can be affected by a
number of items including: water-cement ratio, cement-fine aggregate ratio, type and grading of fine aggregate, manner of mixing and
molding specimens, curing conditions, size and shape of specimen, moisture content at time of test, loading conditions and age
(Mindess and Young, 1981). Since cement gains strength over time, the time at which a strength test is to be conducted must be
specified. Typically times are 1 day (for high early strength cement), 3 days, 7 days, 28 days and 90 days (for low heat of hydration
cement). When considering cement paste strength tests, there are two items to consider:

 Cement mortar strength is not directly related to concrete strength. Cement paste strength is typically used as a quality
control measure.
 Strength tests are done on cement mortars (cement + water + sand) and not on cement pastes.

WATER

Any water that is potable is acceptable as mixing water. Some water that is not potable may also be suitable for concrete. Tests should
be performed, however, to determine if desired properties can be achieved.

Acceptance criteria for mixing water are given in ASTM C94. Impurities that make water not fit for drinking may affect the setting time,
strength, appearance, and resistance to degradation.

Salt water should not be used as mixing water in steel-reinforced concrete.

AGGREGATES

AGGREGATE is a granular material such as sand, gravel, crushed stone, crushed hydraulic cement concrete, or air cooled iron blast
furnace slag, used with hydraulic cement to produce either concrete or mortar.

Classified into two groups by size: fine aggregates and coarse aggregates.

Fine aggregates – material passing 4.75mm sieve No. 4

Coarse aggregates - material retained 4.75mm sieve No. 4

Classification of aggregates according to density:

1. Normal weight aggregates
2. Low density aggregates (Lightweight Aggregates)
3. High density aggregates (Heavyweight Aggregates)
 NORMAL WEIGHT AGGREGATES

Concrete made with normal-weight fine and coarse aggregates generally weights about 144 lb / ft3. In a portland-cement
concrete mix, the coarse and fine aggregates occupy about 60 to 75% of the total mix volume. For asphaltic concrete, the
aggregates represent 75 to 85% of the mix volume. Consequentially, the aggregates are not inert filler materials. The individual
aggregate properties have demonstrable effects on the service life and durability of the material system in which the aggregate
is used, such as portland-cement concrete, asphaltic concrete, mortar, or aggregate base.

LIGHTWEIGHT AGGREGATES

That have an air dried density at 28 days usually range of 1440-1850 kg/m3. Lightweight aggregates produce concrete with low
thermal conductivities, which equate to good fire protection. When concrete is exposed to extreme heat, the moisture present
within the concrete rapidly changes from a liquid to steam having a volume of up to 15 times larger. The large number and large
sizes of pores within lightweight aggregates create pressure-relief regions. Concretes with lightweight aggregates are most
commonly used in roof deck systems, where the advantages including insulating value and improved fire resistance.

HEAVYWEIGHT AGGREGATES

Ranging in density from about 2880 to 5600 kg/m3. Heavyweight aggregates may be used instead of gravel or crushed stone to
produce a dense concrete; for example, for shielding of nuclear reactors as specified in ASTM C637.

THREE PRINCIPAL PROBLEMS OF AGGREGATES THAT MAY AFFECT THE PROPERTIES OF CONCRETE MIXTURE
1. Segregation – destroys the grading uniformity.
2. Contamination – inclusion of deleterious material. Test Method for Organic Impurities in Fine Aggregates for Concrete,‟‟
ASTM C40.
3. Maintenance of uniform and stable moisture content in the aggregates as batched.
A practical method of reducing segregation to a minimum in coarse aggregate is to separate the material into several size
fractions and batch these fractions separately. As the range of of sizes in each fraction is decreased and the number of size
separations is increased, segregation is further reduced.

ASTM C33 Standard Specifications of Fine Aggregates and Nominal Maximum Sizes of Coarse Aggregates

Combined fine and coarse aggregates grading is specified to ensure that a satisfactory amount of aggregate with a minimum
amount of void spaces is obtained. This is enable the use of a minimum amount of paste (water and cementitious material) in
concrete, improving the dimensional stability and durability.

CHARACTERISTICS OF THE AGGREGATE ARE OF PRINCIPAL CONCERN IN AFFECTING THE STRENGTH OF THE
CONCRETE
1. Particle shape
2. Surface texture and cleanness
3. Size range of the aggregates / Nominal Maximum size of aggregates
4. Combination of sizes (grading)
5. Strength
6. Elastic modulus of the aggregates

Particle Shape

Natural sand and gravel have a round, smooth particle shape. Crushed aggregate (coarse and fine) may have shapes
that are flat and elongated, angular, cubical, rodlike. These shapes result from the crushing equipment employed and the
aggregate mineralogy. Extreme angularity and elongation increase the amount of cement required to give strength,
difficulty in finishing, and effort required to pump the concrete. Flat and elongated particles also increase the amount of
required mixing water. The bond between angular particles is greater than that between smooth particles. Properly graded
angular particles can take advantage of this property and decrease the water required to produce concrete and the
strength equal to that of a smooth-stone mix.

Surface Texture and Cleanness of Aggregates

The adhesion of the cement paste to the aggregate particles is affected. The presence of adherent soil and clay, the
roughness and the texture of the aggregates affect the adhesion. Soil affects the bond excessive fines increase the water
demand which could reduce the strength of concrete.
GRADING

When the w/cm is the same and the mixtures are plastic and workable, considerable changes in grading will not have a
large effect on concrete strength. The principal effect of changing the aggregate grading is the change the amount of
cement and water needed to make the mixture workable with the desired w/cm.

Nominal Maximum size of aggregates

As nominal maximum size of aggregate is increased, the amount of water needed fort the same workability is reduced. As
the same cement content, strength is therefore greater because the w/cm is lower.

The smallest sieve opening through which the entire amount of aggregate is permitted to pass is called the nominal
maximum size. It is the largest sieve that retains 10% or more of the total aggregate mixture.
Note: Higher sieve number, smaller sieve opening.

Hardness

Coarse-aggregate hardness is measured by the Los Angeles Abrasion Test (ASTM C131 or C595). These tests break
the aggregate down by impacting it with steel balls in a steel tumbler. The resulting breakdown is not directly related to
the abrasion an aggregate receives in service, but the results can be empirically related to concretes exhibiting service
lives.

Soundness

Aggregate soundness is measured by ASTM C88, „„Test Method for Soundness of Aggregates by Use of Sodium Sulfate
or Magnesium Sulfate.‟‟ This test measures the amount of aggregate degradation when exposed to alternating cycles of
wetting and drying in a sulfate solution.

Volume Stability

Volume stability refers to susceptibility of aggregate to expansion when heated or to cyclic expansions and contractions when
saturated and dried. Aggregates that are susceptible to volume change due to moisture should be avoided.

ADMIXTURES FOR CONCRETE

Admixtures are anything other than cement, water, and aggregates that are added to a concrete mix to modify its properties.
Included in this definition are chemical admixtures (ASTM C494), mineral admixtures such as fly ash (C618) and silica fume,
corrosion inhibitors, colors, fibers, and miscellaneous (pumping aids, dampproofing, gas-forming, permeability-reducing agents).

MAJOR REASONS FOR USING ADMIXTURES

1. To reduce the cost of concrete construction
2. To achieve the certain properties in concrete more effectively
3. To ensure the quality of concrete during the stages of mixing, transporting, placing and curing in adverse weather
conditions.
4. To overcome certain emergencies during concrete operations.

The effectiveness of admixture depends upon such factors as type, brand and amount of cement ; water content,
aggregate shape, gradation and proportions, mixing time, slump and temperatures of concrete and air.

AIR ENTRAINING ADMIXTURES, CHEMICAL AND MINERAL ADMIXTURES

Chemical admixtures used in concrete generally serve as water reducers, accelerators, set retarders, or a combination. ASTM
C494, „„Standard Specification for Chemical Admixtures for Concrete,‟‟ contains the following classification:

Type Property
A Water reducer
B Set retarder
C Set accelerator
D Water reducer and set retarder
E Water reducer and set accelerator
F High-range water reducer
G High-range water reducer and set retarder
 Air-Entraining Admixtures

These create numerous microscopic air spaces within concrete to protect it from degradation due to repeated freezing and
thawing or exposure to aggressive chemicals. For concrete exposed to repeated cycles of freezing and thawing, the air gaps
provide room for expansion of external and internal water, which otherwise would damage the concrete.

The „„Standard Specification for Air-Entraining Admixtures for Concrete,‟‟ ASTM C260, covers materials for use of air-entraining
admixtures to be added to concrete in the field.

CHEMICAL ADMIXTURES

Water-Reducing Admixtures

These decrease water requirements for a concrete mix by chemically reacting with early hydration products to form a
monomolecular layer of admixture at the cementwater interface. This layer isolates individual particles of cement and reduces
the energy required to cause the mix to flow. Thus, the mix is „„lubricated‟‟ and exposes more cement particles for hydration.

The Type A admixture allows the amount of mixing water to be reduced while maintaining the same mix slump. Or at a constant
water-cement ratio, this admixture allows the cement content to be decreased without loss of strength. If the amount of water is
not reduced, slump of the mix will be increased and also strength will be increased because more of the cement surface area
will be exposed for hydration.
Similar effects occur for Type D and E admixtures. Typically, a reduction in mixing water of 5 to 10% can be expected.
Type F and G admixtures are used where there is a need for high-workability concrete. A concrete without an admixture typically
has a slump of 2 to 3 in. After the admixture is added, the slump may be in the range of 8 to 10 in without segregation of mix
components. These admixtures are especially useful for mixes with a low water-cement ratio. Their 12 to 30% reduction in water
allows a corresponding reduction in cementitious material.

The combination of admixtures used in a concrete mix should be carefully evaluated and tested to ensure that the desired
properties are achieved. For example, depending on the dosage of admixture and chemistry of the cement, it is possible that a
retarding admixture will accelerate the set. Note also that all normal-set admixtures will retard the set if the dosage is excessive.
Furthermore, because of differences in percentage of solids between products from different companies, there is not always a
direct correspondence in dosage between admixtures of the same class. Therefore, it is important to consider the chemical
composition carefully when evaluating competing admixtures.

Superplasticizers are high-range water-reducing admixtures that meet the requirements of ASTM C494 Type F or G. They are
often used to achieve highstrength concrete by use of a low water-cement ratio with good workability and low segregation. They
also may be used to produce concrete of specified strengths with less cement at constant water-cement ratio. And they may be
used to produce self-compacting, self-leveling flowing concretes, for such applications as longdistance pumping of concrete from
mixer to formwork or placing concrete in forms congested with reinforcing steel. For these concretes, the cement content or
watercement ratio is not reduced, but the slump is increased substantially without causing segregation. For example, an initial
slump of 3 to 4 in for an ordinary concrete mix may be increased to 7 to 8 in without addition of water and decrease in strength.

Set-Accelerating Admixtures

These are used to decrease the time from the start of addition of water to cement to initial set and to increase the rate of
strength gain of concrete. The most commonly used set-accelerating admixture is calcium chloride. Its use, however, is
controversial in cases where reinforcing or prestressing steel is present. The reason is that there is a possibility that the
accelerator will introduce free chloride ions
into the concrete, thus contributing to corrosion of the steel.
Admixtures used to speed up the initial set of concrete. Calcium chloride is commonly used to accelerate the setting and
strength development of concrete. This is used when concrete is to be placed at low temperatures or when urgent repair work is
required.

Retarding Admixtures

To some extent, all normal water-reducing admixtures retard the initial set of concrete. A Type B or D admixture will allow
transport of concrete for a longer time before initial set occurs. Final set also is delayed. Hence, precautions should be taken if
retarded concrete is to be used in walls. Depending on the dosage and type of base chemicals in the admixture, initial set can
be retarded for several hours to several days. A beneficial side effect of retardation of initial and final sets is an increase in the
compressive strength of the concrete. A commonly used Type D admixture provides higher 7- and 28-day strengths than a Type
A when used in the same mix design.
Retarders are useful in concreting during hot weather when the normal setting time is shortened by the high temperature and in
preventing the formation of cold joints. Also used to reduce the incidence of thermal cracking and to maintain concrete
workability during large pour or long ready mix hauls.

MINERAL ADMIXTURES

FLY ASH

Major classifications are Class F and Class C.

Class F fly ash is primarily pozzolanic in nature, which means it reacts chemically with the cement hydration products form
compounds that the cementitious.
Class C fly ash besides having pozzolanic properties, which means it can gain strength by itself when mixed with water.

When properly used fly ash can be beneficial in concrete. Some of the major benefits are:
1. Reduces the water demand
2. Reduces the permeability
3. Reduces the heat of hydration
4. Can aid in finishability and pumping
5. Can be used in high strength applications
6. Can reduce or eliminate alkali silica reaction

GGBF SLAG (Ground Granulated Blast Furnace)

Another material that is commonly referred to as mineral admixtures. While it is considered a mineral admixture, it is in reality
hydraulic cement. That is, it gains, considerable strength when mixed with water.

It is manufactured material which is derived from a by product of the manufacture iron. During the production of iron, the one is
fluxed primarily with limestone which is tapped from the blast furnace as a molten slag. This slag is rapidly quenched and the
resulting granules are found to fineness similar to cement. It is blended with Portland cement either at a cement mill or at a
concrete batch plant. It is rarely used as the sole cementing materials in concrete.

ASTM C989 The specification that covers the production of GGBF.

MICRO SILICA

Is a material that is by product of the production of silicon metals. This is also referred as silica fume.
ASTM C1240 – The specification that covers silica fume.

Micro silica is very reactive source of silica that reacts with cement hydration products which provides unique properties to
concrete. These are very low permeability and high strength. Because of its fineness, it is generally used with significant
dosages of a high range water reducer to control the water demand of the concrete mix. Concrete that contains micro silica has
a very little or no bleed water, which besides contributing to difficulty in finishing, also makes the concrete more susceptible to
cracking while it is in plastic condition. This type of cracking is referred to as plastic shrinkage.