Portland Cement

Hydraulic binders: PORTLAND CEMENT
 The Portland cement clinker is produced by firing to partial fusion, at a
temperature of approximately 1400‐1500°C, a well‐homogenized and finely ground
mixture of limestone, chalk, or marl and an appropriate quantity of clay or shale.

 Limestone, chalk, and marl are the source of lime (calcium oxide CaO) . As typically
80% of the raw mix consists of limestone, it is referred to as the primary raw material.
The secondary raw material, which provides the necessary silica (silicon dioxide SiO2),
alumina (Al2O3) and iron oxide (Fe2O3), is normally shale or clay.

Shale

Chalk Limestone 
Chalk

 The reaction between CaO and SiO2 is very difficult to achieve, even at high firing temperatures.
Chemical combination is greatly facilitated if small quantities of alumina and iron oxide are present
(typically 5% Al2O3 and 3% Fe2O3), as these help to form a molten flux through which the lime and
silica are able to partially dissolve, and then react to yield C3S and C2S. Therefore, when sufficient
amounts of iron and alumina minerals are not present in the primary raw materials, these are
purposely incorporated into the raw mix through addition of secondary materials such as bauxite
(Al2O3.xH2O) and iron ore.
Sources of Raw Materials Used in Manufacture of Portland Cement 

Calcium  Iron Silica  Alumina Sulfate

Alkali waste Blast‐furnace flue  Calcium silicate Aluminum‐ore refuse Anhydrite
Aragonite dust Cement rock Bauxite Calcium sulfate
Calcite Clay Clay Cement rock Gypsum
Cement‐kiln dust Iron ore Fly ash Clay
Cement rock Mill scale Limestone Copper slag
Chalk Ore washings Loess Fly ash
Clay Pyrite cinders Marl Fuller’s earth
Fuller’s earth Shale Ore washings Granodiorite
Limestone Quartzite Limestone
Marble Rice‐hull ash Loess
Marl Sand Ore washings
Seashells Sandstone Shale
Shale Shale Slag
Slag Slag
III.1. MANUFACTURING PROCESS OF PORTLAND CEMENT

Dry process for the  PC manufacture 

Grinding  90µm

decarbonation
III.1. MANUFACTURING PROCESS OF PORTLAND CEMENT
III.1. MANUFACTURING PROCESS OF PORTLAND CEMENT
 Blending of limestone (or chalk) and clay (or shale) in carefully controlled proportions
(normally 80/20) and interground in ball or roller mills until most or all of the particles
are smaller than 90 µm (it may be necessary to add small quantities of other materials
such as ground sand or iron oxide).

 Heating of this mixture to about 1400–1500°C. First the mixture is fed into the top of a
pre‐heater tower. As it falls through this it is flash‐heated to about 900°C for a few
seconds, during which about 90% of the carbonate component decomposes into
calcium oxide and carbon dioxide (decarbonation).

 The preheated and partially calcined raw mix enters at the higher end of the rotary
kiln and is transported to the lower end at a rate controlled by the slope (≈ 3 degrees)
and the speed of the kiln rotation. Pulverized coal, oil, or a fuel gas is injected at the
lower end in the burning zone (1400‐1500°C) and the chemical reactions involving the
formation of Portland cement compounds are completed (clinker).
 III.1. MANUFACTURING PROCESS OF PORTLAND CEMENT

 The final operation consists of pulverizing the clinker to an average particle (10 ‐15
μm). The operation is carried out in ball mills (finish mills). A small amount of gypsum
(5‐6%) or other calcium sulfate source is added during grinding to regulate the setting
time of the cement and to improve shrinkage and strength development properties

Belite

Alite

Polished thin section of PC clinker alite

(C3S light angular crystals), and belite (C2S
darker rounded crystals). Magnification
400X. Typically, C3S appears as hexagonal‐
plate crystals, C2S as rounded grains, and
C3A and C4AF as interstitial phases».
III.1. MANUFACTURING PROCESS OF PORTLAND CEMENT: Chemistry

 Decarbonation of CaCO3
When limestone is heated above 825°C, carbon dioxide is driven off leaving free lime:
Heat
CaCO3 CaO (free lime) + CO2
825°C
III.1. MANUFACTURING PROCESS OF PORTLAND CEMENT: Chemistry

Source: Mindess, Young, and Darwin, 2004
 III.1. MANUFACTURING PROCESS OF PORTLAND CEMENT: Chemistry
As the temperature increases, some of the lime combines with silica to form belite (C2S) :
Heat
2CaO + SiO2 Ca2SiO4 or (2CaO.SiO2)
1200°C

At temperatures above 1250°C, some of the belite combines with the unreacted lime to form alite (C3S):
Heat
CaO + Ca2SiO4 Ca3SiO5 or (3CaO.SiO2)
1250°C

At temperatures above 1300°C, unreacted lime and alumina combine into tricalcium aluminate (C3A):
Heat
3CaO + Al2O3 Ca3Al2O6 or (3CaO.Al2O3)
1300°C

As the semi‐molten mixture cools, crystals of tetracalcium aluminoferrite (C4AF) form from free lime,
tricalcium aluminate and ferrite:

CaO + Ca3Al2O6 + Fe2O3 Ca4Al2Fe2O10

 Although twenty to thirty percent of the mix becomes molten during the process the majority of the
reactions which take place are solid‐state in nature and therefore liable to be slow.
 III.2. COMPOSITION OF CLINKER
Most PC clinkers contain four principal chemical compounds, which are normally referred
to as the clinker minerals. These are:
Typical level  Typical range 
Abbreviation Chemical formula Mineral name
(mass%) (mass%)
Alite (Tricalcium 
C3S 3CaO.SiO2 silicate)
57 37‐65

Belite (Dicalcium 
C2S 2CaO.SiO2 silicate)
16 10‐37

Aluminate (Tricalcium 
Major C3A 3CaO.Al2O3 aluminate)
9 5‐15

Ferrite (Tetracalcium 
C4AF 4CaO. Al2O3Fe2O3 aluminoferrite)
10 6‐18

Cement chemists shorthand CaO = C; SiO2 = S; Fe2O3 = F; Al2O3 = A

In addition to these four major minerals, there are a small amount of free calcium oxide,
magnesium oxide, and alkali in cement which are clearly prescribed in the national
standards that the total amount should not be more than 10%.
 III.3. Calculation of PC clinker compound composition 
 Since properties of Portland cement are related to the compound composition, it is
important to carry out a quantitative analysis of Portland cement clinker.
 Although PC consists essentially of 4 compounds of calcium, it is a common practice in
the cement industry to compute the compound composition of Portland cement from
the oxide analysis by using a set of equations originally developed by Bogue in 1929.

Direct quantitative analysis of PC

clinker can be carried out by X‐
silica ray Diffraction method (XRD).
alumina
iron oxide
lime 

Offers a convenient way to

determine the mineralogical
analysis of crystalline solids.

Typical chemical  Requires special equipment

Composition  of PC clinker  and skill. It is not necessary for
routine quality control.
 III.4. Hydration, setting and hardening of PC
 Mixed with water, cement can turn into a plastic paste. Normally 2‐4 hours after
mixing at normal temperatures, the mix starts to stiffen (initial set). However, it still
has little or no strength, and hardening, or strength gain starts some hours later (final
set) . The process from the initial setting to the final setting is known as setting*.

 The initial set defines the time limit for handling and placing the concrete and the final
set indicates the start of the development of mechanical strength.
 The hydration of PC involves the reaction of the anhydrous calcium silicate and
aluminate phases with water to form hydrated phases. This process can be described
in five stages.

*The setting and hardening of cement are a continuous physical and chemical changing process. All these changes decide some properties
of hardened cement paste, which have an important impact on the application of cement.
 III.4. The hydration process
1. Initial reaction: Immediately on mixing, there is a high and short peak lasting only a few
minutes (<15min): rapid heat generation and formation of a layer at the cement grain surface
which acts as a protection cover and slows down significantly the hydration reaction.

2. Induction or dormant period: During the dormant period, the hydration is nearly
stopped and the material is still workable. This stage takes usually some hours (2‐4 hours).

3. Acceleration period: The protection layer (formed during stage 1) breaks open and the
cement starts to hydrate at a high rate, which can be detected by the heat release. The
hydration products increase in volume and start to create bonds between each other and
setting of the material occurs. This stage lasts for several hours.

4. Deceleration period: Hydrate layers form around the cement grains and diminish the
rate of hydration during one to several days (this is observed on the decreasing rate of heat
release).

5. Final slow reaction (steady state): This last stage takes several years. It finishes either
with complete hydration of the cement or when no more water is available for the
hydration reaction.
 III.4. The hydration process: Products of hydration
 When water is added, the cement particles are surrounded by water, the surface of the
mineral granules in clinker reacted with water immediately, a series of new compounds
are generated, and a certain heat is released. The reaction is as follows:

 Hydration of C3A: 
 The behavior of the aluminates is particularly important in the early stages of hydration.
In a pure form, C3A reacts very violently with water, resulting in an immediate stiffening
of the paste or a flash set. This can be prevented by adding gypsum (5‐6% by weight of
the cement) to the clinker.

1. In the absence of gypsum:
C3A + Water → Calcium aluminate hydrates (C3AH6)+ heat
(rapid and highly exothermic reaction)

2. In the presence of gypsum: 
C3A + Water + Gypsum → Calcium sulfoaluminate hydrates (ettringite)
 III.4. The hydration process: Products of hydration
 As the 5–6% of gypsum is consumed, the ettringite reacts with the remaining C3A to
give to calcium monosulfoaluminate, which has a lower sulphate content.

C3A + Ettringite → Monosulfate

 In most commercial Portland cements there will be insufficient sulfate available to sustain
the formation of ettringite, thus monosulfate is always formed.

 The hydration product of cements with more than 5% potential C3A, as calculated by Bogue
equations, contains monosulfate hydrate which is unstable when exposed to a sulfate
solution. Ettringite is the stable product in a sulfate environment, and conversion of the
monosulfate to ettringite is generally associated with expansion and cracking.
 III.4. The hydration process: Products of hydration
 Hydration of Calcium silicates: 
 Calcium silicates C3S and C2S form the bulk of unhydrated cement, and it is their
hydration products that give hardened cement most of its significant engineering
properties such as strength and stiffness; their reactions and reaction rates therefore
dominate the properties of the hardened cement paste (HCP) (and concrete) and are
extremely important.
 The C3S (alite) is the faster to react.

Calcium silicate + Water → Calcium silicate hydrates (C‐S‐

H)+ Portlandite (CH)

 Hydration of Ferrite: 
 Many studies have shown that the hydration of C4AF is analogous to that of C3A but
proceeds more slowly (Taylor, 1997).
 III.4. The hydration process: Summarizing

2 4 1 3

To sum up, the Portland cement reacts with water and generates hydrate mainly
containing calcium silicate hydrate, calcium ferrite hydrate gel, calcium aluminate
hydrate, and the crystals of calcium hydroxide. In the complete‐hydrated cement paste,
the calcium silicate hydrate accounts for about 50%, and the calcium hydroxide accounts
for about 25%.
 III.4. The hydration process: Comments 
Ettringite is the first hydrate to crystallize
due to the high sulfate/aluminate ratio in
the solution phase during the 1st hour of
hydration.
A few hours later, large prismatic crystals of
CH and very small fibrous crystals of C‐S‐H
begin to fill the empty space formerly
occupied by water and the dissolving
cement particles.
After some days (A/S ratio) ettringite may
become unstable and decomposes to form
monosulfoaluminate.
cp properties evolve from those of a viscous
fluid to those of a solid material. The initial
setting of the paste occurs when the
hydration products first form a continuous
matrix rather than isolated islands.

Simplified illustration of hydration

of cement paste
 III.4. The hydration process: Comments 
Illustration of the hydration
of a single grain of PC.

 The very early products form a surface layer on the cement grain, which acts as a barrier to
further reactions during the dormant period.
 The dormant period ends when this layer is broken down enabling hydration to proceed more
rapidly.
 The hydration products (known as the gel) consist of:

1. needle‐like crystals of ettringite, deposited early in the hydration

2. an amorphous mass, mainly C‐S‐H, of small, irregular fibrous particles, some solid, some hollow
and some flattened, typically 0.5‐2 µm long and less than 0.2 µm diameter, with very high surface
area estimated to be of the order of 200,000 m2/kg, i.e. approaching a thousand times greater than
the fresh cement grains from which it has been formed.
3. large hexagonal crystals of portlandite interspersed in the fibrous matrix.
 III.4. The hydration process: Comments 
Scanning electron micrograph of typical crystals of
monosulfate hydrate and needlelike crystals of
ettringite formed by mixing calcium aluminate and
calcium sulfate solutions.
 III.4. The hydration process: Comments 

 Although PC can evolve heat for many years, the rate of heat generation is greatest at
early ages. A large amount of heat evolves within the first three days with the greatest
rate of heat liberation usually occurring within the first 24 hours.

 The heat release is advantageous in cold weather and in precast operations where the
temperature rise accelerates strength development. However, in large concrete pours
the temperature rise, and in particular the temperature difference between the
concrete core and the surface can generate stresses which result in thermal cracking.

 The amount of heat generated is dependent chiefly upon the chemical composition of
the cement, with C3A and C3S being the compounds primarily responsible for high heat
evolution. The water‐cement ratio, fineness of the cement, and temperature of curing
also are factors. An increase in the fineness, cement content, and curing temperature
increases the heat of hydration.
 III.4. The hydration process: Comments 
 When a cement is hydrated, the compounds react with water to acquire stable, low‐
energy states and the process is accompanied by the release of energy in the form of
heat. In other words, the hydration reactions of PC compounds are exothermic.

 The rate of hydration corresponds to the rate of heat release. Its kinetics and magnitude
are dependent on the binder (cement) composition.

The rates of heat liberation from the hydration of the

2 individual compounds can be used as indices of their
4 reactivity. Cement heat of hydration (during the first ~ 48
hours) is highest for finely ground cements with a high C3S
1
content (>60%) and a high C3A content (>10%).
3
 III.4. THE HYDRATION PROCSS: Comments
 The chemical hydration reactions of the four main cement compounds occur at different rates,
and contribute differently to the overall strength of the hcp. Most of the strength comes from the
hydration of alite and belite, with most of the early strength coming from the alite, and the later
strength development (after 30 days) coming from the belite. Both the tricalcium aluminate and
the tetracalcium aluminoferrite contribute relatively small amounts to the final strength of the
hcp.

Strength development over time as the four main compounds of PC hydrate.

60.5% C3S2H3 and 39.5% CH

82% C3S2H3 and 18% CH
 III.6.  TYPES OF PORTLAND CEMENT
Main generic types of Portland cement produced around the world

The descriptions given in the table are very general. National standards have specific limits for the contents of
constituents and there may be several different «sub‐types» of cement with different levels of fly ash and blast‐furnace
slag and even mixtures of slag, fly ash and limestone.
 III.6. TYPES OF PORTLAND CEMENT
 Composite (blended) types: Composite cements are cements in which a proportion of the PC
clinker is replaced by industrial by‐products, such as granulated blastfurnace slag (GBS) and power
station fly ash (also known as pulverized‐fuel ash or pfa), certain types of volcanic material (natural
pozzolanas) or limestone. The GBS, fly ash and natural pozzolanas react with the hydration
products of the PC, producing additional hydrates, which make a positive contribution to concrete
strength development and durability.
 In some European countries, notably Belgium, France, the Netherlands and Spain, the quantity of
composite cements produced considerably exceeds that of «pure» PC. Currently most of the ready‐
mixed concrete produced in the UK contains either GGBS (at ~50% level) or fly ash (at ~30% level).

 Pozzolanic materials contain reactive (usually in glassy form) silica and alumina, which are able to
react with the calcium hydroxide released by hydrating cement, to yield additional C–S–H hydrate
and calcium aluminate hydrates. This reaction is much slower than the hydration of the clinker
silicates and the strength development of pozzolanic cements is slower than that of «pure» PC.
Provided moist curing is maintained, ultimate strengths may be higher than those of «pure» PC
concrete.
 The reaction between a pozzolan and calcium hydroxide is called the pozzolanic reaction. The
technical advantage of using pozzolan cements and slag cements is derived mainly from three
features of the pozzolanic reaction. First, the reaction is slow; therefore, the rates of heat liberation
and strength development will be accordingly slow. Second, the reaction is lime‐consuming instead
of lime‐producing, which has an important bearing on the durability of the hydrated paste in acidic
environments. Third, pore size distribution studies of hydrated cements have shown that the
reaction products are very efficient in filling up capillary spaces, thus improving the strength and
impermeability of the system.
 III.6.2. THE EUROPEAN STANDARD FOR COMMON CEMENTS (EN 197-1)
 EN 197‐1 (release in 2002)
1. Replaces earlier standards and certification codes for all types of PC and blended‐PC
throughout Europe.
2. Outlines the specification requirements for different cements that are classified into
five main cement types, described as follows:
1) CEM I:
 covers traditional Portland cements comprising at least 95% PC‐clinker and up to 5%
additional constituents (such as gypsum, limestone).

2) CEM II:
 covers 19 varieties of blended PC containing at least 65% PC clinker. A letter notation
identifies the blending constituents (blast furnace slag, siliceous fly ash, calcareous fly
ash, natural uncalcined and calcined pozzolan, burnt shale, limestone, and silica fume.
Each cement type is available either with 6‐20% or 21‐35% of the blending constituent
by mass except the silica‐fume cements, which shall contain 6‐ 10% silica fume.

3) CEM III:
 covers three varieties of blended P‐slag cements containing more than 35% GBFS,
namely 36‐65%, 66‐80%, and 81‐95% slag.

4) CEM IV: covers two P‐pozzolan cements containing 11‐35% or 36‐55% pozzolan.
 III.6.2. THE EUROPEAN STANDARD FOR COMMON CEMENTS (EN 197-1)
5) CEM V:
• Covers two composite PC containing either 36‐60% or 61‐80% of a mixture of blending
components, namely, blast‐furnace slag, fly ash, and other pozzolans.

EN 197‐1 also provides six strength grades of cement 32.5, 42.5, and 52.5 (minimum
28‐day compressive strength, MPa). Moreover, a cement may also be classified as a rapid‐
hardening (letter R) or normal‐hardening (letter N) on the basis of its early strength.

Strength setting time and soundness requirements in EN 197‐1

(min)

 Compressive strength is determined using the EN 196‐1 mortar prism procedure.

Cement types and compositions permitted by EN 197‐1
 III.6.3. ASTM TYPES OF PORTLAND CEMENT
 ASTM C 150, Standard Specification for Portland cement, provides for eight types of 
PC using Roman numeral designations as follows:
1. Type I Normal
2. Type IA Normal, air‐entraining
3. Type II  Moderate sulfate resistance
4. Type IIA Moderate sulfate resistance, air‐entraining
5. Type III High early strength
6. Type IIIA High early strength, air‐entraining
7. Type IV Low heat of hydration
8. Type V High sulfate resistance
Typical chemical compositions and physical properties of different Portland cements
 III.6.3. ASTM TYPES OF PORTLAND CEMENT
Type I (reference)
• suitable for all uses (pavements, floors, reinforced concrete buildings, bridges, tanks,
reservoirs, pipe, masonry units, and precast concrete products) where the special
properties of other types are not required.
Type II 
• has a moderate sulfate resistant properties (contains no more than 8% C3A), thus it is
used where precaution against moderate sulfate attack is important.
• It is used in normal structures or elements exposed to soil or ground waters where sulfate
concentrations are higher than normal but not unusually severe.

Type III 
• Compared to type I, type III has more C3S (60%) and less C2S (15%) and a larger fineness
value. As a result, the early strength of type III at 1 day is doubled as compared to that of
type I. Meanwhile, the heat released by type III increases to 500 J/g (type I is 330 J/g).
• It is used when forms need to be removed as soon as possible or when the structure
must be put into service quickly. In cold weather its use permits a reduction in the length
of the curing period. Although higher‐cement content mixes of Type I cement can be
used to gain high early strength, Type III may provide it easier and more economically.
 III.6.3. ASTM TYPES OF PORTLAND CEMENT
Type IV (rarely available) 
• Type IV has less C3S (25%) and more C2S (50%). Hence, the early strength of type IV at 1
day is only half of that of type I. However, the heat released by type IV greatly decreases
to 210 J/g, and thus is called‐low heat Portland cement.
• It is used where the rate and amount of heat of hydration must be minimized (massive
concrete structures, such as large gravity dams, to minimize the temperature rise during
hardening).
Type V  
• Its sum of C3A and C4AF is only 14% and much less than the 20% of type I. Since these
two compounds readily react with sulfate, the lower content gives it less opportunity to
be attacked by sulfate ions*.
• It is used in concrete exposed to severe sulfate action.
*The high sulfate resistance of Type V cement is attributed to a low C3A content (not more than 5%). Use of a low water
to cementitious materials ratio and low permeability are critical to the performance of any concrete exposed to
sulfates.
From the information provided above, we can evaluate the behavior of each type of cement. The various behaviors
provide the basic justification in selecting cement for engineering practice (ex. for massive concrete structures,
hydration heat is a big consideration because too much heat will cause a larger temperature gradient, thermal stress,
and cracking. Hence, type IV cement should be the first candidate and type III should not be used. For a marine
structure, high sulfate resistance and lower ettringite are needed; thus, type V should be selected. If high early strength
is needed, type III will be the best choice. Generally, type I is the most popular cement used in civil engineering.