Concrete Technology

LECTURE

2 Cements

Menglim Hoy, Ph.D. (Civil Engineering)

Associate Professor, School of Civil Engineering,

Suranaree University of Technology,
111 Univ. Avenue, Muang, Nakhon Ratchasima 30000, Thailand
Office: C1 Building, Room CE09
[email protected]

[For study only, not for commercial]

 582312 : CONCRETE TECHNOLOGY

CEMENTS
The history of Portland (calcium silicate-based) cement

Course Learning Outcomes Ordinary Portland

The mains and objectives of this lecture are:
Cement (PC)
Ordinary Portland cement well known as
o To describe the nature of Portland
cements Portland cement (PC) is essentially a calcium
silicate cement, which is produce by firing to
o To understand the manufacturing
process and the control procedure partial fusion, at a temperature of
employed approximately 1500oC, a well-homogenized
o To review the cement hydration and finely ground mixture of limestone or
process and the development of chalk (calcium carbonate) and an appropriate
hydrate structures quantity of clay or shale. The composition is
o To outline influence of cement commonly fine-tuned by the addition of sand
chemistry and compound composition and/or iron oxide.
on strength development of concrete
PC concrete is the most popular and widely
used building madeira, due to the available of
the basic raw materials all over the world, and
its ease of use in preparing and fabricating all
sorts of shapes.

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 1 Development of Portland Cement

The development of Portland cement can be summarized as follows:

James Parker, 1796 (England)

In 1791, he was granted a patent “Method of Burning Bricks, Tiles, Chalk”.

This second patent in 1796 “A certain cement or a natural hydraulic cement”.

Louis Vicat, 1813 (France)

He was a French engineer who studied the setting of mortars and developed
his own, which know as Artificial hydraulic lime.

He also invented the Vicat needle that is still in use for determination of setting
time of concretes and cements.

Joseph Aspdin, 1824 (England)

Portland cement was developed by Joseph Aspdin in 1824, so named because

its color and quality are similar to a kind of limestone, Portland stone
(Portland, England).

2 History of Portland Cement Manufacture

First calcium silicate cements were produced by the Greeks and Romans, who discovered that
volcanic ash, if finely ground and mixed with lime and water, produced a hardened mortar, which
was resistance to weathering.
The reaction is known as pozzolanic reaction and it is the basis of the contribution made to strength and
concrete performance by materials such as fly ash, microsilica and metakaoline in modern concrete.

Ancient roman
pantheons
(Temple of Gods)
It’s built in 128 AD, it has 43.2 m
diameter dome, a record for 1800 years.
The wall and dome thickness is 6 m and
is made of line-pozzolana concrete.

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 Eddystone Lighthouse
It is a lighthouse that is located on the dangerous Eddystone
Rocks, 9 statute miles south of Rame Head in England.
The resited upper part of the former Eddystone Lighthouse. Built
in 1759 by John Smeaton and re-erected on Plymouth Hoe on a
new base in 1882.

In the mid eighteenth-century John Smeaton discovered that certain impure limes (silica and alumina)
had hydraulic properties. It could react with water to yield durable hydrate, which resisted the action of
water.
He experimented with hydraulic cements made by heating limestone and clay to eliminate water and
carbon dioxide, and found a product that was superior to pozzolana cement for underwater use. Smeaton
used this material in the mortar used to construct the Eddystone Lighthouse in 1759.

Joseph Aspdin, 1824

Portland cement, one of the mankind’s most
important manufactured materials, was
patented by Joseph Aspdin in 1824.
In his kitchen stove, he heated a mixture of
finely ground limestone and clay and ground
the mixture into a powder to produce a
hydraulic cement.

Portland cement is the mixing together calcareous and argillaceous (lime with clay) or other silica-,
alumina-, and iron oxide-bearing materials, burning them at a clinkering temperature, and gridding the
resulting clinker.
Joseph Aspdin was not the first to produce a calcium silicate cement but his paten gave him the priority
for the use of the term “Portland cement”.

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 3 Chemistry of clinker manufacture

Raw materials
Cement making is essentially a chemical process
industry, which consist mainly of four chemical
constituents (oxides) including: CaO (lime), SiO2
(silica), Al2O3 (alumina) and Fe2O3 (iron oxide).
Table 1. A simplified oxide of elements of clinker:
Oxides of elements Abbreviation
Lime CaO C
Silica SiO2 S
Alumina Al2O3 A
Iron oxide Fe2O3 F

Figure 1. Typical chemical composition of Portland cement clinker.

From a chemical analysis of Portland cement clinker, its typical chemical composition can be expressing
as shown Figure 1. The source of lime for cement making is usually limestone or chalk. It is a
primarily raw material, which as typically 80% of the raw mix consists of limestone. The secondary
raw material, which provide the necessary silica, alumina, and iron oxide, is normally shale or clay.

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 When the raw materials react with water, it creates the bonds, which compose 4 major compounds of
Portland cement as follows:
Table 2. Major compounds of ordinary Portland cement.

Figure 2. Major compounds of ordinary Portland cement.

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 The calculation of clinker compound composition can be expressed mathematically (in mass %) that
first proposed by Bogue in 1929 (see Bogue, 1955) as follows:
C3S = 4.071CaO − 7.600SiO 2 − 6.718Al2 O3 − 1.430Fe 2 O3

=C2S 2.867SiO 2 − 0.7544C3S

=C3 A 2.65Al2 O3 − 1.692Fe 2 O3

C3 AF = 3.043Fe 2 O3

The oxides element can be determined by quantitative X-ray diffraction or by microscopic point
counting.
Typical contents of the four principal oxides in a simplified cement making operation utilizing only two
raw materials are presented in Figure 3.

Figure 3. Typical chemical analyses of cement operational materials.

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 4 Manufacture of Portland cement

Portland cement is made by blending an appropriate mixture of limestone and clay or shale together,
and by heating them to 1450oC in rotary kiln. With modern technology, the capacity of a rotary kiln can
reach 10,000 metric tons daily. Figure 4 show a model production line of cement.

Figure 4. Manufacturing process of Portland cement (Zongjin, 2011).

The primary reactions during the calcination process are listed as below:
a. Clay is mainly providing silicates (SiO2) together with small amount of Al2O3 and Fe2O3.

b. Limestone (CaCO3) is mainly providing calcium (CaO) and is decomposed at 1000oC.

c. Iron ore and iron oxide (Fe2O3) help to form calcium silicates at low temperature.
d. At various temperatures (1000 – 1450 oC), different chemical compounds are formed as follows:

e. The final product from the rotary kiln is called clinker. Pulverizing the clinker into small size
(<75 μm) with addition of 3 – 5% gypsum or calcium sulfate produces the Portland cement.
Gypsum added is to control fast setting caused by 3CaO.Al2O3.
The majority of cement particles sizes are from 2 to 50 μm. Figure 4 shows the plots of typical particle
size distribution of cement.

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 Figure 4. Typical particle size distribution of Portland cement (Zongjin, 2011).

Important Point
Why is calcium sulphate added when grinding Portland cement?
In the absence of calcium sulphate, C3A hydrates very rapidly in the form of hydrogarnets, so concrete
loses its slump in a matter of minutes. In the concrete industry this type of accident is called ‘flash set’.
If it occurs the only thing to do is fill the mixer with water as rapidly as possible to wash out the concrete;
otherwise, it will be necessary to break the hardened mass of concrete with a hammer jack, which is a
long and painful exercise.

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 5 Portland cement hydration

The hydration of Portland cement involves the reaction of the anhydrous calcium silicate and aluminate
phases with water to form hydrated phases.
5.1 Hydration of C2S, C3S and C3A, C4AH
Cement hydration is complex and it is appropriate to consider the reactions of silicate phases (C3S and
C2S) and the aluminate phase (C3A and C4AF) separately.
They hydration reaction of C3S and C2S can be represented schematically the following equation.

(C2S, C3S) + Water = C-S-H + portlandite

Both C3S and C2S react with water to produce an amorphous calcium silicate hydrate known as calcium
silicate hydrate (C-S-H) gel, which is the main ‘glue’ that binds the sand and aggregate particles together
in concrete. Note that the mineral C3S has a moderate of the reaction, while C2S has a slow reaction rate.
In the presence of calcium sulphate, the interstitial phase (C3A + C4AF) is transformed into ettringite
and monosulphoaluminate according to the following equation:

Calcium monosulpho
(C3A, C4AF) + sulphate + water = ettringite +
aluminate

C4AF: does not affect the behavior significantly, however, it reacts with gypsum to form calcium
sulphoferrite and its presence may accelerate the hydration of the silicates.

5.2 Hydration of Portland cement

The hydration of Portland cement is rather more complex than that of the individual constitute minerals
described above. The characteristic of hydration of the cement compounds are summarized in Table 3.
A simplified illustration of the development of hydrate structure in cement paste is given in Figure 5.

Table 3. Characteristics of hydration of the cement compounds.

Contribution to Cement

Compounds Reaction Rate Strength Heat Liberation

C3S Moderate High High

C2S Slow Low to high Low
C3A + CSH2 Fast Low Very high
C4AF + CSH2 Moderate Low Moderate

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 Figure 5. Simplified illustration of hydration of cement paste.

(a). portlandite (b). ettringite (c) C4AF crystal

Figure 6. Microscopic image of: a). portlandite, b). ettringite, and c). hydrated C4AF crystal.

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 The temperature rise during the hydration of Portland cement experience depends on a number of
factors, which include:
- Concrete placing temperature
- Cement content
- Minimum pour dimensions
- Type of formwork
- Cement type (fineness, C3S and C3A contents)
Cement heat of hydration (during the first 48 hours) is highest for finely ground cements with a high
C3S content (>60%) and a high C3A content (>10%).
By 28 days a typical Portland cement cured at 20oC can be expected to be approximately 90% hydrated.
The extent of hydration is strongly influenced by cement finesses and in particular the proportions of
coarse particles in the cement. Cement grains which are coarser than about 30 microns will probably
never fully hydrate. Thus, cement particle size distribution has a strong influence on a long-term
compressive strength. The hydration process of fresh cement paste is schematically illustrated in Fig. 7.

Figure 7. Setting of fresh cement paste.

6 Techniques used to study hydration

The following techniques are commonly used to study the hydration of cement:
X-ray diffraction (XRD) Scanning Electron Microscopy (SEM)

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 7 Types of Portland cements

According to the ASTM standards, there are five basic types of Portland cement:
• Type I Regular Cement (ordinary Portland cement)
• Type II Modified Cement (moderate sulfate resistance)
• Type III High Early Strength (increase C3S)
• Type IV Low Heat
• Type V high Sulfate Resistance

Chemical compositions and physical properties of different PC

70 Fineness 350 m2/kg Fineness 350 m2/kg Fineness 450 m2/kg Fineness 300 m2/kg Fineness 350 m2/kg
60
1day-UCS = 7 MPa 1day-UCS = 6 MPa 1day-UCS = 14 MPa 1day-UCS = 3 MPa 1day-UCS = 6 MPa
50
40
30
20
10
0
Type I Type II Type III Type IV Type V
C3S 50 45 60 25 40
C2S 25 30 15 50 40
C3A 12 7 10 5 4
C4AF 8 12 8 12 10
CSH2 5 5 5 4 4

C3S C2S C3A C4AF CSH2

Figure 8. strength development of cement pastes with different types of cement.

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 In British Standard Institute (BSI), four basic Portland cement are standardized and benchmark to ASTM
as follows:

British Standard Institute (BSI) ASTM

Ordinary Portland cement (OPC) Type I

Rapid hardening Portland cement (RHPC) Type III

Low-heat Portland cement (LHPC) Type IV

Sulfate-resistance Portland cement (SRPC) Type V

Note: there is no Portland cement similar to type II in BSI

Application of Type I
Ordinary Portland Cement
It is a general-purpose cement used in concrete for making
pavements, floors, reinforced concrete buildings, bridges,
tanks pipes, etc.
It is for all uses where the special properties of other cement
types are not required, such as sulfate attack from soil and
water, or to an objectionable temperature rise.

Application of Type II
Modified Portland Cement
This type of cement is used where precaution against
moderate sulphate attack is important. Like where concrete
will come in contact with ground or buried in ground i.e., in
drainage structure, large piers, retaining wall etc.
It usually generates less heat of hydration at a slower rate than Type II
type I cement and therefore can be used in mass structure
such as large foundation. It is preferred in hot weather.

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 Application of Type III
High Early Strength PC
It is chemically and physically similar to Type I cement, except
that its particles have been ground finer. It provides high early
strengths at an early age, usually a week or less.
It is used where formwork is to be removed quickly or
sufficient strength for further construction is required. It is
preferred in cold weather for reduction in the curing period due
to high heat generation. It should not be used in mass
concreting or large structural section.

Application of Type IV
Low-Heat Portland Cement
This type of cement is sued in mass concreting because it
generates less heat. It develops strength at a slower rate than
other cement types. Though is provide a high strength in
longer curing period. Its design strength is 90-days.
It suitable for massive concrete structure: large gravity dams,
where the temperature rise resulting from heat generated Type IV
during hardening and must be minimized to control the
concrete cracking.

Application of Type IV
High Sulphate Resistance
This cement has a low C3A content so as to avoid sulphate
attack from outside the concrete. When concrete is exposed
to highly alkaline soil or water having high sulfate content
this type is used.
It is used only in concrete exposed to severe sulfate action
i.e., where soils or ground waters have a high sulfate
content. It is not resistance to acids and other highly
corrosive substances.

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 Other types of cement
There are more than just ASTM or BSI types of cement, which are developed to the market requirement
such as SCG production below:

White Cement
For example, White Cement, is used for architectural
purpose, white concrete, a pastel color pain finish. It has low
C4AF and it is expensive.

8 Cement production quality control

The cement properties of water demand (workability), setting behavior and strength development are
largely determined by the following KEY cement quality control parameters:
 Cement fineness
 Loss in ignition (LOI) (burning at a high temperature)
 Clinker alkalis and SO3
 Clinker-free lime
 Clinker compound composition (mainly calculated C3S and C3A levels)
Therefore, some basic tests of Portland cement will be covered in this course including Fineness Test
(surface area/weight), Normal Consistency Test (ASTM C187), Setting Time Test and Strength Test.

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Review Discussion Questions
1) Tricalcium aluminate: why it is so important to discuss this particular mineral found in Portland cement
when it usually represents only between 2% and 10% of its composition?
2) It has been seen in this lecture that for economic reasons it is essential for Portland cement contain
some C3A. How much is the appropriate?
3) Why tests on cement necessary in a cement plant?
4) What are the major compounds in Portland cement?
5) What are the minor compounds in Portland cement? What is their role?
6) What are the purposes of using different types of cement?
7) What is the different between ordinary Portland (Type I) cement and Type III cement? Which of these
cements would you use for mass concrete?
8) Why is sulfate resisting (Type V) cement suitable for concrete exposed to sulfate attack?
9) Why is the amount of gypsum added to clinker carefully controlled?
10) What cement would you use for minimizing heat of hydration and sea-water attack?
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References

Neville, A. M., and Brooks, J. J., (1993) Concrete technology, Essex, England: Longman Scientific and
Technical.
Zongjin, L. (2011). Advanced concrete technology. Hoboken, New Jersey: John Wiley & Sons, Inc.
Mindess, S., Young, F. J., & Darwin, D. (2003). Concrete 2nd Editio. Technical Documents.

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