Cement, in the general sense of the word, can

be described as a material with adhesive and cohesive properties which make it capable of bonding mineral fragments into a compact whole. This
definition embraces a large variety of cementing
materials.
For constructional purposes, the meaning of
the term cement is restricted to the bonding materials used with stones, sand, bricks, building
blocks, etc. The principal constituents of this type
of cement are compounds of lime, so that in
building and civil engineering we are concerned
with calcareous cement. The cements of interest
in the making of concrete have the property of
setting and hardening under water by virtue of
a chemical reaction with it and are, therefore,
called hydraulic cements.

Manufacture of Portland cement

From the definition of Portland cement given
above, it can be seen that it is made primarly
from a calcareous material, such as limestone or
chalk, and from alumina and silica found as clay
or shale. Marl, a mixture of calcareous and argillaceous materials, is also used. Raw materials for
the manufacture of Portland cement are found in
nearly all countries and cement plants operate all
over the world.

Boggis

The calculation of the potential composition

of Portland cement is based on the work of R.
H. Bogue and others, and is often referred to
as Bogue composition. Bogues 1.2 equations for
the percentages of main compounds in cement
are given below. The terms in brackets represent
the percentage of the given oxide in the total mass
of cement.
C 3 S = 4.07(CaO) 7.60(SiO 2 )
6.72(Al 2 O 3 ) 1.43(Fe 2 O 3 )
2.85(SO 3 )
C 2 S = 2.87(SiO 2 ) 0.75(3CaO.SiO 2 )
C 3 A = 2.65(Al 2 O 3 ) 1.69(Fe 2 O 3 )
C 4 AF = 3.04(Fe 2 O 3 ).
There are also other methods of calculating
the composition, 1.1 but the subject is not considered to be within the scope of this book. We
should note, however, that the Bogue composition underestimates the C 3 S content (and overestimates C 2 S) because other oxides replace some
of the CaO in C 3 S; as already stated, chemically
pure C 3 S and C 2 S do not occur in Portland cement clinker.
In addition to the main compounds listed in
Table 1.1, there exist minor compounds, such as
MgO, TiO 2 , Mn 2 O 3 , K 2 O and Na 2 O; they usually
amount to not more than a few per cent of the
mass of cement. Two of the minor compounds
are of particular interest: the oxides of sodium
and potassium, Na 2 O and K 2 O, known as the al-

kalis (although other alkalis also exist in cement).

They have been found to react with some aggregates, the products of the reaction causing disintegration of the concrete, and have also been observed to affect the rate of the gain of strength of
cement. 1.3 It should, therefore, be pointed out that
the term minor compounds refers primarily to
their quantity and not necessarily to their importance. The quantity of the alkalis and of Mn 2 O 3
can be rapidly determined using a spectrophotometer.

Hydration of cement
The reactions by virtue of which Portland cement
becomes a bonding agent take place in a watercement paste. In other words, in the presence
of water, the silicates and aluminates listed in

Table 1.1 form products of hydration which in

time produce a firm and hard mass the hydrated
cement paste.

There are two ways in which compounds of

the type present in cement can react with water.
In the first, a direct addition of some molecules
of water takes place, this being a true reaction of
hydration. The second type of reaction with water
is hydrolysis. It is convenient and usual, however,
to apply the term hydration to all reactions of cement with water, i.e. to both true hydration and
hydrolysis.
Le Chatelier was the first to observe, about
130 years ago, that the products of hydration of
cement are chemically the same as the products
of hydration of the individual compounds under
similar conditions. This was later confirmed by
Steinour 1.6 and by Bogue and Lerch, 1.7 with the
proviso that the products of reaction may influence one another or may themselves interact with
the other compounds in the system. The two calcium silicates are the main cementitious compounds in cement, and the physical behaviour of
cement during hydration is similar to that of these

two compounds alone. 1.8 The hydration of the individual compounds will be described in more
detail in the succeeding sections.
The main hydrates can be broadly classified
as calcium silicate hydrates and tricalcium aluminate hydrate. C 4 AF is believed to hydrate into
tricalcium aluminate hydrate and an amorphous
phase, probably CaO.Fe 2 O 3 .aq. It is possible also
that some Fe 2 O 3 is present in solid solution in the
tricalcium aluminate hydrate.
The progress of hydration of cement can be
determined by different means, such as the measurement of: (a) the amount of Ca(OH) 2 in the
paste; (b) the heat evolved by hydration; (c) the
specific gravity of the paste; (d) the amount of
chemically combined water; (e) the amount of
unhydrated cement present (using X-ray quantitative analysis); and (f) also indirectly from the
strength of the hydrated paste. Thermogravimetric techniques and continuous X-ray diffraction
scanning of wet pastes undergoing hydration 1.50
can be used in studying early reactions. The microstructure of hydrated cement paste can also be
studied by back-scattered electron imaging in a
scanning electron microscope.

Properties of
aggregate
Because at least three-quarters of the volume of

concrete is occupied by aggregate, it is not surprising that its quality is of considerable importance. Not only may the aggregate limit the
strength of concrete, as aggregate with undesirable properties cannot produce strong concrete,
but the properties of aggregate greatly affect the
durability and structural performance of concrete.
Aggregate was originally viewed as an inert
material dispersed throughout the cement paste
largely for economic reasons. It is possible,
however, to take an opposite view and to look on
aggregate as a building material connected into
a cohesive whole by means of the cement paste,
in a manner similar to masonry construction. In
fact, aggregate is not truly inert and its physical,
thermal, and sometimes also chemical properties
influence the performance of concrete.
Aggregate is cheaper than cement and it is,
therefore, economical to put into the mix as much
of the former and as little of the latter as possible.
But economy is not the only reason for using aggregate: it confers considerable technical advantages on concrete, which has a higher volume stability and better durability than hydrated cement
paste alone.
General classification of aggregates
The size of aggregate used in concrete ranges
from tens of millimetres down to particles less
than one-tenth of a millimetre in cross-section.
The maximum size actually used varies but, in

any mix, particles of different sizes are incorporated, the particle size distribution being referred
to as grading. In making low-grade concrete, aggregate from deposits containing a whole range
of sizes, from the largest to the smallest, is sometimes used; this is referred to as all-in or pitrun aggregate. The alternative, always used in the
manufacture of good quality concrete, is to obtain the aggregate in at least two size groups, the
main division being between fine aggregate, often called sand (for example, in BS EN 12620 :
2002), not larger than 4 mm or in., and coarse
aggregate, which comprises material at least 5
mm or in. in size. In the United States, the division is made at No. 4 ASTM sieve, which is 4.75
mm ( in.) in size (see Table 3.14). More will
be said about grading later, but this basic division makes it possible to distinguish in the ensuing description between fine and coarse aggregate. It should be noted that the use of the term aggregate (to mean coarse aggregate) in contradistinction to sand is not correct.