Lecture 1: Introduction to Cement
Manufacturing Technology
CERE 156: Cement Manufacturing Technology
Dr. Ruben L. Menchavez
Cement is a finely ground hydraulic binding medium
for mortar and concrete, consisting substantially of
compounds of calcium oxide with silicon dioxide,
aluminium oxide and ferric oxide, which have been
formed by sintering or partial fusion.
Portland cement is made from portland cement clinker
with an admixture of sulphate.
Types: Portland blastfurnace cements or slag
cements additionally contain blastfurnace slag, while
trass cement additionally contains trass.
Other types: high-alumina cement and
supersulphated cement.
History
The first attempts to produce cement by the burning of an
artificial mixture of limestone and clay were made in
France, especially by Vicat, in the early years of the 19th
century.
Although these attempts were successful, the results were
not followed up in that country.
It was the achievement of Joseph Aspdin, a British
bricklayer from Leeds, to produce an excellent hydraulic
line, in 1824, by burning a mixture containing certain
proportions of lime and clay at a high temperature.
Portland cement was named because the artificial stone
made with this cement was though to resemble Portland
stone that is an oolitic limestone found in southern Britain.
However, it was not yet a true portland cement as we now
know it.
This step was achieved by his son William, who succeeded
in 1843, by applying even higher temperatures, to produce
a material which contained a substantial proportion of
sintered matter in addition to the underburned mass of the
earlier product.
Portland stone is a type of building stone that was quarried
on the Isle of Portland in Dorset, England
The position occupied by cements and allied binding media in the so-called
Rankin diagram of the ternary system
Portland cement is made by heating a mixture
of limestone and clay, or other materials of similar
bulk composition and sufficient reactivity, ultimately
to a temperature of about 1450°C
Partial fusion occurs, and nodules of clinker
are produced.
The clinker is mixed with a few per cent of
calcium sulfate and finely ground, to make the
cement.
The clinker typically has a composition in the
region of 67% CaO, 22% SiO2, 5%
Al2O3, 3% Fe2O3 and 3% other components.
Several other phases, such as alkali
sulfates and calcium oxide, are normally
present in minor amounts.
Hardening results from reactions
between major phases in clinker and
water.
Four major phases of clinker:
1. Alite is the most important constituent of all
normal Portland cement clinkers, of which it
constitutes 50-70%.
It is tricalcium silicate (Ca3SiO5) modified in
composition and crystal structure by ionic
substitutions.
It reacts relatively quickly with water, and in
normal Portland cements is the most important of
the constituent phases for strength development;
at ages up to 28 days, it is by far the most
important.
2. Belite constitutes 15-30% of normal Portland
cement clinkers.
It is dicalcium silicate (Ca2SiO4) modified by ionic
substitutions and normally present wholly or largely
as the β polymorph.
It reacts slowly with water, thus contributing little to
the strength during the first 28 days, but substantially
to the further increase in strength that occurs at later
ages.
By one year, the strengths obtainable from pure
alite and pure belite are about the same under
comparable conditions.
3. Aluminate constitutes 5-10% of most
normal Portland cement clinkers.
It is tricalcium aluminate (Ca3Al2O6), substantially
modified in composition and sometimes also in
structure by ionic substitutions.
It reacts rapidly with water, and can cause
undesirably rapid setting unless a set-controlling
agent, usually gypsum, is added.
4. Ferrite makes up 5-15% of normal
Portland cement clinkers.
It is tetracalcium aluminoferrite (Ca2AlFeO5),
substantially modified in composition by variation in
Al/Fe ratio and ionic substitutions.
The rate at which it reacts with water appears to be
somewhat variable, perhaps due to differences in
composition or other characteristics, but in general is
high initially and low or very low at later ages.
Clinker
-almost black in color
Clinker microstructure
C3S, C2S, C3A, C4AF
150 micron
Alite and belite are embedded in
aluminate and ferrite phases
C3S
Alite is yellowish brown and
angular often pseudohexagonal
at about 15-20μm
C2S
Belite is blue or red and rounded
, normally striated at about 25-
40μm
Aluminate is grey and ferrite is
brightly reflective.
Reflected light micrograph
3.59/13.3
Assignment 1: By Lineal Intercept Method, determine the percentage of the 4 major phases as
well as the approximate grain sizes.
150 micron
8 1
12
7
C3A
C4AF
ferrite phase causes the brownish gray color in cements
A pictorial representation of a cross-section of a cement grain. Adapted from
Cement Microscopy, Halliburton Services, Duncan, OK.
calcium aluminoferrite (C4AF) forms a continuous phase around the other
mineral crystallites, as the iron containing species act as a fluxing agent
Type of Portland Cements
….. Refer to separate PPT
file in lecture Ib
Cement chemical nomenclature and
other abbreviations
Chemical formulae in cement chemistry are
often expressed as sums of oxides; thus
tricalcium silicate, Ca3SiO5, can be written
as 3CaO-SiO2.
Abbreviations:
Techniques of analysis:
Materials abbreviations:
C-S-H = poorly crystalline or amorphous calcium
silicate hydrate of unspecified composition.
Ggbs = ground granulated blastfurnace slag.
Hep = hardened cement paste. Pfa = pulverized fuel
ash (flyash).
Properties or reactions
AR = alumina ratio (alumina modulus). ASR = alkali silica reaction.
DEF = delayed ettringite formation. LSF = lime saturation factor.
SR = silica ratio (silica modulus). Cx = analytical (total) concentration
of x, irrespective of species, [x] = concentration of species x.
{x} = activity of species x. RH = relative humidity. Na2Oe = equivalent
Na2O (mass %Na2O + 0.66 K2O).
(+)2V, (-)2V, optic sign and optic axial angle.
Crystal structure and chemical
composition of four major phases:
1. Alite
The pure compound, when cooled to room
temperature, is thus T1 In production clinkers,
due to the incorporation of substituent ions, the
form present at room temperature normally
approximates to M1 or M3 or a mixture of these.
Crystal data for the C3S polymorphs
Structure of alite and substituents
---it was built from Ca2+, SiO4- and O2- ions, the last
being bonded only to six Ca2+ ions, as in CaO.
The structural differences between the polymorphs affect the
coordination of the Ca2+ ions and the O atoms of the SiO4-
tetrahedra.
For each polymorph, there are several crystallographically
distinct Ca sites, having different coordination, and for a given
site, the coordination sometimes varies between individual
atoms due to orientational disorder in the surrounding SiO4
tetrahedra.
In relation to reactivity towards water, the coordination of the
oxygen atoms is possibly more important than that of Ca.
Ca
Crystal structure of the R-modification of C3S
Solid solution of alite
Ca2+ could be partly replaced by Mg2+ and that both
Ca2+ and Si4+ could be partly replaced by Al3+ or Fe3+
maximum content of MgO to be 2-0% at 1550°C,
falling to 1-5% at 1420°C
The limits for Al2O3 and Fe2O3 were 1.0% and 1.1%
respectively, but Al3+ and Fe3+ competed for sites, and
the limit for each was lowered if the other was present.
M3 alite with density of 3150 kg/m-3
2. Belite
Crystal structure and composition
five polymorphs of C2S exist at ordinary
pressures
Crystal data for the dicalcium silicate polymorphs
The structures of all are built from Ca2+ and
SiO4-4 ions.
The arrangements of these ions are closely
similar in the α, αH‘ and αL‘ and β polymorphs, but
that in γ-C2S is somewhat different.
γ -C2S is much less dense than the other
polymorphs, and this causes crystals or sintered
masses of β-C2S to crack and fall to a more
voluminous powder on cooling, a phenomenon
known as dusting.
belite contains enough stabilizing ions to prevent the
transformation to γ-C2S from taking place
Crystal structures of C2S polymorphs
Composition of belite in clinker
contain 4-6% of substituent oxides, of which the chief are
usually Al2O3 and Fe2O3
With increased substitution the crystallinity tended to
decrease, causing broadening of XRD powder peaks
Thermal behavior of belite
On heating, β-C2S shows endotherms beginning at
693°C and 1450°C, due respectively to the β αL' and
αH‘ α transitions;
With γ-C2S, the 693°C endotherm is replaced by a broad
one beginning at about 748°C due to the transition to αL'
The curve obtained on cooling α-C2S from 1500°C
shows exotherms beginning at about 1456°C, 682°C and
530°C, due respectively to the α αH‘ , αL' β and β γ
transitions.
The αH‘ αL' transition gives only a very weak effect at
1160°C.
3. Aluminate
pure C3A does not exhibit polymorphism. It is cubic, with a = 1.5263
nm, space group Pa3 and Z = 24;
the structure is built from Ca2+ ions and rings of six AlO4 tetrahedra,
of formula Al6O1818- These rings are highly puckered, such that the Al
atoms lie near to six of the corners of a cube (Fig. 1.6). The unit cell is
composed of 64 (43) subcells, of edge length 0.3816 nm.
Of these subcells, 8 are occupied by Al6O18 rings; the Ca2+ ions occur
at the body centres of some of the remaining subcells and near the
corners of others.
The coordination of those near the corners is octahedral, while that of
those at the body centres is irregular, with either 5 or 6 oxygen atoms
within 0.28 nm.
A16O18 ring in the structure of C3A, showing the situations
of the aluminium atoms near to the corners of a cube
aluminate incorporates Na2O through
solid solutions
Higher degrees of substitution lead to a series of
variants of the structure
Aluminate in production clinker:
-- contains cubic or orthorhombic forms of aluminate,
alone or in combination.
The orthorhombic modification is also known as
the prismatic, dark interstitial material, and is sometimes
pseudotetragonal. It can arise only if sufficient alkali is
available, but its formation appears to be favoured also by
rapid cooling and by bulk compositions potentially able to
yield a relatively high proportion of aluminate.
Cubic aluminate in clinker is often finely grained and
closely admixed with dendritic crystals of ferrite; when it
forms larger crystals, these tend to be equidimensional.
Composition of clinker aluminates
Pure C3A contains 62.3% CaO and 37.7% Al2O3. Substantial
proportions of both Ca and Al are thus replaced, the total
content of substituent oxides being typically around 13% for
the cubic and up to about 20% for the orthorhombic
modification.
Cubic modification with 3064 kgm-3 and a=1.5240nm
(K0.03Ca2.76Mg0.08Ti0.01)(Fe0.22Al1.60Si0.18)O6
Orthorhombic modification with 3053 kgm-3
(Na0.292Ca2.792)(Fe0.150Al1.725Si0.125)O6
4. Ferrite (C4AF)
Crystal structure and composition in the Ca2(AlxFe1-x)2O5
series
Composition of clinker ferrites
In many clinkers, the ferrite is closely mixed with
aluminate; due to a similarity in cell parameters, oriented
intergrowth can occur.
the substituent ions (10%) being contained essentially in
the octahedral and tetrahedral sites
C4AF (46.1% CaO, 21.0% AI2O3, 32.9% Fe2O3)
Ca2AlFe0.6Mg0.2Si0.15Ti0.05O5
Properties:
If clinker ferrites are cooled in air, they are
commonly almost black.
If the substituted ferrite is cooled in N2 or quenched in water,
the dark colour disappears. Its disappearance seems to be
due to the absence of Fe4+ rather than the presence of Fe2+
Brownmillerite is a preferred crystal structure of
ferrites
Ca2AlFe0.6Si0.15Ti0.05O5, is 3570kgm-3
