Mineralogy of Clinker

Mineralogy of Clinker (Phases)
Portland cement clinker is not a homogenous substance and consists

substantially of the four crystalline clinker phases: alite, belite, calcium
aluminate and calcium aluminoferrite. Their chemical composition is
rather complicated because of the existence of soild solutions with
minor constituents.
 Tricalcium silicate 3CaOSiO2 (C3S)

 Dicalcium silicate 2CaOSiO2 (C2S)
 Tricalcium aluminate 3CaO Al2O3 (C3A)
 Teracalcium aluminoferrite 4CaO.Al2O3.Fe2O3 (C4AF)
Alite: It is a crystalline tricalcium silicate (C 3S), modified in composition

and crystal structure due to the incorporation of foreign ions. The
crystals are pseudo-hexagonal with well-defined faces.
Belite: It is a crystalline dicalcium silicate (C 2S), modified in composition
and crystal structure due to the incorporation of foreign ions. Belite has
rounded crystals marked by striations.
Calcium aluminate: It is tricalcium aluminate modified in composition
and crystal structure due to the incorporation of foreign ions. The
crystals are cubic in shape when pure.
Ferrite: A solid solution of tetracalcium aluminoferrite modified in
composition by variations in alumina/iron ratio and foreign ions. It is
characterized by high reflectivity in polished section.
These minerals are present in the clinker in the form of interlocking
crystals. None of the major compounds exist in the cement in their pure
form and all of them either substitute or form other compounds and
solid solutions with small amounts of every element that is present in
clinker i.e. sodium, potassium, phosphorous pentoxide, sulphur
compounds and titanium oxide etc. free MgO or CaO may also be
present in small quantity as a separate crystalline phase. If present in
small amounts, they may not significantly alter the crystallographic
nature and reactivity of the compounds with water but larger amounts
can do so.
Characteristics of Various Minerals (Phases)

Four major compounds/minerals in Portland cement contribute to the
behavior of the cement as it proceeds from the plastic to the hardened
state after hydration. These compounds are important to the speed of
setting of cement, to its heat during setting and its resistance to
sulphate and alkalies. The properties of cement vary in proportion to
the presence of these major compounds. The proportions of these
compounds are commonly but not so accurately calculated from the
oxide analysis by using Bogue’s calcutations.
Modifications of this formula based upon X-ray diffraction analysis are
considerd to be more precise but the Bogue’s calculations are still
included in British and ASTM standards for Portland cements. However
there is a wide agreement that by Bogue’s calculations C 3S and C3A
contents differ significantly. The percentage of alite is usually found
higher by X-ray analyser than by Bogue’s calculation. Also, the
percentage of C3A determined by X-ray is substantially less than the
calculated value.
C 3S
Tricalcium silicate 3CaO.SiO2.three molecules of lime to one of silica.
C3S is formed by the reaction of C2S and CaO. Pure C3S contain 73.7%
of CaO and 26.3% of SiO2.
There are six allotropic forms of C 3S, namely, three triclinic, two
monoclinic and one rhombohedral. The monoclinic form is the one
usually found in Portland cement. Pure C 3S is stable up to 2070 c
where it melts in congruently, giving CaO and a liquid. The range of
stability includes the temperatures at which cement clinkering takes
place during burning. Below 1250 c it is unstable and decomposes to
C2S and free CaO, if subjected to very slow and prolonged heat
treatment at lower temperatures especially if it contains ferrous iron
due to reducing atmosphere in the kiln. The rate of decomposition is
very slow and below 700c, C3S exists indefinitely. This is one of the
reasons why the clinker must be cooled rapidly.
C3S is frequently referred to as alite, which is not pure C 3S but
contains up to 4% of small amounts of substitutent oxides like Al 2O3,
MgO, Na2O, K2O and TiO2. The amount of such impurities depend
upon the raw materials composition of the clinker and burning
conditions as well as the manner the clinker is subsequently cooled.
Such impurities usually influence the properties of C 3S. The various
properties of pure C3S are not identical with to those of alite. Alite
reacts more rapidly with water than pure C3S. The compressive
strength of C3S and setting time are affected by the presence of
gypsum.
In the ordinary clinker C3S ranges 50-55%. Clinker with more than
60% C3S is difficult to manufacture as it has an adverse effect on the
coating in the kiln and usually produces unsound cement, unless-the
raw materials are ground very fine.
A substituted C3S had been reported to exist in nature under the
mineral name of hatrurite, which contains phases similar to those in
clinker.
C2S
Dicalcium silicate 2CaO.SiO2 two molecules of lime to one of silica) it is
formed from the reaction of CaO and SiO2. Pure C2S contains 65.1% of
CaO and 34.9% of SiO2.
Chemically pure C2S is not found in Portland cement clinker. It contains
foreign oxides such as Fe2O3, Al2O3, MgO, Na2O, K2O, TiO2, SO3 and P2O5
to extent of 6%, chiefly Al2O3 and Fe2O3. Pure C2S has at least four
crystal forms:
 α Form
 α’ Form
 β Form
 ϒ Form
α Form:
It is stable at 1425 c and melts at 2130 c. on cooling, it changes
reversibly to α’ form. Its density is 3.07 kg/m3.
α’ Form:
It is stable from about 830c to 1447c but on cooling, it changes
reversibly to β form at 650 -670c. Its density is about 3.31 kg/m 3.
β Form:
Pure βC2S is unstable under equilibrium conditions but can be
stabilized by the presence of small amount of contaminants like alkalies
and iron and also by the addition of oxides such as 0.1% B2O3 or 1%
Cr2O3 and by rapid cooling. This stabilized impure ΒC2S present in
Portland cement is called belite. Pure ΒC2S undergoes to further
inversion to the ϒ form at about 520 C. The rate of inversion may be
delayed or restrained indefinitely due to the presence of various
impurities. The β modification of C2S is the second most important
constituent of Portland cement possessing hydraulic properties and is
the form in which this compound is present in cement clinker at room
temperature. The density of ΒC2S is 3.28 kg/m 3. In ordinary Portland
cement clinker, it ranges from 25-30%. ΒC2S, modified by solid solution
occurs in nature as mineral larnite.
ϒ Form:
The change from β to ϒC2S, which occurs after cooling, is accompanied
by a 10% increase in volume, which causes the crystal mass to fall apart
into a fine powder known as dusting. This is due to different densities
of β and ϒ form, which are 3.28 kg/m3 and 2.97 kg/m3. On slow
cooling, dusting takes place but on rapid cooling, no inversion occurs
even after months. This is hydraulically inactive and less dense than the
ΒC2S. It is stable below 725-830 C, above that it inverts to α.
Tricalcium Aluminate:
3CaO Al2O3 three molecules of lime and one of aluminate phase. Pure
C3A contains 62.3% of CaO and 32.7% of Al2O3.
Pure C3A is cubic and hence undergoes no polymorphism. Solid
solutions with alkali however result in formation of one orthorhombic,
one tetragonal and one monoclinic form. C3A melts with
decomposition at approximately 1542 C but is stable under clinkering
conditions. Other calcium aluminates such as CA and C12A7 are
probably formed in the early reactions in the kiln but disappear during
later reactions and not normally found in Portland cement. C3A is
present from 8-15%.
Tetracalcium aluminoferrite:
(4CaO.Al2O3.Fe2O3) four molecules of lime to one of alumina and one
of iron oxide or ferrite phase. Pure C4AF contains 46.1% of CaO, 21.0%
of alumina and 32.9% of Fe2O3.
C4AF reduces the clinkering temperature, thereby assisting in the

manufacture of clinker. It acts as flux in the burning the clinker. It is a
ternary compound of CaO, Al2O3 and Fe2O3 having composition
varying from C6AF2-C6A2F, the medium value fairly close to C4AF or
C2Al2O3. 0.5 Fe known as Brownmillerite having orthorhombic in form.
For this reason it is known as ferrite phase. The C6A2F is an end
member of the solid solutions of the highest alumina content. It
alumina ratio is less than 0.638, a ferrite solid solution of C4AF and C2F
is formed. As the iron content increases, the reactivity of the ferrite
phase decreases. It forms a light interstitial matter present in Portland
cement clinker up to 15%. It is the ferrite phases that give colour to the
cement. Pure C4AF is brown but with magnesia, it is dark grey or green
in colour. SiO2, MgO, TiO2, Mn2O3 and Cr2O3 form solid solutions with
the ferrite phase. In its impure form, it is called celite.

Mineralogy of Clinker

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Mineralogy of Clinker (Phases)

Portland cement clinker is not a homogenous substance and consists

 Tricalcium silicate 3CaOSiO2 (C3S)

Alite: It is a crystalline tricalcium silicate (C 3S), modified in composition

Characteristics of Various Minerals (Phases)

C4AF reduces the clinkering temperature, thereby assisting in the

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