Module 2 CSAF System

CemNet Training - Course CKPC01
Module 2.2
Cement Kiln
Process Chemistry
Module 2. Cement clinker quality and composition.
2.2 The CSAF quaternary system.
Cement Kiln Chemistry
2.2 CASF System
All the cement clinker minerals belong to the CaO-SiO2-Al2O3Fe2O3 (CSAF) quarternary system..the most important clinker
minerals are the silicates C3S and C2S and these belong to the CaOSiO2 (CS) binary system.. that is a good place to begin our
exploration of the quaternary system.
2.2 CASF System
Lime, CaO, and silica, SiO2, form four distinct compounds

together, in order of increasing CaO content these are:
1. Calcium metasilicate, CaSiO4, CS.
2. Rankinite, Ca3Si2O7, C3S2.
3. Calcium orthosilicate, Ca2SiO4, C2S.
4. Tricalcium silicate, Ca3SiO5, C3S.
C3S
100
CaO
90
80
C2S C3S2
70
60
CS
50
40
Reducing CaO content (Weight %)
30
20
10
SiO2
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Module 2.2
2.2 CASF System
Lime, CaO, and silica, SiO2, form four distinct compounds

together, in order of increasing CaO content these are:
As Portland cement manufacturers we are principally interested
in the higher CaO content silicates C3S, C2S and CaO.
3. Calcium orthosilicate, Ca2SiO4, C2S.
4. Tricalcium silicate, Ca3SiO5, C3S.
C3S
100
90
80
CaO
C2S C3S2
70
60
CS
50
40
30
20
10
SiO2
2.2 CASF System
Lime, CaO, melts at 2570C.

C2S, melts at 2130C.
C3S, melts incongruently at
2150C to form solid CaO and
liquid.
2570C
CaO + Liquid
C3S
100
90
80
CaO
C2S C3S2
70
60
CS
50
40
30
20
10
SiO2
2.2 CASF System
C3S, is unstable below 1250C and slowly decomposes to solid

CaO and C2S.
This decomposition is very slow,
and below 700C, so slow that
2570C
C3S exists indefinitely.
CaO + Liquid
CaO + C3S
C3S
CaO + C2S
100
CaO
90
80
C2S C3S2
70
C3S
60
C2S
CS
50
40
30
20
10
SiO2
Module 2.2
2.2 CASF System
Between C3S and C2S there is a eutectic melting point at 2050C.

For completeness C3S2
melts incongruently at
1464C forming C2S and
liquid.
C3S + Liquid
C2S + Liquid
2570C
CaO + Liquid
C3S +
CaO + C3S
C2S
C3S + C3S2
C3SC2 3S2+ CS CS
CaO + C2S
100
90
80
70
C3S
CaO
60
C3S2
C2S
50
CS
CS melts at 1544C and

the eutectic melting point
between C2S and CS is at
1460C.
40
30
20
10
SiO2
2.2 CASF System

As Portland cement
manufacturers we are not
concerned by the low CaO
parts of the system.
C3S + Liquid
C2S + Liquid
2570C
CaO + Liquid
2050C
C3S +
CaO + C3S
C2S
C3S + C3S2
CaO + C2S
100
90
C3S2
80
70
C3S
CaO
+ CS
60
C3S2
C2S
50
CS
The melting temperatures

in the high CaO part of the
system are in excess of
2050C .. ..much
higher than can be achieved
in a cement rotary kiln.
40
30
20
10
SiO2
2.2 CASF System

C3S + Liquid
C2S + Liquid
2570C
CaO + Liquid
2050C
As Portland cement
manufacturers we are not
concerned by the low CaO
parts of the system.
The melting temperatures

in the high CaO part of the
system are in excess of
C S+ C S
2050C .. ..this is
CaO + C S
+ CS
CS
why Al2O3 and Fe2O3
must be present to form a
liquid30 and20increase
the
rate
90
80
70
60
50
40
10
0
CS
CS
CS CS
of%)C3S formation. SiO2
Reducing CaO content (Weight
C3S +
CaO + C3S
C2S
100
CaO
3 2
3 2
3 2
Module 2.2
2.2 CASF System
The complete CaO-SiO2, CS, binary system down to SiO2 is as

follows:
C3S + Liquid
C2S + Liquid
2570C
CaO + Liquid
2 Liquids
C3S +
CaO + C3S
SiO2 + Liquid
C2S
C3S + C3S2
CaO + C2S
100
90
C3S2
80
70
C3S
CaO
C2S
60
C3S2
CS + SiO2
+ CS
50
CS
40
30
20
10
SiO2
2.2 CASF System
Before considering the ternary system with addition of Al2O3, and

the quaternary system with addition of Fe2O3, we need to look at
the binary systems with alumina, Al2O3, and Fe2O3.
2.2 CASF System
Lime, CaO, and alumina, Al2O3, again form four distinct

compounds together, in order of increasing CaO content these are:
1. CaO.6Al2O3, CA6.
2. CaO.2Al2O3, CA2.
3. Calcium aluminate, CaO.Al2O3, CA.
4. Tricalcium aluminate, 3CaO.Al2O3, C3A.
C3A
100
CaO
90
80
70
60
CA
50
40
CA2
30
20
CA6
10
Al2O3
Module 2.2
2.2 CASF System
In air with normal humidity the compound C12A7 is also formed, but
this contains some hydroxyl ions and is therefore not strictly binary.
1. CaO.6Al2O3, CA6.
2. CaO.2Al2O3, CA2.
C3A
100
90
80
CaO
70
60
C12A7
50
CA
40
CA2
30
20
CA6
10
Al2O3
2.2 CASF System
Again, as Portland cement manufacturers we are not particularly

concerned about the lower lime aluminates CA6, CA2 and CA.
1. CaO.6Al2O3, CA6.
2. CaO.2Al2O3, CA2.
C3A
100
90
80
CaO
70
60
C12A7
50
CA
40
CA2
30
20
CA6
10
Al2O3
2.2 CASF System
Again, as Portland cement manufacturers we are not particularly

concerned about the lower lime aluminates CA6, CA2 and CA.
If the course covered the chemistry of the manufacture of
calcium aluminate cements we would certainly be interested in
...and C12A7.
these...
C3A
100
CaO
90
80
70
60
C12A7
50
CA
40
CA2
30
20
CA6
10
Al2O3
Module 2.2
2.2 CASF System
C3A melts incongruently at 1539C to form CaO and a liquid.

C12A7, melts in the cement kiln
atmosphere at 1392C.
2570C
The eutectic melting point

between C12A7, and C3A is at
1360C.
CaO + Liquid
CaO + C3A
100
90
C3A
80
CaO
70
C3A +
C A
C12A7 12 7
60
C3A
50
C12A7
CA
40
CA2
30
CA6
20
10
Al2O3
2.2 CASF System
Again the lower lime aluminates are not involved in Portland cement
manufacture, but the diagram is completed as follows.
2570C
CaO + Liquid
CA6 +
Al2O3
C12A7
C3A +
CaO + C3A
C12A7
100
90
80
CaO
70
60
C3A
50
C12A7
+ CA
CA + CA2
CA
40
CA2 + CA6
CA2
30
20
CA2
CA
CA6
10
0
CA6
Al2O3
2.2 CASF System
Lime, CaO, and Fe2O3 form three distinct compounds together, in

order of increasing CaO content these are:
In high Fe2O3 mixes, oxygen is lost
forming Fe2+ and therefore the
system is no longer binary between
CaO and Fe2O3, which contains
only Fe3+.
1. CaO.2Fe2O3, CF2.
2. CaO.Fe2O3, CF.
3. 2CaO.Fe2O3, C2F.
C2F
100
CaO
90
80
70
60
50
40
CF
30
CF2
20
10
Fe2O3
Module 2.2
2.2 CASF System
Lime, CaO, and Fe2O3 form three distinct compounds together, in

order of increasing CaO content these are:
However, in the CaO rich mixtures
involved in cement manufacture the
system is binary.
1. CaO.2Fe2O3, CF2.
2. CaO.Fe2O3, CF.
3. 2CaO.Fe2O3, C2F.
None of these CaO-Fe2O3 binary

compounds are present in Portland
cement.
C2F
100
90
80
CaO
70
60
50
40
CF
30
CF2
20
10
Fe2O3
2.2 CASF System
C2F melts congruently at 1450C.

The eutectic melting point
between C2F and CaO lies at
1438C, very close to the
composition of C2F.
2570C
C2F
100
90
80
CaO
70
60
50
40
C2F
CF
30
CF2
20
10
Fe2O3
2.2 CASF System
We now need to consider the ternary system between CaO-SiO2SiO2

Al2O3, CSA.
To complete the
ternary system we
need the SiO2-Al2O3,
SA, binary system.
10
20
30
40
CS
C3S2
C2S
C3S
50
60
70
80
90
CaO
100
90
80
70
60
C3A
50
40
30
CA
20
CA2
10
Al2O3
CA6
Module 2.2
2.2 CASF System
Silica, SiO2, and alumina, Al2O3, form one binary compound

together, mullite, 2Al2O3.SiO2 or A2S.
No alumino-silicate compounds are present in cement, although
they are important in refractory materials.
The clay minerals used as secondary raw materials in cement
manufacture are hydrated alumino-silicates.
A2S
100
90
80
SiO2
70
60
50
40
30
20
10
Al2O3
Reducing SiO2 content (Weight %)
2.2 CASF System

Mullite melts incongruently at 1880C to form Al2O3
(corundum) and liquid.
A2S
100
90
80
SiO2
70
60
50
40
30
20
A2S
10
Al2O3
2.2 CASF System

The eutectic melting point between SiO2 and mullite is at
1547C.
A2S + Al2O3
SiO2 + A2S
100
SiO2
90
80
70
60
50
40
30
20
A2S
10
Al2O3
Module 2.2
2.2 CASF System
Returning to the ternary system between CaO-SiO2-Al2O3, CSA.

SiO2
We can now
complete the ternary
system.
10
10
20
In 2-dimensions the
ability to represent
CS
temperature has been C S 50
lost to show the third 60
CS
oxide component.
20
30
30
40
40
50
3 2
60
70
C3S
70
A2S
80
80
90
90
CaO
100
90
80
70
60
50
40
C3A
30
CA
20
10
CA2
Al2O3
CA6
2.2 CASF System

SiO2
Primary phase fields are

shown on the ternary
phase diagram.
10
10
20
The primary phase is

the first compound to CS
crystallise out of melt C S 50
of the composition at 60
CS
any point in the
70
ternary diagram. C S
20
30
30
40
40
50
3 2
60
70
A2S
80
80
90
90
CaO
100
90
80
70
60
50
40
C3A
30
CA
20
10
CA2
Al2O3
CA6
2.2 CASF System

SiO2
Two ternary compounds

are formed in the CSA
system:
10
10
20
20
30
1. Anorthite, CAS2.
30
40
2. Gehlenite, C2AS.
40
CS
C3S2
Neither of these
CS
ternary compounds 70
CS
is present in
80
Portland cements.
50
50
CAS2
60
60
70
A2S
C2AS
80
90
90
CaO
100
90
80
70
60
C3A
50
40
30
CA
20
CA2
10
Al2O3
CA6
Module 2.2
2.2 CASF System

SiO2
The primary phase fields

are as follows:
10
10
20
20
SiO2
30
30
40
40
A2S
CS
50
50
CAS2
60
60
C3S2
70
C2S
70
C2AS
80
80
C3S
Al2O3
90
CaO
100
90
80
70
60
90
CA
C3A
CaO
50
40
30
20
10
C12A7
Al2O3
CA6
2.2 CASF System

SiO2
Portland cements lie in the

highlighted zone of the
system.
10
10
20
20
SiO2
30
C3S forms an invariant

point with CaO and
.and an
C3A.
invariant point with
C2S and C3A.
30
40
40
A2S
CS
50
50
CAS2
60
60
C3S2
70
C2S
70
C2AS
80
80
C3S
Al2O3
90
CaO
100
90
80
70
60
90
CA
C3A
CaO
50
40
30
20
C12A7
10
CA2
Al2O3
CA6
2.2 CASF System

SiO2

system.
10
10
20
20
SiO2
The invariant point with

40
CaO and C3A lies at
1470C. .the
50
invariant point with
60
CS
C2S and C3A lies at
70
CS
1455C therefore the
crystallisation path 80 C S
leads from one to 90
CaO
another.
CaO
30
30
A2S
40
CS
50
CAS2
60
3 2
70
C2AS
80
100
90
80
Al2O3
C3A
70
60
90
CA
50
40
C12A7
30
20
CA2
10
Al2O3
CA6
Module 2.2
2.2 CASF System

SiO2

system.
10
10
20
20
SiO2
C2S forms a ternary

40
eutectic with C3A and
C12A7 1335C.
50
.this is the point
60
CS
at which Portland
70
CS
cement
compositions will 80 C S
finally crystallise. 90
CaO
30
30
40
A2S
CS
50
CAS2
60
3 2
70
C2AS
80
Al2O3
100
90
80
70
60
90
CA
C3A
CaO
50
40
30
20
C12A7
10
CA2
Al2O3
CA6
2.2 CASF System

SiO2

system.
10
10
20
20
SiO2
The temperatures in the

ternary diagram within the 40
Portland cement zone
50
range from
60
CS
1700~2000C.
70
CS
.these
80
temperatures are
CS
not approached in 90
CaO
a cement kiln. CaO
30
30
40
A2S
CS
50
CAS2
60
3 2
70
C2AS
80
100
90
80
Al2O3
70
60
90
CA
C3A
50
40
30
20
C12A7
10
CA2
Al2O3
CA6
2.2 CASF System

SiO2

system.
10
10
20
20
SiO2
However the temperatures

40
on the diagram are those
where the first phase
50
crystallises out of a melt 60
CS
of that composition.
70
CS
.below these
temperatures there 80 C S
90
is a mixture of
CaO
solids and liquids.
CaO
30
30
A2S
40
CS
50
CAS2
60
3 2
70
C2AS
80
100
90
80
Al2O3
C3A
70
60
90
CA
50
40
C12A7
30
20
CA2
10
Al2O3
CA6
Module 2.2
2.2 CASF System

In a 3 dimensional
representation
temperature can again be
shown:
SiO2
These zones are

mixed liquid and
solid.
C3S +
CaO
C3S2
C2S
C2S +
CaO
CaO
100
90
80
70
60
50
40
30
20
10
Al2O3
2.2 CASF System

In a 3 dimensional
representation
shown:
SiO2
C3S +
CaO
C3S2
C2S
C2S +
CaO
CaO
100
90
80
70
60
50
40
30
20
10
Al2O3
2.2 CASF System

In a 3 dimensional representation
represented:
SiO2
CaO
100
90
80
70
60
50
40
30
20
10
Al2O3
Module 2.2
2.2 CASF System

In a 3 dimensional representation
represented:
SiO2
The final point

of crystallisation
of Portland
cement
compositions.
CaO
100
90
80
70
60
50
40
30
20
10
Al2O3
2.2 CASF System
When Fe2O3 is added to the quaternary system between CaO-SiO2Al2O3-Fe2O3, CSAF, the ability to represent temperature is entirely
lost.
Fe2O3
The 6 edges are
A regular
the binary
tetrahedron is used
systems, CS,
to represent a
CA, CF, SA, SF
quaternary system.
and AF.
The 4 sides of the
SiO2
tetrahedron are the
4 ternary systems,
CSA, CAF, CSF
and SAF.
CaO
100
90
80
70
60
50
40
30
20
10
Al2O3
2.2 CASF System
When Fe2O3 is added to the quaternary system between CaO-SiO2Al2O3-Fe2O3, CSAF, the ability to represent temperature is entirely
lost.
Fe2O3
Before looking
further at the
quaternary system
we need to
consider the CaOAl2O3-Fe2O3, CAF,
ternary system.
SiO2
CaO
100
90
80
70
60
50
40
30
20
10
Al2O3

The CaO-Al2O3,-Fe2O3, CAF,
ternary system is interesting
because of the existence of the
ternary compound C4AF which is
a constituent of Portland cement.
2.2 CASF System
Fe2O3
10
10
20
20
30
30
This ternary compound is

actually a solid solution
series whose composition
can vary along the line
70
linking C2F with a
80
hypothetical C2A.
C2F 40
40
50
50
60
60
C4AF
70
80
90
90
CaO
100
90
80
70
60
C3A
50
C2A
40
30
CA

ternary compound C4AF which is
a constituent of Portland cement.
This ternary compound is
actually a solid solution
series whose composition
can vary along the line
70
linking C2F with a
80
hypothetical C2A.
20
10
CA2
Al2O3
CA6
2.2 CASF System

The solid
solution series
ends at the
composition
C6A2F.
Fe2O3
10
10
20
20
30
30
C2F 40
40
50
50
60
60
C4AF
70
C6A2F
80
90
90
CaO
100
90
80
70
60
C3A
50
C2A
40
30
CA

ternary compound C4AF which is a
constituent of Portland cement.
The composition of this
ternary compound is
between C6AF2 and
C6A2F, but is usually
close to C4AF.
20
10
CA2
Al2O3
CA6
2.2 CASF System

The solid
solution series
ends at the
composition
C6A2F.
Fe2O3
10
10
20
20
30
30
C2F 40
40
50
50
60
60
C4AF
70
70
C6A2F
80
80
90
90
CaO
100
Module 2.2
90
80
70
60
C3A
50
C2A
40
30
CA
20
CA2
10
Al2O3
CA6

The part of the ternary system
between CaO-Al2O3,-Fe2O3, CAF,
of relevance to cement chemistry is
as follows:
Module 2.2
2.2 CASF System
Fe2O3
10
10
20
20
30
30
C2F 40
40
50
50
60
60
70
70
C4AF
80
80
CaO
90
C3A
CaO
100
90
C12A7
90
80
70
60
50
40
C3A
30
CA
20
10
CA2
Al2O3
CA6
2.2 CASF System
Returning to the quaternary system between CaO-SiO2-Al2O3-Fe2O3,

CSAF.
A smaller, irregular
tetrahedron, extending
from CaO-C2S-C4AFC12A7 includes the entire
range of Portland cement
clinker compositions.
Fe2O3
SiO2
C4AF
C2S
CaO
100
90
80
70
60
C A
50 12 740
30
20
10
Al2O3
2.2 CASF System
This smaller quaternary system allows the volumes of the primary

phases to be visualised.
The primary phase
volume of the C3S is
shown.
We will refer to this
quaternary system
frequently in the coming
sessions of the course.
CaO
C4AF
C2S
C12A7
Module 2.2
Cement Kiln
Process Chemistry
Module 2. Cement clinker quality and composition.
2.2 The CSAF quaternary system.

Module 2 CSAF System

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CemNet Training - Course CKPC01

Cement Kiln Chemistry

2.2 CASF System

Cement Kiln Chemistry

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Lime, CaO, and silica, SiO2, form four distinct compounds

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2.2 CASF System

Lime, CaO, and silica, SiO2, form four distinct compounds

Reducing CaO content (Weight %)

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2.2 CASF System

Lime, CaO, melts at 2570C.

Reducing CaO content (Weight %)

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C3S, is unstable below 1250C and slowly decomposes to solid

Reducing CaO content (Weight %)

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2.2 CASF System

Between C3S and C2S there is a eutectic melting point at 2050C.

CS melts at 1544C and

Reducing CaO content (Weight %)

Cement Kiln Chemistry

2.2 CASF System

Between C3S and C2S there is a eutectic melting point at 2050C.

The melting temperatures

Reducing CaO content (Weight %)

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2.2 CASF System

Between C3S and C2S there is a eutectic melting point at 2050C.

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Cement Kiln Chemistry

2.2 CASF System

The complete CaO-SiO2, CS, binary system down to SiO2 is as

Reducing CaO content (Weight %)

Cement Kiln Chemistry

2.2 CASF System

Before considering the ternary system with addition of Al2O3, and

Cement Kiln Chemistry

2.2 CASF System

Lime, CaO, and alumina, Al2O3, again form four distinct

Reducing CaO content (Weight %)

CemNet Training - Course CKPC01

Cement Kiln Chemistry

2.2 CASF System

Reducing CaO content (Weight %)

Cement Kiln Chemistry

2.2 CASF System

Again, as Portland cement manufacturers we are not particularly

Reducing CaO content (Weight %)

Cement Kiln Chemistry

2.2 CASF System

Again, as Portland cement manufacturers we are not particularly

Reducing CaO content (Weight %)

CemNet Training - Course CKPC01

Cement Kiln Chemistry

2.2 CASF System

C3A melts incongruently at 1539C to form CaO and a liquid.