CemNet Training - Course CKPC01

Module 2.5

Cement Kiln
Process Chemistry
Module 2. Cement clinker quality and composition.
2.5 Deviation from Bogue compound
composition.

Cement Kiln Chemistry

2.5 Bogue deviation

In the preceding two sessions of the course we saw that the clinker
mineral composition, i.e. the C3S, C2S, C3A and C4AF content, is
controlled by proportioning the raw materials to lime saturation,
silica modulus and alumina modulus targets. ..and that
the clinker mineral composition can be calculated from the oxide
composition using the Bogue methodology.
This is considered sufficient by most cement companies.
However, the clinker mineral composition according to Bogue is
only another way of expressing the oxide composition.
The real clinker mineral composition can differ quite widely
.the reasons for
from the Bogue composition.
that deviation will be explored in this session of the course.

Cement Kiln Chemistry

2.5 Bogue deviation

The real clinker mineralogy can be determined and monitored using

microscopy or X-ray diffraction (XRD).
XRD will give a more accurate
assessment of the phase assemblage
and crystal mineral forms in the
clinker.
Microscopy will allow the crystal sizes
sizes and inter-relationships to be
examined, which can give insights into
the processing of the clinker in the
kiln.

This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd
http://Training.CemNet.com

CemNet Training - Course CKPC01

Cement Kiln Chemistry

Module 2.5

2.5 Bogue deviation

The real clinker mineralogy can be determined and monitored using

microscopy or X-ray diffraction (XRD).
If either technique is combined with
the determination of the oxide
composition by X-ray fluorescence
(XRF) then the relationship between
oxide and real clinker mineral
composition can be determined for
any particular clinker.
Dr Chromys techniques for real
clinker mineralogy control.

Cement Kiln Chemistry

2.5 Bogue deviation

The real clinker mineralogy can be determined and monitored using

microscopy or X-ray diffraction (XRD).
The first and most important reason
for deviation between the real clinker
mineralogy and that calculated by
Bogue is the effect of the cooling rate
of the clinker in the cement kiln.

Cement Kiln Chemistry

2.5 Bogue deviation

The real clinker mineralogy can be determined and monitored using

microscopy or X-ray diffraction (XRD).
The first and most important reason
for deviation between the real clinker
mineralogy and that calculated by
Bogue is the effect of the cooling rate
of the clinker in the cement kiln.
After the clinker passes under the
flame in the kiln the clinker cools in
the outlet section of the kiln before
falling into the cooler.

This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd
http://Training.CemNet.com

CemNet Training - Course CKPC01

Cement Kiln Chemistry

Module 2.5

2.5 Bogue deviation

Cement clinker is produced by sintering the kiln feed at a

temperature where 20~30% of the material melts to form a liquid
flux.
The final clinker formation reaction
takes place by the solid reactants,
C2S and CaO, dissolving in this
flux... ...and the solid
product, C3S, crystallising out of
this flux.
If chemical equilibrium was maintained between the reactants
and products during the cooling from the sintering temperature of
~1450C to ambient temperature then the clinker
mineral composition would conform with that
calculated by the Bogue mineralogy.

Cement Kiln Chemistry

2.5 Bogue deviation

Cement clinker is produced by sintering the kiln feed at a

temperature where 20~30% of the material melts to form a liquid
flux.
However, this equilibrium cooling
from the sintering temperature of
~1450C is far from the reality in an
industrial cement kiln.
The cooling is much more rapid and
the flux is either frozen as a
glass.. or crystallises independently of the solid
reactants and products.
This is the explanation for Leas assertion that cement
clinker approximates to an equilibrium product at its
sintering temperature.

Cement Kiln Chemistry

2.5 Bogue deviation

Cement clinker is produced by sintering the kiln feed at a

temperature where 20~30% of the material melts to form a liquid
flux.
What is the effect of this nonequilibrium cooling on the clinker
mineral composition?

This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd
http://Training.CemNet.com

CemNet Training - Course CKPC01

Cement Kiln Chemistry

Module 2.5

2.5 Bogue deviation

Cement clinker is produced by sintering the kiln feed at a

temperature where 20~30% of the material melts to form a liquid
flux.
In the first scenario where the flux
fails to crystallise at all and is frozen
as a glass no C3A or C4AF are
present and the glass content of the
clinker is given by:
%Glass = 2.95 x %Al2O3 + 2.2 x %Fe2O3

The following corrections are made to the C3S and C2S content
of the clinker:
%C3S = Bogue Value + 1.8 x %Al2O3 - 2.8 x %Fe2O3
%C2S = Bogue Value - 2.1 x %Al2O3 + 1.9 x %Fe2O3

Cement Kiln Chemistry

2.5 Bogue deviation

Cement clinker is produced by sintering the kiln feed at a

temperature where 20~30% of the material melts to form a liquid
flux.
In the second scenario where the
flux crystallises independently of
the solid phases the corrections to
be applied to the Bogue mineralogy
are dependent on the alumina
modulus of the clinker.
For alumina modulus from 0.9 to 1.7 then Bogue mineralogy
does not need to be corrected.

Cement Kiln Chemistry

2.5 Bogue deviation

Cement clinker is produced by sintering the kiln feed at a

temperature where 20~30% of the material melts to form a liquid
flux.
In the second scenario where the
flux crystallises independently of
the solid phases the corrections to
be applied to the Bogue mineralogy
are dependent on the alumina
modulus of the clinker.
For alumina modulus over 1.7 the following corrections apply:
%C3S = Bogue Value + 1.8 x %Al2O3 - 2.8 x %Fe2O3
%C2S = Bogue Value - 1.4 x %Al2O3 + 2.1 x %Fe2O3
%C3A = Bogue Value + 2.5 x %Al2O3 - 1.6 x %Fe2O3
%C4AF = No Correction

This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd
http://Training.CemNet.com

CemNet Training - Course CKPC01

Cement Kiln Chemistry

Module 2.5

2.5 Bogue deviation

Cement clinker is produced by sintering the kiln feed at a

temperature where 20~30% of the material melts to form a liquid
flux.
In the second scenario where the
flux crystallises independently of
the solid phases the corrections to
be applied to the Bogue mineralogy
are dependent on the alumina
modulus of the clinker.
For alumina modulus over 1.7 the following corrections apply:
In the frozen equilibrium there will also be some C12A7 present:
%C12A7 = 2.1 x %Fe2O3 - 1.4 x %Al2O3

Cement Kiln Chemistry

In the Bogue calculation of equilibrium
clinker mineral composition C12A7 is
not present.
However, with nonequilibrium cooling the
final crystallisation is not
at the ternary invariant
point between C3S, C2S
and C3A..
.but at the
ternary eutectic
between C2S, CaO
C3A and C12A7.

2.5 Bogue deviation

SiO2

SiO2

A2S
CS
CAS2
C3S2
C2S

C2AS

C3S

Al2O3

CaO

CA

C3A

Al2O3
C12A7

Cement Kiln Chemistry

This arises because more C3S is present
at the sintering temperature than can be
present at equilibrium, with the flux is
correspondingly deficient in CaO.
Some C3S would
redissolve during
equilibrium cooling to
yield C2S and C3A.
.but at the
ternary eutectic
between C2S, CaO
C3A and C12A7.

2.5 Bogue deviation

SiO2

SiO2

A2S
CS
CAS2
C3S2
C2S

C2AS

C3S

Al2O3

CaO
C3A

CA

Al2O3
C12A7

This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd
http://Training.CemNet.com

CemNet Training - Course CKPC01

Cement Kiln Chemistry

However with non-equilibrium cooling
some C2S and C3A must redissolve in
the liquid to make up for the deficiency
in CaO.
The C12A7 is formed to
take up the alumina which
is no longer combined in
the C3A.

2.5 Bogue deviation

SiO2

SiO2

A2S
CS
CAS2
C3S2
C2S

.but at the
ternary eutectic
between C2S, CaO
C3A and C12A7.

Module 2.5

C2AS

C3S

Al2O3

CaO

CA

C3A

Al2O3
C12A7

Cement Kiln Chemistry

2.5 Bogue deviation

SiO2

However with non-equilibrium cooling

some C2S and C3A must redissolve in
the liquid to make up for the deficiency
SiO
in CaO.
These corrections mean
AS
that the C3S content of
CS
clinker is up to 10%
CAS
CS
higher than calculated
C
S
C
AS
by Bogue. with C2S content correspondingly lower.
The
C S higher the alumina modulus above 1.7,
.but at the
Al O
the greater
will be the increase in C3S
ternary eutectic
CaO
CA
C
A
between C2S, CaO content.
Al2O3
C A
C3A and C12A7.
2

3 2

12

Cement Kiln Chemistry

2.5 Bogue deviation

SiO2

In effect this means there is more C3S in

the clinker and less C2S and C3A.
The higher the alumina
modulus is, above 1.7, the
greater will be the
increase in C3S content.

SiO2

A2S
CS
CAS2
C3S2
C2S

.but at the
ternary eutectic
between C2S, CaO
C3A and C12A7.

C2AS

C3S

Al2O3

CaO
C3A

CA

Al2O3
C12A7

This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd
http://Training.CemNet.com

CemNet Training - Course CKPC01

Cement Kiln Chemistry

Module 2.5

2.5 Bogue deviation

The third scenario is where the alumina modulus is below 0.9.

In this scenario the C3S content of clinker resulting from nonequilibrium cooling is lower than that calculated by the Bogue
methodology.
More CaO is dissolved in the liquid flux at the sintering
temperature than could be present at ambient temperature with
equilibrium cooling.
Some additional C2S would therefore dissolve in the melt
during equilibrium cooling.. ..and combine with the
excess CaO and crystallise out of the melt as C3S.

Cement Kiln Chemistry

2.5 Bogue deviation

The third scenario is where the alumina modulus is below 0.9.

In this scenario the C3S content of clinker resulting from nonequilibrium cooling is lower than that calculated by the Bogue
methodology.
More CaO is dissolved in the liquid flux at the sintering
temperature than could be present at ambient temperature with
equilibrium cooling.
During non-equilibrium cooling this does not occur..
..the C3S content of the clinker is lower than calculated
by the Bogue methodology and some free CaO crystallises
out of the melt on cooling.

Cement Kiln Chemistry

2.5 Bogue deviation

Non-equilibrium cooling from the sintering temperature is only one

cause of deviation between the real clinker mineralogy and that
calculated by Bogue.
Another factor is the presence of minor components which
prevent combination of the clinker minerals, or decompose the
clinker minerals after they have formed.
Three species which are present in cement clinker with some
regularity can have these effects, K2O, SO3 and P2O5.
We will consider the effects of these minor components on
clinker mineral composition in session 2.6 of the course.

This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd
http://Training.CemNet.com

CemNet Training - Course CKPC01

Cement Kiln Chemistry

Module 2.5

2.5 Bogue deviation

Non-equilibrium cooling from the sintering temperature is only one

cause of deviation between the real clinker mineralogy and that
calculated by Bogue.
A further factor is that the clinker minerals produced from an
industrial cement kiln are not composed of pure C3S, C2S, C3A
..each of these minerals contains some
or C4AF.
minor components in solid solution in the crystal structure of
the mineral and this causes deviation from the composition
calculated by the Bogue methodology.
We will consider the effects of solid solution on clinker mineral
composition, and particularly the polymorphic form of the
minerals and their associated hydraulic reactivity, in session 2.7
of the course.

Cement Kiln Chemistry

2.5 Bogue deviation

Non-equilibrium cooling from the sintering temperature is only one

cause of deviation between the real clinker mineralogy and that
calculated by Bogue.
Finally the processing, and
particularly the combustion
conditions in the cement kiln
result in changes in both the
composition, and hydraulic
reactivity of the clinker minerals.
We will consider these effects in session 2.8 of the course.
None of these topics can be considered in isolation. .the
course has been divided to promote understanding of these
inter-related issues affecting quality and composition.

Cement Kiln
Process Chemistry
Module 2. Cement clinker quality and composition.
2.5 Deviation from Bogue compound
composition.

This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd
http://Training.CemNet.com