Ss Polymorphs

CemNet Training - Course CKPC01
Module 2.7 SS Polymorphs
Cement Kiln
Process Chemistry
Module 2. Cement clinker quality and composition.
2.7 Solid solution & polymorphic crystal
form.
2.7 Polymorphs
Cement Kiln Chemistry
In the preceding sessions of the course we have already introduced

the fact that the clinker minerals are not pure C3S, C2S, C3A and
C4AF.. ..each mineral takes minor components into its
crystal structure in solid solution.
This solid solution will inevitably lead to deviations from the
clinker mineralogy calculated according to Bogue...
...MgO substituting for CaO in C3S will effectively release
more CaO for combination with C2S to form further C3S.
...solid solution of Al2O3 in C2S or C3S means that less Al2O3
is available to form C3A, etc.
2.7 Polymorphs

Typical ranges of solid solution of minor components in the
clinker minerals are available in the literature:
Minor component
Al2O3
Fe2O3
MgO
C3S
0.7~1.7
0.4~1.6
0.3~1.0
SiO2
Na2O
K2O
TiO2
0.1~0.3
0.1~0.4
C2S
1.1~2.6
0.7~2.2
0.2~0.6
0.2~1.0
0.3~1.0
0.1~0.3
4.4~6.0
0.4~1.0
2.1~4.2
0.3~1.7
0.4~1.1
0.1~0.6
0.4~3.2
1.2~6.0
0.0~0.5
0.0~0.1
0.9~2.6
SO3
Solid Solubility (%)
C3A
C4AF
0.1~0.3
(After: Lea, Chemistry of Cement)
From this the greater solubility of Al2O3, Fe2O3, Na2O

and K2O in C2S rather than C3S and therefore their
inhibiting properties can be seen.
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2.7 Polymorphs

Minor component
Al2O3
Fe2O3
MgO
SiO2
Na2O
K2O
TiO2
SO3

C3S
0.7~1.7
0.4~1.6
0.3~1.0
C2S
1.1~2.6
0.7~2.2
0.2~0.6
0.2~1.0
0.3~1.0
0.1~0.3
4.4~6.0
0.4~1.0
2.1~4.2
0.3~1.7
0.4~1.1
0.1~0.6
0.4~3.2
1.2~6.0
0.0~0.5
0.0~0.1
0.9~2.6
C3A
C4AF
0.1~0.3
0.1~0.3
0.1~0.4
Also the greater solubility of MgO in C3S rather than

C2S and therefore its mineralising properties.
2.7 Polymorphs

Minor component
Al2O3
Fe2O3
MgO
C3S
0.7~1.7
0.4~1.6
0.3~1.0
SiO2
Na2O
K2O
TiO2
0.1~0.3
0.1~0.4
C2S
1.1~2.6
0.7~2.2
0.2~0.6
0.2~1.0
0.3~1.0
0.1~0.3
4.4~6.0
0.4~1.0
2.1~4.2
0.3~1.7
0.4~1.1
0.1~0.6
0.4~3.2
1.2~6.0
0.0~0.5
0.0~0.1
0.9~2.6
SO3
C3A
C4AF
0.1~0.3
Corrections to Bogue mineralogy could be made on the basis of

.but minimum, maximum
these solid solubilities.
or mean would have to be used.
2.7 Polymorphs

Minor component
Al2O3
Fe2O3
MgO
C3S
0.7~1.7
0.4~1.6
0.3~1.0
SiO2
Na2O
K2O
TiO2
0.1~0.3
0.1~0.4
C2S
1.1~2.6
0.7~2.2
0.2~0.6
0.2~1.0
0.3~1.0
0.1~0.3
4.4~6.0
0.4~1.0
2.1~4.2
0.3~1.7
0.4~1.1
0.1~0.6
0.4~3.2
1.2~6.0
0.0~0.5
0.0~0.1
0.9~2.6
SO3
C3A
C4AF
0.1~0.3
Corrections to Bogue mineralogy could be made on the basis of

these solid solubilities. .without microprobe data the correct
solubility for the particular clinker would not be known.
2.7 Polymorphs

Minor component
Al2O3
Fe2O3
MgO
SiO2
Na2O
K2O
TiO2
SO3

C3S
0.7~1.7
0.4~1.6
0.3~1.0
C2S
1.1~2.6
0.7~2.2
0.2~0.6
0.2~1.0
0.3~1.0
0.1~0.3
4.4~6.0
0.4~1.0
2.1~4.2
0.3~1.7
0.4~1.1
0.1~0.6
0.4~3.2
1.2~6.0
0.0~0.5
0.0~0.1
0.9~2.6
C3A
C4AF
0.1~0.3
0.1~0.3
0.1~0.4
For MgO we see solid solubility ranging up to 3.2% in C4AF

this is the reason the MgO contribution is limited to
2% in the Flux1338, Flux1400 and Flux1450 equations.
2.7 Polymorphs

Maximum 2%
LSF = (%CaO + 0.75x%MgO)/
(2.8x%SiO2 + 1.18x%Al2O3 + 0.65x%Fe2O3)
Minor component
Al2O3
Fe2O3
MgO
C3S
0.7~1.7
0.4~1.6
0.3~1.0
SiO2
Na2O
K2O
TiO2
0.1~0.3
0.1~0.4
C2S
1.1~2.6
0.7~2.2
0.2~0.6
0.2~1.0
0.3~1.0
0.1~0.3
4.4~6.0
0.4~1.0
2.1~4.2
0.3~1.7
0.4~1.1
0.1~0.6
0.4~3.2
1.2~6.0
0.0~0.5
0.0~0.1
0.9~2.6
SO3
C3A
C4AF
0.1~0.3
MgO substitutes for CaO in the clinker minerals when

the LSF equation is corrected the MgO is limited to 2% as
this is the approximate maximum that can replace CaO.
2.7 Polymorphs

In high MgO clinkers this is particularly important. any
MgO above 2% will be present as free MgO, periclase.
Minor component
Al2O3
Fe2O3
MgO
C3S
0.7~1.7
0.4~1.6
0.3~1.0
SiO2
Na2O
K2O
TiO2
0.1~0.3
0.1~0.4
C2S
1.1~2.6
0.7~2.2
0.2~0.6
0.2~1.0
0.3~1.0
0.1~0.3
4.4~6.0
0.4~1.0
2.1~4.2
0.3~1.7
0.4~1.1
0.1~0.6
0.4~3.2
1.2~6.0
0.0~0.5
0.0~0.1
0.9~2.6
SO3
C3A
C4AF
0.1~0.3
Periclase crystals in clinker only hydrate very slowly with

accompanying expansion potentially causing long-term
unsoundness of concrete from high MgO cement.
2.7 Polymorphs

Minor component
Al2O3
Fe2O3
MgO
SiO2
Na2O
K2O
TiO2
SO3

C3S
0.7~1.7
0.4~1.6
0.3~1.0
C2S
1.1~2.6
0.7~2.2
0.2~0.6
0.2~1.0
0.3~1.0
0.1~0.3
4.4~6.0
0.4~1.0
2.1~4.2
0.3~1.7
0.4~1.1
0.1~0.6
0.4~3.2
1.2~6.0
0.0~0.5
0.0~0.1
0.9~2.6
C3A
C4AF
0.1~0.3
0.1~0.3
0.1~0.4
Periclase crystals in clinker only hydrate very slowly with

accompanying expansion this is why MgO content is
limited to 4, 5 or 6% in international cement standards.
2.7 Polymorphs

Minor component
Al2O3
Fe2O3
MgO
C3S
0.7~1.7
0.4~1.6
0.3~1.0
SiO2
Na2O
K2O
TiO2
0.1~0.3
0.1~0.4
C2S
1.1~2.6
0.7~2.2
0.2~0.6
0.2~1.0
0.3~1.0
0.1~0.3
4.4~6.0
0.4~1.0
2.1~4.2
0.3~1.7
0.4~1.1
0.1~0.6
0.4~3.2
1.2~6.0
0.0~0.5
0.0~0.1
0.9~2.6
SO3
C3A
C4AF
0.1~0.3
High MgO clinkers must be rapidly cooled to prevent MgO

growing into large crystals in the clinker small crystals
will hydrate quickly with less long-term expansion.
2.7 Polymorphs
Solid solution of minor components in the clinker minerals, C3S,

C2S, C3A and C4AF is very important for stabilising the different
polymorphs of the minerals.
The different solid solution and polymorphic form of the clinker
minerals explains the variation in hydraulic performance of
cements made from clinkers with apparently similar chemical
composition but from different kilns or cement factories.
Understanding and optimising the polymorphic form of the
clinker minerals is one of the keys to enhancing clinker and
cement hydraulic reactivity and quality.
2.7 Polymorphs

...the
C2S can be present in , , or polymorphs
reversible transitions between the different polymorphs take
place at the following temperatures:
520C
820C
1447C
-C2S is the only polymorph with any significant hydraulic

properties therefore the presence of this polymorph must be
promoted.
This is achieved by solid solution of minor components in C2S
and rapid cooling...we have already seen in the previous
session that too much P2O5 and hence C3P can stabilise the
higher temperature polymorphs and -C2S.
2.7 Polymorphs

...the
C2S can be present in , , or polymorphs
reversible transitions between the different polymorphs take
place at the following temperatures:
520C
820C
1447C
Inversion to -C2S is accompanied by an increase in the crystal

...this shatters the clinker crystal
volume of ~10%.........
structure and causes the clinker to break down into dust... ..a
phenonema known as dusting of the clinker.
Solid solution of Al2O3, Fe2O3, SO3, K2O and Na2O,
coupled with rapid cooling, all contribute to
preventing this inversion to -C2S .
2.7 Polymorphs

C3S can be present in three triclinic polymorphs, T1, T2,T3,
...three monoclinic polymorphs, M1, M2, M3, ...and a
rhombohedral or trigonal polymorph, R1.
The transitions between the different polymorphs take place at
the following temperatures:
T2 920C
T3 980C
M1 990C
M2 1060C
M3 1070C
R1
T1 620C
The monoclinic and rhombohedral polymorphs incorporate
more solid solution in their crystal lattices and this renders them
more hydraulically reactive. ...solid solution in
industrial clinkers means the C3S is normally present in
the monoclinic polymorph.
2.7 Polymorphs

T2 920C
T3 980C
M1 990C
M2 1060C
M3 1070C
R1
T1 620C
The monoclinic and rhombohedral polymorphs incorporate
more solid solution in their crystal lattices and this renders them
more hydraulically reactive. ...hydraulic reactivity
therefore increases in the order:
triclinic<monoclinic<rhombohedral
2.7 Polymorphs

However, the hydraulic reactivity does not simply rise with the
order of temperature transition between the polymorphs.
T2 920C
T3 980C
M1 990C
M2 1060C
M3 1070C
R1
T1 620C
In particular the M1 polymorphs is more reactive than the M3
polymorph. ...maximum disorder is present in the
C3S crystals just after transition to M1 from T3, or R1 from
M3 ...subsequent transitions M1 M2 M3
reduce the disorder and strains in the C3S structure.
2.7 Polymorphs
Arthur Harrisson of Rugby Cement has reported that the combined

MgO and SO3 solid solution in C3S has an important part to play in
determining the monoclinic polymorph of C3S that dominates.
Increasing
MgO
solid
solution
in C3S
Predominatly M3 C3S,
less reactive clinker.
Mixed
M1 & M 3
C3S.
more reactive clinker.
Increasing SO3 solid solution in C3S
2.7 Polymorphs

Increasing
MgO
solid
solution
in C3S
less reactive clinker.
Mixed
M1 & M 3
C3S.
This provides an explanation for

the close correlation between
rising MgO content of clinker
and falling compressive
strength.
More MgO means more solid
solution in C3S, more M3 alite,
lower reactivity and lower
strengths.
2.7 Polymorphs

Increasing
MgO
solid
solution
in C3S
This adverse affect of rising

MgOPredominatly
content of M
clinker
3 C3S, on
less reactive
clinker.
compressive
strength
can be offset by increased
Mixed
SO3 content of clinker, solid
M1 & M
M3
solution of SO3 in C3S, more
C S. 1
alite, higher reactivity and 3
strengths .
2.7 Polymorphs
Arthur Harrissons work illustrates that it is the combined effects of

solid solution of minor components that determines the polymorphic
form of C3S Lea reports that the stabilisation of
triclinic or monoclinic C3S depends on the combined solid solution
of MgO and Al2O3.
Increasing
MgO
solid
solution
in C3S
High
(>1.5%) MgO
solid solution,
Monoclinic C3S.
Low
(<1.5%) MgO &
Al2O3 (<0.7%)
solid solution,
Triclinic C3S.
1% MgO &
Al2O3 (>0.9%)
solid solution,
Monoclinic C3S.
Increasing Al2O3 solid solution in C3S
2.7 Polymorphs

T2 920C
T3 980C
M1 990C
M2 1060C
M3 1070C
R1
T1 620C
The rhombohedral polymorph is the most disordered and
hydraulically reactive....incorporation of fluoride ions into
the C3S structure is reported to stabilise the rhombohedral
form. ...a further benefit of mineralisation.
2.7 Polymorphs

MgO, SO3, Al2O3, P2O5 and F solid solution therefore all have
an effect on the polymorphic form of C3S.. ...but it may
not be possible for a cement factory to adjust the levels of these
minor components in their clinker.. ...how else can the
polymorphic form of the C3S be controlled?
The heating and cooling regime of the clinker are important
factors determining C3S polymorphic form. ...rapid
heating and cooling are the ways to attain and stabilise the
most reactive crystal forms.
2.7 Polymorphs
Rapid heating of the clinker is achieved by sharp temperature profile

and a high rotational speed of the kiln.
Temperature
Kiln Inlet
Cement rotary kiln
Outlet
2.7 Polymorphs

Temperature
A sharp temperature profile means the

transitions T1T2T3M1M2M3R1
take place very quickly
.the newly formed C3S is in
contact with the flux for the minimum
time and large crystals cannot grow.
.maximum disorder is obtained in the
crystals with insufficient time for reordering of the structures to take place.
Rapid cooling means the crystals are
frozen in their high temperature,
polymorphs.
Cement rotary kiln
Kiln Inletdisordered
Outlet
2.7 Polymorphs

Temperature
A sharp temperature profile is achieved by a

.this
short, hot flame in the kiln
is achieved by optimising the combustion
in the main burner.
Rapid cooling is achieved by minimising
the cooling zone in the rotary section of
the kiln before the clinker falls into the
cooler
the main burner must be
inserted the minimum practical distance
the rotary section
the kiln
kiln.
Cementof
rotary
Kiln Inletinto
Outlet
We will expand on the impact of combustion conditions in

the next session of the course.
Cement Kiln
Process Chemistry
Module 2. Cement clinker quality and composition.
2.7 Solid solution & polymorphic crystal
form.

Ss Polymorphs

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CemNet Training - Course CKPC01

Module 2.7 SS Polymorphs

Cement Kiln Chemistry

In the preceding sessions of the course we have already introduced

Cement Kiln Chemistry

In the preceding sessions of the course we have already introduced

Solid Solubility (%)

(After: Lea, Chemistry of Cement)

From this the greater solubility of Al2O3, Fe2O3, Na2O

CemNet Training - Course CKPC01

Module 2.7 SS Polymorphs

Cement Kiln Chemistry

In the preceding sessions of the course we have already introduced

Solid Solubility (%)

(After: Lea, Chemistry of Cement)

Also the greater solubility of MgO in C3S rather than

Cement Kiln Chemistry

In the preceding sessions of the course we have already introduced

Solid Solubility (%)

(After: Lea, Chemistry of Cement)

Corrections to Bogue mineralogy could be made on the basis of

Cement Kiln Chemistry

In the preceding sessions of the course we have already introduced

Solid Solubility (%)

(After: Lea, Chemistry of Cement)

Corrections to Bogue mineralogy could be made on the basis of

CemNet Training - Course CKPC01

Module 2.7 SS Polymorphs

Cement Kiln Chemistry

In the preceding sessions of the course we have already introduced

Solid Solubility (%)

(After: Lea, Chemistry of Cement)

For MgO we see solid solubility ranging up to 3.2% in C4AF

Cement Kiln Chemistry

In the preceding sessions of the course we have already introduced

Solid Solubility (%)

(After: Lea, Chemistry of Cement)

MgO substitutes for CaO in the clinker minerals when

Cement Kiln Chemistry

In the preceding sessions of the course we have already introduced

Solid Solubility (%)

(After: Lea, Chemistry of Cement)

Periclase crystals in clinker only hydrate very slowly with

CemNet Training - Course CKPC01

Module 2.7 SS Polymorphs

Cement Kiln Chemistry

In the preceding sessions of the course we have already introduced

Solid Solubility (%)

(After: Lea, Chemistry of Cement)

Periclase crystals in clinker only hydrate very slowly with

Cement Kiln Chemistry

In the preceding sessions of the course we have already introduced

Solid Solubility (%)

(After: Lea, Chemistry of Cement)

High MgO clinkers must be rapidly cooled to prevent MgO

Cement Kiln Chemistry

Solid solution of minor components in the clinker minerals, C3S,

CemNet Training - Course CKPC01

Module 2.7 SS Polymorphs

Cement Kiln Chemistry