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The influence of SO3

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CEMENT CHEMISTRY

I The influence of SO3

by Sayed Horkoss, Roger Lteif
and Toufic Rizk, University of
Saint Joseph, Lebanon
During the past years, the usage of high-sulphur fuel in the cement kilns
has gained ground. This change has increased the sulphate levels in
Portland cement clinker, which affects the microstructure of the clinker.
In the literature the influence of sulphate on the silicate phases has been
documented since 1968, but its effect on the C3A is still not that clear.

T
he form and distribution of
sulphate in the clinker is not only
affected by the total percentage of
SO3 in the clinker but also by the ratio of
SO3/alkali.9 As long as this ratio is low,
the sulphate is present mainly as acranite
(K2SO4) and aphtihitalite (K3Na(SO4)2).13
Increasing the ratio will lead to decreased
percentages of both previous phases
and an increased percentage of calcium
langbeinite (Ca2K2(SO4)3)13. In an
extremely high ratio of SO3/alkali and
SO3 content, the anhydrite (CaSO4)
has been detected in a very particular
clinker.7, 5, 9, 20
In addition to the above sulphate
phases, the sulphate is found in the major
clinker phases, principally in alite and
belite.19 The concentration in belite is
four to five times that in alite.19
Influence of sulphur on the
clinker phases
Minor or trace components derived from
raw meal, fuel, and refractory can affect
the reactions of the clinker formation. Eg,
moderate sulphate amounts in the raw
meal accelerate the clinkering process by
reducing the formed melt viscosity.15
The SO3 is present at the clinkering
temperature in a separate liquid phase,
immiscible with the main clinker liquid.
During cooling, some redistribution of
alkali cations and sulphate ions between
liquids may be expected to occur, the
sulphate finally solidify below 900°C.18
Influence of sulphur on
silicate phases alite (C3S) and
belite (C2S)
Sulphate affects the C3S phase from both
sides: quantity and size. Moreover, it will
influence C2S reactivity and quantity.
Sulphates stabilise C2S crystals, and
lead to a decreased amount of C3S in the
clinker.6 This conclusion was assured by
many investigations carried out later. 12,
15, 16 The stabilisation of C2S is due to
the reduction in the viscosity and surface
tension of the liquid.4 The infiltration of
SO3 will improve the reactivity of C2S.2
Alite crystal structure is expanded by
replacing SiO2 with up to 1.5 per cent
Al2O3 and 0.5 per cent SO3.2 Strunge
et al have reported that the alite crystal
size grows by a factor of three when the
percentage of SO3 increases from 0 to
2.6 per cent.17 In another study, the alite
size is related to bulk clinker SO3 in the
following linear equation:
The median long diameter Y of alite =
45 X +20 where X = SO3 (0.09 to 1.1 per the Claiss machine for sample preparation
cent) in a clinker.3
Influence of sulphur on
aluminates C3A
The quantity of aluminates is affected
by many parameters including the kiln
atmosphere.11 In the literature we found
a contradiction in the influence of SO3 on
the amount of aluminates.
• First opinion
In the absence of sulphate, one of the
forms of sodium oxide Na2O in the
clinker is the Na2O.8CaO.3AL2O3. In
the presence of sulphate, this compound
is unstable at clinkering temperature, it
will react with SO3 to produce Na2SO4
and C3A.14 Increasing the amount of SO3
will lead to raised amount of C3A in the
clinker – this was also observed in 1990
by Hamou and Sarker in their study.8
• Second opinion
The percentage of C3A is not affected by
the level of SO3 in the clinker.10, 16
• Third opinion
Increasing the amount of SO3 in the
clinker (mineralisation) decreases the
percentages of C3A, as the aluminum
atoms are to a higher degree incorporated
in the silicate phases.1
Project and methodology
Based on the above contradiction we
started our investigation to detect the
influence of SO3 on the percentages of
C3A using the available technology.
The clinker samples were selected
from different kilns, different burning
conditions and different SO3 and MgO
percentages.
Two factors were fixed: the theoretical
percentages of C3A (2.65*Al2O3
– 1.692* Fe2O3) was fixed between 5-6
per cent and the percentages of alkalis
(Na2O and K2O) in the lower levels.
For the chemical analysis, the ARL
9800, calibrated with NIST standards, and
at the Cimenterie Nationale Laboratory
(CNL) were used.
For the percentages of C3A two
XRD methods for the determination of
the clinker phases were used. The first
was the ARL9800 with XRD at CNL,
calibrated with special NIST standard
for phases in addition to many samples
analysed in references laboratories.
The second is the XRD using Rietveld
method in Titan’s R&D Center, Greece.
In addition to the XRD methods, the
optic microscope (ZEISS Axioskop 40)
technique based on ASTM C1356
was utilised. The sample preparation
was done by Struers TegraPol-15 and
TegraForce-1, and the etching of the
samples was done by Nital (99ml iso-
propyl-alcohol + 1ml concentrated
HNO3) at CNL.
Results and discussion
The clinker samples were selected from
different clinker burning conditions (large
fluctuations in the free lime). The parasite
oxides such as P2O5 and TiO2 were fixed
to avoid any interaction. The percentages
of C3A were measured with the XRD of
ARL 9800 (see Table 1).
The results in Table 1 show a big
influence of the SO3 percentages on
the amount of C3A in the clinker. In all

82 ICR AUGUST 2009

 CEMENT CHEMISTRY

Table 1: chemical and mineralogical composition of the clinker samples

LOI SiO2 CaO Al2O3 Fe2O3 SO3 MgO Na2O K2O TiO2 P2O5 Free C3A C3A
lime calcul. measured
by ARL

1 0.11 21.17 65.30 4.35 3.56 2.00 1.41 0.05 0.36 0.39 0.59 1.46 5.50 2.15
2 0.21 20.92 65.76 4.37 3.63 2.05 1.41 0.05 0.35 0.39 0.59 1.40 5.44 1.91
3 0.12 20.33 65.63 4.49 3.84 2.19 1.41 0.05 0.36 0.40 0.58 2.58 5.40 2.24
4 0.28 21.05 64.93 4.51 3.57 2.10 1.39 0.05 0.38 0.41 0.58 1.55 5.91 2.07
5 0.37 21.29 65.39 4.44 3.51 2.14 1.39 0.05 0.39 0.40 0.58 1.42 5.83 2.07
6 0.49 20.16 65.66 4.55 3.79 1.92 1.44 0.04 0.36 0.40 0.58 2.65 5.64 2.06
7 0.22 21.37 65.40 4.57 3.94 2.03 1.39 0.03 0.33 0.43 0.56 1.56 5.44 2.33
8 0.18 20.39 65.78 4.59 3.83 2.05 1.42 0.04 0.35 0.42 0.57 1.80 5.68 2.12
9 0.36 20.27 65.74 4.49 3.78 2.09 1.40 0.04 0.36 0.41 0.57 2.55 5.50 2.16
10 0.14 20.05 66.12 4.53 3.80 2.06 1.44 0.06 0.36 0.42 0.59 2.76 5.57 2.04
11 0.42 20.13 66.03 4.53 3.81 2.30 1.40 0.13 0.41 0.43 0.58 2.44 5.56 2.29
12 0.46 20.38 65.93 4.50 3.75 2.00 1.41 0.06 0.36 0.40 0.58 3.06 5.58 2.04
13 0.42 20.41 65.99 4.52 3.79 1.87 1.38 0.05 0.37 0.43 0.58 1.90 5.57 2.30
14 0.44 20.29 66.49 4.53 3.82 1.78 1.40 0.04 0.36 0.43 0.57 2.80 5.54 2.14
15 0.26 20.48 65.90 4.55 3.76 1.79 1.41 0.07 0.35 0.41 0.61 3.15 5.70 2.25
16 0.36 20.66 65.85 4.42 3.63 1.88 1.37 0.05 0.34 0.40 0.58 1.77 5.57 1.99
17 0.44 20.32 66.63 4.52 3.85 1.43 1.41 0.13 0.38 0.43 0.57 2.37 5.46 2.52
18 0.43 20.33 65.97 4.50 3.84 1.91 1.38 0.05 0.36 0.43 0.58 1.36 5.43 2.13
19 0.29 20.27 65.09 4.53 3.90 2.61 1.39 0.12 0.41 0.43 0.57 1.20 5.41 2.12
20 0.07 20.28 65.85 4.46 3.89 2.02 1.39 0.03 0.35 0.42 0.57 1.64 5.24 1.97
21 0.14 20.48 66.18 4.46 3.83 1.82 1.40 0.04 0.36 0.41 0.57 1.70 5.34 2.11
22 0.06 20.22 66.89 4.29 3.72 1.51 1.41 0.05 0.30 0.39 0.55 0.82 5.07 3.12
23 0.17 20.79 67.22 4.74 4.00 0.65 1.03 0.03 0.20 0.46 0.55 0.79 5.79 4.19
24 0.23 20.24 67.54 4.34 3.78 1.01 1.26 0.04 0.26 0.40 0.52 1.76 5.11 2.77
25 0.07 20.81 67.88 4.46 3.84 0.70 1.29 0.05 0.24 0.40 0.52 0.46 5.32 3.27
26 0.41 20.17 66.55 4.41 3.87 1.77 1.27 0.07 0.36 0.41 0.47 2.23 5.14 2.58
27 0.39 20.46 66.57 4.63 4.08 0.87 1.42 0.05 0.33 0.43 0.49 1.06 5.37 3.00
28 0.07 20.71 66.09 4.59 3.92 1.91 1.48 0.07 0.35 0.43 0.57 1.56 5.53 2.24
29 0.32 20.30 65.76 4.31 3.78 2.56 1.43 0.05 0.37 0.39 0.57 2.41 5.03 1.95
30 0.28 20.45 65.52 4.44 3.84 1.99 1.47 0.04 0.37 0.40 0.57 2.97 5.27 1.94

samples the measured percentages of C3A
were lower than the calculated.
The sample with the lower percentage
of SO3 (0.65) contains the higher
percentage of C3A (4.19). When the
percentage of SO3 exceeds 1.5 per cent,
the amount of C3A became around two
per cent.
The correlation between the amount of
C3A and the total percentages of SO3 in
the clinker was not linear – it is possibly
related to the fact that the incorporation
of SO3 and Al2O3 in the silicate phases
(C2S & C3S) is limited.
To assure the above results, parts of
the samples were sent to the R&D Center
at Titan, Greece, to be tested by XRD
Rietveld methods.
The tendency of the results found in
Greece by Rietveld method (see Table 2
and Figure 1) were comparable with that
found by the ARL 9800, the deviation
between both methods was acceptable.
In order to get better information we
did an investigation using the microscope
technique. The C3A was detected only
on the sample with low SO3 especially
sample number 23, as Figure 2 on the
next page demonstrates.
In the other samples, especially those
with over two per cent SO3, the C3A
phases were not detected and the
colour of the liquid phases became more
reflected (Figure 3). The difficulty of
C3A crystal detection, when the C3A
percentages dropped down less than three
per cent, is perhaps the result of the fine
size of the C3A crystals in the interstitial
material, this could be the results of their
microscopic identification limitation.
Conclusion
The SO3 in the clinker with low alkali
decreased the percentages of C3A. The
correlation is not linear which could
be due to the influence of several
parameters. With calculated C3A between
5-6 per cent the real amount of C3A
dropped to around two per cent, when
the total clinker SO3 exceeds 1.5 per cent.
This finding was also supported by an
optical microscope.
In the low alkali clinker, increasing
the percentages of SO3 will reduce the
amount of C3A.This could be due to
the high incorporation of aluminum
and sulphur in the solid phases. This
incorporation is limited at certain level.
References
1 borgholM, H E and jons, E

AUGUST 2009 ICR 83

CEMENT CHEMISTRY

Figure 1: comparison of C3A percentages

calculated and measured
Table 2: Comparison between the C3A results

C3A measured C3A measured C3A calculated

by ARL by Rietveld

1 2.15 1.60 5.50

2 1.91 1.20 5.44
6 2.06 1.30 5.64
10 2.04 2.30 5.57
13 2.30 1.70 5.57
15 2.25 2.00 5.70
17 2.52 1.90 5.46
23 4.19 4.25 5.79
24 2.77 3.00 5.11
29 1.95 1.30 5.03

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84 ICR AUGUST 2009

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