CEMENT and CONCRETE RESEARCH. Vol. 23, pp. 1351-1356, 1993. Printed in the USA.

0008-8846/93. $6.00+00. Copyright © 1993 PergamonPress Ltd.

RELATIONSHIP BETWEEN RAW MIXTURE AND MINERALOGICAL

COMPOSITION OF SULPHOALUMINATE BELITE CLINKERS
IN THE SYSTEM CaO-SiO2-AI203-Fe203.SO3

J. Majling, S. Sahu, M. Vlna and Della M. Roy*

Department of Ceramics, Glass and Cement
Slovak Technical University
812 37 Bratislava, Czecho-Slovakia
*Materials Research Laboratory, Pennsylvania State University,
University Park, PA 168 02, USA

(Refereed)
(Received August 10, 1992; in final form July 16, 1993)

ABSTRACT

The mineralogical (phase) composition of sulphoaluminate belite cement clinkers was

calculated using phase compatibility data of the relevant portion of the five component
oxide system CaO-SiO2-A1203-Fe203-SO 3 and was plotted in the plane of three
component raw mix. In result a phase fields map (PFM) was obtained showing
equilibrium changes in phase composition of clinkers on changes in the raw mixture
composition.

Introduction

Sulphoaluminate belite cement clinkers contain C2S and C4A3S as major phases and
essentially belong to the five component oxide system CaO-SiO2-A1203-Fe203-SO 3 (1-5). It
was already shown(6) that the phase composition of these clinkers can be calculated in a way
similar to Bogue's computation which is in principle based on solving linear equations (7).
Bogue's computation refers, however, to individual, given phase assemblages, e.g. to cases in
which a link between chemical and mineralogical composition is established beforehand.

Such limitations do not exist in the case of a generalised Bogue's calculation (8), in which
all mineral assemblages are defined in advance and the considered chemical composition of a
system is matched to the relevant mineral assembly in the course of a trial and error computation.
The common feature of such computation is moreover establishing of changes in phase
composition along some particular join of the system. Real or potential raw components can be
preferentially taken as the join end members. The major benefit of such a computation is then
the survey of mineralogical compositions in dependence with the raw mixture composition.

The availability of the phase compatibility data of the system C-S-A-F-S (9) made it
possible to perform the referred computation also for belite- sulphoaluminate clinkers. In the

1351
1352 J. Majling et al. Vol. 23, No. 6

present case the computation has been extended to consider three raw components
simultaneously.

Individual phase areas established in computation correspond to burnt and equilibrated

raw mixtures. The set of phase areas is further referred to as a phase fields map (PFM). It can be
seen to be useful in getting a good insight into the complex raw mixture and mineralogical
composition relationship, both in qualitative as well as in a quantitative way.

Results of Computation

The Fig. 1 shows the position of a belite - sulphoaluminate clinker's area in the three
component raw mixture system Limestone - Fly Ash - Gypsum. The enlarged portion of this area
(PFM) is given separately in Fig.2. The chemical composition of raw mixture components is
given in Table 1.

Individual phase fields in Fig. 2 correspond to phase assemblages which are listed in
Table 2 and represent five phase regions. Boundaries between phase compatibility areas in Fig.2.
were established via "step scanning" computations of changes in mineralogical composition of
binary mixtures at constant levels of the third component (gypsum) and represent four phase
regions. The basic, individual computation of phase changes was done according to the
procedure given in [8]. Fig.3 and 4 are results of such computations, corresponding to 0 and 5
wt.% of gypsum respectively. Underlying computed data for the establishment of graphical
dependencies in Fig.3. are given in Table 3. Similar data were received also for the other "step
scan" computations. The phase composition corresponding to singular raw mix compositions (of
Fig.2.) is given in Table 4.

GYPSUM

0 20 40 60 80 100
LIMESTONE (wt.%) FLY ASH

Figure 1. Sulpoaluminate Belite Zone in the System Limestone-Fly Ash-Gypsum

Vol. 23, No. 6 RAW MIXTURE,COMPOSITION, MINERALOGY,SULFOALUMINATEBELITE CLINKERS 1353

~._~ 10
,;S 12
lli/ 7 / /
..~6 17 '5

0
20 24 28 Cwt.Z) 32 36 40
LIMESTONE FLY ASH

Figure 2. Phase Fields Map for the Raw Mixture system Limestone-Fly Ash-Gypsum

Table 1. Chemical Composition of Raw Components (wt.%)

Oxides Limestone Fly ash Gypsum

CaO 53.44 3.64 32.55
SiO 0.36 53.65 -
A1203 1.18 28.26
Fe203 0.08 7.00 -
SO 3 0.04 0.05 46.51
MgO 1.02 2.99 -

TiO 2 1.50

LOI 42.33 2.40 20.04

Discussion

As it was shown in [ 1] the synthesis of sulphoaluminate belite clinkers, needs at least one
raw component high in alumina content. Similarly it also needs one component high in sulphate
content. This requirement is fulfilled by the present raw mix containing high alumina fly ash as
one of the components which is more over a waste material. The sulphates can be potentially
supplied by waste gypsum e.g. phosphogypsum, flue gas desulphurized gypsum etc.

The phase fields map in Fig.2 gives the consistent picture of adjoining phase regions of
the system corresponding to the particular plane of chemical compositions. The chemical
compositions are defined via the chemical compositions of the raw mix components and their
proportions.
1354 J. Majling et al. Vol. 23, No. 6

Table 2. Phase Assemblages Encountered in the Phase Fields Map +

1 C2S - C - C 3 A - C 4 A F - C 4 A 3 S
3 C2S - C - C 4 A F - C 4 A 3 S - C S
5 C2S - C3A -C 12A7 - C 4 A F - C 4 A 3 S
6 C2S - C12A7 - C A - C 4 A F - C 4 A 3 S
7 C2S - C A - C F - C F 2 - C 4 A 3 S
8 C2S - C A - C F - C 4 A F - C 4 A 3 S
9 C2S - C A - C F 2 - C2AS - C 4 A 3 S

10 C2S - C 2 F -CF - C 4 A F - C 4 A 3 S
11 C2S - C 2 F -CF - C 4 A F - C S
12 C2S - C 2 F - C 4 A F - C 4 A 3 S - C S
13 C2S - C F - C F 2 - C 4 A 3 S - C S
15 C2S - C F 2 - F - C 2 A S - C S
17 C2S - C F 2 - C 2 A S - C 4 A 3 S - C S

+ The full list of phase assemblages relevant to belite - sulphoaluminate clinkers is given in (7)

The phase area 3 of Fig.2, comprising phases C - C 2 S - C 4 A F - C 4 A 3 S - C S is the area

(assemblage) most c o m m o n l y encountered in current syntheses of belite-sulphoaluminate
clinkers.

F r o m the point of view of a technology we may consider this phase area as a safe area
because o f its extent. In contrast to this, small areas in Fig.2 indicate that products from this
range of raw mixture compositions will be uncertain in their phase composition, even in cases

100
1°°t
80 1 8O

I----
6O
Z
i,i
I.--
Z
0
40 4O
LJ / \ C3S2
CO
C3A C2AS \ / -
'ra-
m
20 /x
0
20 24 28 (wt.~) .52 .36 40
LIMESTONE FLY AS H

Figure 3. Changes in Phase Composition in the System Limestone-Fly Ash

Vol. 23, No. 6 RAW MIXTURE, COMPOSITION,MINERALOGY, SULFOALUM1NATEBELITE CLINKERS 1355

100
1°°t
~ 8oI t 80

F-
6O 60
Z
td
F-
Z
0
o 4o 40
I,I
t/3
n-
13_
2O 20

,C,AF . . , . , .

0 0
20 24 28 32 36 40
LIMESTONE (wt.~) FLY ASH

Figure 4. Changes in phase composition in the system Limestone-Fly Ash-Gypsum

(5 wt.% of Gypsum)

Table 3. Phase Content (composition) at Boundary points + in the System Limestone - Fly Ash

Phases Fly Ash (wt. %)

25.94 28.62 30.34 31.25 31.49 34.98 35.03 35.33 39.79
C2S 62.70 67.90 71.20 72.90 73.40 53.80 53.50 53.80 0.0
C3S2 49.0
C3A 27.9
C 12A7 21.9
CA 18.3 22.0 22.0
CF 4.4
CF2 3.9 4.3 4.2
C4AF 8.8 9.5 9.8
F 3.6 4.0
C2AS 41.4 42.0 42.2 45.9
C4A3S 0.4 0.4 0.4 0.4 0.4 0.4
Cg 0.1 0.1 0.1

+As boundary points are taken only those from 28.62 to 35.33 wt.% of the fly ash respectively.
They lie on the straight line phase boundaries of Fig.2 and correspond to four phase regions.
1356 J. Majlinget al. Vol.23, No. 6

Table 4. Phase composition of clinkers at singular points of interception (Fig.2.) (wt.%)

I. II. III. IV.

C9S 67.5 67.7 68.5 68.9
C2F 5.20
CF 4.2
CF 2 3.7
C4AF 9.2
C4A3 ~ 23.8 26.9 27.2 27.3

when we would concentrate to keep the raw mixture composition of the system as steady as
possible.

The Present computation is performed with limitations which are inherent to Bogue's
calculations (the true equilibrium is not achieved within the short period of burning, the presence
of glassy phase is not considered and the participating phases are taken as stochiometric).

The most practical benefit of the performed computation is to be seen in providing the
general overview on the raw mixture/phase composition relationship. This relationship may help
in the better estimation of raw component potentials for the synthesis of a particular kind of
cement clinker.

Conclusion

The derived phase fields map shows equilibrium phase changes in a small portion of the
plane section in the system C-S-A-F-S where C2S, one of the clinker minerals, is present. This
computational procedure could be extended to the whole area of the system when all phase
compatibility data are available.
This approach provides a ready-made method to estimate the suitability of raw
components (raw component substituents) for preparation of the raw mix and the synthesis of
clinkers.
References

1. Mehta, P.K., World Cement Tech. 11(4), 166 (1980).

2. Sudoh, G., Ohta, T., Harada, H., 7 th Int. Cng. on the Chem. of Cem., Vol. V, Paris, 1980,
p152.
3. Den Jun-An, Ge Wen-Min, Su Mu-Zhen, 8 th Int. Cng. on the Chem. of Cem., Vol. II, Rio
de Janiero, 1986, p300.
4. Ikeda, K., 7 th Int. Cng. on the Chem. of Cem., Vol. II, Paris, 1980, p 31.
5. Majling, J., Znasik, P., Jesenak, V., and Lacek, J., Stavivo, 3, 100 (1989).
6. Kuznesova, T.V., "Aluminate and Sulphoaluminate Cements ", Strojizdat, Moskva, 1986,
p132.
7. Taylor, F.M., Advances in Cement Research, 2. 73 (1989).
8. Majling J., Jesenak V., Roy D.M., Roy R., J. Mater. Res.,4 (2), 447 (1989).
9. Sahu S., Majling J.," Phase Compatibility in the System CaO-SiO2-A1203-Fe203-SO3
Referred to Sulpoaluminate Belite Cement Clinker" Cement Concr.Res., 23, 1331 (1993).