CEMENT and CONCRETERESEARCH. Vol. lO, pp. 753-758, 1980. Printed in the USA.

0008-8846/80/060755-06502.00/0 Copyright (c) 1980 Pergamon Press, Ltd.

SULFATES IN CEMENTCLINKERING: IMMISCIBILITYBETWEEN

SULFATE AND OXIDE MELTSAT 1350C.

F.P. Glasser

and

J. Marr

Department of Chemistry, University of Aberdeen

Meston Walk, Old Aberdeen AB9 2UE, Scotland

(Communicated by J. Skalny)
(Received July 21, 1980)
ABSTRACT
An oxide liquid having an i n i t i a l composition CaO = 54.8, A~203= 22.7,
Fe203 = 16.5, Si02 = 6.0 (wt %) was equilibrated at 1350C with molten
CaSO,-K2SO,-Na2SO, mixtures.
Five melts showed macroscopic liquid
immiscibility.
Chemical analyses of the coexisting liquids are
presented showing the partition of chemical components. The relevance
of extensive oxide-sulfate liquid immiscibility to cement clinkering
is discussed.
Oxid-Schmelzen mit einer anf&nglichen Zusammensetzung CaO = 54.8,
A~203 = 22.7, Fe203 = 16.5, Si02= 6.0 (Gew. %) wurden bei 1350C mit
geschmolzenen CaSO,-K2SO,-Na2SO,-Mischungen ins Gleichgewicht
gebracht. Funf Schme!,zen erwlesen slch makroskop]sch als unmischbar.
Die koexistierenden flussigen Phasen wurden analysiert und daraus die
V~rteilung der chemischen Komponenten bestimmt. Die Bedeutung der
haufig auftretenden Unmischbarkeit von Oxid- und Sulfat-Schmelzen
fur die Zementklinker-Bildung wird diskutiert.
II

Introduction
Sulfur is known to play an important role in the cement clinkering cycle,
although insufficient thermodynamic and phase equilibria data are available to
account for its behavior in a systematic manner. In previous papers, the
mineralogy of the condensed phases is described and phase equilibria data
presented on portions of the CaO-A~203-Fe203-SiO2-CaSO,-K2SO, system relevant
to cement (I-4). A sulfate liquid phase may develop at temperatures <850C,
but these eutectic liquids are poor solvents for both CaO and Si02; at lO00C,
CaO and ~'Ca2SiO, are soluble only to the extent of ~I.0%. W.C. Taylor (5)
reported that at higher temperatures, such that an oxide liquid developed,
melts containing sulfates and oxides showed signs of immiscibility. The
present paper confirms the existence of this immiscibility and gives quantitative data on element fractionation between the two immiscible liquids.
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F.P. Glasser, J. rlarr

Experimental
Samples containing sulfates and oxides were equilibrated in sealed s i l i c a
tubes, lined with Pt f o i l to prevent contact between the charge and Si02 tube.
The composition of the oxide fraction was chosen so that i t s i n i t i a l
composition lay at the eutectic between C3S, C2S, C3A and C4AF. Table 1
compares the analysis with the intended composition, which was taken from Lea
and Parker's phase equilibrium data (6).
The charge was prepared from
analytical reagent grade carbonates and oxides. After an i n i t i a l s i n t e r i n g ,
the charge was repeatedly fused in a Pt crucible at 1450C and quenched until
a homogeneous glass was obtained.
Portions of this crushed glass were used
as one s t a r t i n g material.
TABLE I.

For the study of l i q u i d immiscibili t y , weighed portions of dry powdered

Oxide Liquid Composition
oxide glass were blended with the
Oxide
Composition, wt %
calculated amounts of pure, well dried
Component
Intended
Determined c r y s t a l l i n e sulfates (CaS04, K2S04 and
Na2S04). Moisture, i f present in the
CaO
54.8
54.7
charges, caused the Si02 tubes to
AL203
22.7
21.1
rupture when subsequently heated.
Fe203
16.5
17.6
Approximately equal weights ( ~ 0 . 3 g)
Si02
6.0
6.4
of oxide and sulfate fractions were
used, giving ~0.6 g charges.
These
K20
0.0
0.04
were tamped into P t - f o i l crucibles and
S03
0.0
0.0
subsequently sealed into evacuated
I00.0
99.8
thick-walled Si02 tubes, 8 mm internal
diameter. These often survived heating
for 0 . 5 - I . 0 h at 1350C, a f t e r allowing an extra 0 . I - 0 . 2 h for the tube and
contents to reach thermal equilibrium with the furnace.
Although the Si02
tubes were very soft at 1350C they showed l i t t l e signs of swelling or
collapse: we suppose that the i n t e r n a l , self-generated pressure of v o l a t i l e s
must have balanced the external pressure of ~ I bar. Vapor-phase transport
of species away from the l i q u i d phase(s) was inhibited by keeping the top of
the tubes s l i g h t l y hotter than the bottom, or l i q u i d phase(s) end.
At the conclusion of each experiment the tube, cradled in a l i g h t
r e f r a c t o r y - b r i c k holder, was removed from the furnace and allowed to cool
quickly. The Pt l i n e r did not adhere strongly either to the Si02 tube or to
the charge and could often be peeled back to reveal the charge. Two
immiscible liquids were found and the frac~ons could be separated under a
binocular microscope for subsequent chemical analysis.
Results
After heating, the intimate mechanical mixture had melted completely and
undergone phase separation.
The oxide melt was s t i l l mainly glassy:
it
gave only a very weak X-ray powder pattern of proto C3A (7), a phase which is
believed to c r y s t a l l i z e readily from undercooled melts.
The sulfate l i q u i d
was white in color and, on account of i t s lower density, constituted the
upper layer.
In runs of short duration, t y p i c a l l y 0.I - 0.2 h, l i q u i d l i q u i d separation was incomplete and globules of one l i q u i d were frequently
found dispersed in the other.
But in 0.5 - 1.0 h, phase separation was
v i r t u a l l y complete and the two liquids had a sharp meniscus.
The appearance
of the two-liquid interface is shown at two magnifications in Fig. I .
The
sulfate l i q u i d c r y s t a l l i z e d completely during the quench and thus shows a
fracture surface c h a r a c t e r i s t i c of p o l y c r y s t a l l i n e materials, whereas the

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SULFATES, OXIDES, CEMENTCLINKER, LIQUID IMMISCIBILITY

FIG.

Scanning electron micrographs of the l i q u i d - l i q u i d interface.

(Left) Low magnification view : the white bars are O.l mm.
The smooth dark grey area is the glassy oxide liquid and the
brighter and rougher area is the sulfate melt, i n i t i a l l y KNaSO,.
(Right) Higher magnification view : the white bars are O.l mm.
The orientation is such that the oxide liquid is at the bottom.
The sulfate melt has crystallized and cracked during cooling.

oxide melt looks dark and has a smooth conchoidal fracture. This microscopic interpretation was supported by chemical analyses of the coexisting liquid, the results of which are presented in Table 2. Owing to the
inclusion of a small but variable amount of Pt in each sample, the
analytical totals of the elements determined were in the range 92 - 96% :
the values shown have been rescaled to I00%.

Discussion
All ions present in the mixtures may, in theory, be partitioned between
the two coexisting liquids. At 1350C, however, A~203, Fez03 and Si02 are
comparatively insoluble in the sulfate liquid and S042- is v i r t u a l l y
insoluble in the oxide melt, whereas Ca, K, and Na are appreciably soluble
in both liquids. In equilibrations made using K2SO4-Na2S04 liquids, the CaO
content of the sulfate liquid increased; the extra CaO was, of course gained
by abstraction of CaO from the oxide liquid.

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F.P. Glasser, J. Marr
Table

Compositions of Coexisting Liquids

Equilibration : 1 hr at 1350C, self-generated atmosphere.

l.

Sulphate composition i n i t i a l l y Na20 = 14.48, K20 = 36.12, SO3 = 49.40 wt %.

Oxide, wt %
CaO
A~203
Fez03
Si02
Na20
K20
S03

2.

52.18
22.03
16.61
6.58
1.66
0.94
0.00

CaO
A~203
Fe203
SiOz
Na20
K20
S03

51.31
22.17
16.76
6.23
2.86
0.67
0.00

53.42
21.93
16.37
6.40
0.90
0.97
0.00

2.49
0.0
0.08
0.0
26.84
17.71
52.88

13.17
0.0
0.19
0.0
II.46
22.73
52.45

Sulphate Composi:tion i n i t i a l l y Na20 = 21.90, K20 = 18.89, CaO = 6.15,

SO3 = 53.04 wt. %
Oxide, wt %
CaO
A~203
Fe203
SiO~
Na20
KzO
S03

5.

Sulphate, wt %

Sulphate composition i n i t i a l l y Na20 = I0.52, K20 = 24.07, CaO = 12.96,

SO3 = 52 .45 wt %
Sulphate, wt %
Oxide, wt %
CaO
A~203
Fe203
Si02
Na20
K20
S03

4.

2.23
0.0
0.17
0.0
13.32
34.77
49.41

Sulphate composition i n i t i a l l y Na20 = 29.16, K20 = 17.96, SO3 = 52.88 wt %.

Oxide, wt %

Sulphate, wt %

52.80
21.96
16.76
6.04
1.81
0.62
0.00

Sulphate, wt %
6.74
0.0
0.24
0.0
21.49
18.47
53.06

Sulphate composition i n i t i a l l y Na20 = 10.71, I(20 = 32.70, CaO = 6.23,

SO3 : 50.56 wt %.
Oxide, wt %
Sulphate, wt %
CaO
52.85
6.32
A~z03
22.14
0.0
Fe203
16.57
0.28
SiO~
6.37
0.17
Na~O
1.12
If.04
K~O
0.96
31.65
S03
0.0
50.56

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757
SULFATES, OXIDES, CEMENTCLINKER, LIQUID IMMISCIBILITY

N a 2 SO4
Oxide

(~2 o)

coso~ co~K2(so34) K2s~o

(K20)

7--Oo \
yLv~
"%

/~
COS04

""'---...~

co2K2(so
)3
FIG.

K2so4

Partition of Na20 and K20 between immiscible clinker liquids.

The partition of alkalis between the two immiscible liquids is of some

significance to cement clinkering.
The choice of experimental conditions and
hence, the restraints imposed, suggest that the partition may be visualized
as shown in Fig. 2. The inset to this Figure shows a tetrahedron, one vertex
of which represents the i n i t i a l composition of the clinker oxide melt, while
each of the remaining three vertices represents one of the sulfate components CaSO,, K2SO, and Na~SO,. The plane defined by these three vertices is shown
in more detail in the main portion of the Figure, where data points show the
compositions of the sulfate melts studied. I t is helpful to think of the
triangular grid marks on this plane representing not only CaSO,, K2SO, and
Na2S04, but also <CaO>, <K20> and <Na~O>, respectively, where < >
represents a species or component in solution in the oxide melt. Contours
projected on this plane thus show the amount of <K20> and <Na20>
dissolved in the oxide liquid, and the amount of alkali present in the oxide
liquid can then be correlated with the composition of the sulfate liquid.
Phase equilibrium determinations thus predict that cement clinkers
which retain alkali sulfates to~1350C will develop two immiscible liquids.
However, loss by evaporation of sulfate is enhanced by the relatively high
vapor pressure of this liquid. I t is not feasible to form dilute solutions

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Vol. I0, No. 6

F.P. Glasser, J. Marr

of sulfate dissolved in oxide, thereby lowering the vapor pressure of alkali

sulfates.
Considering the potential mineralizing action of sulfates on clinker,
i t is d i f f i c u l t to see how they can act effectively in the high-temperature
part of the cycle. First, the high vapor pressure of molten sulfates leads
to their ready evaporation. Secondly, any alkali sulfate which escapes
evaporation and is retained in the clinker is l i k e l y to be present as
isolated pools of l i q u i d which not only have a low s o l u b i l i t y for CaO, AL203,
Fe203 and SiO2, but which are also immiscible with the main oxide melt phase.
References
I.

Y.B. Pliego-Cuervo and F.P. Glasser, Cement Concr. Res., 7, 477 (1977).

2.

Y.B. Pliego-Cuervo and F.P. Glasser, Cement Concr. Res., 8, 455 (1978).

3.

Y.B. Pliego-Cuervo and F.P. Glasser, Cement Concr. Res., 9, 51 (1979).

4.

Y.B. Pliego-Cuervo and F.P. Glasser, Cement Concr. Res., 9, 573 (1979).

5.

W.C. Taylor,

6.

F.M. Lea,

7.

R.M. Herath Banda and F.P. Glasser,

J. Res. Nat. Bur. Standards,

29, 437 (1942)

R.P. 1512.

The Chemistry of Cement, Edward Arnold (London) 1970 (3rd Edn.)

Cement Conc. Res.,

8, 665 (1978).