HALSTEAD G MOORE-CALCIUM ALUMINOSULPHATE I N CEMENT 413

THE COMPOSITION AND CRYSTALLOGRAPHY OF A N

ANHYDROUS CALCIUM ALUMINOSULPHATE OCCURRING
I N EXPANDING CEMENT
By P. E. HALSTEAD and A. E. MOORE

The existence of a compound of composition 4Ca0,3Al20,,SO, is confirmed and the structure,

which has body-centred cubic symmetry, is deduced t o be of the 'ultramarine' type. The high-
temperature stability of the compound is discussed, together with its potential applications in an
expanding cement.

Introduction
The possibility of making cements capable of producing an isotropic expansion in
concrete might permit self-stressing of reinforced units. The means of producing permanent
expansion which seems most promising is the introduction of materials which promote the
formation of a calcium sulphoaluminate hydrate, which may be either the low sulphate form
(3Ca0,A120,,CaS04,12H,0)or the high sulphate form (3Ca0,A1,0,,3CaS04,31-32H,0,i.e.
ettringite). The latter is thought to produce the greater expansion. The search for materials
capable of generating these compounds has directed attention to the anhydrous system
CaO-Al,O,-SO,. No ternary compounds in this system had been reported until 1957 when
Ragozinal described the synthesis of a compound to which she assigned the composition
16--3.6(CaO,A1,O3) ,CaSO,. This material was prepared by firing mixes of tricalcium aluminate
(3CaO,A1,0,) and calcium sulphate, as gypsum, at 1200" and dissolving out free lime and excess
calcium sulphate with 1N-acetic acid. The residue of insoluble calcium aluminosulphate was
identified by refractive index measurements and its composition deduced from the proportions
of lime and calcium sulphate in the material dissolved away. In 1958, Klein & Troxellz noted
that some of the material they obtained in the course of preparation of expanding cements gave
a hitherto unknown X-ray diffraction pattern. They prepared clinkers by firing mixtures of
calcium hydroxide or calcite, gypsum, and bauxite or aluminium sulphate, at about 1350"
and deduced that they had synthesised two anhydrous calcium aluminosulphates, estimating
their composition as 5Ca0,2A1,03,S0, and 9Ca0,4A120,,3S0,. I n 1961 Fukuda3 reported the
preparation of clinkers by firing mixtures of bauxite, lime and gypsum at 1350" and claimed to
have identified 3Ca0,3A1,O3,CaSO, as the major constituent in all of them.
In the present paper is described the preparation by various methods of a compound
3Ca0,3A1,O3,CaSO, (or 4Ca0,3A1,0,,S03) which gave crystallographic data which make it
clear that this is the substance reported by Klein & Troxell and Fukuda. It seems to be the
sole ternary compound occurring in the system CaO-Al,O,-SO, below 1350" and is therefore
presumably the compound prepared by Ragozina. As might be expected, it reacts with water
to form predominantly calcium aluminate hydrates, since its content of alumina is in excess of
that required to form either ettringite or the 'low' form of calcium sulphoaluminate hydrate.
In order to convert the whole of the alumina to ettringite, which might be desirable if this
compound were to be used in an expanding cement, some 6% of extra lime and 20% of extra
calcium sulphate would be needed.
Experimental
Mixtures containing CaO, A1,0, and SO, in the proportions shown in Table I were heated
in platinum containers in a platinum-rhodium-wound alumina mume furnace. No special steps
were taken to control the furnace atmosphere, but evidence from other preparations for which
the furnace had been used showed that reducing conditions were unlikely to occur. Initially
the mixtures were fired a t progressively higher temperatures from 1000" in 100" steps. It was
found from the X-ray diffraction patterns of the products that reaction went to completion a t
about 1350" and that prolonged heating at 1400" gave little further change. Later mixtures
were all fired a t 1350" for 4-12 h. Reagent-grade CaCO,, A1,0, and CaS04,2H,0 were used
for the preparations. The AI,O, and CaSO, were ignited at 1000" before use t o remove water
and were well mixed together with the calcium carbonate before firing. The dissociation pressure
of SO, over CaSO, as anhydrite has been reported4 as 29 mm. Hg a t 1350" and thermobalance
studies indicated that no measurable decomposition of the CaSO, occurred below 1250". After
firing, the preparations were examined by X-ray powder diffraction with both a camera and a

J. appl. Chem., 12, September, 1962

 414 HALSTEAD 6 MOORE-CALCIUM ALUMINOSULPHATE I N CEMENT

Table I
Compositions of products obtained by heating mixtures containing calcium sulphate, alumina and lime to 1350'
Molar proportions Molar proportions in
in mix before mix after firing (by
firing chemical analysis-SO
lost) Diffractometric analysis of product after firing (approx. yo by wt.)
Mix, ____ _ _ _ _ _ - ~ _~
No. CaO Al,O, SO, CaO A1,0, SO, CaO 3CaO,A1,0, 12Ca0,7A1,03 CaO,AI,O, Ca0,2Al,O, 4Ca0,3A1,03,
Free Com-
bined
- __..__.__~__~ _______. ~-
40 2.5 1 1 19 18.5 5s
47 2 2 1 65 2-5 24
48 1 0.75 1 0.02 4.8 3.6 1 5 5 90
49 4 3 1 0.013 4.39 3.34 1 5 2 93
SO 4.6 3.6 1 5 13 81
51 2.6 1.6 1 7 6 81
52 2 1 1 13 7-5 76
55 4 1 1 9.4 5.2 3.5 1 37 7.5 50
56 3 1 1 4.8 6.4 3.8 1 20 14 55

Geiger counter diffractometer. The rough quantitative analyses given in Table I were made
from diffractometer traces, quartz being the internal standard. The analyses of preparations
containing free CaO may be less accurate than those where free CaO was absent because of
hydration of the CaO during the taking of diffractometer records. Diffractometric analysis of
the Ca(OH), so formed proved impracticable as the two strong lines of this compound overlap
two of the lines due to the new compound.
Some of the preparations were also analysed chemically for total CaO, A1,0, and SO,
and for free CaO by a modified Franke5 method. The results of these analyses are also given
in Table I.

Results
The two mixtures giving the highest yield of the ternary compound were those corresponding
to Fukuda's formula 3Ca0,3A1,03,CaS0,. Mixture 48 is especially interesting; in this all calcium
was added as CaSO,, but, after 9 h. firing, only SO, in excess of that required to form the
,
3Ca0,3A1,03,CaS0 had been lost. Thermobalance measurement showed that SO, was evolved
at 1250" until this composition was reached and thereafter was not lost until above 1400".
Mixes 50 and 51 were prepared to check Ragozina's suggestion that the ratio of CaO,Al,O, to
CaSO, in the compound can vary. The results do not confirm this; the preparation from a
mixture corresponding to 3.6(Ca0,A1,O3),CaSO, gave a strong X-ray pattern of CaO,Al,O,
and that with 1-6(CaO,AI,O,),CaSO4a pattern showing the lines of free CaO and 3Ca0,A1,03.
MarchaP has suggested that addition of alumina to anhydrite lowers its dissociation tem-
perature, and it seems likely that this may be due to reaction giving the ternary compound.
The equilibrium pressure of SO, over 4Ca0,3A1,03,S03 is probably lower than that of SO,
over CaSO, at 1400", since the rate of decomposition of CaSO, at that temperature was estimated
from thermobalance traces to be about 30 times greater than that of 4Ca0,3A1,03,S03.
The melting point of CaSO, is reported4 to be 1623", while Lea7 gives the melting points
of CaO,A1,0, and 12Ca0,7A1,03 as 1600" and 1415" respectively, and of the eutectic between
the two (46% CaO, 54% Also,) as 1390". This would suggest that a mixture of material with
CaO/Al,O, ratio 4 : 3 would melt at between 1480" and 1500". An attempt was made to measure
the melting point of 4Ca0,3A1,0,,S03 by a rough differential thermal analysis method, but no
steps were taken to maintain the SO, pressure a t equilibrium. A value between 1590" and 1600"
was indicated. The maximum temperature reached was 1600" (a limit set by the furnace) and
subsequent examination showed that the part of the charge which had contained the thermo-
couple had melted while the remainder had not.
,
Crystallogru~hy(4Ca0,3A1,03,S0 or Ca,AI 60,,s0),
Table I1 gives the observed X-ray powder data which were obtained with a Geiger counter
diffractometer and Cu Kcr radiation. Intensities were estimated by measurement of peak heights.
The reflections can be indexed assuming a cubic cell with side length a = 18.39 A. Reflections
with (h+k+E) odd are absent, indicating body-centering, and (h00) reflections with h # 4n are

J. appl. Chem., 12, September, 1962

 HALSTEAD G MOORE-CALCIUM ALUMINOSULPHATE I N CEMENT 415

Table I1
Observed and calculated X-ray data for Ca4Al,0,,S0, and hauynite
Ca4A1,0iz,SO, Hauynite*
d (obs.) I (obs.) hkl Nt N PS d (calc.) d i
~~

6.55 1 220 8 2 6.503 6.45 3

4.92 5 321 14
~~ 4.915
~ __
~

4.61 <l 400 16 4 4.598 4.56 1

4.33 2 411 18 4.335
3.76 100 422 24 6 3.754 3.72 10
3.25 8 440 32 8 3.251
3.16 2 530,433 34 3.154
2.99 2 532,611 38 2.984
2.91 7 620 40 10 2.908 2.88 3
2.84 2 54 1 42 2.838
~ ~ ~ ~~ ~~

2.65 25 444 48 12 2.6547 2.63 5

2.60 1 7 10,550,543 50 2,6011
2.51 1 72 1,633,552 54 2.5028
2.46 7 642 56 14 2.4578 2.44 2
2.42 1 730 58 2.4 150
--.. _ _ _ _ ~ _~
2.338 <1 732,651 62 2.3359
2.297 3 800 64 16 2.2990
2.261 2 811.74 1 66 2.2634
2.192 2 554,653 70 2-1983
2.166 22 822,644 72 18 2.1675 2.159 3
__
2.135 4 831,750 74 2.1381
2-055 <1 743,840 80 20 2.0563
2.029 1 910,833 82 2.0310
1.984 1 921,761,655 86 1*9832
1*959 1 664 88 22 1.9606 1.94 1
1.876 2 844 96 24 143772
1.857 2 941,853,770 98 14578
14 0 3 3 862, 10.2.0 104 26 14034 1.79 3
1.786 1 950,943 106 1.7865
1.751 <1 952,765 110 1.7534
1.679 1 10.4.2 120 30 1.6785 1.66 1
1.664 1 11.1.0, 873 122 1-6653
1-624 8 943,800 128 32 1.6236 1-61 3
1.576 4 10.6.0. 866 136 34 1.5772
1.531 2 12.0.0, 884 144 36 1.5329
1.491 4 12.1.1, 10.6.4 152 38 1.4918
1.388 3 12.4.4 176 44 1.3865
1.356 2 12.6.2 184 46 1.3558
1.326 2 8.8.8 192
-~ 48 1-3274
1.253 2 14.4.2, 10.10.4 216 54 1.2524
{ 12.6.6
N=ha+h2+Za N t for tans cell Nps for pseudocell

absent (at least up to 14, 0,O) which suggests that the space group is I 4,32. Optically, the
crystals are isotropic, which confirms the cubic symmetry; the refractive index is 1.57. The
density (measured by displacement of kerosene) was found to be 2-61. If the unit cell contents
are assumed to be 16 (Ca,AI,O,,,SO,) the calculated density is also 2.61. The error of the
experimental determination is f 0.02, but the experimental material may also have contained
enough CaO,AI,O, (density = 2.98) to raise the density by about 0.02.
All reflections which cannot be indexed on a body-centred cubic cell with a = 9-195
(= + x 18.39)A are very weak; their intensities are all less than 5% of that of the strongest
reflection. There is therefore a well-marked pseudo-structure with cell contents 2(Ca4A1,0,,S0,).
The size and contents of the unit cell suggest that the compound is an end member of the sodalite-
noselite-haiiynite series (Table 111) with all the silicon replaced by aluminium and all sodium
by calcium atoms. The members of this series have the ultramarine structure (Fig. 1) and
space group either I i 3m or Pz 312, and the space group I< 3m is compatible with the data for
the pseudo-structure in this case. It is difficult to deduce what modifications t o this structure

J. appl. Chem., 12, September, 1962

416 HALSTE.4 I1 & MOORE-CALCI U M ALUJVlINOSULPHATE I N CEMENT

Table I11
Composition and proferties of crystals of the sodalite-haiiynite series
Unit cell Unit cell Refractive Specific
Compound composition side length a. index gravity

Sodalite Na,(AlSiO,) ,,C1, 8.888t 1.483* 2.14-2.30*

Noselite Na,(AlSiO,) ,,SO, 8.98 t 1.48-1.495* 2,25-2.40*
Hadynite NauCa,(A1SiO,),, (SO 4 ) 2 9.127 1 ‘496- 1.498* 2.4-2,5*
Calcium aluminosulphate
(pseudo-ccil) , (SO,),
Ca 8A1,202 9.19 1,569 2.63 (calc.)
2.61 (measured)
t Taken from Donnay & Nowacki, ‘Crystal Data’
* Taken from E. S. Dana, ‘Textbook of Mineralogy’

0 0 ALUMINIUM
Fig. 1. Diagrams of ultranzavine structure
The structure is a repetition of the units shown, forming a continuous three-dimensional network. In
Ca,Al,O,,,SO ,, the vertices of the polyhedron on the left are all occupied by A1 in tetrahedral co-ordination,
replacing the Si of sodalite and noselite; the oxygen atoms lie approximately a t centres of edges and thosc
sticking out from the vertices form part of the next unit. The Ca atoms lie a t the centres of hcxagonal faces
replacing the Na of sodalite, etc., and the SO, tetrahedra lie at the centre of each unit

produce the double-cell size and altered space-group, and to date it has been impossible t o
produce crystals of adequate size for single-crystal X-ray work which would permit us to settle
the problem. If this interpretation of the structure is the correct one, there is no reason t o
write the formula 4Ca0,3A1,O3,SO,; the form Ca,Al,O,,,SO, is more suitable.

Discussion
The foregoing results suggest that a compound 4Ca0,3A1,O3,SO, exists in a well defined
crystalline form and the combined evidence from chemical analyses and X-ray powder diffraction
photographs seems to indicate that the proposed formula is reasonable and correct. I t is difficult
to be sure that the phase does not include traces of oxides other than CaO, A1,0, and SO, as
does, for example, the ‘alite’ modification of tricalcium silicate, but purified materials were used
in the syntheses and care was taken t o avoid contamination during the firings. Moreover, the
proposed crystal structure does not require, or perhaps even permit, additional ions in its
framework.
This new compound is interesting for a number of reasons. It is the only ternary compound
so far detected in the CaO-A1,03-S0, system, its stability is unusual, its structure is of a rare
type and it is of potential commercial interest in cement manufacture.

J. appl. Chem., 12, September, 1962

 H A L S l E A D 6 MOORE-CALCIUM ALUMINOSULPHATE I N CEMENT 417

The stability of 4Ca0,3A1,O3,SO, is unusual because, in order t o effect combination between

lime and alumina at a reasonable rate, preparations must be heated to about 1350". At this
temperature the dissociation pressure of SO, over CaSO, as anhydrite is 29 mm. The dis-
sociation pressure of SO, over Al,(SO,), is of course much higher. I t seems that the SO, is
held in this compound in a particularly firm fashion because at 1350" its dissociation pressure
is lower even than that of SO, over CaSO,. From thermobalance studies it has been estimated
that at 1350" the rate of decomposition (i.e. loss of SO,) of CaSO, is about 30 times that of
4Ca0,3A1,0,,S03. The crystal structure proposed requires the SO, tetrahedra t o be enclosed in
a CaO-Al,O, framework which is sufficiently rigid at 1350" to retain them very firmly. The
SO, in its turn seems to stabilise the CaO-Al,O, lattice, since the melting point of
4Ca0,3A1,0,,S03 is about 1600" whereas that of a 4Ca0/3AlZ0, mixture is about 1500" and
calcium sulphate melts a t 1623".
This high-temperature stability suggests that 4Ca0,3A1,O3,SO, might be formed and remain
undecomposed during the manufacture of high-alumina cement or Portland cement if a fuel of
high sulphur content were used. The compound was first detected in laboratory preparations
of calcium aluminates being made via A1,(S04), in which it had been assumed that all SO,
would be lost during firing at 1350". A similar retention of SO, might occur in cement manu-
facture. I t would be less likely in blast-furnace slag production because of the reducing conditions
which normally prevail.
In the manufacture of expansive cements the aim has been t o produce a material which
would produce calcium sulphoaluminates on hydrolysis by water. Lafumas reports that in
preparations of calcium sulphoaluminate admixtures there was no ternary compound formed,
but only anhydrite, calcium aluminates (mainly 'C J,') and dicalcium silicate. The temperature
of preparation is not disclosed, but is presumably too low to form the ternary compound; however,
in similar studies by Klein & Troxell, the firing temperature seems t o have been high enough to
produce 4Ca0,3A1,O3SO,. It is not necessary to form this compound to produce an expansive
cement, but, if a stable substance of known composition is required as a component of an
expansive cement, 4Ca0,3AlZO,,SO, could be a convenient material, particularly as rate of
solution is an important factor in producing a controlled expansion. The compound contains
alumina in excess of what is required for either of the calcium sulphoaluminate hydrates, and
would therefore require both extra lime and extra SO, for total utilisation of its expansive
potential.
The compound is hydrolysed rapidly by water t o form predominantly calcium aluminate
hydrates. It is therefore unlikely to occur naturally, although structurally it may be regarded
as an end member of the sodalite-hauynite series of naturally occurring minerals.

Acknowledgment
This work was undertaken as part of the research programme of the Cement and Concrete
Association at Wexham Springs and is published by permission of the Director of Research,
Dr. A. R. Collins, M.B.E.
Cement & Concrete Association,
Wexham Springs,
Stoke Poges,
Bucks.
Received 28 February, 1962

References
1 Ragozina, T. A., Zh. prikl. Kham., 1957, 30, 1682
Klein, A . . & Troxell, G. E., Proc. A.S.T.M., 1958,
58, 986
3 Fukuda, N., Bull. chem. Soc. J a p a n , 1961, 34, 138
4 Tschappgt, Ch., & PiBce, R., Helv. chim. A d a ,
1956, 39, 1427
5 Pressler, E. E., Brunauer, S., & Kantro, D. L.,
Analyt. Chem., 1956. 28, 896.
a Marchal, G., J . chem. Phys., 1926, 23, 38
7 L ~ F,~M,,, 'Chemistry of cementand concrete',
2nd ed., 1956, p. 52 (London: Edward Arnold)
* Barth, T. F. W., 2. Krist., 1932, 83, 405
Lafuma, H.. Proc. Third I n t . Symp. Chent. Cement
(London), 1952, 1954, p. 584 (London: Cement
& Concrete Ass.)

J. appl. Chem., 12, September, 1262

C