Advances in Cement Research, 1999, 11, No. 1, Jan.

, 27-34

Generalized Bogue computations to forecast the

mineralogical composition of sulfoaluminate
cements based on fly ashes
J. Majling,* J. Strigac* and D. M. Royf

Slovak Technical University; The Pennsylvania State University

Fly ashes, from an extensive database showing extremes in ratios of major oxides, are considered as potential
raw meal ingredients for preparation of sulfoaluminate cements. Simple algorithmized, essentially Bogue-like,
computations are performed in order to create a link between the chemical composition of raw meals and their
mineralogical composition, as expected to result from their burning. The computations refer to a set of three-
component raw meals, all containing limestone and gypsum but differing in the kind of fly ash introduced as the
third raw meal component. The individual raw meal compositions are identified in computations, yielding three
phase products, composed of C2S, C4A3S and C4AF. The content of each phase is within the following limits:
C2S, 60-7-83-4 wt%; C4A3S, 4-2-27-2 wt%; and C4AF 2-6-30-5 wt%. As a result, fly ashes are thus convenient
raw sources for production of sulfoaluminate cements. Of special interest are fly ashes low in SiOilAiOj or
Si02l(Al20i + Fe203) ratios, providing clinkers with the preferred proportions of the mineral phases.

Introduction
Sulfoaluminate cements are a novel class of cementi-
1 2
tious materials. ' They require at least three compo-
nents for their preparation. In addition to limestone and
clay, or bauxite, they need a raw meal component
providing sulfates (e.g. gypsum). Their clinker miner-
alogy tends to be confined to the phases C, C2S, C4AF,
C4A3S and CS,3 which, simultaneously, creates an
equilibrium phase assemblage in the oxide system C -
S - A - F - S . 4 Supreme representatives of sulfoaluminate
cements are Chinese industrially produced cements,
which exceed in some strength parameters even Port-
land cements.5
We have shown previously6 that by simple, essen-
tially Bogue-like, algorithmized computations (general-
ized Bogue computations) it is possible to gain an
* Slovak Technical University, Department of Ceramics, Glass and
Cement, 812 37 Bratislava, Slovak Republic,
t The Pennsylvania State University, Materials Research Laboratory,
PA 16802, USA.
(ACR 312) Paper received 24 April 1998; accepted 20 October 1998
insight into the phase chemistry of sulfoaluminate
cements in more general terms,7 that is, without
confinement to a single phase, such as their most
relevant phase assemblage (C-C2S-C 4 AF-C4A3S-
CS).3 This approach requires, firstly, that the other
phase assemblages relevant to sulfoaluminate cements
are defined 4 and, secondly, a means to associate the
clinker chemical compositions of interest to a particular
phase assemblage, from among all the potential phase
assemblages,6'7 in order to be able to set up the
adequate linear equations (e.g. see Taylor8 for a Port-
land cement case).
In cement technology, environmental concerns in-
creasingly demand the substitution of natural raw
sources by appropriate, or at least tolerable, industrial
by-products. Fly ashes, because of their similarity in
chemical composition to the natural argillaceous raw
components used for cement manufacture, are utilized
in cement technology both as a filler in blended
Portland cements or as a direct raw meal component.9
A subclass of sulfoaluminate cements, essentially the
high-alumina sulfoaluminate ones, has prevailing
amounts of the dicalcium silicate phase.3 For such
27

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 Majling et al.

cements use of the common fly ashes as raw materials Gypsum /

would appear to be quite straightforward. 10 ' 11 More-
over, bottom and fly ashes from fluidized-bed coal
combustion (with a desulfurization of flue gases),
which contain calcium sulfate and some unused lime,
may be disposed of advantageously by incorporating
them in sulfoaluminate cements. 12
Correspondingly, in this contribution we try to fore-
cast limits to the phase composition of sulfoaluminate
cements when produced using different kinds of fly
ashes.
Method of computation
6 7
As stated previously, ' the basic step in these
computations is setting up and solving the linear equa-
tions. Example linear equations are given, correspond-
ing to the phase assemblage C - C 2 S - C 4 A F - C 4 A 3 S -
CS. Table 1 lists the weight fractions of oxides in the
individual phases necessary to set up the equations.
The explicit form of the equations is given in Table 2.
The algorithmizing of computations consists of mak-
ing incremental changes to the chemical composition
(bi values) along specified lines and associating these
compositions to their relevant phase assemblages, from
among all the potential phase assemblages of sulfoalu-
minate cements (Table 5). 4
The process of computation is illustrated schemati-
cally in Fig. 1. As seen in Fig. 1 an area belonging to a
three-component raw meal can have a set of parallel
lines superimposed. Along each line, including the
basal limestone-fly ash line, the same computations
are performed in a stepwise (scan) manner, that is,
biased to chemical compositions correspondingly to the
equally spaced join lines.
The result shows that, for example, chemical compo-
Table 1. Weight fractions of oxides in individual phases
C2S C4A3S C4AF CS
c 0-6512 0-3676 0-4616 0-4119
s 0-3488
A 0-5012 0-2098
F 0-3286
S 0-1312 0-5881
/ /... y..±
»/ /
/ a / b
1 2
Lime *• Fly ash
or
limestone
Fig. 1. A construction of the phase field ('1234') in the raw
meal phase diagram from phase ranges (a, b) established for
individual lines (ji, initial point of a certain line; je, its
corresponding end point)
sitions corresponding to points lying between points 1
and 2 are only 'compatible' with assemblage 'b' from
among all the potential phase assemblages tested. Sim-
ilar boundaries for the phase assemblage 'b' can also
be found for other joins. Correspondingly, area '1234'
in the raw meal diagram encompasses an area (phase
field) belonging to the phase assemblage ' b \ and firing
raw meals with a composition corresponding to this
area will produce phases belonging to this specific
phase assemblage.
Results and discussion
Three-component raw meals for the production of
hypothetical sulfoaluminate cements were created from
lime and gypsum, with a fly ash as the third raw meal
component. The chemical compositions of the fly ashes
were obtained from a comprehensive database. 13 Fly
ashes which had shown extremes in ratios of their
major oxides were considered.
The chemical composition of fly ashes is given in
Table 3, together with their reference numbers in the
source list.1 The minimum and maximum ratios of the
considered oxides are given in Table 4.
C The results of computations are extended to phase
0-1000 field maps, given in Figs 2 - 6 . These maps represent
the raw meal compositions relevant to the preparation
of sulfoaluminate cements (expected green state) over-
laid (superimposed), for practical reasons, by the
corresponding phase compositions potentially obtained

Table 2. Linear equations corresponding to the phase assemblage C-C2S-C4AF-

C4A3S-CS
E/O AT, = C 2 S X2 = C4A3S x3 = C4AF *4 = CS *5=C Composition
(1) C 0-6512*, +0-3676*2 +0-4616*3 +0.4119*4 +0.1000*5 = 6,
(2) S 0-3488*, = 62
(3) A +0-5012*2 +0-2098*3 = 63
(4) F +0-3286*3 = 64
(5) S +0-1312*2 +0-5881*4 = 65

28 Advances in Cement Research, 1999, 11, No. 1

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 Forecast of mineralogical composition

Table 3. Chemical composition of selected fly ashes maps then correlate the chemical and phase composi-
Fly Oxides: wt% Reference
tions of the 'burnt' systems in the five-component oxide
ash No.13 system C a 0 - S i 0 2 - A l 2 0 3 - F e 2 0 3 - S C > 3 .
CaO Si02 A120 Fe 2 0 3 SO3 As is evident, Figs 2 - 6 show the same pattern of
1 16-4 58-4 12-6 5-6 10 830021 phase fields. These are explicitly denoted by field
2 31-3 30-8 21-9 4-7 20 82-2006 numbers (1-10) only in Fig. 2, and correspondingly
3 6-9 620 201 20 0-6 87-0219 listed in Table 5. The straight-line boundaries between
4 7-3 48-9 18-5 21-8 0-5 87-0239 individual phase fields correspond to four-phase re-
5 10 47-7 33-6 12-4 0-5 81-0219
gions. The intersection of boundary lines are unique
points, denoted in Fig. 5 by numbers (I-IV) corre-
sponding to three-phase compositions (Table 6). In
Table 7 the phase compositions as well as the raw
Table 4. Extreme values for the ratios of selected oxides in
the reference set of fly ashes mixture compositions of invariant points (I) are given.
These points are saturation points defining the mini-
Oxides Maximum Fly Minimum Fly mum content of lime and of calcium sulfate necessary
ratio ash ratio ash
to transform silica, alumina and ferric oxides in the raw
Si0 2 /Al 2 0 3 4-63 1 1-47 2 meal (in a burning process) to C 2 S, C4A3S and C4AF,
Si0 2 /Fe 2 0 3 31-0 3 2-24 4 respectively. Their increased contents do not change the
Al 2 0j/Fe 2 0 3 10-05 3 0-84 4
proportions of the three aforementioned clinker phases,
Si02/(A1203 + Fe 2 0 3 ) 3-2 1 1-03 5
but lead only to certain amounts of either free lime,
(free) anhydrite or both in the corresponding cement
clinkers. Consequently, the ratios of C 2 S, C4A3S and
C 4 AF depend solely on the chemical composition of
on burning (expected equilibrium state). The green the fly ash.
state, as expressed by the chemical composition of the Phase field 1 in Figs 2 - 6 shows the raw meal limits
raw meal components and of their ratios, represents the when remaining in the phase assemblages of clinker
composition of 'calcined' raw meals, that is, their state phases. However, the most relevant raw meal composi-
after liberation of H 2 0 and CO2. When omitting the tions are those with zero, low or high content 10 ' 4 of
content of minor oxides of the raw meal components, free lime, and zero, low or high content of anhydrite.
as done in the present computations, the phase fields Thus, raw meals with compositions located in the area

Lime: wt% Fly ash 1:wt%

Fig. 2. Phase fields of the raw mixture lime-fly ash 1-gypsum

Advances in Cement Research, 1999, 11, No. 1 29

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 Majling et al.

10

62 64 74
Lime: wt % Fly ash 2: wt %

Fig. 3. Phase fields of the raw mixture lime-fly ash 2-gypsum

48
Fly ash 3: wt %

Fig. 4. Phase fields of the raw mixture lime-fly ash 3-gypsum

of phase fields, starting from point I, and coinciding
with the corresponding upward boundary lines, or
extending as appropriate somewhat to their left, are of
interest.
30
On comparison of phase fields the difference in the
positions of the unique points can be clearly seen for
individual fly ashes used as raw components. This can
be expressed as the gypsum content of the raw meal
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 Forecast of mineralogical composition

10

52 54
Fly ash 4: wt %

Fig. 5. Phase fields of the raw mixture lime-fly ash 4-gypsum

52 54
Fly ash 5: wt %

Fig. 6. Phase fields of the raw mixture lime-fly ash 5-gypsum

(which varies from ~ 0-8% in Fig. 5 up to ~ 6% in
Fig. 6) in a relation to its fly ash content (which varies
from 44-9% in Fig. 4 to 68-4% in Fig. 3) and, secondly,
as a 'density of boundary lines' relative to the x axis
Advances in Cement Research, 1999, 11, No. 1
scale, and/or the amount of gypsum which brings the
unique points corresponding to assemblages containing
the calcium aluminoferrite phase (I) to those points
corresponding to calcium ferrite phases (II-IV).
31

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 Majling et al.

Table 5. Phase fields/assemblages in Figs 2-6 Table 5). All phases in corresponding phase assem-
Field No. Assemblage
blages are explicitly hydraulic, likely to bring about
new properties for hydrated cement structures. A
1 C-C2S-CS-C4AF-C4A3S
problem in their real application might be similar to
2 C-C2S-C3A-C4AF-C4A3S
3 C2S-C3A-C12A7-C4AF-C4A3S
that mentioned above: a marked change in the phase
4 C2S-Q2A7-CA-C4AF-C4A3S composition with relatively small changes in the com-
5 C2S-CA-CF-C4AF-C4A3S position of raw meals.
6 C2S-C2F-CF-C4AF-C4A3S The positions of the unique point I are given
7 C2S-C2F-CS-C4AF-C4A3S
separately in Fig. 7, in which they are depicted inside a
8 C2S-C2F-CF-CS-C4A3S
9 C2S-CF-CF2-CS-C4A3 S
phase diagram of the corresponding clinker mineral
10 C2 S-CA-CF-CF 2 - C 4 A3 S components.
11 C2 S-CA-CF 2 - C 2 AS-C 4 A3 S Clinkers close to point A are more or less belite
clinkers with a relatively low participation of nearly
equal portions of C4A3S and C4AF.3 The clinkers close
to point D are belite-calcium aluminoferrite clin-
Table 6. Phase assemblages of the points kers. 3 ' 15 ' 16 Clinkers corresponding to point B are be-
I-IV (see Figs 2-6) lite-calcium sulfoaluminate clinkers. 3,15-17 All other
Point Assemblage
clinkers can be considered as intermediates to these
clinker end-members. Clinker C is essentially a mixture
I C2S-C4AF-C4A3S of clinkers A and B, and clinker E a mixture of clinkers
II C2S-C2F-C4A3S
III C2S-CF-C4A3S
B and D. This additivity rule implies a possibility of
IV C2S-CF2-C4A3S mixing the different kinds of fly ashes inside a raw
meal in order to get the desired mineralogical composi-
tions of a final clinker.
When a comparison of Fig. 7 with Fig. 1 of Mehta 3
Table 7. Raw mixture composition and phase compositions is made, clinkers B and E can be expected to exhibit
of clinkers A-E corresponding to the points 7' (raw mixture the highest early strength.
composition, see Figs 2-6; phase composition, see Fig. 7) The non-appearance of the phase C5S2S in the phase
Clinker Raw mixture Phase composition: % assemblages implies that the phase relationship in the
composition: %* phase field maps relates to temperatures at which this
phase is not stable and decomposes to C2S and CS
Fly ash Gypsum C2S C4A3S C4AF
( > 1200—1250°C).18
A 48-5 1-6 83-4 81 8-2 The computations performed are basic, considering
B 68-4 4-7 63-6 27-2 8-9
44.9 the stoichiometric composition of the phases present.
C 4-3 80-4 16-8 2-6
D 45-9 0-8 650 4-2 30-5 Further effort should be aimed at building up a more
E 45-8 61 60-7 22-7 16-3 advanced model of phase compatibility, considering the
phases as solid solutions. Only limited literature data
* Lime content is supplemental to 100%.
are available at present to build up such a model, 1 9 - 2 6
so more phase equilibrium studies are needed inside
The last two aspects relate to a potential behaviour the relevant part of the five-component oxide system
of systems based on specified raw meals in real C-S-A-F-S.
applications, that is, the extent of changes in the A question remains concerning comparison of the
mineralogical composition of clinkers as effected by calculated and experimental (X-ray) phase composi-
the unit step changes in the compositions of raw tions of sulfoaluminate cements. Sulfoaluminate ce-
mixtures. It is seen from Fig. 4 that a change in the fly ments have the potential to be low-energy cements, 3 so
ash content as small as 0-5% causes a system to 'pass' their burning temperature in prevailing cases would be
through three different phase fields (assemblages). In expected to be kept as low as possible. Not much of the
such a case it would be practically impossible to melt, in general, would be expected to be present in
maintain the preselected mineralogical composition of clinkers during their firing, so one serious limitation of
a clinker within any of the phase fields 5 - 1 0 . the Bogue computation would be removed. The real
An inspection of the phase fields of Figs 2 - 6 shows phase composition of sulfoaluminate cements will,
a great variety in the potential clinker mineralogical however, be markedly related to the burnability of raw
compositions. The raw meals located 'below' the posi- meals used for their production, the presence of
tion of the unique point I are sulfate-deficient mixtures. impurities, mineralizers, fluxing agents, etc. 27
Alumina is only partially combined into the calcium A comparison of the computed and experimental
sulfoaluminate phase (C4A3S) and of C4AF. Experi- phase compositions of the sulfoaluminate cements con-
mentally less explored are clinkers containing C4A3S sidered in this study, for different sets of raw meal
next to other pure calcium aluminates (fields 2 - 4 in components, is a subject of our further work.
32 Advances in Cement Research, 1999, 11, No. 1

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C 2 S: wt %
Fig. 7. Phase composition of clinkers A-E corresponding to the single point I
Conclusions
The established relationship between raw mixture
compositions and mineralogical compositions of the
'burnt' raw mixtures provides a basic understanding
required for the development of sulfoaluminate belite
clinkers based on fly ashes. Fly ashes are convenient
raw meal components in this role; especially suitable
are fly ashes high in alumina, and alumina and iron
oxides, which yield clinkers with advantageous propor-
tions of clinker minerals.
Acknowledgements
The authors acknowledge the support of the NSF
International Cooperative program NSF-INT-9001204,
partial support by grant 1/990976 of the Slovak Minis-
try of Education and by the grant COPERNICUS CIPA
CT 94-0105.
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30 July 1999
Advances in Cement Research, 1999, 11, No. 1