Cement and Concrete Research 131 (2020) 106009

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Cement and Concrete Research

journal homepage: www.elsevier.com/locate/cemconres

Formation, composition and stability of ye'elimite and iron-bearing solid T

solutions
F. Bullerjahna,c, , T. Scholtenb, K.L. Scrivenerc, M. Ben Hahaa, A. Wolterb
⁎

a
HeidelbergCement AG, 69181 Leimen, Germany
b
Institute for Non-Metallic Materials, Technical University of Clausthal, Zehntnerstrasse 2a, 38678 Clausthal-Zellerfeld, Germany
c
Laboratory of Construction Materials, Ecole Polytechnique Fédérale de Lausanne, EPFL-STI-IMX-LMC, Station 12, 1015 Lausanne, Switzerland

ARTICLE INFO

Keywords:
Ye'elimite
Formation
Stability
Decomposition
Calcium aluminates

1. Introduction
Ye'elimite (Ca4Al3O12SO4 or C4 A3S ) is the main phase of Calcium
SulfoAluminate (CSA) type clinkers. Those clinkers are traditionally
produced from sintering mixes of virgin raw materials such as lime-
stone, bauxite, clay and calcium sulfate. The production is very similar
to that of Portland cement clinker, whereby oxidizing conditions [1] [2]
and sintering temperatures of about 1250 °C should be applied [2] [3]
[4]. The optimal production temperature depends on the type of raw
materials used, the raw mix formulation [2], the formation of inter-
mediate phases [5] and the mineralizing effect of some elements [6]. A
comprehensive summary about the actual advances in understanding
ye'elimite-rich cements was recently published [7]. Belite-rich CSA
types, a subclass sometimes referred to as “belite ye'elimite ferrite
(BYF)” are gaining increasing interest recently. This is due to the po-
tential to substitute virgin raw materials such as bauxite (expensive) or
limestone (source of CO2) with industrial by-products and wastes [8]
[9] [10]. Besides a significant reduction of costs and of CO2 emissions,
that could increase the content of minor elements such as alkali,
phosphor and heavy metals and in particular iron [9] [10]. In some
cases, the formation of iron-rich clinkers is even targeted [11] [12]. It
was already reported that the presence of iron affects the polymorphism
and hydraulic reactivity of CSA, BYF [10] [13] and of synthetic
ye'elimite [14] [15] [16] [17] [18]. The authors lately reported, that
the alteration of the hydration kinetics is linked to the formation of
secondary mayenite rather than to the hydration kinetics [18]. How-
ever, it remains unclear, why or better how the formation of mayenite
occurs in the first place. Mayenite can form either as an intermediate
phase at low sintering temperatures [19], whereby minor elements such
as iron can have a mineralizing and stabilising effect [20] [21] [22].
Alternatively, mayenite can be formed as a secondary product from the
decomposition of ye'elimite and due to the associated loss of sulphate
by the volatilization of SOx (mainly as SO2) [1]. This was lately con-
firmed by thermodynamic calculations [23], demonstrating the impact
of high sintering temperatures and or low SOx partial pressures on the
thermal stability of ye'elimite.
Stoichiometric ye'elimite has cubic symmetry at temperatures above
800 °C and undergoes a phase transition leading to an orthorhombic
symmetry at room temperature [14] [24] [25] [26]. However, litera-
ture reports the simultaneous presence of both types in CSA and BYF
clinkers [10] [27]. Several research groups reported the possible sta-
bilisation of a pseudocubic symmetry by incorporating foreign ions
such as iron [13] [14] [28]. However, results regarding the composition
or thermal stability ye'elimite(−rich) clinkers are difficult to compare,
due to distinct differences in the synthesis protocols, lack of information
and the different characterisation techniques applied. This is especially
of relevance, as several aspects such as the raw material fineness and
homogenization, heating rate, synthesis temperature, dwell times and
(kiln) atmosphere as well as the repetition of the sintering has a pro-
found impact on the clinker formation, composition and ultimately, the
hydraulic reactivity [19]. Several studies have demonstrated that for-
eign elements can have a fluxing and mineralizing effect [29] [30] [31].
Consequently, the presence of such elements may alter the optimum
process conditions and the achieved composition of CSA or BYF

⁎
Corresponding author at: HeidelbergCement AG, 69181 Leimen, Germany
E-mail address: frank.bullerjahn@heidelbergcement.com (F. Bullerjahn).

https://doi.org/10.1016/j.cemconres.2020.106009
Received 23 September 2019; Received in revised form 30 January 2020; Accepted 3 February 2020
0008-8846/ © 2020 Elsevier Ltd. All rights reserved.
F. Bullerjahn, et al. Cement and Concrete Research 131 (2020) 106009

clinkers. Ultimately, this may affect another critical related aspect,
namely the thermal stability of the sulfur-bearing clinker phases such as
anhydrite or ye'elimite [32] [33].
The motivation of this work was to better understand the para-
meters linked to the formation and thermal stability of ye'elimite, in-
cluding the role of iron. For this purpose several synthesis campaigns
were carried out, varying the raw materials types, fineness, homo-
genization and the synthesis protocol. Ultimately, the obtained clinkers
were characterized using a multi-method approach to assess the se-
quence of phase formation, the clinker microstructure and the ele-
mental composition of ye'elimite. The thermal stability of ye'elimite and
of the iron-bearing solid solutions was investigated, by assessing the
impact of the sintering temperature and dwell time. The findings were
finally compared to the decomposition rate of several ye'elimite types
by thermal analyses.
2. Materials and methods
Several ye'elimite synthesis campaigns in different labs were carried
out. The campaign specific characteristics will be given in Sections 2.1
and 2.2 below.
2.1. Materials for the evaluation of the ye'elimite formation and
composition
Three synthesis campaigns were carried out to determine the op-
timum material and process conditions to produce ye'elimite, including
the impact of iron. Reagent grade materials were used for all tests. The
gypsum “G1” was calcined for 2 h at 700 °C to obtain anhydrite. This
anhydrite was then used for the synthesis campaigns S1 and S2. The
gypsum “G2” was used as received for series S3. The composition of the
starting materials is given in Table 1.
The raw mixes of the series 1 (S1) are designed to achieve a stoi-
chiometric pure phase, i.e. 100% ye'elimite. However, a loss of sulfur
was observed after each sintering step [15]. Consequently, 5% of an-
hydrite was added prior to 3rd sintering in order to compensate for the
measured sulfur loss. The mixes from series 2 (S2) and series 3 (S3)
should give a clinker composed of 95% ye'elimite and 5% of excess
anhydrite. The excess of 5% anhydrite was targeted to compensate the
potential volatilization of SO2 throughout the sintering, as reported
earlier for S1 [15] and in agreement to other studies [19] [34]. The raw
mixes of S2 were not analysed and there is no sample left. The differ-
ences in the targeted mineralogy of S1 and S3 can be seen by the higher
Al2O3 content and lower CaO and SO3 contents in S1 compared to S3.
See for more details also Table 6 and Fig. 13 in the supporting in-
formation.
2.2. Materials for the evaluation of the thermal stability of ye'elimite
Two raw meal compositions were tested, namely stoichiometric Y
(C4 A3S ) and another iron-rich solid solution type 0.25Fe-Y
(C4 A2.75F0.25S ). The composition of 0.25Fe-Y was chosen instead of Fe-Y
(i.e. 0.2Fe-Y) to evaluate the thermal stability, as this is closer to the
maximum incorporation level of iron determined in this study (see
Section 3.1.4). Always stoichiometric quantities of the raw materials
(technical grade limestone [ > 98 wt.%], reagent grade for the others)
were weighed with an accuracy of ± 0,001 g and mixed for 30 min
using a multi-shaft pugmill mixer (Gebrüder Lödige). The achieved
chemistry was checked by X-ray fluorescence analyses. Always 50 g of
the raw mixes were tempered for 24 h at 650 °C in a laboratory vacuum
furnace [35] to release all water and carbon dioxide. The low tem-
perature of 650 °C was chosen to avoid any phase formation (e.g. such
as calcium aluminates or ferrites), which was checked and confirmed by
X-ray diffraction. The obtained powders were pressed to pellets (dia-
meter of 20 mm and height of 15 mm) using a pressure load of 3 MPa
for 30 s. The pellets were placed in an open platinum crucible. The
batch sintering trials were done in a lab muffle furnace at ambient air.
The muffle furnace was set to different temperatures ranging from
950 °C to 1400 °C using intervals of 25 °C or 50 °C. The already tem-
pered sample was placed directly in the furnace at a given temperature.
Two types of sintering trials were than carried out:
1) The mixes were sintered for 48 h at chosen temperatures (Section
3.2.1)
2) The sintering duration was varied from 5 min to 180 min for chosen
temperatures (results reported in the supporting information Section
5.x.y Fig. 21 and Fig. 22)
The thermal stability of anhydrite and of four types of ye'elimite
(with x = 0.00, 0.05, 0.13 and 0.2 in C4 A3 x Fx S) were assessed by
thermogravimetry in another set of experiments. For that, anhydrite
was prepared from gypsum by tempering for 24 h at 650 °C in a la-
boratory vacuum furnace [35]. The same was applied for the four
stoichiometric mixes for the synthesis of ye'elimite. Moreover, the
mixes were sintered afterwards at 1250 °C, till ye'elimite was the only
XRD detectable sulfate-bearing phase. All obtained clinkers were
ground after cooling by hand in an agate mortar to a fineness of
d90 < 63 μm. The ground materials were finally stored under vacuum.
2.3. Methods
The following methods used are described in detail elsewhere [36]
and are only summarized here. The specific surface area (SSABET) was
determined by five-point N2 absorption/desorption isotherm

Table 1
Measured chemical composition (XRF) of the raw materials (for all synthesis campaigns) and the produced raw mixes in g/100 g; L.o.I = loss of ignition at 1050 °C.
CaCO3 Al2O3 Fe2O3 “G1” “G2” RM Y RM Fe-Y RM Y RM Fe-Y
CaSO4·2H2O CaSO4·2H2O S1 S1 S3 S3

L.o.I. 43.56 0.05 1.90 20.81 20.54 18.05 18.25 17.78 17.94
Free of L.o.I.
SiO2 0.67 0.03 0.25 0.25 0.04 0.12 0.10 0.23 0.37
Al2O3 0.18 99.88 0.05 0.00 0.00 51.80 46.91 47.60 45.16
TiO2 0.02 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
MnO 0.02 0.00 0.15 0.00 0.00 0.00 0.01 0.00 0.01
Fe2O3 0.11 0.00 99.51 0.00 0.00 0.02 5.10 0.39 5.28
CaO 98.20 0.00 0.00 41.29 41.49 35.60 35.50 36.23 34.89
MgO 0.56 0.01 0.00 0.48 0.01 0.51 0.48 0.14 0.15
K2O 0.05 0.00 0.00 0.01 0.00 0.00 0.01 0.01 0.01
Na2O 0.02 0.08 0.03 0.00 0.00 0.02 0.02 0.01 0.02
SO3 0.07 0.00 0.00 57.97 58.46 11.93 11.85 15.36 14.07
P2O5 0.12 0.00 0.02 0.00 0.00 0.00 0.00 0.02 0.02
Sum 1050 °C 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00

2
F. Bullerjahn, et al.
measurements using a NOVA Touch NT4LX-1 from Fa. Quantachrome
and applying the BET-equation. The particle size distribution (PSD) was
determined by laser diffraction using a Malvern MasterSizer 2000 ap-
plying the Fraunhofer model. The qualitative and quantitative phase
assemblages of the tempered and sintered materials were examined
using X-ray diffraction (XRD) analysis coupled with Rietveld refine-
ments (QXRD). The XRD patterns were obtained at room temperature
using a Bruker D8 Advance in a θ-2θ configuration with a monochro-
matic CuKα radiation (λ = 1.54059 Å) and equipped with the LYN-
XEYE (1-d) detector. The generator settings were 40 kV and 40 mA. The
measurement range was 5° to 70° 2θ with a step-size of approximately
0.02°. Continuous rotation was applied during the data acquisition.
Topas 5.0 was used for quantitative analysis. The same refinement
strategy and crystallographic structures were used as reported earlier
by us [18] [36].
Thermogravimetric analyses (TGA) coupled with a mass spectro-
meter (MS) were carried out in order to determine the thermal stability
of sulfate bearing phases. The set-up enables the combined, continuous
measurement of the mass loss over the temperature range of interest,
linked to the composition of the respective gaseous phase. For that
purpose a Netzsch TG/STA-QMS 403D Aëolos device was used. Always
a fixed sample mass of 20 ± 1 mg was tested. The apparatus includes a
mass spectroscopy unit, enabling the characterisation and quantifica-
tion of the emitted vapour phases such as e.g. water, CO2, SO2 and O2.
Several heating rates ranging from 2.5 to 10 K/min were applied, as
indicated in the respective Fig. A blank reference measurement was
done prior to each analysis, in order to enable the air buoyancy cor-
rection. Thus, a baseline correction could be applied for each sample
and measurement condition. Nitrogen was typically used as purging
gas, if not stated otherwise. Some trials were carried out using synthetic
air with different oxygen levels. The gas volume flows were kept con-
stant at 50 ml/min in all segments of the device. The control of the
calibration and quantification of the released vapour composition,
using reagent grade gypsum as reference material, was lately presented
by one of the authors [37].
The microstructure of the clinkers was assessed on polished samples
using a scanning electron microscope (SEM). The device was further
coupled with energy-dispersive X-ray spectroscopy (EDS) to determine
the elemental composition of ye'elimite and especially the level of the
aluminium by iron substitution. The microstructural and chemical SEM
analyses were supplemented using a scanning transmission electron
microscope (STEM) coupled with a Bruker XFlash EDS detector. For
that, thin sections (100–150 nm) were prepared using a Focused Ion
Beam (FIB). The details can be found in [38] for SEM-EDS and [31] for
STEM.
3. Results and discussion
3.1. Part I - ye'elimite formation and composition
3.1.1. Ye'elimite formation sequence, intermediate phase compositions and
role of iron
In the first sintering campaign “S1”, we investigated the impact of
the applied sintering temperature and repetition on the achieved
clinker mineralogy. For that, the raw mixes were ground and homo-
genized as a suspension in a vibration disc mill (VDM) and dried for
24 h at 110 °C. The mixes were sintered three times for 1 h at the
respective temperature. The clinkers were ground after each sintering
step for 1 min as dry powder in the VDM. The quantitative results after
each sintering cycle are shown in Fig. 1.
Only an orthorhombic ye'elimite type is present in Y, whereas it is
predominantly a cubic type in Fe-Y. Moreover, the fraction of “alumi-
nates” is mainly composed of krotite (CA) together with some grossite
(CA2) or mayenite (C12A7). It is important to note, that grossite is only
detectable at low sintering temperatures such as 1100 °C (traces at
1150 °C) and disappears at higher ones. This indicates that grossite is
3
Cement and Concrete Research 131 (2020) 106009
formed initially as intermediate phase, which further reacts with lime
to from krotite. This is consistent with the results presented in Fig. 2.
The fraction “others” sums up corundum, lime, anhydrite and traces of
spinel. Additionally, some hematite was found in the Fe-Y clinkers. The
temperature-related quantity of the calcium aluminates is significantly
increased in the Fe-Y sample compared to Y after the 1st sintering cycle
at sintering temperatures below 1200 °C. The formation of ye'elimite is
strongly enhanced in Fe-Y at 1200 °C and 1250 °C compared to Y.
Those results suggest that the calcium aluminates represent an in-
termediate step and react further with anhydrite to form ye'elimite.
Moreover, the formation of ye'elimite is a transport-limited process
(seemingly limited by ion diffusion and less by permeation as the ma-
trix is highly porous, see Section 3.1.2). The presence of iron allows for
a larger quantity of flux to form, particularly at lower temperatures (see
also Section 3.1.2). This in turn facilitates the dissolution, transport and
homogenization of the elements, the densification of the microstructure
and the formation of intermediate products such as (ferro-) aluminate
phases. The transport limitation concept is supported by the experi-
mental results (see for more details also the tables Table 7 to Table 9
and Fig. 18 to Fig. 20 in the supporting information). The faster for-
mation of the intermediate (ferro-) aluminate phases in turn promotes
the formation of (solid solution) ye'elimite as already proposed in [39]
[40]. The beneficial impact of iron on the ye'elimite formation at lower
sintering temperatures vanished already with the 2nd sintering, i.e. after
the 1st intermediate grinding, indicating that increasing the fineness
and homogeneity promotes, as expected, the formation of ye'elimite.
Additionally, the beneficial effect of iron seems to matter only at sin-
tering temperatures up to about 1250 °C. Already at 1300 °C a higher
ye'elimite content is reached in Y compared to Fe-Y after the 1st cycle.
The optimum sintering temperature is in between 1200 °C to 1250 °C
for Fe-Y, whereas it is about 1300 °C for Y. This is consistent with [29]
[41].
The XRD analyses were supplemented with SEM-EDS analyses of
polished sections of Y after the 3rd sintering repetition at 1300 °C (see
Fig. 2). It is important to note, that those transition textures are typi-
cally rare in the final clinker but were observed in the products of all
three series (see e.g. Fig. 4). Corundum is present in the center of the
particle. This phase is surrounded by a rim of grossite, followed by
krotite with some intermixed mayenite. Finally, ye'elimite appears,
which also contains some traces of “residue” anhydrite. The composi-
tion of the particle is further visualized by an idealized scheme. Those
results further verify our XRD analyses. Additionally, it also strengthens
the hypothesis that the aluminate phases form as intermediate products
and that the formation of ye'elimite is a transport limited process.
Due to the faster formation of ye'elimite in the presence of iron by
the enhanced formation of intermediate calcium (ferro-) aluminates, it
is important to understand how iron influences those “precursor”
phases. The formation of grossite was observed only at the lowest tested
sintering temperatures of 1100 °C. This phase disappears at higher
temperatures, consistent with the findings of Kurdowski [42]. Those
results indicate a narrow stability field of grossite. We assume that the
solid state reactions are delayed or shifted towards higher sintering
temperatures in the case that coarse materials are used. Whether sulfate
plays a role on the formation and stability of grossite remains unknown.
The limited substitution of Al by Fe into grossite was reported by Dayal
[43], whereas no information regarding the impact on its stability are
available. Krotite has a relatively wide stability field and can in-
corporate up to 5% of iron [44] [45]. Again, it remains unknown if iron
affects the stability of krotite. Mayenite is a non-stoichiometric phase
with a more narrow stability field, and also can incorporate iron [44].
Mayenite is typically intermixed or embedded within other phases like
krotite or ferrite [44] [46] and seems to occur as a precursor for krotite
[47]. Several elements are known to stabilize mayenite, i.e. enlarge the
stability field of this phase. Those include iron [44] [45] [20] [21] [22],
fluoride, chloride, cyanide, sulphide [48], magnesium [20] [22] and
silica [20] [22] [49]. In some cases mayenite is not present as
F. Bullerjahn, et al. Cement and Concrete Research 131 (2020) 106009

Phase evolution in Y
100 100 100
1st sintering 1st sintering
90 90 2nd sintering 90 2nd sintering
3rd sintering 3rd sintering
80 80 80
Others
70 70 70

Content (%)
Content (%)

Content (%)
60 60 60

50 50 50
Sum of aluminates
40 40 40

30 30 30

20 st
1 sintering 20 20

10 2nd sintering 10 10
Ye'elimite 3rd sintering
0 0 0
1100 1150 1200 1250 1300 1100 1150 1200 1250 1300 1100 1150 1200 1250 1300
Temperature (°C) Temperature (°C) Temperature (°C)

Phase evolution in Fe-Y

100 100 100

90 90 90

80 80 80

70 70 70
Content (%)

Content (%)
Content (%)

60 60 60
Sum of aluminates + ferrites Others
50 50 50

40 40 40

30 30 30

20 20 20

10 10 10
Ye'elimite
0 0 0
1100 1150 1200 1250 1300 1100 1150 1200 1250 1300 1100 1150 1200 1250 1300
Temperature (°C) Temperature (°C) Temperature (°C)

Fig. 1. Evolution of the clinker mineralogy (measured by QXRD) of the Y and Fe-Y clinkers from series 1 linked to the applied sintering temperature and sintering
repetition; 5% anhydrite added prior to 3rd sintering; others = anhydrite, corundum, free lime (+portlandite), periclase and spinel.

crystalline phase, but as amorphous mayenite glass [49] [50] [51] [52].
Unfortunately, we could not analyse the level of iron incorporated in
grossite, krotite or mayenite as those phases were typically always in-
tergrown with others such as ye'elimite or calcium ferrites.
3.1.2. Clinker microstructure and effect of iron
Representative SEM micrographs of fractured and polished samples
of Y and Fe-Y (S3) are shown in Fig. 3. The crystals in the Y clinker have
a well-developed morphology as shown by the characteristic polyhedral
grains of an average size around 1 μm. The particles in the Fe-Y clinker
tend to be on average larger and with a more rounded morphology,
which is consistent with Zupančič et al. [29]. They attributed the
growth of the particles and the densification of the microstructure to
the formation of a liquid phase and its interaction with ye'elimite.
The evolution of the microstructure in the presence of various iron
contents was assessed in more detail for the clinkers of the S2 series
(selected results in Fig. 4). Ye'elimite mainly forms by solid-state re-
actions of anhydrite with intermediate calcium aluminate phases [53]
at high remaining porosity. The presence of iron results in more in-
terconnected and densified ye'elimite particles. Not all iron could be
bound to ye'elimite in the case of 0.4Fe-Y. Hence, clusters of ferritic
particles were formed. Those also contain partly molten ye'elimite
crystallites, as revealed by the partly rounded ye'elimite particles cov-
ered by a ferritic phase. This effect can be seen more clearly in Fig. 5).
Obviously and consistent with earlier findings [29] [54] the presence of
iron causes the formation of a ferrous liquid phase, which promotes the
raw mix burnability.
The formation of a liquid phase is a typical feature of iron-bearing
ye'elimite-rich clinkers [29] [54] [55] [56]. It is caused by the rela-
tively low melting points of calcium ferrite phases [57], which can be
formed either as primary or secondary phases. Primary ones are formed
from the raw materials or from the crystallisation of an initially formed
liquid phase. Secondary ferritic phases are formed from the decom-
position of solid solution ye'elimite, via the formation of an inter-
mediate liquid phase when SO3 is volatized [55]. Both ways result in
the densification of the clinker microstructure and a likely higher
hardness, i.e. a more difficult to grind material.
3.1.3. Synthesis campaigns - achieved mineralogy
The mineralogical compositions of the clinkers from the three
campaigns are shown in Table 2. All samples achieved a composition
close to the targeted one. Literature reports that stoichiometric ye'eli-
mite undergoes a cubic to orthorhombic temperature dependent phase
transformation [14] [24] [25]. The partial substitution of AL3+ by Fe3+
within the crystal structure of ye'elimite stabilizes the cubic symmetry
during cooling [14] [28]. Consistent with those findings, a pseudocubic
type of ye'elimite is formed at expense of the orthorhombic type at iron
contents of x above 0.05 (with x in C4 A3 x Fx S). Rather iron-rich mixes
such as 0.4Fe-Y and 0.8Fe-Y demonstrate a decline of the achieved
ye'elimite contents. Additionally, the binding potential for iron in
ye'elimite was exceeded, as non-consumed iron was still present as
wustite or maghemite. Those phases persisted in 0.8Fe-Y even after an
intermediate grinding and the second sintering step.
Fig. 6 shows sections of the XRD patterns of the clinkers produced
throughout the several campaigns. The formation of the pseudo-cubic
over the orthorhombic ye'elimite type can be observed by the dis-
appearance of some of the reflections only occurring for the orthor-
hombic type.
Moreover, the main peak around 23.7° 2/Theta and the triplet
around 41.7° 2/Theta are shifted to lower angles, i.e. revealing an in-
creasing d-spacing, with increasing iron contents. Additionally, the
triplet disappears. This is linked to the substitution of Al3+ (0.535 Å) by

4
F. Bullerjahn, et al. Cement and Concrete Research 131 (2020) 106009

a) Polished section of Y Combined elements from Scheme of Y particle

clinker SEM-EDS analyses highlighting the phases

b) Elemental distribution of the Y particle above

Fig. 2. SEM-EDS analyses of a polished section of Y; a) presenting the BSE micrograph of the area of interest (left), a plot of the EDS analyses (center) and a drawn
scheme of the mineral distribution in a Y particle (right); b) presenting the element distribution of all measured elements (except oxygen); traces of Mg and Si present
in the used raw materials (magnesium oxide, present in the used calcium carbonate and sulfate, is exclusively enriched in the calcium aluminates layer [identified as
spinel type phase by XRD], silicon is present as minor element in the used calcium carbonate and sulfate and seems to be incorporated in all clinker phases).

the larger Fe3+ (0.645 Å) within the crystal structure of ye'elimite and chemistry (Al3+ by Fe3+ substitution), consistent to the findings of
the stabilisation of a pseudo-cubic type. These observations are con- Schmidt [58]. This is the case for several reasons. The simultaneous
sistent with complementary studies [14] [17] [28]. However, there was incorporation of other elements such as silicon or magnesium occurs
no linear correlation between the cell volume and the determined

Fig. 3. Scanning electron micrograph of fractured powder samples of Y (left) and Fe-Y (right) from S3 (single sintering step).

5
F. Bullerjahn, et al. Cement and Concrete Research 131 (2020) 106009

Nominal magnification x400 Nominal magnification x2000

Fig. 4. Scanning electron micrograph of polished sections of 0.4Fe-Y from S2 of two times repeated sintering with an intermediate grinding step.

(see Section 3.1.4). Moreover, we can neither exclude that the iron is
present in several oxidation states, nor that the applied sintering tem-
perature and cooling procedure does not alter the cell volume evolu-
tion, as reported by others [14] [24] [25]. Finally, the use of mass
balance calculations to determine the degree of Fe incorporation was
not satisfactory. This is related to the fact, that the minor phases de-
tected by SEM, including iron-bearing ones, are often below the XRD
detection limit. Consequently, the indirect determination of the Al3+ by
Fe3+ substitution degree in ye'elimite from XRD, following lattice vo-
lume evolution is not possible. Thus, we analysed the elemental com-
position of ye'elimite by SEM-EDS of polished sections only.
3.1.4. Synthesis campaigns - achieved ye'elimite composition
In a first step, only ye'elimite particles were analysed by placing
SEM-EDS measurement points randomly by hand. In the case of Y up to
0.08Fe-Y about 300 to 600 points were collected. For the samples with
higher iron additions up to 1000 points were collected as often some
inhomogeneous areas with high iron enrichment were observed. In a
second set of experiments 6 frames were collected including a raster of
200 points per frame (only for the samples of the S3). The following
elements were quantified from the measured spectra: (main) Al, Ca, Fe,
S and (minors) Si, Na, K, Mg. A clear distinction of the several alumi-
nate phases and ye'elimite by their respective grey levels was not pos-
sible. To enable a proper determination of the elemental composition of
ye'elimite, a set of elemental filters based on atomic ratios was used (see
Table 3). Thus, the counts of minor phases such as grossite, krotite,
mayenite, ferrites, spinel and anhydrite could be removed.
The filtered data was used to calculate a solid solution degree of the
ye'elimite. The results were normalized to 16 atoms of oxygen for
ye'elimite to facilitate comparison among different samples [6] [55].
We assumed that the valence state of iron is exclusively Fe3+ and only
the substitution of AL3+ by Fe3+ occurs, as one cannot assess the oxi-
dation state and in that respect valence state of iron by SEM-EDS. The
results of the SEM-EDS analyses are presented in Table 4 together with

Nominal magnification x4000

Fig. 5. Scanning electron micrograph of a polished sections of 0.4Fe-Y from S2 (repeated sintering with an intermediate grinding step); frames = highlighting the
partly rounded ye'elimite particles covered by a ferritic phase.

6
F. Bullerjahn, et al. Cement and Concrete Research 131 (2020) 106009

Table 2
Mineralogical composition of the clinkers (measured by QXRD); n.d. = not detected; the absolute error can go
up to 3% by the total mass of clinker [27] but is typically around 1% [19]; the relative error of the minor phases
and traces can be rather high particularly for phases present only in traces; Rwp values are for all samples in the
range of 6.7 to 7.4 [19].

*1
Addition of 5% extra anhydrite prior to third sintering to compensate for the observed loss of sulfur, i.e. by
volatilization of SO2.
*2
Target to reach a minimum content of 90% ye'elimite.
*3
Minor changes of composition after 2nd sintering: slightly reduced ye'elimite content, formation of srebro-
dolskite, maghemite and mayenite over krotite, wustite and calcium ferrite.
*4
Originating from the presence of impurities and contaminations of the raw materials and mixes.

Fig. 6. XRD waterfall plot of the synthesised ye'elimite from the three series.

7
F. Bullerjahn, et al. Cement and Concrete Research 131 (2020) 106009

Fig. 7. XRD zoomed section plot of the main peak of ye'elimite and for the peak triplet highlighted in Fig. 6; for data as measured; same y-axis scale for each area of
interest highlighted in Fig. 7 in order to enable a relative comparison.

Table 3 ye'elimite samples, except for S1, are close to the theoretical values (4
Set of filters based on atomic ratios (−). for Ca, 6 for ∑(AL + Fe) and 1 for S) and in agreement to com-
Ca/(Al + Fe) S/Ca S/(Al + Fe) Fe/Al depending on x
plementary studies [6] [55], same as was determined in natural formed
ye'elimite [59]. Too high sintering temperatures and sintering repeti-
> < > < > < > < tions in the case of S1 (total sintering time of 3 h) caused the partial
decomposition of ye'elimite, volatilization of sulfur and formation of
0.60 0.80 0.20 0.30 0.10 0.23 0.00 0.20
secondary phases such as calcium aluminates and ferrites. Those sec-
ondary phases were finely intermixed, embedded within the ye'elimite
the achieved substitution degree and calculated molecular weight of the particles and the applied filters were not suitable to provide highly
solid solution ye'elimite (molecular weight of stoichiometric ye'elimite accurate results.
is 610.3 g/mol). The calculated chemical compositions of almost all Substitution levels of Al3+ by Fe3+ above 90% of the target were

Table 4
Calculated elemental compositions (atomic form from SEM-EDS analyses) of the produced ye'elimite clinkers throughout several campaigns, results were normalized
for 16 atoms of oxygen.

C4 A3 x Fx S Calculated compositions Target Achieved Mol. Wt.

Fe (−) Fe (−) [%] (g/mol)

S1
Y Ca4.06Mg0.08Na0.02Al5.91Fe0.01Si0.03S1.02O16 – – 612.3
Fe-Y Ca4.02Mg0.09Na0.02Al5.63Fe0.24Si0.04S1.00O16 0.40 0.24 [60%] 617.6
S2
Y Ca3.84Mg0.16Na0.05Al5.99Fe0.01Si0.11S0.92O16 – – 610.4
0.05Fe-Y Ca3.91Mg0.15Na0.04Al5.90Fe0.09Si0.06S0.93O16 0.10 0.09 [91%] 614.0
0.08Fe-Y Ca3.87Mg0.16Na0.03Al5.85Fe0.15Si0.08S0.92O16 0.16 0.15 [94%] 615.2
Fe-Y Ca3.85Mg0.15Na0.03Al5.69Fe0.29Si0.10S0.92O16 0.40 0.29 [73%] 618.7
0.4Fe-Y Ca4.01Mg0.13Na0.02Al5.54Fe0.47Si0.05S0.91O16 0.80 0.47 [59%] 627.4
0.8Fe-Ya Ca3.99Mg0.01Na0.01Al5.47Fe0.55Si0.03S0.97O16 1.60 0.55 [31%] 626.7
S3
Y Ca4.01Mg0.02Al5.99Fe0.05Si0.03S0.95O16 – – 612.9
Fe-Y Ca4.01Mg0.03Al5.67Fe0.39Si0.03S0.94O16 0.40 0.39 [97%] 622.9

a
The sample was prepared following the same protocol but in another facility. As a result, the quantified contents of Mg, Na, and Si are lower and within the error
of the applied technique.

8
F. Bullerjahn, et al.
Table 5
Elemental ratios of ye'elimite present in Y and Fe-Y clinker of the S3 series measured by SEM-EDS and STEM-EDS (anhydrous residues);
bulk = all measured data points, i.e. not filtered data.
/ /
SEM STE SEM
Ye’elimit M Ye’elimit
Ø bulk
e e
0.65 0.66
Y 0.669 0.159
4 5
0.667 0.167
0.74 0.74
Fe-Y 0.707 0.166
2 0
0.714 0.179
only achieved for 0.05Fe-Y and 0.08Fe-Y (S2) and for Fe-Y from series
S3, i.e. when applying optimized synthesis parameters. The results from
S2 further suggest that an “optimum” iron content lays in the range of x
from 0.05 to 0.1, consistent with the findings of Schmidt [58]. The
maximum achieved substitution of A by F, x in C4 A3 x Fx S, was about
0.27 (about 7.2 wt% Fe2O3) for the sample 0.80Fe-Y. This value is
clearly below the ranges of 0.3 to 0.35 reported in literature [29] [55]
[60]. The contents of Mg, Na and Si are partly linked to the respective
contents in the used raw materials but also to the contamination of the
samples [19]. We assume that this is important to note, since others
targeted the stabilisation of iron-bearing ye'elimite by silicon and so-
dium [14] [17] [28].
In addition to SEM-EDS, the samples Y and Fe-Y (S3) are char-
acterized by STEM-EDS analyses of the anhydrous particles (from [19]).
The results are presented in Table 5 and are very consistent with the
SEM-EDS analyses. We further used mass balance calculations to derive
the bulk chemical composition by combining the QXRD and SEM-EDS
analyses and compare those results to the chemistry measured by X-ray
fluorescence analyses. The calculated and measured compositions were
almost identical, indicating reasonably good analytical results (see also
[19]).
3.2. Part II - thermal stability of ye'elimite
3.2.1. Effect of sintering temperature and the role of iron
Literature reports the impact of the sintering temperature and the
presence of iron on the formation and stability of ye'elimite [41] [61],
starting from tricalcium aluminate and anhydrite. The authors found
that already 1% of Fe2O3 (x = 0.05 in C4 A3 x Fx S) reduces the formation
and decomposition activation energies by about 20% (184 ± 25 kJ/
mol) and 34% (523 ± 17 kJ/mol), respectively, compared to stoi-
chiometric ye'elimite (231 ± 42 kJ/mol and 792 ± 64 kJ/mol). This
means that the presence of iron promotes the (faster) formation of
ye'elimite but also its decomposition.
Additional synthesis campaigns targeted stoichiometric Y (C4 A3S ),
and one solid solution, 0.25Fe-Y (C4 A2.75F0.25S ), ye'elimite type. This was
done in order to study the impact of the sintering temperature but also
of high iron contents. The applied sintering temperatures ranged from
950° to 1400 °C, using 25 °C intervals. An iron content close to our
derived maximum substitution limit (atomic Fe about 0.5, see Table 4)
was chosen, starting from a mix of krotite and anhydrite for the
synthesis of Y. The targeted iron content is above the maximum re-
ported substitution level for krotite. Thus, we used a mix of basic raw
materials for 0.25Fe-Y instead. A relatively long sintering duration of
48 h was applied, assuming that quasi-equilibrium conditions could be
reached. Hence, the differences in the formation kinetics resulting from
the different choice of raw materials should not be of importance.
Additionally, the well-known impact of the sintering duration was
9
Cement and Concrete Research 131 (2020) 106009
/ STEM
Number
STE SEM STE of
M Ye’elimit M measure
Ø bulk Ø bulk
e d areas
0.16 0.15 0.00 0.01
0.008 40
5 1 7 0
--
0.18 0.16 0.11 0.06
0.069 50
4 4 3 5
0.071
checked at various sintering temperatures. The results are not presented
in this article but are included in the supporting information (see
Fig. 21 and Fig. 22).
Fig. 8 shows the evolution of the ye'elimite content. Furthermore,
the isoline is plotted. The points would be allocated on the line, if the
amount of ye'elimite would be equal with and without Fe. Points that
are located above the line indicate that more ye'elimite was formed in
the iron-bearing sample, whereas points that are below demonstrate
that the stoichiometric composition is favoured instead. Consistent with
the results presented in Section 3.1, iron strongly promotes the for-
mation of ye'elimite at lower sintering temperatures up to about
1200 °C. On the contrary, the thermal stability of the solid solution
ye'elimite seem to be reduced compared to the stoichiometric type, as
indicated by the faster decreasing contents at temperatures above
1300 °C. This is especially evident at sintering temperatures above
1325 °C, from which onwards an accelerated decomposition of the solid
solution ye'elimite was observed.
The detailed data about the phase evolution from Fig. 8 together
with the gaseous phase composition is shown in Fig. 9. It is important to
note, that neither an internal nor external standard was measured to
follow the evolution of the X-ray amorphous phase content. Never-
theless, the data reveal that the faster formation of ye'elimite is as ex-
pected linked to the faster consumption of other phases such as anhy-
drite and calcium aluminates. Hence, it also means that the formation
of the intermediate or “pre-cursor” calcium aluminate phases such as
(solid solution) krotite needs to occur faster. It is important to note, that
mayenite is present in both samples and at almost all temperatures.
Hence, we cannot differentiate between “primary” (from the reaction of
the raw materials) and “secondary” (from the decomposition of ye'eli-
mite) mayenite. The same applies for the ferritic phases. However, the
main ferric phase at lower sintering temperatures is srebrodolskite
(C2F), whereas it is an alumina-rich brownmillerite type (C4AF) at
higher sintering temperatures. This indicates the partial melting of
ye'elimite into the formed ferrous liquid phase.
No formation of secondary anhydrite from the decomposition of
ye'elimite was detected, as the volatilization of sulfur occurs (Fig. 9).
This is consistent with experimental results [1] and thermodynamic
calculations [23] reported in complementary studies. It further in-
dicates that ye'elimite is more stable at higher sintering temperatures
compared to anhydrite. Touzo and co-workers [55] reported the high
volatility of sulfur in their study and in addition, all analysed ferrites
were free of sulfate. The authors reported that the liquid phase facil-
itates the formation of ye'elimite but that sulfate is not well retained
and tends to outgas. In contrast, within this study the ferritic phases
typically contain around 0.6% to 0.9% of sulfate (results not shown, see
[19] for more details) indicating the dissolution of sulfate into the
ferritic phase. Those values are in a similar range as reported by Strigác
et al. [6]. The observed differences between our study and that of Touzo
F. Bullerjahn, et al. Cement and Concrete Research 131 (2020) 106009

Fig. 8. Particle size distribution of both raw meals (left) and sum of formed ye'elimite in Y and 0.25Fe-Y at different sintering temperatures and a fixed sintering
period of 48 h measured by QXRD (right); RM = raw mix, C = CaO, CA = krotite, A = Al2O3, F = Fe2O3 and CŠ = CaSO4.

et al. [55] are probably related to the differences in the experimental
set-up. However, the influence of the ferrites/liquid phase on the sulfur
volatilization remains unknown.
Another aspect that can be derived from Fig. 9 is the thermal sta-
bility of the sulfate phases. A higher loss of SO2 is observed for Y
compared to Fe-Y in the temperature from about 1150 °C to 1300 °C.
Within the same temperature range the amount of ye'elimite is higher
for Fe-Y compared to Y. On the contrary, the loss of SO2 is higher for Fe-
Y above 1300 °C, whereby only traces of anhydrite are remaining in
both samples. Thus, it seems that ye'elimite has a higher thermal sta-
bility than anhydrite and that anhydrite starts to decompose at around
1200 °C. This could explain the lower observed loss of SO2 measured for
Fe-Y compared to Y below 1300 °C. This is consistent with the findings
reported in literature [32] [62] and will be further detailed in Section
3.2.3.
Selected XRD plots of the 0.25Fe-Y clinkers showing the phases
evolution are presented in Fig. 10. Below 1000 °C, only the formation of
orthorhombic (likely stoichiometric) ye'elimite occurs. At the same
time, a significant amount of ferrites is formed, including at least one
brownmillerite type and some srebrodolskite. Equal quantities of or-
thorhombic and pseudocubic (solid solution) type are present at about
1050 °C. And already at 1075 °C, the massive formation of a
pseudocubic (solid solution) over the orthorhombic type and con-
sumption of the ferritic phases occurs. The pseudocubic type remains
the dominant type up to about 1250 °C. The orthorhombic ye'elimite
type becomes the main type again at above 1300 °C. Anhydrite got
depleted around up to about 1200 °C and its depletion hinders the
further formation of ye'elimite in the 0.25Fe-Y samples. The content of
krotite decreases strongly till about 1200 °C reaching contents below
1 wt%. The contents starts to rise (secondary type) strongly from about
1300 °C, due to the partial decomposition of ye'elimite. The srebro-
dolskite content decreases with the rising temperature and the phase
got depleted at around 1250 °C. Only at least one Al-rich brownmillerite
type remains at higher temperatures. Traces of a cubic tricalcium alu-
minate (C3A) and magnetite (Fe3O4) become detectable from about
1350 °C, whereas the amount of ye'elimite massively drops and also
mayenite disappears.
3.2.2. Thermal stability of sulfates
The thermal stability of sulfates such as anhydrite and ye'elimite is a
function of the temperature and the partial pressure of SO2 and O2 [23]
[32] [33] [63] [62] [64] [65] [66]. The decomposition of sulfates is
associated with the release of SO2 and O2 as shown in the Eqs. (1)-(4).
Thus, the equilibrium between educts and products, including the

Fig. 9. Phase evolution (QXRD) of raw mixes sintered for 48 h at target temperature (derived from Fig. 8 (right)); solid line with filled symbols = 0.25Fe-Y and
dashed lines with empty symbols = Y; Others = anhydrite, corundum, lime, krotite, mayenite, tricalcium aluminate and only in Fe-Y ferrites together with traces of
magnetite (only at the highest sintering temperatures); SO2 and O2 derived from TGA-MS measurements.

10
F. Bullerjahn, et al. Cement and Concrete Research 131 (2020) 106009

Fig. 10. Waterfall XRD plots of selected 0.25Fe-Y clinkers sintered for 48 h at different temperatures, including zoomed sections of interest but with data as
measured; CA = krotite, CŠ = anhydrite, F = ferrites and Y = ye'elimite.

vapour phase, under the given experimental conditions lays on the side clinkers, as anhydrite is often present as a minor phase [10] [27]. For
of SO2 + O2. Consequently, following the law of mass action the in- example, an excess amount of anhydrite can be targeted in the clinker,
crease of any of those species in the starting atmosphere will result in a in order to stabilize ye'elimite [13] [19] [63]. In that regard, Pryce [67]
higher thermal stability of the educts, i.e. a higher sintering tempera- reported earlier that high concentrations of gaseous SO2 cause the
ture or longer duration is needed to achieve the same decomposition stabilisation of sulfate-bearing phases such as anhydrite, ternesite and
degree. ye'elimite towards higher sintering temperatures. Alternatively, the
The decomposition reaction of stoichiometric ye'elimite could be stabilisation can be achieved by increasing the oxygen partial pressure
expressed as follow: [1] [37]. However, too high oxygen levels should be avoided at in-
1 dustrial scale, as the increase of the O2 content is linked to the rise of
C4 A3S 3 CA + C + SO2 ( )+ O2 ( ) excess air and heat losses.
2 (1)
Thus, we compared finally the rate of the thermal decomposition of
Typically, the formation of mayenite instead of free lime is observed synthetic anhydrite and stoichiometric ye'elimite by TGA, using a low
[1] changing the reaction to: heating rate (2.5 K/min) and oxygen-free atmosphere (neat N2). It is
1 important to note, that the ye'elimite used was sintered till the point,
C4 A3S 1.6 CA + 0.2 C12 A7 + SO2 ( )+ O2 ( )
2 (2) that no other sulfate-bearing phase could be detected by XRD. The
degree of decomposition can then be calculated at given time steps by
The presence of iron would alter the reaction accordingly:
measuring the weight loss, the exhaust gas composition and the solid
C4 A3 x Fx S 2 CA + C2 A1 x Fx + SO2 ( )+
1
O2 ( ) residue composition. The measured weight loss is then linked with the
2 (3) release of SO2 and O2 and the decomposition degree “α” can be cal-
The decomposition reaction of anhydrite could be expressed as culated according to Eq. (5), with m(ϑ) = sample mass at temperature ϑ
follows: and mSO3, total = total amount of available SO3. It is important to note,
that no alternative sources of S, SO2 or SO3 should be present.
1
CS C + SO2 ( )+ O2 ( )
2 (4) 100 m( )
( )=
Anhydrite is thermally stable until 1100 °C, even at low oxygen mSO3,total (5)
partial pressures or under reducing conditions [64] [65] [66]. The rate
The results are shown in Fig. 11. As expected, anhydrite starts to
of the decomposition of anhydrite is initially low but accelerates once
decompose earlier than ye'elimite. The slope of the decomposition rate
the temperatures rise above 1300 °C or at strongly reducing conditions.
is almost identical and only shifted towards higher temperatures.
The increase of the oxygen or sulfur dioxide partial pressure results in
the strong slowdown of the decomposition reaction [64].
Experiments carried out by Halstead and Moore [33] indicated that 3.2.3. Thermal stability of ye'elimite and its iron bearing solid solutions
sulfur is more strongly bound in ye'elimite compared to anhydrite. Choi Then, we analysed the thermal decomposition rates of stoichio-
and Glasser [62] measured the vapour pressure of various solid sulfate metric Y and of several solid solutions of ye'elimite. The amount of
phases, including those of ye'elimite and anhydrite, revealing the lower sulfur trioxide in 20 mg (as used for TGA analyses) of the respective
values for ye'elimite. Hence, both studies suggest that anhydrite should clinkers was 2.45 mg, 2.30 mg, 2.00 mg and 1.7 mg for Y, 0.05Fe-Y,
start to decompose prior to ye'elimite, which is consistent with later 0.13Fe-Y and Fe-Y, respectively. This in turn would correlate to
studies on the phase stabilities in the system CaO–Al2O3–Fe2O3–SO3 ye'elimite contents of about 94%, 88%, 76 and 65%. Those quantities
[32] [37]. This can be beneficial for the production of CSA and BYF were also found by XRD. The same experimental conditions were used

11
F. Bullerjahn, et al.
Fig. 11. Thermal decomposition of anhydrite and stoichiometric ye'elimite measured by TGA.
as for the results reported in Fig. 11, except that a heating rate of 7 K/
min was applied. The TGA results are presented in Fig. 12, together
with those for Y at a heating rate of 2.5 K/min. The thermal stability
decreases measurably with the increasing iron content. The trend is
consistent with the results presented in Fig. 8. The applied heating rate
has a significant impact on the decomposition rate and upper stability
temperature of the stoichiometric ye'elimite since more time is provided
at lower heating rates to reach equilibrium conditions.
However, it is still not yet fully clear what exactly causes the lower
thermal stability of iron-bearing ye'elimite. Several aspects may be
linked to the faster decomposition, including the:
• Substitution of Al 3+
by Fe3+ with Fe3+ having a larger ionic radius,
which may alter the
o Crystal lattice, e.g. including the associated change of symmetry
o Lowering the formation and decomposition activation energies
[41]
• The potential partial substitution of Ca2+ by Fe2+ [68] at elevated
temperatures and resulting destabilisation of clinker phases
• The faster formation of intermediate, iron-bearing solid solution
calcium aluminates and hence of solid solution ye'elimite, which in
turn causes a longer sintering duration / thermal exposure of al-
ready formed ye'elimite [19]
• Formation of a ferrous liquid phase which
Fig. 12. Evolution of the thermal decomposition of different ye'elimite types over temperature derived from TGA.
12
Cement and Concrete Research 131 (2020) 106009
o Has a low sulfur binding potential [55] and promotes the volati-
lization of sulfur. Consequently, the faster “depletion” of anhy-
drite, i.e. the sulfate buffer, and onset of the ye'elimite decom-
position occurs.
o Promotes the dissolution of formed ye'elimite [19].
• Reduction of the free energy of formation of the secondary phases
formed by the decomposition of ye'elimite and the potentially as-
sociated volatilization of sulfur
The substitution of Al3+ by Fe3+ seems not to fully explain the
lower thermal stability. The incorporation of iron results in the for-
mation of ye'elimite with a seemingly higher symmetry. Additionally,
the crystallites tend to grow larger. Thus, one would expect a higher
thermal stability. The exact impact of the other parameters remains
unknown. Especially the role of the primary and secondary phases
needs to be further addressed. This includes the impact of the formation
of intermediate iron-bearing solid solution calcium aluminates and
their role on the ye'elimite formation rate. The positive impact of iron
on the raw meal burnability due to the formation of a ferrous liquid
phase is well known and studied [44]. What remains unknown is the
extent to which the liquid phase facilitates the faster dissolution of
ye'elimite and how this is associated with the sulfur-binding potential
and volatilization. The sulfur binding potential of the liquid phase is
especially of relevance, as a secondary liquid phase is formed from the
F. Bullerjahn, et al.
decomposition of iron-bearing ye'elimite.
4. Conclusion
Stoichiometric ye'elimite is formed by solid-state reactions of cal-
cium aluminates with anhydrite. Higher raw materials fineness, espe-
cially of the aluminium source, and raw meal homogenization sig-
nificantly improves the ye'elimite formation. Iron shows a fluxing and
mineralizing effect. The fluxing effect can be seen by the formation of a
liquid phase, whereas the mineralizing effect results from the sub-
stitution of Al3+ by Fe3+ in the crystal structure of ye'elimite. The
maximum achieved substitution level, e.g. expressed as value of x in
C4 A3 x Fx S, was about 0.27 (7.2 wt% Fe2O3), whereby a high excess of
iron needs to be present in the mix. On the contrary, the (almost) full
incorporation of added iron can be achieved only for lower values of x
around 0.05 to 0.10 (5 wt%). The partial substitution of Al3+ by Fe3+
within the crystal structure of ye'elimite stabilizes a pseudocubic form
down to ambient temperature. Iron promotes the conversion of the raw
materials by the formation of intermediate phases such as the calcium
aluminates and ferrites. Consequently, the formation of ye'elimite is
accelerated. The improved burnability seems to be linked to the pre-
sence of a ferrous liquid phase. However, the thermal stability of
ye'elimite is reduced in the presence of iron at higher temperatures. The
decomposition of ye'elimite causes the formation of secondary phases
and the volatilization of sulfur. The decay can be reduced by several
measures such as the increase of the oxygen or sulfur dioxide partial
pressure, by reducing the sintering temperature and or dwell time.
Finally, secondary mayenite almost exclusively occurs in the iron-rich
ye'elimite clinkers produced at sintering temperatures above 1200 °C.
Those findings demonstrates that it should be possible to adjust the
production conditions for a given raw meal composition not only for
synthetic ye'elimite but as well for CSA and BYF clinker at industrial
scale. For example, higher sintering temperatures and/or dwell times
could be used for the production of ye'elimite-containing clinkers with
low iron contents. Contrary, lower sintering temperatures and/or dwell
times should be used for iron-rich mixes.
Further research is needed to investigate the mechanism(s) causing
the lower thermal stability of iron-bearing solid solution ye'elimite.
Those studies need to address the role of the primary and secondary
phases such as solid solution krotite and of the ferrites. Moreover, it is
important to study aspects such as the sintering temperature, dwell
time, the content of free oxygen or sulfur dioxide in the vapour phase,
i.e. kiln atmosphere, which may promote the stabilisation of ye'elimite.
Acknowledgements
This work was funded by the HeidelbergCement AG and supported
by the HeidelbergTechnology Center. The authors would like to ac-
knowledge E. Boehm-Courjault and Pawel Durdzinski for their experi-
mental support in the laboratory and for the helpful discussions. The
Center of Microscopy of EPFL (EPFL-CIME) is also warmly acknowl-
edged for technical and scientific support. The Institute of Nonmetallic
Materials at Clausthal Technical University gave deeply welcomed
support in experimental arrangements. Finally, we like to thank the
anonymous reviewers for the positive and helpful feedback.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.cemconres.2020.106009.
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