Materials and Structures (2015) 48:3895–3911
DOI 10.1617/s11527-014-0451-z
ORIGINAL ARTICLE
CSA raw mix design: effect on clinker formation
and reactivity
Frank Bullerjahn • Maciej Zajac •
Mohsen Ben Haha
Received: 22 April 2014 / Accepted: 13 October 2014 / Published online: 21 October 2014
Ó RILEM 2014
Abstract This study assesses the impact of varia-
tions of the raw mix design, with respect to the type and
proportions of materials, on the formation of calcium
sulphoaluminate belite (CSA) type clinkers. Addition-
ally, the hydraulic reactivity, depending on both the
raw mix design as well as on the clinker composition, is
addressed. Various industrial byproducts and wastes
were used to produce raw mixes for different classes of
CSA clinkers. The clinkers differed in the ye’elimite
over belite ratios: 60/20, 40/40 and 20/60. It was
possible to produce all classes of CSA with a relatively
comparable mineralogy for a given ye’elimite over
belite ratio. The formed clinkers show profoundly
different hydration characteristics at early age, depend-
ing on the initial raw mix composition. However, after
24 hours, a very comparable hydration development
was observed by means of isothermal calorimetry. The
hydrates assemblage after 2 days of hydration consists
mainly of AFt, X-ray amorphous phases and traces of
poorly crystalline phases like aluminium hydroxide
and strätlingite. The cement notation is used through-
out the document: A = (Al)2O3, C = CaO, F =
(Fe)2O3, H = H2O, K = H2O, M = MgO, S = SiO2,
T = TiO2, S = (SO)3.
F. Bullerjahn (&)  M. Zajac  M. Ben Haha
HeidelbergCement Technology Center GmbH, Leimen,
Baden-Württemberg, Germany
e-mail: frank.bullerjahn@htc-gmbh.com;
frank.bullerjahn@epfl.ch
Keywords CSA  Industrial by-products  Mixture
proportioning  X-ray diffraction  Calorimetry 
Thermodynamic modelling
1 Introduction
In the previous research paper [1], advances in the
development of a new class of cements in China, and
its uses, mainly for rapid-setting applications, were
reported, namely calcium sulfoaluminate cements
(CSA). CSA cements are currently considered as a
low CO2 alternative to ordinary Portland cement
(OPC). CSA type clinkers are typically produced by
burning raw materials like limestone or marl, clay,
bauxite and sulphate source within a temperature
range between 1,250 and 1,350 °C. This temperature
range is considerably lower than that used for OPC
synthesis (1,450–1,550 °C). CSA clinkers have lower
calcium content than OPC clinker. The corresponding
reduction of the limestone content in the raw mix
results in a reduction of CO2 emissions [2]. Addition-
ally, the CSA clinkers are easier to grind when
compared to OPC clinker. The strength development
of CSA cements depend mainly on the reactivity of the
mineral ye’elimite (Ca4Al6O12SO4 or C4 A3 S) [2–8],
the clinker mineral phase proportions [1–3, 8] and the
cement composition [1, 3, 4, 8]. But CSA cements
show a faster reaction at early ages of hydration as well
as different hydrates assemblages compared to OPC
3896
[3–7]. Many parameters are not fully understood and
are gradually becoming a subject of intense research.
For example, the effect of raw mix composition, by
means of raw material types and proportions, on the
clinker formation and mineralogy needs to be assessed.
The clinker formation and composition is influenced
by physical parameters (fineness of the material and of
present minerals, hardness, microstructure, etc.) and
the mineralogical as well as chemical composition of
individual raw mix components.
Studies [8–11] and [13–18] reported successful
usages of ashes, slags and other by-products like
phosphogypsum as the major raw meal components
for the formation of CSA type clinkers. In recent
studies by some of the authors of this paper [12], the
effect of the sulphate content of the raw mix in
combination with a special sintering procedure was
investigated showing a pronounced effect on the
clinker mineralogy and reactivity. In [3], CSA clinkers
were synthesized from reagent-grade materials with
C4 A3 S to C2S ratios comparable to those investigated
in this study.
Despite the existing literature and research pro-
grams, no comprehensive data investigating the role of
the raw mix design, especially the use of alternative
raw material sources, on the formation of different
CSA type clinkers are available. Especially the influ-
ence of the raw mix proportioning, to produce CSA
with C4 A3 S to C2S ratios, on the clinker mineralogy
should be assessed. This is important, as clinkers rich
in C2S have a higher ratio of SiO2 over CaO. This
allows the use of higher quantities of industrial by-
products as raw material in the mix design, as they are
typically rich in SiO2. However, by increasing the
amount of industrial by-products in the raw mix, the
quantities of minor elements increase as well. The
presence of minor elements could result in a fluxing or
mineralizing effect, to a change of the mineralogical
composition and the formation of solid-solutions. As a
result thereof, impacts on the early hydration kinetics
need to be considered.
The purpose of the presented research work is to
determine the effect of the raw mix design and of
materials proportions on the formation and uniformity
of CSA clinkers. Three clinker types with varying
C4 A3 S to C2S ratio were targeted. Different types of
raw materials were used as (major) raw material
source to form similar products for a chosen C4 A3 S to
Materials and Structures (2015) 48:3895–3911
C2S ratio. The composition and reactivity of the
obtained clinkers were assessed by quantitative X-ray
diffraction (XRD) coupled with the Rietveld refine-
ment method, calorimetry, thermogravimetry (TGA)
and thermodynamic modelling.
2 Materials and methods
2.1 Raw materials and raw mix designs
The materials used in this study are:
1. Two limestones—LS1 (low CaCO3 content), LS2
(high CaCO3 content),
2. Three fly ashes of various compositions, two
calcareous fly ashes (acc. to EN 197-1) with
nearly the same chemical composition but differ-
ent mineralogy (FA1 & FA2) and siliceous fly ash
(FA3),
3. Two granulated blast furnace slag qualities—S1
(tempered to produce crystalline material), S2 (as
received, mostly amorphous),
4. Anhydrite (CS),
5. Gibbsite powder (AH3) from Merck.
The chemical compositions determined by XRF
and the physical properties of the investigated raw
materials are given in Table 1 and 2. The respective
mineralogical compositions, determined by the Riet-
veld analysis (for further details see the chapter 2.3
below), are given in Table 3. Most of the raw materials
were used as received. The used limestones are
industrial products and were delivered already ground.
Only the slag S1 was ground separately for 30 s in a
vibration disc mill after the tempering.
Approximately 50 g of the raw material compo-
nents were prepared. In the first step, the mixes were
homogenized for 60 min in a multi-axial rotating
mixer (Turbula). Secondly, for further homogeniza-
tion and to break potentially present agglomerates as
well as big particles of unburnt carbon, the mixes were
homogenized by hand in a ceramic mortar. Ethanol
was added as dispersive medium. The prepared raw
meal cakes were dried for 24 h at 60 °C.
The raw mix design was chosen according to an
adapted reverse Bogue calculation (see e.g. [8, 18]).
The focus was set to the formation of required amounts
of ye’elimite and belite while using maximum
Materials and Structures (2015) 48:3895–3911 3897

Table 1 Chemical raw materials composition

LS1 LS2 FA1 FA2 FA3 S1 S2 CS

LOI 1050 °C g/100 g 38.5 43.1 3.5 0.1 2.8 0.0 1.8 4.6
SiO2 9.8 1.5 35.7 45.6 47.3 36.8 36.7 4.2
Al2O3 3.8 0.4 21.8 20.6 27.7 11.7 11.7 1.4
TiO2 0.1 0.0 1.2 0.7 1.4 0.9 0.9 0.0
MnO 0.0 0.0 0.0 0.1 0.1 0.4 0.4 0.0
Fe2O3 1.4 0.2 6.2 8.2 6.3 0.5 0.5 0.4
CaO 43.6 54.5 25.8 19.3 7.8 38.6 38.5 37.4
MgO 1.0 0.2 1.3 2.2 2.3 7.7 7.7 1.8
K2O 1.1 0.0 0.1 1.6 1.5 0.4 0.4 0.3
Na2O 0.1 0.0 0.1 0.3 0.6 0.2 0.2 0.1
SO3 0.3 0.0 4.0 1.1 0.3 2.7 2.7 49.8
P2O5 0.0 0.0 0.2 0.2 1.8 0.0 0.0 0.0
3
Density g/cm 2.66 2.64 2.59 2.66 2.30 2.81 2.86
Blaine cm2/g 5,300 3,350 6,380 3,350 4,270 4,370 4,400 4,380
NAD (BET) m2/g 6.29 1.81 21.79 0.89 1.51 – – –

Table 2 Particle size distribution parameters determined by laser diffraction (Model—Fraunhofer; dispersant—propan-2-ol)
LS1 LS2 FA1 FA2 FA3 CS

d90 lm 75.73 129.69 77.74 314.88 145.08 41.14

d50 9.94 9.37 22.03 37.51 23.78 10.78
d10 1.42 1.50 2.74 1.95 2.93 1.67
D4,3 27.31 44.35 32.44 108.03 52.23 16.88
Span – 7.48 13.68 3.40 8.45 5.98 3.66
RRSB 0.77 0.68 0.89 0.52 0.80 0.91
Rosin–Rammler parameter: slope

quantities of the by-products. The calculated compo-
sitions and the specific nomenclature are presented in
Table 4. As seen in Table 4, the amount of used by-
products increases gradually, from the HL to the LH
series. This leads to an artificially increase of iron
content for the mixes containing ashes. As a result, the
quantity of ferrites differs strongly between the ash
and slag containing samples. The compositional
ranges are given below, instead of unique values, to
account for impact of Fe2O3 and MgO present in the
selected raw materials. In total 14 different raw mixes
were investigated.
The intended mineralogical clinker compositions of
the three basic series were:
HL: High ye’elimite–Low belite content
60–65 % C4 A3 S (ye’elimite), 20–25 % C2S (belite),
1–10 % C2(A,F) (ferrite) and minors
MM: Middle ye’elimite–Middle belite content
40–45 % C4 A3 S (ye’elimite), 40–45 % C2S (belite),
1–10 % C2(A,F) (ferrite) and minors
LH: Low ye’elimite–High belite content
20–25 % C4 A3 S (ye’elimite), 60–65 % C2S (belite),
1–10 % C2(A,F) (ferrite) and minors.
2.2 Clinkering
For the clinkering, the raw mixes were compacted by
hand in a corundum crucible using a pestle. Small
portions of the mix were filled into the corundum
crucible and compacted till all material was trans-
ferred. Afterwards, the crucibles were placed in the
oven (without lid) directly at the targeted temperature
of 1,250 °C. No adjustment of the oven atmosphere
was conducted. The samples were then sintered for 1 h
3898 Materials and Structures (2015) 48:3895–3911

Table 3 Mineralogical raw LS1 LS2 FA1 FA2 FA3 S1 S2 CS

materials composition g/100 g
determined by Rietveld
analysis Amorphous 48.0 88.0 58.9 98.0
Quartz 3.5 0.9 7.5 1.3 9.8 0.5 3.5
Feldspars 2.4 8.0
Muscovite 9.6
Mullite 3.6 1.9 25.1 0.8
Cristobalite 1.2
Maghemite 1.8 1.6 1.4
Hematite 2.4 0.8
Rutile 0.3
Perovskite 2.4
Free lime 2.4 2.8 0.9
Periclase 1.1
Calcite 83.4 99.1 1.6 2.0 3.2
Ankerite 1.1
Dolomite 7.1
Anhydrite 4.5 1.3 0.6 84.1
Gypsum 2.1
Ye’elimite 1.2
Åkermanite 56.0
Gehlenite 8.9 26.8
Augite 14.6
Ternesite 1.3
Alite 1.0
Belite beta 6.5 1.4 1.1
Ferrite (C2(A,F)) 0.7

at 1,250 °C, cooled down to 850 °C in the oven (for
*45 min). Afterwards, the samples were fast cooled
at air (clinker still placed in the crucible). Finally, the
synthesized clinkers were removed from the crucibles
and ground for 30 s in a vibration disc mill. No
analysis of the ground clinker fineness was conducted
as this was not in the focus of this study. However, it is
worth to mention that the grindability of the clinker
can change noticeably due to the differences in
hardness of ye’elimite and belite and as a result of
the changing ye’elimite over belite ratio. The pro-
duced as described cement clinkers may vary in the
particle size distribution. Consequently, the hydraulic
reactivity was generally assessed not involving the
detailed hydration studies.
The potential volatilization of SO3 at 1,300 °C was
tested prior to this study and no loss of sulphate was
observed during the clinkering procedure applied for
that work. Consequently, no measures were under-
taken to control or to adjust the oven atmosphere.
However, the tested mixes were based purely on
limestone, bauxite, iron ore, quartz and anhydrite.
Therefore, impacts arising from the presence of e.g.
unburnt carbon were not tested.
All produced clinkers were stored in a desiccator
above blue silica gel. No vacuum was applied.
2.3 X-ray diffraction analysis
The quantitative phase composition of the clinkers was
examined using the XRD analysis coupled with the
Rietveld refinement method. The XRD patterns were
obtained at room temperature (24 ± 2 °C) using a
Bruker D-8 Advance in a h–2h configuration with a
monochromatic CuKa radiation (k = 1.54059Å) and
equipped with the LYNXEYE (1-d) detector. The
Materials and Structures (2015) 48:3895–3911 3899

Table 4 Raw mix designs

HL1 HL2 HL3 MM1 MM2 MM3 MM4 LH1 LH2 LH3 LH4 LH5 LH6 LH7
g/100 g

LS1 51.5 61.4 59.1 69.0 65.8

LS2 40.3 39.0 47.3 44.3 54.3 40.6 41.3 41.3 59.1
FA1 10.3 25.1 9.7 49.8 21.0
FA2 7.9 19.1 6.4 30.5 16.0
FA3 28.3
S1 41.1
S2 41.1
CS 19.5 19.0 18.2 15.7 14.4 14.8 14.4 11.7 9.5 11.5 11.3 11.0 11.0 11.9
AH3 32.2 31.6 30.4 18.0 16.2 17.4 16.9 3.5 0.1 3.5 1.9 6.7 6.7 0.8
Elemental ratios
CaO/SiO2 6.2 6.2 5.1 3.5 3.5 3.5 3.5 2.6 2.6 2.6 2.6 2.6 2.6 2.6
CaO/Al2O3 1.3 1.3 1.3 2.2 2.2 2.2 2.2 4.5 4.5 4.5 4.5 4.5 4.5 4.5
Al2O3/Fe2O3 29.0 30.5 27.6 9.4 9.9 10.5 10.7 3.4 3.6 3.6 3.8 28.4 28.4 4.8
SO3/(Al2O3 ? Fe2O3) 0.4 0.4 0.4 0.5 0.5 0.5 0.5 0.5 0.5 0.6 0.5 0.7 0.7 0.6

Table 5 ICDD-PDF and ICSD collection codes for all clinker phases used for Rietveld refinements
PDF-code ICSD code Ref. PDF-code ICSD code Ref.

C4 A3 S  o 01-085-2210 80361 [21] C12A7 01-070-2144 6287 [29]

C4 A3 S  c 01-071-0969 9560 [22] Fe2O3 00-039-1346 87119 [30]
a-C2S 01-086-0399 81097 [23] Fe3O4 00-019-0629 20596 [31]
b  C2 S 01-086-0398 81096 [23] C2AS 01-079-2421 67687 [32]
c  C2 S 01-086-0397 81095 [23] M 01-074-1225 26958 [33]
C5 S2 S 01-070-1847 4332 [24] CS 01-072-0916 16382 [34]
C2(A,F) 01-071-0667 9197 [25] CT 01-078-1013 62149 [35]
C2F 00-047-1744 14296 [26] KS 01-070-1488 2827 [36]
C3A-c 01-070-0839 1841 [27] C 00-037-1497 75785 [31]
CA 01-070-0134 260 [28] C2 KS3 01-074-0404 40989 [37]

generator settings were 40 kV and 40 mA. The mea-
surement range was 5°–70° 2h with a step-size of
approximately 0.02°. A continuous rotation was applied
during the data acquisition. DIFFRACplus EVA search/
match graphic software was used for the qualitative
spectra evaluations together with the PDF-2 database
(release 2010). The TOPAS 4.2 [19] software package
was used for quantitative analysis. The crystallographic
structures used during the refinement of the clinkers are
given in Table 5. A more detailed description is
available in [12]. Contrary to [12], the crystal size of
ye’elimite was kept fixed at 2,000 nm for the cubic and
at 1,000 nm for the orthorhombic form, respectively. As
revealed by the preliminary investigations, the relative
amount of ye’elimite changes by around 3 %
(±0.8–2.0 wt% for the LH and HL series, respectively),
depending on the refinement strategy (i.e. whether the
crystal size of the orthorhombic or cubic form was
refined or kept fixed, or only one of the two modifica-
tions was used during the refinement).
2.4 Hydration study
For the hydration study, cements were produced in the
following way: 85 % of each ground clinker, regard-
less its ye’elimite content, was homogenized in a
multi-axial rotating mixer together with 15 wt% of
ground natural anhydrite for 60 min. The amount of
3900
15 wt% anhydrite was kept the same for all type of
clinkers (HL, MM and LH). Preliminary studies have
shown that this amount is sufficiently high for all
clinker compositions and that some unconsumed
anhydrite is present after 48 h of hydration. This
should avoid phase transformations during hydration
from e.g. ettringite to monosulphate. In addition,
anhydrite was chosen instead of gypsum as it is
typically present in commercial products [4] and it
allows observing more details of the cement hydration.
The blending of clinker with anhydrite only slightly
changes the intrinsic reactivity of the clinker (e.g. the
measurements of the neat clinker and clinker blended
with anhydrite show very comparable trends/curves).
In contrast, preliminary studies have revealed that
gypsum leads to a more uniform hydration develop-
ment and differences between materials are hardly to
observe. Similar findings were reported by [4] [20].
The volume stability of cements, related to the clinker–
sulphate ratio, was not a targeted aspect of this study.
The hydration kinetics was investigated by isother-
mal conduction calorimetry measurements using a
TAM AIR calorimeter at 20 °C. For this purpose, all
materials (cements and water) were stored for at least
24 h at 20 ± 1 °C. Cement pastes were prepared by
external mixing at a w/c ratio of 0.7 to achieve full
hydration. The heat flow was measured over 48 h. The
resulting hardened pastes were crushed (\63 lm),
immersed in isopropanol for 15 min, flushed with
ether and dried for 15 min at 40 °C on a pre-heated
glass plate. The resulting powders were investigated
by thermogravimetric analysis and XRD measurement
and coupled Rietveld analysis.
TGA was carried out in a Netzsch STA 409 device
on about 50 mg of the resulting powder. Temperature
ranged from 30 to 1,050 °C, heating rate of 20 K/min
and continuous purging with N2 were used. This
heating rate was chosen as compromise between
measuring time and a still sufficient resolution of
thermal events (shapes and position).
The mineralogy of hydrated samples is quite
complex and has to be interpreted carefully. Before
the quantification of the hydrated samples, the Riet-
veld refinement of each anhydrous clinker was done.
This refinement was then used as a starting file for the
Rietveld quantification of the hydrated samples.
Contrary to analysis of the anhydrous clinker, high
quantities of X-ray amorphous phases (hydrates) are
expected. As a result, the Rietveld analyses were
Materials and Structures (2015) 48:3895–3911
achieved by adding 10 wt% corundum as an internal
standard. Finally, the quantitative phase compositions
of cement pastes were calculated and normalised,
taking into account the amount of bound water deduced
by the TGA.
2.5 Thermodynamic modelling
Thermodynamic calculations were carried out to
investigate the effect of the variation of the clinker
composition on the hydrate assemblage. The geo-
chemical modelling software GEMS [38, 39] was
used. A set of thermodynamic data existing in PSI-
GEMS database [40, 41] extended with a specific
cement data [42, 43] successfully applied for the
modelling of CSA systems [4] was considered.
For the thermodynamic modelling, the mineralog-
ical composition of the cement clinker was varied;
C2S content was varied between 10 and 55 % and the
C4 A3 S content was varied between 63 and 18 %. The
content of the other phases was as follows:C4AF =
5.0 %, C12A7 = 1.0 %, M = 1 %, CS = 20 %. These
composition ranges are representative for the exper-
imentally investigated systems in this study. In the
case of CS, 20 % were chosen to account for the
amount of hard-burnt anhydrite present in the clinker.
Two thermodynamic calculations were carried out; at
a hydration degree of 100 % and at hydration degree
of the cement phases as follow: C2S = 15 %,
C4 A3 S = 90 %, C4AF = 80 %, C12A7 = 100 %,
M = 50 %, CS = 100 %. These values correspond
approximately to the measured ones in hydrated pastes
after 48 h of reaction. A similar set up of thermody-
namic model was used as in [4].
3 Results
3.1 Effect of the raw mix design
on the mineralogical clinker composition
The targeted clinker compositions are reached for
almost all mixes independent of the investigated raw
materials (see Tables 6, 7, 8). Differences in the
clinker compositions within one series are mainly
related to the mineralogical and chemical variations of
the starting materials. Particularly, the LH series is
characterized by a very complex mineralogy. Further-
more, the formation of an iron-rich solid-solution of
Materials and Structures (2015) 48:3895–3911 3901

Table 6 Mineralogical clinker composition determined by Table 8 Mineralogical clinker composition determined by
quantitative Rietveld analysis quantitative Rietveld analysis
HL1 HL2 HL3 LH1 LH2 LH3 LH4 LH5 LH6 LH7
g/100 g g/100 g

C4 A3 S  o 50.1 49.6 44.5 C4 A3 S  o 9.1 – 11.5 5.4 16.0 16.5 5.6

C4 A3 S  c 13.7 15.7 15.6 C4 A3 S  c 13.8 5.1 6.5 4.2 6.0 6.1 3.7
P P
C4 A3 S 63.7 65.3 60.1 C4 A3 S 22.9 5.1 18.0 9.6 22.0 22.6 9.3
b  C2 S 21.7 23.2 27.2 a-C2S 1.9 3.6 – 3.2 3.2 1.1 3.1
C2(A,F) 2.7 3.3 2.1 b  C2 S 59.8 48.5 60.4 59.2 60.1 53.6 62.7
C 1.5 1.2 – c  C2 S – 3.1 – – – – –
P
M 0.9 0.9 1.4 C2 S 61.7 55.1 60.4 62.3 63.2 54.7 65.8
CS 7.2 5.2 4.0 C2(A,F) 4.4 2.5 7.8 11.1 3.1 2.1 12.0
KS 1.0 0.9 1.2 C12A7 – – – 2.7 – – 8.1
C2 KS3 1.1 – 4.0 CA – – – – – – 1.5
C3A-c – 4.9 – 6.4 – – –
Bold value indicates sum of the two major clinker phases /
phases of major interest Fe3O4 1.1 – – – – – –
C2F 1.2 – 1.8 0.8 – – –
Table 7 Mineralogical clinker composition determined by Fe2O3 – 3.6 – – – – –
quantitative Rietveld analysis M 1.3 – 2.0 1.7 4.2 3.8 1.5
MM1 MM2 MM3 MM4 CT – 0.2 – – – 0.5 –
g/100 g C2AS – 28.2 – – – – –

24.4 26.4 26.9 25.4 CS 4.9 – 2.9 1.1 6.5 3.5 –

C4 A3 S  o
15.3 15.2 8.2 7.8 C5 S2 S – – – – – 12.1 –
C4 A3 S  c
P KS – 0.4 1.2 0.8 1.0 – –
C4 A3 S 39.7 41.6 35.0 33.2
a-C2S 4.9 3.3 1.3 0.9 C2 KS3 2.6 – 5.8 3.5 – 0.7 1.8

b  C2 S 45.0 38.8 44.8 44.0 Bold value indicates sum of the two major clinker phases /
P
C2 S 49.9 42.1 46.1 44.9 phases of major interest
C2(A,F) 4.4 6.1 6.6 6.9
C12A7 – – – 2.0
C3A-c – – – 6.7 mix designs, the targeted phase composition was
C – – 0.8 – achieved. The main phase are C4 A3 S (orthorhombic
M 1.6 0.9 1.6 1.6 and cubic polymorph) and b-C2S as the only detect-
CT 0.5 – – – able dicalcium silicate polymorph.
CS 3.9 2.8 4.5 0.7 In the clinker HL1 and HL2 produced from the high
C5 S2 S – 5.0 – – quality limestone (LS2), only a hard burnt anhydrite is
KS – 0.7 0.7 0.2 found after clinkering. In the clinker HL3 produced
C2 KS3 – 0.8 4.6 3.7 from the low quality limestone (LS1), calciolangbe-
inite (C2 KS3 ) and the hard burnt anhydrite are both
Bold value indicates sum of the two major clinker phases /
present in comparable quantities.
phases of major interest

ye’elimite, by the substitution of alumina by iron, 3.1.2 MM series

stabilises the cubic form.
3.1.1 HL series
Table 6 shows the mineralogical composition of the
high ye’elimite containing clinkers. For the three raw
Table 7 shows the mineralogical composition of the
MM series. The raw mix designs MM1–MM3 are
characterized by a clinker composition close to the
intended one, regardless of the starting raw mix. In the
MM4 clinker, the amount of C4 A3 S is lower than
3902 Materials and Structures (2015) 48:3895–3911

expected while high quantities of C3A and C12A7 (R

8.7 %) are present.
In the clinker MM2, calcium sulpho-silicate (as
pure mineral: named ternesite or often in cement
industry called sulpho-spurrite) is detected. On a slow
cooling from 1,250 °C, C5 S2 S formed from CS and
C2S according to the formula (1) and (2). [44, 45]
2 C2 S þ CS C5 S2 S ðCa5 ðSiO4 Þ2 SO3 Þ; ð1Þ

2CS þ 2C þ CS  C5 S2 S ðfrom internal studiesÞ

ð2Þ
Fig. 1 Heat flow of cement pastes from HL series
The processes occur at temperatures ranging from
1,000 to about 1,200 °C. This was achieved by the
slow cooling in the oven described earlier.

3.1.3 LH series

Table 8 shows the mineralogical composition of

clinkers with low ye’elimite content. Samples LH1,
LH3, LH5 and LH6 are characterized by the phase
compositions close to the targeted one. Samples LH2,
LH4 and LH7 show lower ye’elimite content than
targeted. The belite content in those samples is close to
60 %, as targeted. Minor phases present in the clinkers
are magnetite (Fe3O4), maghemite (Fe2O3), srebrod-
olskite (C2F), periclase (M) and perovskite (CT)
depending on the tested industrial by-products.
In the LH2 clinker, gehlenite (C2AS) and some C3A
are present at the expenses of C4 A3 S. High quantities
of C3A and C12A7 (Ø R 9.0 %) are present in the
clinkers LH4 and LH7. These samples contain only
traces or even no hard burnt anhydrite at all.
In the case of the clinker LH5 and LH6, the same
raw materials and the same raw mix design were used.
The only difference was that the clinker LH5 contains
the (fully) crystalline and LH6 an almost fully amor-
phous slag. Significant differences were observed with
respect to the mineralogy. The clinker LH6 contains
around 12 % ternesite whereas this phase was not
formed in the sample LH5. The reason for the absence
is discussed in detail in Sect. 4.2. Additionally, both
clinkers show high quantities of hard-burned periclase.
3.2 Hydraulic reactivity of the formed clinkers
The early hydration kinetics of the cements obtained
from the synthesized clinkers were assessed by
Fig. 2 Heat flow of cement pastes from MM series
isothermal conduction calorimetry (see Figs. 1, 2, 3,
4). The measured heat flow curves present very
variable multi peak forms different from those of
traditional OPC system. The first 4 hours of the
hydration are characterized by rapid reactions between
cement and water. The reactions begin immediately
upon wetting and are characterized by several intense
exothermic effects. Three or even more partly over-
lapping peaks were measured.
However, the occurrence, the shape and the inten-
sity are characteristic for each sample or more
specifically for each raw material combination. As
the results reveal, some raw materials or combinations
of them can have similar impact on kinetics, indepen-
dently of the targeted clinker composition. On the one
hand, both mixes composed of limestone (LS1) and fly
ash (FA1) (samples MM4 and LH4) show a compa-
rably intense heat release directly after mixing
(approximately 130–160 mW/g) followed by
Materials and Structures (2015) 48:3895–3911 3903

Fig. 3 Heat flow of cement pastes from LH series

Fig. 5 Consumption of Y ? A ? F, versus the cumulative

heat after 48 h of hydration, Y = ye’elimite, A = aluminates,
F = ferrites and C$ = anhydrite

Table 9 Quantitative phase compositions (main reactive

clinker phases and formed hydrates), determined by XRD plus
Rietveld and thermogravimetric analysis, of the H-series
(normalises to 100 g paste) and of the hydrated samples
HL1 HL2 HL3

Hydrates (g/100 g)
Fig. 4 Heat flow of cement pastes from LH series AFt 28.7 26.3 26.1
C2ASH8 0.5 – 1.2
continuously decreasing heat flow up to approximately Amorphous 23.0 29.4 30.5
8 h of hydration. On the other hand, mixes of LS2 and Degree of reaction (%)
P
FA1 (samples HL2 and MM2) show a significantly C 4 A3 S 66.6 80.6 85.5
P
lower heat release directly after mixing (approxi- C2 S 7.1 8.2 7.2
mately 50–60 mW/g); a short dormant period between C2(A,F) 43.4 81.7 75.7
30 min to 1 h followed by an intensive continuous
heat flow reaching its maximum between 8 to 10 h.
Plotting the released heat over a period of 48 h sample HL1, it is approximately 15–19 % lower than
against the total amounts of reactive phases (excluding in samples HL2 and HL3, respectively. The degree of
belite) shows a strong correlation (see Fig. 5). This C2(A,F) reaction differs for approximately 30–40 %.
implies that the released heat mainly depends on the The quantified degrees are given in Table 9. In
ye’elimite, aluminates and ferrites contents and reac- general, the samples HL1 reached the lowest degree
tions degrees. Further, this proves the robustness the of hydration which is consistent with the observed
applied Rietveld refinement procedure. cumulative heat (*380 J/g for HL1 and 420 J/g for
HL2 and HL3).
3.3 Hydrates assemblages The main or even the only XRD-detectable crys-
talline hydrate is ettringite. Traces of poorly crystal-
3.3.1 Experimental results line strätlingite and of an X-ray amorphous hump at
the position of the main gibbsite reflection (AH3) are
3.3.1.1 HL-series After 48 h, the degree of present. AFm phases like monosulphate or monocar-
hydration of C4 A3 S is high in all samples. In the bonate are not observed by means of X-ray diffraction.
3904 Materials and Structures (2015) 48:3895–3911

Table 10 Quantitative phase compositions (main reactive

clinker phases and formed hydrates), determined by XRD plus
Rietveld and thermogravimetric analysis, of the M-series
(normalises to 100 g paste) and of the hydrated samples
MM1 MM2 MM3 MM4

Hydrates (g/100 g)
AFt 27.0 19.7 27.0 17.7
C2ASH8 – 1.6 1.3 1.3
Amorphous 24.8 30.3 21.4 30.4
Degree of reaction (%)
P
C 4 A3 S 98.3 97.5 94.4 91.2
P
C2 S 27.9 24.0 19.9 22.9
C2(A,F) 52.6 76.6 26.5 68.3
C 5 S2 S – 28.0 – –
Fig. 6 Hydrates predicted by thermodynamic modelling as a
function of C2S and C4 A3 S content. Full hydration of cement
assumed. Et ettringite, AFm monosulphate, Ht hydrotalcite, Goe main hydrate formed. However, contrary to the XRD
goethite measurements, AH3 is detectable in significant quan-
tities via its water loss between approximately
250–300 °C. The overall weight loss of the three
cements is in average 25.5 %.

3.3.1.2 MM-series The degree of reaction of the

Fig. 7 Hydrates as predicted by thermodynamic modelling as a
function of C2S and C4 A3 S content. Assuming an average
reaction degree corresponding to experimental findings after
48 h of hydration. Et ettringite, AFm monosulphate, Ht
hydrotalcite, Goe goethite, Gy gypsum
These results agree with the modelling as shown in
Figs. 6 and 7. The modelling predicts precipitation of
very small quantities AFm phase in the range of
clinker composition corresponding to HL series.
The XRD results are confirmed by the thermo-
gravimetric analyses. After 48 h of hydration, ettring-
ite (main weight loss between 100 to 180 °C [3]) is the
clinker phases C4 A3 S, C2(A,F), C2S and C5 S2 S is given
in Table 10. All phases show a moderate (e.g. C2S,
C5 S2 S and C2(A,F)) to high (e.g. C4 A3 S) degree of
reaction. Ye’elimite and belite of the MM series show
significantly higher degrees of consumption compared
to the HL series. The observed reaction of belite (MM)
is the highest of all the investigated clinkers with an
average value of 23.7 % compared to 7.5 % (HL) and
12.3 % (LH). The same trend is achieved by
comparing the total quantities of the reacted belite.
The total amounts of the reacted belite are
approximately 11 g/100gcement (MM series; assumed
average belite content of 45 %), 2 g/100gcement (HL
series; assumed average belite content of 23 %) and
7 g/100gcement (LH series; assumed average belite
content of 60 %). As predicted by the thermodynamic
modelling and as in the series HL, the main detectable
crystalline hydrate is ettringite. Furthermore, traces of
strätlingite and of an X-ray amorphous hump (gibbsite
reflection) are again detected by the XRD. The overall
weight loss of the four cements is in average 23.1 %.
3.3.1.3 LH-series The degree of reaction of the
main clinker phases differs among investigated
samples as shown in Table 11. The consumption of
Materials and Structures (2015) 48:3895–3911 3905

Table 11 Quantitative phase compositions (main reactive magnesium and iron from the dissolution of the
clinker phases and formed hydrates), determined by XRD plus clinker minerals, thermodynamic modelling predicts
Rietveld and thermogravimetric analysis, of the L-series
the formation of hydrotalcite (magnesium–aluminium
(normalises to 100 g paste) and of the hydrated samples
bearing layered double hydroxide) and goethite (iron
LH1 LH2 LH3 LH4 LH5 LH6 LH7 hydroxide). Hydrotalcite, formed under the conditions
Hydrates (g/100 g) as for cement, e.g. temperatures around 25 °C, is a
AFt 15.5 6.0 16.8 19.6 19.6 18.2 18.0 poorly crystalline and it is could be present as an X-ray
Amorphous 17.2 6.3 14.1 16.0 10.7 14.7 15.6 amorphous phase [47]. Goethite is predicted to form as
Degree of reaction (%)
the only iron bearing phase [48, 47]. However, the
P latest findings indicate that iron may precipitate as Fe-
C 4 A3 S 100 100 100 100 100 100 100
P siliceous hydrogarnet in cement like systems [48].
C2 S 15.5 15.6 13.0 11.9 10.8 3.9 15.3
When belite content increases, alumina hydroxide
C2(A,F) 60.9 53.7 0.0 34.1 69.9 80.2 28.9
reacts with the released Ca and Si to form additional
C 5 S2 S – – – – – 69.0 –
strätlingite. At high belite contents, the modelling
predicts a formation of C–S–H and AFm phases
belite varies from approximately 10–16 %. The instead of strätlingite and alumina hydroxide.
samples with ternesite (LH6) presented the lowest Figure 7 gives the results of the thermodynamic
degree of belite reaction (*4 %) while ternesite modelling assuming the hydration degree similar to
shows a degree of reaction of approximately 70 %. that measured after 48 h of hydration. At lower belite
The degree of reaction of C2(A,F) varies from 0 to contents, the main hydration product is ettringite,
80 %. C4 A3 S is fully reacted in all hydrated samples of monosulphate and alumina hydroxide. These phases
the LH series. are the hydration products of the ye’elimite and other
AFt is, with the exception of the X-ray amorphous alumina bearing phases in the presence of a sulphate
compound, the only detectable hydrate. Therefore, the source. Increasing the belite content in the cement
results agree only partly to the assemblage predicted clinker, results in the decrease of the volume of
by thermodynamic modelling. No AFm phases could ettringite, monosulphate and alumina hydroxide,
be identified. The overall weight loss of the six accompanied by formation of gypsum. The initiation
cements is in average 15.7 %. of the gypsum formation shows the point at which
The cement based on clinker LH2 was not included there is a lack of alumina to form more ettringite. The
for the calculation of the average weight loss between belite dissolution has a limited impact on the phase
all hydrated samples, as the clinker is almost fully composition, since the hydration degree of belite is
composed of inert (e.g. gehlenite) and slowly reactive rather low, compared to e.g. C4 A3 S, after 48 h.
(e.g. belite) phases. Therefore, almost no reaction was These modelling results are consistent with another
observed during the investigated period. study [49], in which the chemical and mineralogical
composition of the X-ray amorphous fraction, formed
3.3.2 Thermodynamic modelling during early hydration, was assessed by mass balance
calculations. It was found that during the early
Thermodynamic modelling was used to predict the hydration, the X-ray amorphous fraction should be
hydrated phase composition of the investigated mainly composed of aluminium hydroxide, strätlingite
cements. Results of the thermodynamic modelling and potentially some monosulphate, depending on the
for the fully hydrated cements are shown in Fig. 6. At used sulphate type and amount.
lower belite content, the main hydrates are ettringite, The experimental results are in agreement with the
monosulphate, strätlingite and amorphous alumina predicted hydrates assemblage, for a hydration period
hydroxide. It should be noted that the high hydration of 48 h. XRD as well as TGA proves the presence of
degree of CA, C12A7 and C4AF, next to that of C4 A3 S, AFt and AH3, mainly by TGA, as the main hydration
results in the stabilization of some monosulphate products. Additionally, traces of strätlingite are
instead of alumina hydroxide. This is consistent with detected by XRD which confirms the modelling
the findings in [4]. Because of the release of results. It further proves that belite and/or ternesite
3906 Materials and Structures (2015) 48:3895–3911

Fig. 8 Comparison of the TGA measurements of cement pastes from the HL, MM and LH-series after 48 h of hydration; TG (left) and
DTG (right)

already contributes to the reactions during the first

48 h (see e.g. Fig. 8 and Tables 9, 10, 11).

4 Discussion

4.1 Raw mix design: effect on clinker formation

and composition

Almost all raw mixes allow the formation of highly

reactive calcium sulphoaluminate (CSA) type clinkers
with the main phases C4 A3 S, beta C2S and C2(A,F) (see
e.g. Fig. 9). Furthermore, the position of the main
ye’elimite reflection changes measurably (see Fig. 9).
The results agree to a prior study [12] as well as to
recent observations [50]. The findings indicate the
formation of solid solutions of ye’elimite with a
varying degree of iron incorporation and potentially Fig. 9 Full XRD patterns for the clinkers HL1, MM1 and LH1;
the coexistence of two polymorphs, namely the cubic o = C4AF, # ¼ C4 A3 S, x ¼ CS, b = b-C2S, ? = C, zoomed
and orthorhombic form. Determining clearly the two sections from 20 to 35 2h, deg (CuKa1) and for the main
ye’elimite reflections from 23.4 to 24.0 2h, deg (CuKa1)
polymorphs is quite difficult as the major reflections
strongly overlap. Furthermore, the overall clinker
mineralogy is quite complex which makes the distinc-
tion even more challenging. However, due to the The typically formed minor phases are: C5 S2 S, C2F,
reduction of the refined parameters (crystal size was C3A, C12A7 and CA. This is consistent with other
kept fixed for both ye’elimites; cubic 2,000 nm and studies [3], 8–13, 16–18]. Depending on the raw mix
orthorhombic 1,000 nm) at least trends could be design, the additional sulphate not bound by ye’elimite
observed. Due to the increasing addition of iron-rich is present in the form of hard-burnt anhydrite and
materials, like e.g. ashes, the cubic ye’elimite is calciolangbeinite [44, 45]. Typical minor phases
stabilized. The determined trend is consistent with the present in these clinkers are C2AS (gehlenite), C2 KS3
findings in [12, 50] which show that the formation of (calciolangbeinite), CS (anhydrite), C2F (dicalcium
solid-solutions (e.g. substitution of alumina by iron) ferrite), C3A (tricalcium aluminate), C12A7 (mayenite),
stabilises the cubic form. CA (monocalcium aluminate), M (periclase), CT
Materials and Structures (2015) 48:3895–3911
(perovskite), A (corundum), Fe3O4 (magnetite), Fe2O3
(hematite) and S (quartz) depending on the used
limestone and on the industrial by-product qualities.
Free lime was absent in almost all clinkers.
Clinkers with middle to high ye’elimite contents are
in general less influenced by the raw material qualities.
The additions of the by-products in the raw mix are
limited by the low targeted silica content. All tested
by-products contain high quantities of SiO2. Addi-
tionally, the reactivity of ye’elimite, seems not to be
reduced/affected by the addition of the industrial by-
products within the chosen ranges. These observations
are in accordance to other studies [8–12, 16–18].
The highest level of industrial by-products additions,
ranging from approximately 30–60 %, was applied for
clinkers of the LH series. This high replacement levels
lead to a high complexity of clinker mineralogy. The
changes in the clinker phase formation and composition
are related to the industrial by-product type, the added
amount and other parameters like e.g. the fineness, the
crystallinity or the presence of unburnt carbon. How-
ever, the origin of the formation of the observed
complex mineralogy is not fully understood.
Samples prepared from the FA with high LOI show
higher amounts of calcium aluminates and decreased
amounts or even the absence of calcium or alkali-
bearing sulphates. The LOI is coming from unburnt
carbon and results in a reducing oven atmosphere
during the clinkering. This led to a volatilisation of
SO3, proven by the absence of anhydrite, arcanite or
calico langbeinite and the presence of higher amounts
of SO3-free calcium aluminate minerals. This is in
agreement with earlier studies [46].
C2 KS3 is formed in nearly all clinkers based on
K2O-rich raw mix designs such as low quality
limestone (K2O-rich), FA2 and/or FA3.
If the substitution level of MgO within the crystal
lattice of clinker minerals like e.g. ye’elimite, belite or
ferrite is surpassed, MgO is persistent as hard burnt
(known as dead-burnt) periclase. Dead-burnt periclase
was formed in high quantities in all samples based on
slag as a major raw mix component.
4.2 Calcium silicate and calcium sulpho-silicate
formation
The beta-C2S polymorph is the dominant reactive
calcium silicate formed in all clinkers. The measured
3907
content of belite is close to the targeted one, indepen-
dently of the raw mix design. Almost all clinkers are
free of gamma-C2S, despite the applied low cooling
rate from 1,250 to 850 °C.
The SO3 levels of all raw mixes were relatively high
with a SO3/(Al2O3 ? Fe2O3) ratio ranging from 0.4 to
0.7 whereas ratios of approximately 0.25–0.35 are
theoretically sufficient to form assumed ye’elimite
quantities, taking other solid-solution effects into
account.
It is known from literature that ternesite can be
present in belite-containing CSA type clinkers. For the
formation of ternesite, next to the presence of belite,
an excess anhydrite, a production below or around
1,200 °C and/or a slow cooling rate are obligatory [9–
13, 17]. However, the mineralogy of the raw materials
seems to be of an importance as well. Indeed, the
chemical composition of the raw mixes for the clinkers
LH5 and LH6 was the same. Nevertheless, only the
clinker LH6 contains ternesite. In the case of LH5, the
slag was fully crystalline whereas in the case of LH6
fully amorphous. In the crystalline slag, the calcium
and silica is bound in crystalline phases like e.g.
gehlenite and merwinite (see Table 8). It is possible
that belite needs to be formed as a first step during the
formation of ternesite. Literature data suggest that
ternesite is formed always as results of reaction of
belite and anhydrite [9–12, 13, 17, 18, 44, 45]. The
presence of crystalline phases from slag may delay the
formation of belite and consequently prevents forma-
tion of ternesite. However, internal studies revealed
that C5 S2 S can be formed form the reaction of CS (e.g.
wollastonite) with C and CS.
4.3 Hydraulic reactivity of synthesized clinkers
The major clinker minerals contributing to the early
properties and performance of CSA type cements are in the
following order mainly: C4 A3x Fx S & C12A7, CS 
CA, C3A, C2(A,F) (C2F) and C5 S2 S [ C2S. This order
was determined by the XRD, Rietveld analysis and
thermodynamic modelling.
In a previous study [12], it was observed that the
formation of iron-rich solid-solutions of C4 A3x Fx S
and the stabilisation of the cubic polymorph leads to a
very pronounced change of the hydration kinetics. It is
most likely that the same effect is present here. The
samples from LH series are characterized by a similar
3908
ye’elimite content. However, the heat flow during the
first 48 h differs significantly. Similarly, the hydration
kinetics of clinkers MM1 and MM2, measured by the
heat flow, differs.
A clear interpretation of the observed XRD peaks is
not possible as no in situ XRD measurements were
conducted. Additionally, the cement fineness was not
assessed in this study. It is well known that the cement
fineness has a very pronounced effect on the clinker/
cement reactivity.
The heat release during the initial period, ranging
normally from 0 to 0.5 h and in some case up to 2 h, is
mainly assigned to the wetting of the system, the
dissolution of ready soluble alkalis (e.g. KS, C2 KS3 ),
partial dissolution of anhydrite, aluminates and the
initial precipitation of hydrates (AFt and/or AFm,
AH3) [4] [20].
It was found in [51] that the presence of calci-
olangbeinite in an aluminate-rich Portland cement
leads to a significant improvement of the early age
strength related to a pronounced enhancement of the
hydraulic reactivity. Comparing the results from the
LH series with high and low contents of calciolangbe-
inite, a clear acceleration of the reactions could be
observed. The maximum heat flow of the main
hydration peak of the samples LH3 and LH4 appears
within the first hour of hydration. Instead, it appears in
the range of approximately 3 to even 7 h for the
samples LH5, LH6 and LH7. However, all clinkers
show in general very complex hydration reactions at
early ages and as a result thereof, a comparison based
purely on calorimetry is impossible.
The initial period is usually followed by a lower
activity period (heat flow of maximally 4 mW/g)
ranging from 0.5 to approximately 1 h and in some
cases to 4 or even 8 h. Various theories about the
origin of this ‘‘dormant period’’ could be found in
literature [4, 20, 53–56]. It is not clear to which extent
the described parameters and mechanisms are valid for
our investigated CSA type cements.
The acceleration period, ranging from 1 to even 8 h,
is mainly related to the rapid dissolution of
C4 A3x Fx S, C12A7, CA, C2(A,F), C2F, C5 S2 S, C3A and
C2S and the precipitation of AFt, AH3, AFm phases
and C2ASH8 [4–7, 12, 20, 54–56].
The further effects on calorimetry curve are prob-
ably the results of the reactions of the alumina bearing
clinker phases like e.g. CA, C12A7, C4 A3 S and C2(A,F).
Materials and Structures (2015) 48:3895–3911
As shown in Fig. 5, a clear correlation between the
consumption of the reactive cement phases and the
cumulative heat exists at least up to 48 h of hydration.
From the current results, it can be concluded that
the depletion of the sulphate source, which potentially
initiates the resulting transformation of AFt to AFm or
the formation of AFm from C4 A3x Fx S [3] [20] [52], is
not the source of the measured second maxima. After
48 h of hydration, sufficiently high quantities of CS
are present in almost all cement pastes (see Tables 9,
10, 11). Nevertheless, a contribution of local inhomo-
geneities, as a result of the heterogeneous nature of the
tested materials, could not be excluded. No other
sulphates such as e.g. gypsum were tested to compare
the impact on the dissolution rates and the sulphate
concentration of the pore solutions. From another
study [20], it is known that the addition of gypsum can
lead to a more uniform hydration development for
synthetic ye’elimite compared to anhydrite. A com-
parable effect could be seen in [3], where commercial
CSA products were tested.
4.4 Hydrates assemblage
The ye’elimite-rich cements from the HL series reach
the highest quantities of formed ettringite. However,
the MM series reaches the highest degree of hydration
for both ye’elimite and belite. As a result, the overall
weight loss, related to the chemical bound water, is
almost the same. Furthermore, the precipitation of
strätlingite (in MM series), after already 48 h of
hydration, clearly proves that C5 S2 S and C2S are
contributing to the hydration.
In the LH series, ye’elimite is fully absent after 48 h
of hydration. Nevertheless, the LH series is charac-
terized by the lowest weight loss among of the all
samples. The overall low quantities of reactive
aluminate phases in the clinker and low reaction
degree of belite results in lower quantities of AFt,
AFm and AH3 in agreement with the XRD, TGA and
modelling data.
The reaction degree of the calcium silicates belite
and ternesite differs significantly. In is not clear what
causes the observed differences. One reason could be
the incorporation of foreign ions into the crystal lattice
of the specific phase, depending on the investigated
raw mix design. The incorporation of foreign ions
could change the phase reactivity significantly.
Materials and Structures (2015) 48:3895–3911
Additionally, physical parameters like raw material as
well as clinker fineness (depending on the clinker
microstructure and grindability) play an important role
as well, as the cement fineness is decisive for the
performance of hydraulic binders.
Various studies discuss the low reactivity of
ternesite or even its inert nature [9, 11, 13, 15–18].
The enhancement of its reactivity by autoclaving is
discussed in [56]. However, the actual study reveals
that C5 S2 S reacts, despite the presence of another
sulphate source (e.g. anhydrite), as shown in sample
M2 and L6. In accordance to a previous study [12], the
reaction of C5 S2 S seems to be enhanced in the
presence of reactive alumina. The XRD data suggest
that when ternesite reacts, the reaction of belite is
delayed as shown in Tables 10 and 11.
5 Conclusions
This study investigates the possibility of application of
industrial by-products, e.g. ashes, slags and low
quality limestone, as major raw meal components for
the production of CSA type clinkers.
It was possible to replace aluminium oxide and/or
hydroxide to high extents or even fully by industrial
by-products. One limiting parameter, for the substitu-
tion of e.g. bauxite and limestone by industrial by-
products, is the ratio of SiO2 to Al2O3 and the targeted
C2S and C4 A3 S contents of the clinker. It was
demonstrated that not only the overall raw mix
composition but all the related parameters (e.g.
chemistry, mineralogy, fineness, microstructure,
homogeneity, etc.) influence the clinker mineralogy.
Clinkers characterized by ye’elimite contents above
40 % seem to be less influenced by the used raw
materials. Moreover, the formation of ternesite was
observed due to the applied sintering procedure (low
cooling rate) and the increased SO3/(Al2O3 ? Fe2O3)
ratio.
It was demonstrated that the produced clinkers are
characterized by very different hydration characteris-
tics at early age. However, if only the raw mix
proportions are changed, using the same raw materi-
als, the comparable hydration development was
observed. Furthermore, after 48 h a good correlation
between the cumulative heat and the degree of
hydration was found.
3909
The ternesite, initially supposed to be unreactive,
was shown to react in the investigated systems. We
hypothesize that the availability of the reactive
alumina is a key factor influencing the reactivity of
ternesite. The reactions of C5 S2 S and/or C2S with AH3
lead to the formation of strätlingite already after 48 h
of hydration.
The major phases contributing to the formation of
hydrates assemblage at 48 h of hydration are in the
following order: C4 A3x Fx S, C12A7, CaSO4  C2
(A,F),CA, C3A, (C2F) and C5 S2 S [ C2S. The impact of
a given phase depends on its quantity and specific
reactivity.
Acknowledgments The authors would like to acknowledge
Jan Skocek for his support and the helpful discussions.
Furthermore, we would like to acknowledge the anonymous
reviewers for their critical evaluation and contribution.
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