Advances in Cement Research Advances in Cement Research

http://dx.doi.org/10.1680/jadcr.16.00071
Synthesis and hydration of alite-calcium
sulfoaluminate cement
Chitvoranund, Winnefeld, Hargis, Sinthupinyo
and Lothenbach
Paper 1600071
Received 02/06/2016; revised 21/11/2016; accepted 21/11/2016
Keywords: clinkering/clinkering reactions/modelling/
special cements
ICE Publishing: All rights reserved

Synthesis and hydration of alite-calcium

sulfoaluminate cement
Natechanok Chitvoranund Sakprayut Sinthupinyo
Siam Research and Innovation, Saraburi, Thailand (corresponding author: Siam Research and Innovation, Saraburi, Thailand
natechac@scg.co.th) Barbara Lothenbach
Frank Winnefeld Empa, Swiss Federal Laboratories for Materials Science and Technology,
Empa, Swiss Federal Laboratories for Materials Science and Technology, Laboratory for Concrete and Construction Chemistry, Dübendorf,
Laboratory for Concrete and Construction Chemistry, Dübendorf, Switzerland
Switzerland
Craig W. Hargis
Empa, Swiss Federal Laboratories for Materials Science and Technology,
Laboratory for Concrete and Construction Chemistry, Dübendorf,
Switzerland

An alite-calcium sulfoaluminate (ACSA) clinker containing approximately 50% alite and 10% ye’elimite was
synthesised at 1300°C using a laboratory furnace and 1% calcium fluoride (CaF2) as a mineraliser, ground and blended
with 5% anhydrite. The hydration mechanism of the resulting ACSA cement was investigated experimentally using
quantitative X-ray diffraction and thermogravimetry, as well as by thermodynamic modelling. During the first hours,
mainly alite reacts. Ye’elimite starts to dissolve significantly after 2 d, as it is predominately present as inclusions
within the alite matrix and thus reacts only after sufficient alite has dissolved to expose the ye’elimite domains within
the clinker particles. The main hydration products are calcium–silicate–hydrates (C–S–H), ettringite, monosulfate and
portlandite. Mortars prepared using the ACSA cement rapidly develop compressive and flexural strength at early ages
corresponding to the fast hydration reactions. It was estimated that the manufacture of this ACSA clinker releases
about 11–12% less carbon dioxide than the production of Portland cement clinker.

Notation clinker from calcining raw materials and 370 kg CO2/t of

A minimum asymptote clinker from burning fuel (Damtoft et al., 2008). Calcium sul-
B steepness of curve foaluminate cement (CSA) is an alternative cement which
C inflection point enables potential reductions in carbon dioxide emissions. CSA
CCaF2 weight fraction of calcium fluoride (100%) in the requires a lower burning temperature (1250–1300°C) than PC
external standard (1450°C), requires less energy to grind, and requires less
D maximum asymptote calcium carbonate (CaCO3) in the feedstock (Gartner, 2004;
j weight fraction of each crystalline phase Glasser and Zhang, 2001; Juenger et al., 2011; Metha, 1980;
Q3 cumulative volume density distribution (% passing) Winnefeld and Lothenbach, 2010).
q3 fractional volume density distribution
SCaF2 scale factor of calcium fluoride from Rietveld Alite-calcium sulfoaluminate cement (ACSA) is a type of
analysis CSA which contains alite coexisting with ye’elimite as the
Sj calculated scale factor of each phase main phases in the clinker; therefore, the characteristics of
t hydration time in day ACSA lie in between those of PC and CSA. To synthesise
u
CaF2 mass attenuation coefficient of calcium fluoride ACSA, alite’s formation temperature must be either lowered
VCaF2 unit cell volume of calcium fluoride below ye’elimite’s decomposition temperature of 1350°C, or
Vj unit cell volume ye’elimite must be stabilised at higher temperatures (Ludwig
Wt dry sample weight in grammes at the temperature t and Zhang, 2015). The former is normally achieved by using a
α reaction degree mineraliser, such as calcium fluoride (CaF2), magnesium oxide
μsample
* mass attenuation coefficient of the whole sample (MgO), diphosphorus pentoxide (P2O5) or copper (II) oxide
ρj density (CuO) (Liu et al., 2002; Ma et al., 2006, 2013). Small amounts
ρCaF2 density of calcium fluoride of calcium fluoride in the raw meal act as a fluxing agent by
lowering the temperature of first liquid formation and reducing
Introduction the surface tension of the liquid phase; furthermore the ther-
Portland cement (PC) is widely used as a binder for construc- modynamic stability of alite relative to belite is enhanced
tion. As a consequence of high construction demand, the pro- (Altun, 1999; Klemm et al., 1979; Moir and Glasser, 1992). Its
duction of PC keeps increasing. The production of PC addition influences the phase assemblage of the clinker, as
generates about 530 kg of carbon dioxide per tonne (CO2/t) of surplus fluorine, which is not incorporated in the other clinker

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 Advances in Cement Research
phases, may form fluorellestadite, Ca10(SiO4)3(SO4)3F2
(Duvallet and Robl, 2013). Magnesium oxide can promote the
formation of alite as well, because it decreases the viscosity of
the liquid phase, thus improving the coexistence of alite and
ye’elimite and reducing the free lime content in the clinker as
observed by X-ray diffraction analysis (XRD) (Liu and Li,
2005; Liu et al., 2002). Copper (II) oxide and diphosphorus
pentoxide have similar effects on ACSA clinker phase for-
mation as magnesium oxide (Li et al., 2000; Ma et al., 2006).
The addition of barium oxide (BaO) can be used to extend the
stability of ye’elimite to higher temperatures (Ludwig and
Zhang, 2015; Xin et al., 2000).
In addition to using a mineraliser, control of the firing
sequence can be utilised to manufacture ACSA. Firing at
1450°C to produce alite followed by a dwell step at 1250°C to
produce ye’elimite can make alite and ye’elimite co-exist
together (Ma et al., 2013). Likewise, the temperature and dur-
ation of firing can be used to adjust the clinker phase compo-
sition. For example, when using calcium fluoride to produce
ACSA, increasing the dwell time at 1250°C from 30 to 60 min
can promote the formation of more alite (Duvallet and Robl,
2013).
Besides affecting the reactions during clinkering, minor
elements or mineralisers affect the physical properties of
ACSA cement. Adding 2–5% magnesium oxide improved
strength development but reduced the setting time (Liu and Li,
2005), and a magnesium oxide content of more than 5%
caused an extended setting time and a slightly lower compres-
sive strength at all ages. A small amount of diphosphorus pent-
oxide, less than 0·3%, decreased the early compressive strength
but slightly increased the compressive strength at 28 d (Li
et al., 2000). Using more than 0·5% diphosphorus pentoxide
delayed the setting time and decreased the early and 28 d com-
pressive strengths.
The hydration of an alite–ye’elimite clinker synthesised by the
two-stage firing process with 4·8% ye’elimite content has been
investigated recently (Li et al., 2015). The cement showed a
very short setting time. Moreover, it gave higher early strength
than PC at 1 and 3 d and showed expansive properties. The
heat of hydration of this cement after 72 h was higher than for
PC. The main crystalline hydration products found were ettrin-
gite and portlandite.
Additionally, the hydration of three different ACSA cements
with varying amounts of alite, belite, ye’elimite, ferrite and
gypsum has been investigated (Duvallet, 2014). For the inter-
mediate ACSA clinker (27·2% alite, 25·4% belite, 17·9% ye’eli-
mite and 23·4% ferrite) with 15% gypsum, alite and ye’elimite
were principally consumed by 7 d and totally consumed by
28 d, and ferrite persisted through 180 d. With regard to crys-
talline hydration product development, ettringite was the only
phase to form by 5 h. Then, portlandite formed by 24 h,
2
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Synthesis and hydration of alite-calcium
sulfoaluminate cement
Chitvoranund, Winnefeld, Hargis, Sinthupinyo
and Lothenbach
followed by monosulfate and hemicarbonate at 7 d. In low-
sulfate formulations, an amorphous hump was observed
between 10 and 11° 2θ (CuKα) in the diffraction patterns,
which was suspected by the author to be caused by a poorly
crystalline phase similar to stellerite (CAS7H7). However, it
appears to be more likely that this hump is related to a
calcium monosulfoaluminate (AFm) phase, which is most
probably a solid solution of hemicarbonate and highly hydrox-
ide ion (OH−)-substituted monosulfate (Matschei et al., 2007a;
Pöllmann, 1989). When insufficient gypsum was added to the
ACSA, a conversion from ettringite to monosulfate and a sub-
sequent mechanical property loss was observed.
Former studies have mainly focused on ACSA clinker pro-
duction and physical properties, but few studies have reported
detailed hydration data, such as calcium–silicate–hyrdrates
(C–S–H) composition or thermodynamic modelling. Thus, the
present study focuses on the hydration reactions of ACSA and
how the hydration reactions affect the physical properties. The
experimental data are compared with thermodynamic model-
ling, which is used to calculate the development of the hydrate
phase assemblage with time.
Experimental procedure
Materials
The ACSA clinker was produced by firing 72·5% limestone,
16·9% tuff, 10·6% gypsum and 1% calcium fluoride in a static
furnace at 1300°C for 45 min., followed by quenching by air
cooling. The clinker was ground and then combined with 5%
anhydrite using a three-dimensional mixer (Turbula, WAB) to
make ACSA cement. The particle size distributions of the
anhydrite and ACSA clinker are given in Figure 1. Chemical
compositions were determined by X-ray fluorescence (XRF),
1·0 100
ACSA clinker
Cumulative distribution, Q3: %
Anhydrite
0·8 80
Density distribution, q3
0·6 60
0·4 40
0·2 20
0 0
1 10 100
Particle size: µm
Figure 1. Particle size distributions of the ACSA clinker and
anhydrite measured by laser diffraction. q3, fractional volume
density distribution; Q3, cumulative volume density distribution
(% passing)
 Advances in Cement Research Synthesis and hydration of alite-calcium
sulfoaluminate cement
Chitvoranund, Winnefeld, Hargis, Sinthupinyo
and Lothenbach

and phase compositions were determined by quantitative XRD
(QXRD). The composition, phases and physical properties of
the ACSA clinker and anhydrite are given in Table 1.
Methods of analysis
respectively, where Wt is the dry sample weight in grams at the
temperature t (°C), and MM is molar mass (g/mol). The
derivative curve (DTG) was used to determine the exact temp-
erature boundaries taken into account for BW and CH
calculation.

Investigation of cement pastes W40  W550

All experiments were carried out at 20°C using a water to 1: BW ¼
W550
binder ratio of 0·485. For isothermal conduction calorimetry,
ACSA cement was externally mixed with water for 1 min with
a small stirrer at 600 r/min. Then 6 g of paste were transferred
to glass ampoules, and the heat flow was recorded for 120 h.
The early heat of hydration (up to 30 min) could not be W450  W550 MM of CaðOHÞ2
2: CH ¼ 
observed owing to the external mixing procedure. W550 MM of H2 O

For hydration studies, cement pastes of the composition pre-

viously described were prepared and stored in sealed plastic
containers. To stop hydration, 3 mm slices were cut using a
saw. The slices were then gently crushed in an agate mortar.
The crushed samples were then immersed in isopropanol for
15 min, filtered using a Büchner funnel, rinsed with diethyl
ether and finally dried at 40°C for 8 min to evaporate the
remaining solvent. Afterwards, the dry pastes were investigated
by thermogravimetric analysis (TGA), XRD and scanning
electron microscopy (SEM).
The TGA was carried out using a Mettler Toledo TGA/SDTA
851e directly after stopping hydration. The cement paste
powder, approximately 45 ± 2 mg, was characterised by moni-
toring the weight while heating from 30 to 980°C under a
nitrogen (N2) atmosphere at a heating rate of 20°C/min. This
method was used for determining the chemically bound water
(BW) and the amount of portlandite (CH) in the sample. The
calculation of BW and CH are given by Equations 1 and 2,
The XRD was done using a Panalytical X’pert Pro powder dif-
fractometer with a 2θ-range of 5–80° and CoKα radiation as
incident beam for qualitative and quantitative phase analysis.
Samples were prepared by back loading. Calcium fluoride was
used as an external standard for the Rietveld analysis of the
hydrated pastes. The phase quantification of the anhydrous
ACSA cement and the hydrated samples was performed by
Rietveld refinement of the XRD patterns using the software
Topas 4·2 from Bruker AXS according to the procedures pub-
lished previously (Álvarez-Pinazo et al., 2012; Le Saoût et al.,
2011, 2013; Pelletier-Chaignat et al., 2011). For quantification
of the amorphous content the G-factor method (Equation 3)
(Jansen et al., 2011a, 2011b, 2012; O’Connor and Raven,
1988) was used, based on the calculation of a calibration con-
stant of the standard, where SCaF2 is the scale factor of
calcium fluoride from Rietveld analysis, ρCaF2 is the density
of calcium fluoride, VCaF2 is the unit cell volume of calcium
fluoride, u
CaF2 is the mass attenuation coefficient of calcium

Table 1. Oxide content, phase composition and physical properties of the ACSA clinker and anhydrite
ACSA clinker Anhydrite ACSA clinkera Anhydritea
mass: % mass: % mass: % mass: %

Silicon dioxide (SiO2) 14·91 0·01 C3S (M3) 48·3 CS̄ 93·6
Aluminium oxide (Al2O3) 9·64 0·06 α′-C2S 1·5 CC̄ 1·7
Iron (III) oxide (Fe2O3) 4·22 0·02 β-C2S 10·3 CS̄H2 4·7
Calcium oxide (CaO) 61·61 40·7 γ-C2S 2·2
Magnesium oxide (MgO) 0·78 0·01 C4AF 12·9
Sulfur trioxide (SO3) 6·64 58·04 C4 A3 S̄ (cubic) 9·6
Sodium oxide (Na2O) 0·12 0·03 C 1·5
Potassium oxide (K2O) 0·12 0·01 CS̄ 5·0
Titanium dioxide (TiO2) 0·62 0·01 C2AS 3·3
Phosphorus pentoxide (P2O5) 0·11 0·01 Ff 0·3
Manganese oxide (MnO) 0·08 0·01 C5 S2 S̄ 2·6
Loss on ignition (LOI) 1·08 1·07 M 0·1
Sum 99·94 99·98 CH 2·4
Blaine surface: cm2/g 4480 3420
Density: g/cm3 3·12 2·93
d50: μmb 11·2 11·85 total 100 100

a
Cement chemistry notation utilised: C denotes CaO; M, MgO; S, SiO2; F, Fe2O3; A, Al2O3; H, H2O; f, FeO; S̄, SO3; C̄, carbon dioxide
b
Median diameter

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 Advances in Cement Research
fluoride and CCaF2 is the weight fraction of calcium fluor-
ide (100%) in the external standard.
ρCaF2 VCaF
2
u
CaF2
3: G ¼ SCaF2 2
CCaF2
The weight fraction of each crystalline phase j can be calculated
from the density (ρj ), the unit cell volume (Vj ), the calculated
scale factor of each phase (Sj ) and the mass attenuation coeffi-
cient of the whole sample μsample
* , shown in Equation 4.
ρj Vj2 μ
sample
4: Cj ¼ Sj
G
The degree of reaction of the main anhydrous phases was cal-
culated by normalising to 100 g dry binder as shown in
Equation 2 in order to take into account the solid mass
increase during hydration.
For SEM analysis, a slice of cement paste was immersed first
in isopropanol for 3 d and then in diethyl ether for 15 min.
The solvent was drained, and the sample slice was then dried
at 40°C for 6 h. The slice was impregnated with epoxy resin,
polished and coated with carbon before SEM (Philips ESEM
FEG XL 30) analysis. A beam voltage of 15 keV was chosen
for backscattered electron images (BSE) and element mapping
by energy dispersive X-ray spectroscopy (EDS).
Thermodynamic modelling
Thermodynamic modelling was performed using GEMS-PSI
software (Kulik et al., 2013; Wagner et al., 2012) with the PSI-
Nagra database (Hummel et al., 2002) and the cement-specific
CEMDATA14 database (Dilnesa et al., 2014a; Lothenbach
et al., 2008, 2012; Matschei et al., 2007b). The reaction
degrees of the clinker phases and anhydrite after different
times as obtained from XRD were used to fit sigmoidal
equations to describe the dissolution degree as a function of
time, which was used as kinetic input for GEMS. The so-
called ‘four-parameter logistic non-linear regression model’
(4PL, see Equation 5), with α = reaction degree, t = hydration
time in d, A = minimum asymptote (=0), B = steepness of curve,
C = inflection point and D = maximum asymptote, was applied.
ðA  DÞ
5: α¼ þD
1 þ ½lgðtÞ=C B
In the modelling, gehlenite, ternesite, magnetite and γ-dical-
cium silicate or belite (γ-C2S) are considered as inert com-
ponents in the clinker, as they did not show a significant
reaction during the investigated hydration times. Ternesite is
4
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Synthesis and hydration of alite-calcium
sulfoaluminate cement
Chitvoranund, Winnefeld, Hargis, Sinthupinyo
and Lothenbach
reported to react in CSA cements, but only in the presence of
aluminum hydroxide (Ben Haha et al., 2015).
Physical properties of mortar samples
Mortars were mixed according to ASTM C305 (ASTM, 2013).
The water to binder ratio was fixed at 0·485, and standard
sand (Ottawa sand) was used at 2·75 parts to one part of
cement by weight. Compressive strength of the mortar cubes
(50 mm  50 mm  50 mm) and flexural strength of mortar
bars (40 mm  40 mmm  160 mm) were determined after 1,
3, 7 and 28 d according to ASTM C109M (ASTM, 2013) and
ASTM C348 (ASTM, 2014), respectively.
Results and discussion
ACSA clinker
The ACSA clinker is composed of 48% alite (C3S, monoclinic),
14% belite (three polymorphs of C2S) and 13% ferrite
(C4AF), which is quite similar to PC, but the ACSA clinker
also contains about 10% of ye’elimite (C4 A3 S) ˉ instead of
aluminate (C3A), as shown in Table 1. Ye’elimite occurs in
the cubic form. The ACSA clinker contains less than 5%
of anhydrite (CS),ˉ CH, free lime (C), gehlenite (C2AS)
and ternesite (C5S2S) ˉ as minor phases. Fluorellestadite
(Ca10(SiO4)3(SO4)3F2) could not be identified by XRD. Reverse
Bogue calculations using the clinker phase compositions given
by Taylor (1997) agreed fairly well; however, they showed a sig-
nificantly higher silicon dioxide content than found by XRF
(18·5% compared to 14·9 mass%). However, it has to be kept in
mind that those calculations were designed for conventional PC
and would need to be modified to be accurate for ACSA made
using fluxing agents. Furthermore the presence of an amor-
phous phase cannot be excluded, which would bias both
QXRD and reverse Bogue calculations. Further work on the
compositional analysis of ACSA clinker would be needed to
create a data set large enough to put ranges on the impurities
incorporated into ACSA clinker phases in order to provide a
more accurate reverse Bogue calculation.
The calculation of total carbon dioxide emission reductions
was based on 50% of calcination of raw materials and 40% of
kiln fuel consumption (Benhelal et al., 2013). From the calci-
nation of limestone, 1 t written out previously of calcium oxide
generates 785 kg of carbon dioxide (WBCSD, 2005).
According to Table 2, PC releases about 522 kg CO2/t of
clinker during calcination, while ACSA produces 425 kg CO2/t
of clinker. As a result, the ACSA cement could reduce carbon
dioxide emissions from the calcination of calcium carbonate
by 18%. The other main source of carbon dioxide emissions is
the use of primary fuel in the clinker production. In general,
PC is produced at 1450°C, whereas ACSA clinker is syn-
thesised at 1300°C. It can be assumed that a temperature
reduction of 150°C reduces heat consumption by approxi-
mately 3% (Gartner and Hirao, 2015). From these two contri-
butions, it can be estimated that the ACSA cement synthesised
 Advances in Cement Research Synthesis and hydration of alite-calcium
sulfoaluminate cement
Chitvoranund, Winnefeld, Hargis, Sinthupinyo
and Lothenbach

Table 2. Carbon dioxide emissions from the calcination of raw materials needed to form the main phases of PC and ACSA clinker
Carbon dioxide Phases in PC: Carbon dioxide
released: kg/t phase kg/t clinker emission from PC: kg/t Phases in ACSA used in Carbon dioxide emission
Phases (Gartner, 2004) (Taylor, 1997) clinker this study: kg/t clinker from ACSA: kg/t clinker

Alite 578 667 386 483 279

Belite 511 130 66 140 72
Aluminate 489 70 34 0 0
Ferrite 362 99 36 129 47
Ye’elimite 288 0 0 96 28
Total 522 425

in this study could release approximately 11–12% less carbon clinker, as angular alite crystals are lacking, and it shows a
dioxide than PC if produced on a commercial scale. strong propensity for other phases to be included.

The SEM investigations of the ACSA clinker (Figure 2) show
that the clinker is quite porous, giving an advantage for the
grinding process. The light grey field corresponds to alite in
which 0·4–3·5 μm ye’elimite inclusions are identified as darker
areas. The brightest phase spread over the clinker corresponds
to ferrite. The ye’elimite being principally trapped as inclusions
in an alite matrix is consistent with there being approximately
five times more alite than ye’elimite. Additionally, alite does
not show the same crystal habit that is typically seen in PC
Belite
Ferrite
Alite
Ye’elimite
10 µm
Ye’elimite
Ferrite
Alite
2 µm
Figure 2. Backscattered electron images of ACSA clinker at
different magnifications. Black: porosity
The EDS analyses of the ACSA clinker indicate that the
clinker contains foreign elements in the clinker phases such as
fluorine (F), magnesium (Mg), titanium (Ti), chromium (Cr)
and manganese (Mn). These elements are also generally found
in PC clinker phases. Table 3 shows that the main minor
element which can be found in a detectable amount in every
clinker phase is magnesium. Free lime shows only magnesium
as a foreign element in the composition. The other phases
contain more than one minor element in detectable amounts.
Ye’elimite contains mainly iron (Fe) and silicon (Si) as substi-
tuting elements; it is likely that the Al3+ site in the sodalite fra-
mework is being substituted by Fe3+ and Si4+ (Cuesta et al.,
2014; Hargis et al., 2014). The places that fluorine from
calcium fluoride usually goes into are oxygen sites in the sili-
cate and aluminate phases, for example, in calcium fluoroalu-
minate (C11A7·CaF2) at certain temperature owing to the
similar ionic radius and electronegativity (Taylor, 1997). Alite
in ACSA clinker contains, besides fluorine, also magnesium,
iron, sulfur (S) and titanium. Magnesium, iron and sulfur in
minor amounts are usually present in alite from commercial
PC (Taylor, 1997). Titanium is generally incorporated in PC
clinker, and it is considered a mineraliser. It can form solid sol-
utions with all of the major phases in PC by ion substitution
(Katyal et al., 1999). It has been reported that chromium can
exist in belite under oxidising conditions and can be used as a
stabiliser of belite (Bhatty, 1995; Lea and Hewlett, 1998;
Sinyoung et al., 2011). Accordingly, chromium is found in the
belite of ACSA as well. The minor elements which are not sub-
stituted in alite and belite are left over in the melt at high
temperature. During cooling, those minor elements incorpor-
ated in the melt are crystallised, together with ferrite and alu-
minate (Ludwig and Zhang, 2015). Therefore, in the present
ACSA, which lacks aluminate, ferrite contains most of the
foreign elements, which are fluorine, magnesium, titanium and
manganese. When comparing the relative amount of foreign
ions in ACSA clinker to the typical PC clinker, ACSA shows
similar types of ions specifically incorporated in some phases
to PC. For example, manganese can be found only in ferrite in
both types of clinker (Taylor, 1997). The alite in ACSA shows
a quite high molar calcium/silicon ratio of 3·3. While the possi-
bility in the EDS analyses to catch free lime inclusions below

5
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 Advances in Cement Research Synthesis and hydration of alite-calcium
sulfoaluminate cement
Chitvoranund, Winnefeld, Hargis, Sinthupinyo
and Lothenbach

Table 3. Element ratios from EDS analyses of the ACSA clinker

Alite Belite Ferrite Ye’elimite Lime

Avg: At.% COVa Avg: At.% COV Avg: At.% COV Avg: At.% COV Avg: At.% COV

Fluorine (F) 0·8 0·18 — — 2·7 0·05 — — — —

Magnesium (Mg) 1·0 0·10 0·2b 0·14 2·2 0·07 0·7c 0·07 0·8 0·15
Aluminium (Al) 2·7 0·12 0·8b 0·12 22·7 0·04 50·1 0·02 — —
Silicon (Si) 20·2 0·03 31·4 0·008 0·4 0·23 0·2 0·48 — —
Sulfur (S) 0·3 0·26 0·4 0·35 d
9·2 0·04 — —
Calcium (Ca) 73·8 0·003 66·8 0·003 49·4 0·02 38·8 0·02 99·2 0·001
Titanium (Ti) 0·3 0·4 — — 1·9 0·18 — — — —
Chromium (Cr) e
0·4 0·12 — — — — — —
Manganese (Mn) — — — — 1·1 0·32 — — — —
Iron (Fe) 0·7 0·14 — — 19·5 0·03 1·0 0·14 — —

a
Coefficient of variation
b
Values sensitive to continuum X-ray background fitting
c
On shoulder of Al peak, thus quantification is doubtful
d
Only appeared in four measurements at 0·1% avg with COV = 0·74
e
Only appeared in two measurements at 0·3% avg with COV = 0·09

the surface of the sample cannot be excluded, a calcium/silicon 6 400

ratio different from 3 also originates from the incorporation of
foreign ions. Compared to the Taylor (1997) composition 5

Cumulative heat: J/g ACSA

Heat flow: mW/g ACSA

(which already has a calcium/silicon ratio of 3·04) the C3S in 300

the ACSA contains significantly more aluminium (Al) 4
(+100%) and iron (+50%), and significant amounts of titanium
3 200
and sulfur (VI) are present as well, which all can substitute for
silicon. Magnesium, which substitutes for calcium, is present 2
in a lower amount (only two-thirds) compared to the compo- 100
sition given by Taylor (1997). The incorporation of these 1
foreign ions into the alite structure can possibly explain the
quite high calcium/silicon ratio. 0 0
0 24 48 72 96 120
Hydration Time: h

Isothermal conduction calorimetry
Isothermal calorimetry of ACSA is shown in Figure 3. The first
increase in the heat evolution rate started at 6 h of hydration
followed by a second increase in heat evolution at 2 d. By 3 d,
the cement showed a consistent decline in the rate of heat
evolution. The hydration reactions responsible for the heat
evolutions at 6 h and about 2 d will be explained later by the
XRD results. After 5 d, about 320 J/g heat of hydration had
been liberated which is comparable to a CEM I cement.
X-ray diffraction and thermogravimetric analysis
The hydrated phase compositions through 180 d of hydration
were determined by XRD and TGA. The XRD patterns
(Figure 4) reveal that the main crystalline hydration products
were ettringite, monosulfate and CH. At later ages, low
amounts of iron-containing siliceous hydrogarnet occurred
(Dilnesa et al., 2014a, 2014b). The presence of this phase was
verified by performing a selective dissolution with salicylic
acid/methanol (SAM) according to Gutteridge (1979) using
the ACSA sample hydrated for 91 d (see Figure 9 later, in the
Appendix) and analysing the phase composition of the residue
Figure 3. Heat flow and cumulative heat of hydration of ACSA
cement normalised to the amount of ACSA cement
by XRD afterwards. By this technique, the siliceous clinker
phases and most of the other hydrates are dissolved, and thus
the iron-containing siliceous hydrogarnet is enriched. The
reflections of the siliceous hydrogarnet were best matched by a
hydrogarnet of the composition C3A0·5F0·5SH4 (Schwiete and
Iwai, 1964). This is in line with previous findings in hydrated
PC (Dilnesa et al., 2014b), where the authors identified a silic-
eous hydrogarnet of an average anhydrous composition of
Ca3Al0·9Fe1·0Si0·85O7·55.
Figure 5 presents the XRD quantification. Alite dissolved
more rapidly than ye’elimite through 1 d, which was initially
unexpected because in other studies ye’elimite has been shown
to hydrate very rapidly compared to alite (Pelletier et al., 2010;
Pelletier-Chaignat et al., 2011; Trauchessec et al., 2015). The
SEM images show that the majority of the ye’elimite was
trapped within an alite matrix (see Figure 2). This is able to

6
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 Advances in Cement Research Synthesis and hydration of alite-calcium
sulfoaluminate cement
Chitvoranund, Winnefeld, Hargis, Sinthupinyo
and Lothenbach

Ms CH E An CH A CH silica source (C3S in this case) can convert ettringite to mono-

E E A A
A Ms B F sulfate and produce iron-containing siliceous hydrogarnet.
F HG E E
Ye
C6 ASˉ 3 H32 þ 2C4 AF þ 168C3 S þ 1368H
6:
180 d ! 3C4 ASH ˉ 12 þ 2C3 FS084 H432 þ 104CH

7d
C3FS0·84H4·32 represents an idealised composition in order to
simplify Equation 6, as this phase is present as a solid solution
2h also containing aluminium, as discussed above.

Anhydrous Figure 6 presents the TGA results of ACSA pastes hydrated

10 15 20 25
2θ: degrees CoKα
Figure 4. X-ray diffraction patterns of anhydrous ACSA and after
2 h, 7 d and 180 d of hydration. E, ettringite; Ms, monosulfate;
F, ferrite; HG, iron-containing siliceous hydrogarnet;
CH, portlandite; Ye, ye’elimite; An, anhydrite; A, alite; B, belite
explain the delayed hydration of ye’elimite, as some of the alite
must dissolve before the ye’elimite is exposed to the pore sol-
ution and able to react. Consequently, the maxima in heat flow
in calorimetry at 6 h and 2 d can be shown by XRD results to
be caused by the hydration of first alite and then ye’elimite,
respectively.
Anhydrite reacted to a large extent by 1 d. Ye’elimite and
anhydrite fell below the XRD detection limits by 28 d. Belite
showed little reaction through 28 d but showed considerable
reaction beyond. The paste’s ettringite content increased
through 7 d, but by 180 d the ettringite content had decreased
and the monosulfate content had increased. Equation 6
demonstrates how the reaction of ferrite in the presence of a
100 Alite
Belite
90
Phase content: g/100 g dry binder
through 180 d. The results are entirely consistent and comp-
lementary to the XRD results, showing the CH, C–S–H and
30 35 40 monosulfate contents increasing with time and a slight
decrease of ettringite content between 7 d and 180 d.
Portlandite contents determined by TGA are systematically a
few percent lower than the values derived from XRD (see
Figure 10 later, in the Appendix), which is mainly due to a
slight carbonation of the CH (see weight losses in Figure 6 at
around 700°C). When the TGA data are corrected for CH car-
bonation, they agree quite well with XRD and GEMS (see
Figure 10 in the Appendix). Additionally, the absence of a
large aluminum hydroxide (AH3) peak in a range between 250
and 300°C is expected for this relatively low-ye’elimite and
high-alite cement; since calcium-containing hydration products
consume the AH3 released during ye’elimite hydration
(Winnefeld and Lothenbach, 2010).
Thermodynamic modelling
The thermodynamic modelling of ACSA hydration (Figure 7)
was performed utilising the calculated anhydrous phases’ reac-
tion degrees from the XRD data. The results agree well with
the experimental data from XRD and TGA. The anhydrous
phases are strongly reacting at early ages of hydration through
10 d, after which the reactions slow down. The hydration reac-
tions are almost complete by 100 d.
Anhydrite
Ettringite 0·06
100

Ferrite Portlandite
80 Ye’elimite Amorphous and minor 90 0·04
Derivative weight loss: %/°C

70 crystalline phases
80 0·02
Weight loss: %

60 C–S–H
70 0
50 60 Carbonates
–0·02
40 50 CH
–0·04
30 Ms Anhydrous
40
2h –0·06
20 7d
30
180 d –0·08
10 E
20
0 0 100 200 300 400 500 600 700 800 900 1000
0·01 0·1 1 10 100 Temperature: °C
Time: d
Figure 6. Thermogravimetric analysis of anhydrous ACSA and
Figure 5. X-ray diffraction quantification of the phase after 2 h, 7 d and 180 d of hydration. C–S–H, calcium silicate
development in hydrating ACSA paste hydrates; E, ettringite; Ms, monosulfate; CH, portlandite

7
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 Advances in Cement Research Synthesis and hydration of alite-calcium
sulfoaluminate cement
Chitvoranund, Winnefeld, Hargis, Sinthupinyo
and Lothenbach

Alite, ye’elimite and anhydrite start reacting at early ages of

hydration, but belite and ferrite start to react significantly later.
Alite content decreases strongly at early ages but still remains Alite C–S–H
in the system at very late ages. On the contrary, ye’elimite and
anhydrite are consumed within 10 d. The main hydration pro-
ducts calculated are C–S–H, CH, ettringite and monosulfate.
Iron-containing siliceous hydrogarnet is also found in the mod- C–S–H
elling as a minor hydrate phase, which agrees with the XRD
Alite
data (Figure 4). A small quantity of hemicarbonate, which
could not be identified by XRD, is predicted resulting from the Ye’elimite
dissolution of the traces of calcite present in the anhydrite.

Ferrite
The ACSA cement produces approximately twice as much
C–S–H as ettringite or monosulfate. In agreement with the
experiments, ettringite quantity reaches a maximum after 20 µm
approximately 7 d of hydration. As the sulfate depletes, mono-
sulfate starts forming rapidly, while ettringite content decreases. Figure 8. Backscattered electron image of hydrated ACSA cement
at 28 d of hydration

Scanning electron microscopy

Figure 8 presents a polished surface of hydrated ACSA paste
at a hydration time of 28 d and shows the mixed mineralogy of
ACSA cement hydrates. Around the larger anhydrous clinker
grains, the inner hydration product was C–S–H, and the outer
products were mainly CH, monosulfate and ettringite. EDS
analyses were carried out at the inner products of the hydrated
area around the clinker grains and the outer products precipi-
tated in the pore space around the clinker grains. Element
ratios of calcium/silicon and aluminium/silicon from EDS
analyses of the C–S–H in ACSA at 28 d are about 1·7 and
0·09, respectively, which is comparable to the composition of
C–S–H present in PC (Taylor et al., 2010).
Even at 28 d, some ye’elimite grains were still surrounded by
alite. Clinker phases and anhydrite were still present at 28 d of
hydration, so the reaction could continue at later ages.
Iron-containing siliceous hydrogarnet
140 Hemicarbonate
Pore solution
120 Monosulfate
g/100 g ACSA cement
Strength development
The compressive strength data are shown in Table 4. The
ACSA mortar gained strength rapidly through 7 d and contin-
ued to gain strength at a slower rate through 28 d. At 1 d, the
ratio of flexure strength to compressive strength was 0·3, but at
3, 7 and 28 d the ratio was 0·2. Likewise, from 1 to 3 d, the
compressive strength increased 143%, which was more rapid
than the flexure strength increase of 56%. These results indi-
cate that the ACSA mortar gained flexural strength more
rapidly through 1 d, compressive strength more rapidly from 1
to 3 d, and then both flexural strength and compressive
strength increased slowly from 3 d onwards, which corre-
sponded with the development of heat of hydration.
Conclusions
An alite-calcium sulfoaluminate clinker was synthesised in the
laboratory at 1300°C using 1% calcium fluoride as mineraliser.
The resulting clinker was very porous and thus easy to grind.
Ye’elimite occurs in the phase assemblage in quantities of
approximately 10%, instead of the tricalcium aluminate

present in PC. It is present mainly as inclusions inside the alite.

100 Ettringite The fluorine from the mineraliser is mainly incorporated in the
Anhydrite
80
ferrite phase and to a lower extent in alite.
Ferrite Portlandite
Ye’elimite
60
Belite
The ACSA clinker was blended with 5% anhydrite, and the
C–S–H hydration mechanism of the resulting ACSA cement was
40

Alite Table 4. Strength evolution of ACSA mortar

20

Inert Compressive strength: Flexural strength:

0
Time: d MPa MPa
0·001 0·01 0·1 1 10 100 1000 10 000 100 000
Time: d 1 10·1 ± 0·1 3·0 ± 0·1
3 24·5 ± 1·3 4·7 ± 0·1
Figure 7. Thermodynamic modelling of the phase changes of 7 30·8 ± 2·1 5·5 ± 0·2
ACSA during hydration 28 35·2 ± 0·2 7·1 ± 0·4

8
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 Advances in Cement Research
investigated experimentally and by thermodynamic modelling.
From isothermal calorimetry and XRD data, the hydration
kinetics has been observed. During the first hours, the reaction
starts rapidly, mainly from alite, then ye’elimite reacts later,
after 2 d. This agrees well with SEM images showing that
ye’elimite tends to be present as inclusions in an alite matrix,
so ye’elimite reacts only after sufficient alite has reacted to
expose the ye’elimite grains to the pore solution. Belite begins
reacting significantly only after 28 d.
The hydration products are mainly C–S–H, ettringite, monosul-
fate and CH. Ettringite contents increase until 28 d, then
monosulfate starts forming as the calcium sulfate is depleted.
Small amounts of hemicarbonate and iron-containing siliceous
hydrogarnet are present as minor hydration products. In
addition to the hydration study, the mechanical properties of
ACSA cement were also examined. Mortars prepared using the
ACSA cement rapidly develop compressive and flexural strength
at early ages corresponding to the fast hydration reactions.
It was estimated that the manufacturing of ACSA clinker
releases about 11–12% less carbon dioxide than the production
of PC clinker, which can be attributed to less calcium carbonate
in the kiln feed and to a lower firing temperature. As sufficient
CH is present in the hydrate assemblage, carbonation resistance
should be sufficient to protect carbon steel rebar from corrosion.
Furthermore, the presence of CH offers the possibility to blend
ACSA cement with pozzolanic supplementary cementitious
materials to further reduce the cement’s environmental impact.
CH
E
Ms
F E
E An
E E CH
HG
F 91 d
HH An HH
HH
F
HG
HG
Ye HG HG
91 d after SAM
8 10 12 14 16 18 20 22 24 26 28 30 32 34
2θ : degrees CoKα
Figure 9. XRD patterns of the ACSA cement hydrated for 91 d
before and after selective dissolution with salicylic acid/methanol
(SAM). The SAM extraction, which dissolves alite, belite,
portlandite, C–S–H, AFt and AFm phases and leaves residues of
ferrite, siliceous hydrogarnet and hydrotalcite, was performed
according to (Gutteridge, 1979). E, ettringite; Ms, monosulfate;
HH, hemihydrate; HG, iron-containing siliceous hydrogarnet;
CH, portlandite; Ye, ye’elimite; F, ferrite. The reflections of the
siliceous hydrogarnet were best matched by a hydrogarnet of the
composition C3A0·5F0·5SH4 (Schwiete and Iwai, 1964)
Downloaded by [ Monash University] on [27/12/16]. Copyright © ICE Publishing, all rights reserved.
Synthesis and hydration of alite-calcium
sulfoaluminate cement
Chitvoranund, Winnefeld, Hargis, Sinthupinyo
and Lothenbach
Acknowledgements
The authors would like to acknowledge Siam Cement Group
(SCG) for financial support together with Swiss Federal
Laboratories for Materials Science and Technology (Empa),
Laboratory for Concrete and Construction Chemistry for tech-
nical and facilities support. Special thanks to Axel Schöler for
discussions and comments, Lukas Martin for the SEM analy-
sis and Sared Pukkleang, Luigi Brunetti, Boris Ingold and
Stephan Geis for the technical support. The stay of Craig W.
Hargis at Empa was supported by the EU Marie Curie Action
of the People Programme (FP7) within the co-funding of
Regional, National and International Programmes (COFUND).
Appendix
The appendix provides additional data presented related to the
identification of hydrogarnet in the hydrated phase assemblage
(Figure 9) and to the quantification of portlandite by the
different methods used (Figure 10) as mentioned in the main
manuscript. Further explanations can be found in the relevant
figure captions.
25
XRD
TGA
Portlandite: g/100 g ACSA cement
20 TGA corrected
GEMS
15
10
5
Estimated error of XRD and TGA
0
0·01 0·1 1 10 100 1000
Time: d
Figure 10. Comparison of portlandite contents as determined by
XRD, TGA and GEMS. TGA shows systematically lower values than
XRD, as obviously some carbonation occurred due to sample
preparation (see also Figure 6, weight loss at around 700°C). The
formation of carbonates is related to the stopping method (solvent
exchange) and interaction with environmental carbon dioxide
(Lothenbach et al., 2016; Winnefeld et al., 2016). The accuracy of
portlandite contents determined by XRD is mainly biased by the
strong preferred orientation of the crystal, even if a sample
preparation by backloading (as in the present case) is applied.
When the TGA data are corrected for portlandite carbonation,
they agree quite well with XRD. The first two values at hydration
times < 1 d are higher for GEMS compared to the experimental
values, as hydration kinetics are difficult to fit in a reliable way
at very early ages. For instance all free lime was allowed to
dissolve instantaneously, as no dissolution kinetics were applied to
this phase
9
 Advances in Cement Research
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