Hydration of a Belite-Calcium Sulfoaluminate-Ferrite cement : AetherTM

Morin V1*., Walenta G.2*

Gartner E., Termkhajornkit P., Baco I., Casabonne J.M.

LAFARGE Research Centre, 95 Rue du Montmurier, 38291 Saint-Quentin-Fallavier, FRANCE

Abstract
We used multiple techniques to study the paste hydration, and w/c = 0.50, of a Belite-Calcium Sulfo-Aluminate-Ferrite
(AETHERTM) cement containing about 48% belite (C2S), 28% ye’elimite (C4A3$), 18% ferrite solid solution (C2(A,F))
and 6% anhydrite, over 6 months at 20°C. The XRD-Rietveld method was used in order to identify and quantify the
different crystalline in the clinker and cement as well in their hydration products, and to estimate the total amount of
amorphous phases. TGA and DTA methods were used to confirm the XRD data, and to characterize the main
amorphous hydrate phases formed (AH3 and C-S-H). Isothermal calorimetry and pycnometry were used to measure the
overall hydration rate, and gave results in reasonable accord with the other methods. The hydration could be divided
into three principal steps: initial rapid hydration of ye’elimite plus anhydrite to give ettringite in the first few hours plus
an amorphous hydrated alumina (AH3), followed by a slow reaction period of 2-3 days, after which belite hydrates,
consuming AH3 to form strätlingite. Finally, belite and ferrite phases continue to hydrate slowly, consuming strätlingite
and giving C-S-H plus an iron-rich siliceous hydrogarnet. Ettringite formed initially persists throughout the hydration
and calcium monosulfoaluminate hydrate (AFm) is also formed, increasing slowly in amount, apparently due to slow
hydration of residual ye’elimite physically “trapped” inside large clinker particles.

Originality
This work represents a more thorough study than previously published of the hydration of this new class of cements,
which appear to represent a novel and important approach to producing hydraulic cements with lower manufacturing
CO2 emissions. The analytical methods have been refined relative to previous studies, especially the Rietveld XRD
technique, which now permits a reasonable quantification of the total amount of amorphous phases. Comparison of the
degree of hydration of individual phases measured by specific techniques (XRD, TGA and DTA) with the more general
“bulk thermodynamic” techniques of calorimetry and pycnometry shows reasonable agreement although calorimetry is
not usable for more than the first few days due to baseline errors at low hydration rates.

Chief contributions
The most novel conclusion of this work is the observation that the observed slow continuous formation of
monosulfoaluminate AFm phase throughout the hydration of BCSAF cement is almost certainly due to hydration of
ye’elimite crystals “trapped” inside large clinker grains, such that it cannot hydrate until the surrounding belite and
ferrite phases have been consumed.

Keywords: Belite, calcium sulfoaluminate, cement, hydration, CO2 emissions.

1
Corresponding author: Email vincent.morin@lafarge.com Tel (+33) 474 82 18 24, Fax (+33) 474 82 80 11
2
Corresponding author: Email gunther.walenta@lafarge.com Tel (+33) 474 82 18 28, Fax (+33) 474 82 80 11
Introduction

Cement production consumes large amounts of energy and natural raw materials and is responsible for about
11% of global industrial CO2 emissions. These CO2 emissions emanate mainly from the burning of carbon-
based fuels (about 40%) and from decarbonation of limestone (about 60%). Note that a typical modern
Portland clinker contains at least 60% alite C3S in order to guarantee high early strengths, and this requires a
calcium content of at least 65% expressed as CaO, almost all of which originates from calcium carbonate
(CaCO3), mostly in the form of limestone in the kiln feed. The decarbonation of this CaCO3 is the main
source of CO2 emissions from the cement kiln, not only because of the release of the fossil CO2 contained in
the limestone, but also because about two-thirds of the energy required for clinker formation in a modern
energy-efficient kiln system is simply the energy required for driving this very endothermic decarbonation
reaction, which takes place at about at 900°C at atmospheric pressure. The production of one tonne of
Portland cement clinker in a modern energy-efficient plant results in emission of about 0.8 tonnes of CO2. In
order to reduce these emissions, the cement industry has traditionally used the following four approaches:
1. Improvement of the energy-efficiency of the cement manufacturing process.
2. Replacement of fossil fuels by waste fuels or biomass-derived fuels.
3. Reduction in the clinker content of cements by substitution of clinker with industrial byproducts.
4. Reduction in the calcium carbonate content of the kiln feed by substitution with industrial byproducts.

However, all four of these approaches are close to reaching their practical limits in many locations. So, in
order to achieve a real breakthrough in reduction of CO2 emissions, it is necessary to consider a change in
the composition of the clinker itself, in order to develop a new class of cement which requires less limestone
in the kiln feed and thus emits less greenhouse gases. Thus, Lafarge’s new AETHER low-CO2 cement
technology is based on “BCSAF” clinkers containing belite (impure dicalcium silicate, C2S), ye’elimite
(calcium sulfoaluminate, C4A3$,) and calcium alumino-ferrite solid solution (ferrite or C2AxF1-x) (Gartner
and Li, 2006). The enthalpy of formation of ye’elimite from limestone, calcium sulfate and the other oxides
at 25°C is only 800 kJ/kg compared to 1337 kJ/kg for β-C2S and 1848 kJ/kg for C3S (Sharp et al., 1999),
and their specific CO2 emissions increase roughly in proportion to these enthalpy of formation values
(Gartner, 2004). The raw mix composition of this cement can be based on conventional raw materials
(limestone, clay, bauxite and iron ores) but industrial byproducts or wastes can be used as well (Berekta,
1993, Sahu, 1994) (for example fly ash, pyrite ash, galvanic sludges, metallurgical slags, phosphogypsum,
etc….). Furthermore this new class of cement clinker can be produced in existing installations using a
conventional cement kiln system, and the maximum burning-zone temperature is significantly lower
(around 1250°C) than for Portland cement clinker. Combining all of the above factors, a decrease of total
CO2 emissions by 20-30% compared to a typical Portland cement clinker appears to be industrially
achievable for the manufacture of such AETHER clinkers. The objective of the study reported here was to
improve our understanding of the hydration of such cements, following on from the initial studies of Li et
al. (2007) and Wang et al. (2010).

Specimen preparation

The raw mix used in this work was based on limestone, clay, bauxite, iron ore and anhydrite, all of which
were ground together in the desired proportions and pelletized. The pellets were introduced into a rotary kiln
with a burning-zone temperature of 1280°C. Boric acid was added to this raw mix in order to stabilize α’-
C2S, which is a more hydraulically reactive phase than the β-C2S typically present in Portland cement clinker
(Chae et al. 1996, Jelenic, 1978). This high temperature polymorph can also be stabilized by alkali metals
(Gies et al. 1986) or a mixture of alkali metals and iron (Suzuki, 1980). For cement preparation, the clinker
was ground to a Blaine fineness of about 500 m2/kg, and anhydrite ground to 100% passing 100 µm was
added. The powders were mixed for 30 minutes to give a cement composed of about 94% clinker and 6%
anhydrite, with an overall Blaine fineness of 524 m2/kg.

Analyses

The BCSAF cement composition was determined by quantitative XRD analysis by using the Rietveld
refinement method (Rietveld, 1969), including quantification of the amorphous part (Walenta, 2008). Special
control files dedicated to belite calcium sulfo-aluminate ferrite cement and its hydrated phases were
developed. The chemical composition of the clinker and the phase contents of the cement are given
respectively in tables 1 and 2.

Table 1: Chemical composition of the AETHER clinker studied in this work

SiO2 Al2O3 Fe2O3 CaO MgO K2O Na2O SO3 TiO2 B2O3 Total
15.8% 16.4% 7.7% 52.9% 0.5% 0.69% 0.07% 4.5% 0.3% 1.19% 100%

Table 2: Mineralogical composition of the AETHER cement studied in this work

Ye’elimite Belite Ferrite Anhydrite
C 4A 3$ α’-C2S C2(A,F) C$
28.2% 48.3% 17.8% 5.3%

Hydration studies were conducted on cement pastes with a w/c ratio of 0.50 at room temperature of 20±1°C.
XRD and TGA phase quantification was done on ground cement paste samples after the hydration had been
stopped by the procedure given by Wang et al. (2010). The first analysis was made one hour after mixing.
The XRD equipment was a Philips X’Pert Pro diffractomer with a high speed “X’Celerator” detector.
- For isothermal calorimetry measurements at 20±0.1°C, 10g of anhydrous cement were mixed with 5g of
water for one minute and 8.15g of this paste was poured into a flask lowered to the bottom of the measuring
chamber of a TAM AIR 3115 isothermal micro-calorimeter. The heat released by hydration of the cement
paste was typically monitored from a few minutes to several days after mixing.
- TGA measurements were done with ~100 mg of the “stopped” and dried ground cement paste, heated from
20°C to 1000°C at 20°C/min in nitrogen atmosphere. We also used special DTA equipment developed in our
laboratory to measure the thermal peaks from 20 to 600°C with very high resolution.

Results and discussions

A) Hydration at very early ages

Figure 1: Hydration degree of anhydrous phases Figure 2: Ettringite formation and ye’elimite hydration
(determined by XRD Rietveld) as a function of time. degree determined by XRD Rietveld method as a
function of time.

Figure 1 shows that, at very early ages, the only anhydrous phase consumed significantly is ye’elimite
(C4A3$), which hydrates rapidly for the first 3 hours to form ettringite, (see figure 2). By 3 hours, the amount
of ettringite formed is about 30 % of the initial mass of cement but there is no further increase (at least up to
24 hours). During this same period about 15% of the initial ye’elimite phase remains unreacted. A plausible
explanation for this could be that part of the ye’elimite phase is “trapped” as inclusions in belite and ferrite
phases which hydrate much more slowly.

C4A3$ + 2C$ + 38 H
C3A•3C$•32H + 2AH3 (1)

The initial hydration is assumed to follow equation (1) (Wang et al, 2010), but the amount of anhydrite in
our cement is only about half of that needed to react with all of the ye’elimite in this way, so other hydration
products must also form. The calorimetry curves (figure 3), show three major peaks at very early ages,
(followed by a large peak after 3 days that is assumed to represent the main “later age hydration” reactions)
 Figure 3: Calorimetric curve of the BCSAF cement

The initial peak corresponds to the wetting of the cement and the beginning of ye’elimite dissolution. Only
part of this exotherm is recorded owing to the time required for the mixing procedure. The second and third
peaks occur at around 2 and 3.5 hours, respectively. Zhang (2002) observed similar calorimetric curves for a
commercial calcium sulfo-aluminate cement (CSA) hydrated at a w/c ratio of 0.44 at 25°C. The second peak
can be considered as the main dissolution period of C4A3$ in presence of anhydrite following equation 1. It is
interesting to note that the third peak in figure 3 starts at around 3 hours, which is when the amount of
ettringite reaches a plateau. We suppose that this last peak, which corresponds to an acceleration of C4A3$
hydration, starts when the sulfate concentration in solution is depleted. This accelerated dissolution of C4A3$
after sulphate depletion can also be observed in dilute suspensions by conductimetric methods (Capmas et
al., 1993). At this point, we assume that C4A3$ dissolution leads to monosulfate precipitation following
equation (2):

C4A3$ + 18H
C3A•C$•12H + 2AH3 (2)

Both reactions (1) and (2) also form solid aluminium hydroxides (AH3) which are initially amorphous but
can crystallize as gibbsite. We do not detect any crystalline gibbsite by XRD during 0 and 3 hours but the
Rietveld control file indicates an increase of amorphous phase. The thermo-gravimetric curves between 0
and 6 hours (figure 4) show two peaks, the first around 130-140°C which corresponds to dehydration of
ettringite, and the second around 250°C which is attributed to AH3. In table 3, we present the evolution of the
weight loss in the temperature range 220-450°C that is the main dehydration domains of AH3. We can use
these weight losses to calculate the amount of AH3 present, based on its theoretical weight loss 34.6%
(54/156).

The data in table 3 show that the Rietveld control file calculates an increase of the amorphous phase during
the first hours of hydration, and that this increase is quite well correlated with the amount of AH3 measured
by TGA.

Table 3: AH3 amount determined by TGA and XRD

Rietveld method.
% AH3 (amorphous phase)
Time TGA XRD
Rietveld
(hours)
1 7.5% (weight loss 220-450°C 9%
= 2.6%)
2 9.8% (weight loss 220-450°C 8%
= 3.4%)
3 10.7% (weight loss 220-450°C 12%
= 3.7%)
Figure 4: Thermogravimetric analysis: cement paste
samples hydrated at 1, 2, 3 & 6 hours (at w/c = 0.5)
B) Hydration between 1 and 28 days

Figures 5 and 6 show the amounts of crystalline and amorphous hydrate phases formed in the paste:

Figure 5: Amount of strätlingite, hydrogarnet and Figure 6: Amount of ettringite and monosulfate as a
amorphous phases as a function of time determined by function of time determined by XRD Rietveld method
XRD Rietveld method

Strätlingite starts to form rapidly after about one day, and its formation appears to be proportional to the rate
of disappearance of belite (see figure 1). We thus assume that the main overall reaction in this period is (3):

C2S + AH3 + 5H
C2ASH8 (3)

This reaction consumes the amorphous AH3 formed earlier: TGA data (Fig. 7) confirm that there is little AH3
remaining by 7 days. These results confirm our recent suggestion that reaction (3) is the key to development
of strength after the initial ye’elimite hydration period of typical BCSAF clinkers (Wang et al, 2010).

The presence of large amounts of strätlingite at 28 days is confirmed by TGA measurements: figure 7 shows
an increase in the weight loss around 190-200°C, which can be attributed to strätlingite decomposition
according to Frias (2006). Fig. 7 also shows peaks at 250°C and around 300-320°C, which are respectively
attributed to the decomposition of gibbsite (AH3) and a siliceous hydrogarnet. Fig. 5 shows that a siliceous
hydrogarnet starts to form rapidly after about one week, by which time the ferrite phase has also started to be
consumed significantly. This supports the contention that this hydrogarnet phase contains a significant
amount of iron as well as silicon (Wang et al, 2010). It could form by coupled reaction of belite and ferrite:

C2S + C2(A,F) + 5H
C3(A,F)SH4 + Ca2+(aq) + 2(OH-)(aq) (4)

This reaction releases lime into the solution, but, since no portlandite formation is observed, this lime must
be consumed by a parallel process, presumably the conversion of strätlingite into more siliceous hydrogarnet:

Ca2+(aq) + 2(OH-)(aq) + C2ASH8
C3ASH4 + 5H (5)

Figure 7: TGA of hydrated BCSAF cement pastes Figure 8: DTA of hydrated BCSAF cement pastes
The DTA data at 28 days (Fig. 8) show a strong peak at 110-120°C that is consistent with significant
amounts of C-S-H also being present by this time. This is assumed to be a major product of later-age belite
hydration, according to reaction (6), although the exact composition of the C-S-H formed is not yet known:

C2S + (x+2-y)H
CySHx + (2-y){Ca2+(aq) + 2(OH-)(aq)} (6)

The dissolved calcium hydroxide produced by this reaction is presumably also consumed by reaction (5),
since XRD measurements do not detect any portlandite even at 28 days. The XRD data, however, show a
significant increase in the amount of amorphous phase, which is now presumably mainly C-S-H.

C) Hydration after 28 days

By 28 days ye’elimite has been totally consumed but belite continues to hydrate, reaching a hydration degree
of about 90% by 6 months (Fig. 1). Ferrite is consumed more slowly, only reaching hydration degree of 60%
at 6 months. Strätlingite concentration goes through a maximum of about 17% at 28 days, decreasing to only
about 6% by 6 months, presumably due to reaction (5). This trend was confirmed by DTA measurement
(figure 9) in which the endotherm at around 200°C is more pronounced after 28 days than after 6 months.
During the same period, the endotherm at around 110°C continues to grow more intense, confirming the
increase in C-S-H concentration. But it is important to note that, despite these major changes in hydrate
proportions, the strength of a BCSAF concrete was found to increase throughout this period (Quillin, 2007).

Figure 9: Differential Thermal Analysis: samples

hydrated at 28 days and 6 months (cement paste at Figure 10: Thermogravimetric analysis: sample
W/C = 0,5) hydrated at 6 months (cement paste at w/c= 0.5)

Fig. 10 shows the TGA trace after 6 months of hydration. We can identify several peaks: the first main peak
at around 110°C corresponds to C-S-H and the shoulder at around 130°C corresponds to ettringite. The broad
peak at around 290°C is identified with siliceous hydrogarnet, and there is now an additional peak at around
180°C which we attribute to monosulfate, consistent with the work of Winnefeld et al. (2009). Finally,
although a small portlandite peak appears to be present in the XRD pattern after 6 months, the TGA trace
(Fig. 10) shows no evidence of any portlandite dehydration at 400-500°C.

Conclusions

The hydration of a cement typical of Lafarge’s new AETHER low-CO2 cement technology, composed of
94% BCSAF clinker and 6% anhydrite, was shown to take place in three principal stages:
1. Initial rapid hydration of the calcium sulfo-aluminate phase (ye’elimite) plus anhydrite to give ettringite
plus an amorphous aluminium hydroxide. Due to a shortage of anhydrite, some monosulfoaluminate
was also formed at this time. In the particular BCSAF cement studied here, this stage was essentially
complete after only 4 hours, after which relatively little further reaction occurred for over 2 days.
2. Between 2 and 3 days the hydration re-accelerated, but this time the main reaction was hydration of
belite plus the aluminium hydroxide formed in stage (1) to give strätlingite. The way to manage the onset
of this intermediate stage is a critical point. Ideally, the onset of this period should occur earlier in order
to obtain rapid compressive strength increases after 1 day. This shows the need for a better mechanistic
understanding and also control of the reactivity of the belite and ferrite phases in this class of cement.
3. Once the residual amorphous aluminium hydroxide was depleted, further hydration of belite continued in
the “normal” way to give C-S-H plus (dissolved) calcium hydroxide; however, the calcium hydroxide
 appears to have been largely consumed by the strätlingite formed in stage (2), converting it to a siliceous
hydrogarnet, and so little if any portlandite was formed. At the same time, the ferrite phase hydrated,
combining with silica coming from belite hydration to give a siliceous hydrogarnet enriched in iron.
Interestingly, the amount of ettringite present in the hydrated pastes appeared to remain relatively constant
after the end of stage (1), despite all of the other chemical changes occurring. On the other hand, the amount
of monosulfoaluminate increases slowly but steadily from the first day onwards, presumably due to the fact
that a small fraction (estimated as about 10-15%) of the initial ye’elimite content is “trapped” inside clinker
grains and cannot hydrate before the surrounding belite and ferrite has been consumed.
The hydration path of BCSAF cements appears more complex than that of Portland cements and we are at
the early stage of understanding the mechanisms and their dependence on initial phase proportions and
reactivities. However, it is encouraging to note that initial studies of concretes made with such cements have
indicated continuous steady strength gain over two years and have not shown any excessive volume changes.

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Conference papers

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based on low CO2 clinkers containing belite, ye’elimite and calcium alumino-ferrite, ISCC.

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Patents

- Gartner, E., and Li, G., 2006. World Patent Application WO2006/018569 A2