SYNTHESIS of the SETTING KINETICS PROJECT

SULFATES TOPIC
INTRODUCTION
To study the impact of calcium sulfates added to the grinder (nature and %) on the cement properties
bound to the setting kinetics (workability, set and strength) and on concrete usage qualities, we
selected clinkers on criterias such as the representativity of the quality of the clinkers of the Group
(burning, cooling), as well as on the basis of physical and chemical parameters (soluble alkalis and
C3A contents): Richmond, Matozinhos, Cantagalo, Contes, Villaluenga and Brookfield (see
compositions in appendix).
The Project working group made the choice to operate tests on laboratory made cements by
intergrinding the industrial clinkers with calcium sulfates: Anhydrite (A), Gypsum (G) and Plaster (P),
as a single phase or as binary mixes A/G, A/P and G/P, or even ternary A/G/P. For certain cements,
two rates of total SO3 were aimed at. In the end, 12 to 20 cements were achieved for every clinker.
We measured the following properties on the cements obtained:
- rheology: neat paste protocol (W/C = 0.35) and "maniabilit" (workability LCPC) on
normalized mortar,
- setting time: test of Vicat needle on paste at different W/C,
- setting kinetics: ultrasonic measurements on paste at W/C = 0.35,
- strength at 1, 2, 7 and 28 days on normalized mortar.
Note: the new tools, such as the neat paste protocol (rheology) and ultrasonic measurements, were
not available when the project began. They were used later on the last clinkers studied (Richmond
and Matozinhos).
In addition to the cement properties, the concrete usage qualities were measured on concrete of type
B35 or evaluated from the microconcrete:
- workability: follow-up of the slump (mini slump for the microconcrete) during the workability
period,
- setting time: ultrasonic waves,
- strength: moulds 15*15*15 cm for concrete and 4*4*16 cm for microconcrete.
In addition, we studied on concretes the combined effects of variations of the curing temperature and
the calcium sulfate nature for the cements of Matozinhos.
To facilitate the industrial transfer of the results we obtained, this work is divided in three main
chapters, that correspond to the three major concrete usage qualities: workability, setting time and
compressive strength.

1. WORKABILITY
The effect of the calcium sulfate nature on cement rheology widely depends on the alkali sulfate rate
in the clinker. However whatever the alkali sulfate rate, a high plaster content provokes the false
plaster set.
On the other hand, the risk of aluminate set is eliminated for clinkers having moderate or high alkali
sulfate rates. But another phenomenon can appear: the syngenite precipitation (at low or even
moderate W/C), that can provoke a deterioration of the concrete workability. We will not present all
the results of the "Sulfates" topic, but the most meaningful phenomena.
Note: you can find out the whole detailed results in the progress reports of the project from 1996 to 1998.

Sulfates Topic

SYNTHESIS of the SETTING KINETICS PROJECT

1.1. Influence of the calcium sulfate nature on cement rheology
In figures 1 and 2, we present the evolution of the flow time of the cements of Richmond (Eq. Na2O
sol = 0.07%) and Cantagalo (Eq. Na2O sol = 0.27%). The cement of Richmond has a tendency to the
flash set at 100% anhydrite and to the false plaster set at 100% plaster, that appears lately at 30 min.
This false set is dangerous because it appears on the building site and provokes a deterioration of the
concrete workability.
On the other hand, the cement of Cantagalo (% SO3 total = 2.2) has a very good rheology, whatever
the calcium sulfate nature used (figures 1 and 2). This cement contains a moderate rate of alkali
sulfates (Eq. Na2O sol = 0.27%) and a medium rate of free lime (1.13%), sufficient to form
instantaneously a fine layer of ettringite and to block the hydration of C3A.
For a higher rate of SO3 (3.6%), this cement presents a false plaster set (Progress report October 97).
60
Richmond : workability LCPC at 5 min
50
Cantagalo (SO3 = 2.18) : workability LCPC at 5 min

Time to flow (s)

40

30

20

10

100A

20P/80A

30P/70A

40P/60A

60P/40A

80P/20A

70P/30A

100P

20G/80P

30G/70P

40G/60P

60G/40P

70G/30P

100G

80G/20P

20A/80G

30A/70G

40A/60G

60A/40G

70A/30G

100A

80A/20G

Figure 1: Rheological properties at 5 min

Sulfates Topic

SYNTHESIS of the SETTING KINETICS PROJECT

90
80

Richmond : workability LCPC at 30 min

70

Cantagalo (SO3 = 2.18) : workability LCPC at 30 min

60

Time to flow (s)

50
40
30
20
10

100A

20P/80A

30P/70A

40P/60A

60P/40A

80P/20A

70P/30A

100P

20G/80P

30G/70P

40G/60P

60G/40P

70G/30P

80G/20P

100G

20A/80G

30A/70G

40A/60G

60A/40G

70A/30G

100A

80A/20G

Figure 2: Rheological properties at 30 min

In figure 3, we present the evolution of the yield stress at 5 min for the cements of Matozinhos (Eq.
Na2O sol = 0.24%) with two types of mixing: with the Perrier mixer (280 rpm) and the Waring Blender
(3500 rpm). The cement of Matozinhos presents a tendency to the flash set when sulfated at 100%A
and, unlike the cement of Richmond, it presents an immediate false plaster set when sulfated at
100%P. It is bound to a greater quantity of soluble alkalis in the cement of Matozinhos: the
transformation of plaster in secondary gypsum is accelerated by the alkalis in solution (Progress
report May 99).
Cements of Matozinhos
400

350

300

Yield stress (Pa)

250

200

150

Yield stress
W B yield stress

100

50

100%A

25%P75%A

50%P50%A

75%P25%A

100%P

25%G75%P

50%G50%P

75%G25%P

100%G

75%G25%A

50%G50%A

25%G75%A

100%A

Figure 3: Influence of the calcium sulfate nature on the initial rheology

of cements of Matozinhos
Whatever the sulfate nature, the high shear mixing enables to fluidify the cement paste and to break
the false plaster set when sulfated at 100%P. Since mixing with the Waring Blender corresponds to
the shear level that the cement paste gets in a concrete, the false plaster set is not dangerous for the
cement of Matozinhos: it is destroyed in the mixer, as it occurs very early.

Sulfates Topic

SYNTHESIS of the SETTING KINETICS PROJECT

Remark: the impact of the calcium sulfate nature on rheological properties, and therefore on setting
time (see chapter "Setting time") of cements of Matozinhos (Eq. Na2O sol = 0.24%) and of Cantagalo
(Eq. Na2O sol = 0.27%), is very different whereas they contain almost the same rate of soluble alkalis.
It is bound to the difference of the other characteristics of the clinkers: higher rate of free lime and
lower rate of C3A for Cantagalo. We must not take into account the absolute rate of alkali sulfates but
the balance between sulfates and aluminates.
For cements with a high rate of soluble alkalis (Brookfield and Villaluenga, see appendix), the
tendency to the flash set is eliminated, but the risk of false set remains (high rate of plaster). When
the concentration in alkalis (K2O) is superior to 180 mMol/l (depending on the percentage of alkali
sulfates and the W/C ratio used), the syngenite precipitates and provokes a deterioration of the
cement rheology.
Until now, we presented the results by clinker (permanent rate of alkali sulfates and variation of the
nature and rate of calcium sulfates). It is also possible to work at the same rate and same nature of
calcium sulfate, and to vary the rate of alkali sulfates as explained in the following paragraph.
1.2. Influence of the alkali sulfates on the workability of concretes formulated with the cement
of Brookfield
Three clinkers of the plant of Brookfield were produced, at different rates of SO3 by varying the oxygen
in the kiln (see composition in appendix). The three clinkers have a high rate of C3A of about 12%:
- A (clinker with a moderate rate of alkali sulfates): % SO3 = 0.8, % Na2O eq. sol = 0.33,
- B (clinker with a high rate of alkali sulfates): % SO3 = 1.7, % Na2O eq. sol = 0.68,
- C (clinker with a very high rate of alkali sulfates): % SO3 = 2.55, % Na2O eq. sol = 0.93.
In figures 4 and 5, we present the evolution of the slump of a microconcrete representative of a B35
concrete (W/C = 0.56), formulated with the three cements of Brookfield (sulfated at 100%G and total
rate of SO3 of about 2.8).
For the two types of concrete, without plasticizer (figure 4) and with plasticizer (figure 5), we can make
the following conclusions:
- clinker with a moderate rate of soluble alkalis: the fast decrease of this microconcrete
slump probably represents a false ettringite set (slow formation of ettringite as non-blocking
needles). Even if the sulfates are quickly available, they are not able to block the hydration of
the C3A (12% in clinkers of Brookfield);
- clinker with a high rate of soluble alkalis (% SO3 = 1.7, % Na2O eq. sol = 0.68): we
observe a good maintenance of the slump, the concrete has a very good workability with and
without plasticizer;
- clinker with a very high rate of soluble alkalis (% SO3 = 2.55, % Na2O eq. sol = 0.93): the
workability is damaged again because of the syngenite precipitation (the initial concentration
in K2O is equal to 240 mMol/l).

Sulfates Topic

SYNTHESIS of the SETTING KINETICS PROJECT

14

12

Slump (cm)

10

B1-2.7% SO3 (clinker at 0.8% SO3)

B6-2.7%SO3 (clinker 1.7% SO3)

B13-2.9% SO3 (clinker at 2.55% SO3)

0
0

15

30

45

60

75

90

105

Time (min)

Figure 4: Evolution of the slump of microconcrete (without plasticizer)

during the workability period
14

12

Slump (cm)

10

4
B1-2.7% SO3 (clinker at 0.8% SO3)
2

B6-2.7%SO3 (clinker 1.7% SO3)

B13-2.9% SO3 (clinker at 2.55% SO3)

0
0

15

30

45

60

75

90

105

Time (min)

Figure 5: Evolution of the slump of microconcrete (with plasticizer)

during the workability period: WRDA plasticizer based on lignosulfonate

Sulfates Topic

SYNTHESIS of the SETTING KINETICS PROJECT

2. SETTING TIME
As for workability, the effect of the calcium sulfate nature on the cement setting kinetics widely
depends on the content of alkali sulfates, C3A and free lime of the clinker. To describe the influence of
the calcium sulfate nature on the setting kinetics of cements (or even concretes), clinkers are
classified in two categories: clinker with a low rate of soluble alkali sulfates of old type, and clinker with
a high rate of soluble alkali sulfates.
We present in figures 6, 7 and 9 the results at the same W/C ratio (0.27 and 0.35) in addition to the
W/C ratio corresponding to the water demand at normal consistency (see Measurement tools Topic).
VIS is varying with the W/C ratio (or the water demand); therefore comparing VIS of cements at
normal consistency (then possibly, different W/C) creates problems as it integrates the VIS variation
due to different water demands, and does not allow the comparison of true set time (see
Measurement tools Topic).
A: Clinkers with a low rate of soluble alkalis
The behaviours are standard (figures 6 and 7): tendency to the flash set at almost 100%A and to the
false set at almost 100%P (see chapter Workability):
the increase of the anhydrite content leads to a decrease of the setting time of cements of
Matozinhos and Richmond (figures 6 and 7). This result was observed in the industrial field
(plants of Karsdorf and Retznei).
For the cement of Brookfield (SO3 clinkers = 0.8%), sulfated with 100%G, we obtained a short
setting time, compared to the other sulfate additions. This cement made a tendency to the
ettringite flash set because of its high content in C3A (12%) and of its non-adequate sulfating
system to control the high level of reactive C3A. Every time the cement reaches the limit of the
lack of sulfate to block the hydration of C3A, this phenomenon of setting time shortening is
observed;
when sulfated at almost 100%P, the false set can be immediate (Matozinhos) or slow (Richmond)
(see Workability):
immediate false set (Matozinhos): setting time is relatively slow, same rough size as for
100%G,
Cements of Matozinhos: setting time
350
330
310
290
270

W/C = 0.35
W/C = 0.27
normalized consistency

Setting time (min)

250
230
210
190
170
150
130

100%A

25%P75%A

50%P50%A

75%P25%A

100%P

25%G75%P

50%G50%P

75%G25%P

100%G

75%G25%A

50%G50%A

25%G75%A

100%A

110

Figure 6: Influence of the calcium sulfate nature on the setting time

of cements of Matozinhos (Vicat needle, neat paste)
-

slow false set (Richmond): decrease of setting time, the importance of this decrease
depends on the W/C used (figure 7); the lowest the W/C, the stronger this decrease: high
densification due to gypsum crystals at low W/C.

Sulfates Topic

SYNTHESIS of the SETTING KINETICS PROJECT

Richmond A-G-P system
350

300

Setting time (min)

250

200

150

100

100A

20P/80A

30P/70A

40P/60A

60P/40A

70P/30A

100P

80P/20A

20G/80P

30G/70P

40G/60P

60G/40P

70G/30P

100G

80G/20P

30A/70G

40A/60G

60A/40G

70A/30G

80A/20G

100A

20A/80G

normalized consistency
W/C = 0.35
W/C = 0.27

50

Figure 7: Influence of the calcium sulfate nature on the setting time

of cements of Richmond (Vicat needle, neat paste)
To answer the customers' demands, we developed the ultrasonic measurement of concrete setting
time (see Measurement Tools). It was validated at the end of the program and we used it for the
study on cements of Matozinhos.

We formulated B35 concretes (W/C = 0.5) in lab and studied the impact of the calcium sulfate nature
on concrete setting time:
In figure 8, we observe on concrete the same behaviour as on neat paste: reduction of setting time
when the rate of anhydrite increases. We notice a high stability of the concrete setting time when the
calcium sulfate nature varies, except when sulfated at almost 100%A (reduction of about 1 hour). This
means that, in general, the concrete setting time is robust to the variation of the calcium sulfate
nature.

Setting time (hour)

5
4
3
2
1
0
100A

50A50G 100G

50G50P 100P

50P50A 100A

Figure 8: Influence of the calcium sulfate nature on the setting time of concretes
formulated with cements of Matozinhos (ultrasonic measurements)
The setting time was chosen at a reflection coefficient of 0.95 (in that case, it makes it shorter
than ASTM C403 values)

Sulfates Topic

SYNTHESIS of the SETTING KINETICS PROJECT

B: Clinkers with a moderate rate of soluble alkalis
When sulfated at almost 100%A (very good workability), and in comparison with the previous
cements, setting time tends to increase (figure 9). For the cements of Cantagalo, the clinker has
enough soluble sulfates and free lime (see appendix) to block the hydration of its C3A (low C3A
content of about 5%).
But if C3A is very reactive and its rate is high (Contes: 10%), calcium sulfates have an impact on
setting time, even though the clinker contains a moderate rate of alkali sulfates. For cements of
Contes (Eq. Na2O sol = 0.44%), the sulfate addition with anhydrite enables here again to reduce the
setting time (Progress report October 97).
Cantagalo SO3 = 2.18 A-G-P system
350

300

Setting time (min)

250

200

150

100
normalized consistency
W/C = 0.35
W/C = 0.27

50

0
100A

70A/30G

40A/60G

20A/80G

80G/20P

60G/40P

30G/70P

100P

70P/30A

40P/60A

20P/80A

Figure 9: Influence of the calcium sulfate nature on the setting time of

cements of Cantagalo (Vicat needle, neat paste)

3. COMPRESSIVE STRENGTH

In figure 10, we present the impact of the calcium sulfate nature on compressive strength at 1 and
2 days of Matozinhos cements: we observe a meaningful effect when we change the sulfate
addition from 50A/50G or 50A/50P to 100%A.
With the measurement of the sonic velocity in cement pastes (W/C = 0.35), we also showed that
the strength acquisition curves of cements of Matozinhos cross themselves between 14 to 18
hours: cements having the shortest setting time (almost 100%A) have the lowest strength at 1
day. Therefore, WARNING: do not too quickly associate short setting time and high early
strengths or long setting time and poor early strengths.
At 7 and 28 days, we observed the same phenomenon: compressive strength decreases slightly
when the anhydrite quantity increases.

We studied the impact of the calcium sulfate nature with two rates of SO3 (low and high, situated
on both sides of the rate industrially used in plant) on cements of Villaluenga and Cantagalo. The
rate of SO3 has a strong impact on the compressive strength (optimum of sulfate addition). On
the cements of Villaluenga, we observed a transfer of the sulfate addition optimum between 1 and
28 days.
The recent studies carried out by the CTEC show that the sulfate addition optimum also depends
on the nature of the calcium sulfates used (Cahiers Techniques). Anhydrite tends to transfer this
optimum toward the high levels of SO3 (about 4.5%).

Sulfates Topic

SYNTHESIS of the SETTING KINETICS PROJECT

45,00

40,00

Compressive strength (MPa)

35,00

30,00

25,00

20,00

Cs 1 day
Cs 2 days

15,00

100A

25P75A

50P50A

75P25A

100P

25G75P

50G50P

75G25P

100G

75G25A

50G50A

25G75A

100A

10,00

Figure 10: Influence of the calcium sulfate nature

on the compressive strength of cements of Matozinhos

CONCLUSION
With the results concerning the cement workability, setting time and strength, we can classify the
clinkers in three categories:

A: clinkers with a moderate rate of soluble alkalis: risk of tendency to aluminate set (or false
ettringite set) when we use anhydrite/gypsum sulfates. In that case, setting time decreases
when the anhydrite quantity increases. That result was industrially used (addition of anhydrite) in
the plants of Karsdorf and Retznei. But the compressive strength at 1 day slightly decreases
for an increase of the anhydrite rate. When sulfated at almost 100%P, the false plaster set
appears later (on the building site: cements of Richmond) generally accompanied by a reduction
of setting time (if the rate of SO3 is high).

B: clinkers with a high rate of soluble alkalis: the risk of tendency to aluminate set is eliminated
and the calcium sulfate nature has little influence on setting time and mechanical strength. But
the risk of false plaster set remains, it immediately appears (presence of soluble alkalis in
solution) and is destroyed in the mixer.

C: clinkers with a very high rate of soluble alkalis: risk of false syngenite set. The calcium
sulfate nature has also little influence on setting time and compressive strength. But for these
cements (compared to cements reconstituted from clinkers with a low rate of alkalis), the
presence of alkalis has a beneficial effect on strength at 1 day (57 clinkers).

This separation is not absolute and depends on:

- the rate of C3A: sulfates/aluminates balance (see operating data table of ICS),
- the type of concrete used: the limit of K2O concentration (180 mMol/l for the syngenite precipitation)
depends on the W/C ratio used.

Sulfates Topic

SYNTHESIS of the SETTING KINETICS PROJECT

PERSPECTIVES
The first tests carried out at the end of this program, concerning the combined effects of the curing
temperature and the calcium sulfate nature on concrete usage qualities (from cements of Matozinhos
with a low rate of alkali sulfates), showed that curing temperature has a strong impact on usage
qualities, whatever the sulfate addition.
For cements with a low alkali sulfate rate, workability is better at low temperature than at high
temperature; but setting kinetics is accelerated by the increase of temperature according to the law of
Arrhnius. The concretes made with gypsum/plaster cements seem to be more sensitive to the curing
temperature (workability) than with anhydrite/gypsum cements. These results must be validated on
more cements, representative of the variations of alkali sulfates and C3A of the cements of the Group.
We will therefore draw information about the cement parameters that influence the concrete
consistency (even robustness) towards weathering changes.
With the results that we obtained in this project (measurement tools and physico-chemical
parameters), we can now make pertinent experimental programs towards the fundamental questions
raised (current concrete consistency, selfplacing concrete development, etc.). The developed tests
are representative of the concrete usage qualities and are transferred (or under transfer) to the
cement community.

APPENDIX
Richmond Matozinhos Cantagalo Contes Villaluenga

Brookfield
A

% SO3

0.22

0.39

0.77

0.95

2.1

0.8

1.7

2.5

% totalK2O

0.19

0.55

0.33

0.76

0.92

0.58

0.94

1.38

% solubleK2O

0.04

0.35

0.23

0.56

0.9

0.46

0.83

1.31

% totalNa2O

0.21

0.07

0.26

0.18

0.32

0.08

0.09

0.1

% solubleNa2O

0.04

0.01

0.12

0.07

0.27

0.03

0.06

0.07

Eq. solubleNa2O

0.07

0.24

0.27

0.44

0.86

0.33

0.68

0.93

Molar ratio
SO3/alkalis

0.51

0.7

0.51

1.08

1.76

1.34

1.67

1.96

% free CaO

0.7

0.25

1.13

0.45

0.3

0.3

0.15

0.15

% C3S

65.8

70.8

65.8

64

73.5

60.4

57.4

52.6

% C2S

13.7

6.3

10.6

14.5

8.4

17

17.6

21.5

% C3A

7.2

6.1

5.2

10.1

6.9

12.3

12.3

11.9

% C4AF

10.1

10

12.2

6.8

9.2

6.8

7.1

6.9

Part of chemical analysis of the clinkers studied in the Setting kinetics project

Sulfates Topic

10