Sulfates Topic: Synthesis of The Setting Kinetics Project
Sulfates Topic: 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
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
Sulfates Topic
70
60
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
350
300
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
Sulfates Topic
Sulfates Topic
12
Slump (cm)
10
15
30
45
60
75
90
105
Time (min)
12
Slump (cm)
10
4
B1-2.7% SO3 (clinker at 0.8% SO3)
2
0
0
15
30
45
60
75
90
105
Time (min)
Sulfates Topic
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
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
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
300
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
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.
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
300
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
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
45,00
40,00
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
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).
Sulfates Topic
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