THE INFLUENCE OF ALKALI ACTIVATOR ON THE EARLY HYDRATION AND

PERFORMANCE OF PORTLAND BLAST FURNACE SLAG CEMENT

Arnaldo Forti BATTAGIN, Brazilian Association of Portland Cement, São Paulo, Brazil

ABSTRACT This paper shows the best behaviour of Na2SO4 among other activators of portland
blast furnace slag cement. Sodium silicate, extensively used in alkali activated slag, has a poorer
performance than Na2SO4 in the presence of Ca(OH)2. Depending on the characteristics of
cement and activator, Na2SO4 can increase the early strength gain of blast furnace slag cements
without significantly affecting long term compressive strength. A use of sodium sulfate - rich
waste could be an environmental solution for waste disposal but further studies will be necessary.
Key-words: accelerators, activation, alkali, blastfurnace slag.
INTRODUCTION
Many publications have dealt with the role of chemical activators, mainly sodium silicates (water
glass) on the slag hydration (Shao-Dong Wang et al, 1995). There is a general agreement about
the good behaviour of these compounds as slag activators on so-called alkali-activated slag
cements (AAS) but less work has been done about the study of alkaline activation of slag in
portland cement.

In order to evaluate the most suitable slag activator we carried out preliminary tests based on
compressive strength. Two blast furnace slag cement (BFSC) samples representative of industrial
production in Brazil were chosen. Cements selected have different mechanical performance
according to the Brazilian method by using 50 x 100mm cylindrical test specimens in proportion
1:3 (cement:sand), water cured at 23oC, w/c = 0.48. Both granulated blast furnace slag are basic,
refractive index 1.65 and 95% vitrified. Mixes of 99% cement and 1% of six different chemical
agents (Reagent Grade) were used with the aim of improving the early strength gain. Results are
shown on Table 1.

Table 1 - Effects of different slag activators

Compressive Strength (MPa)
Cement Activator 1 day 3 days 7 days 28 days
None 5.1 17.4 35.3 59.1
K2SO4 8.1 21.2 35.2 49.8
NaOH 7.2 15.7 23.0 33.8
A Na2CO3 6.9 17.3 26.7 37.4
A2(SO4)3 5.5 18.3 32.3 52.1
Na2SO4 8.6 21.0 32.7 47.1
NaSiO3.nH2O 5.5 16.1 27.9 46.2
None 4.3 13.1 20.0 32.8
K2SO4 7.2 15.7 22.4 34.7
NaOH 6.5 14.1 19.1 29.5
B Na2CO3 5.6 14.1 18.7 30.6
A2(SO4)3 4.0 13.0 21.3 36.0
Na2SO4 7.6 16.1 22.5 33.8
NaSiO3.nH2O 4.7 13.2 20.1 32.0

Based on the preliminary results it was decided to detail the investigation of the Na2SO4 activator,
although Jawed and Skalny (1983) have shown it decrease the cement strength at long term age.
Sodium silicate had a poorer and unexpected behaviour compared to those reported in literature
for slag alone.
ACTIVATION WITH Na2SO4 (REAGENT GRADE)
Mixtures of BFSC and Na2SO4 at proportions in mass of BFSC/Na2SO4 of 100/0, 99.5/0.5, 99/1
and 98/2 were made. Compressive strengths were determined at 1, 3, 7, 28, 60 and 91 days and a
conduction calorimeter was used to monitor hydration kinetics. Table 2 shows the results
obtained as well as additional characteristics of materials.
Table 2 - Mechanical and Rheologycal Results
Setting Time Soundness
Na2SO4 Compressive Strength (MPa) (Vicat Test) Le Chatelier
Cement (%)
1 3 7 28 60 91 Initial Final
day days days days days days (h:min) (h:min) (mm)
0
A (reference) 5.1 17.4 35.3 59.1 60.7 68.6 3:55 5:35 0
(58% slag , 5% 0.5 7.1 20.5 34.1 51.5 54.8 57.3 3:45 5:15 0.5
limestone and 419m2.kg-1 1.0 8.6 21.0 32.7 47.1 50.4 54.8 2:55 4:15 0
Blaine surface area) 2.0 10.7 21.9 29.5 39.9 44.3 46.5 2:35 4:15 0
0
B (reference) 4.3 13.1 20.0 32.8 39.9 43.1 3:25 4:55 0
(44% slag, no 0.5 5.6 14.4 20.7 32.1 38.4 42.9 3:05 4:05 0
2
limestone and 342m .kg -1
1.0 7.6 16.1 22.5 33.8 36.0 38.8 3:10 4:20 0
Blaine surface area) 2.0 8.5 17.0 22.0 33.1 37.1 39.5 2:40 4:00 0.5

From Table 2 we can conclude that at early ages (1 and 3 days) the higher the Na 2SO4 content,
the higher the compressive strength for both samples.For cement A, at 7 days and beyond, there
is a remarkable decrease of strength with the increasing quantities of Na2SO4. It can be seen that
strength values can reach only 68% of the reference at 91 days with 2% Na2SO4. However, a
different behaviour was found for sample B showing smaller loss of strength. In fact, at 91 days a
value of 90% of reference for 1% Na2SO4 was observed.

Tables 3 and 4 summarize the results of heat of hydration up to 72 hours, taking into account that
the peak due to the first minutes of hydration was undetected due to operational conditions.
Table 3 - Heat Peak Evolution
Cement Na2SO4 Heat peaks at 23oC (W/g) Time (h:min)
(%) First Second First Second
0 2.32 - 12:25 -
A 0.5 2.40 - 12:30 -
1.0 2.42 - 12:15 -
2.0 2.43 - 11:00 -
0 1.58 1.89 8:40 15:50
B 0.5 1.69 1.78 8:30 17:00
1.0 1.77 1.77 7:10 14:50
2.0 1.73 1.74 8:20 15:20

Table 4 - Total heat liberation up to 72h

Na2SO4 Total heat liberated after (hour) (J/g)
Sample (%) 2 4 6 8 12 16 20 24 30 40 50 60 72
0 1 4 12 22 50 76 91 103 118 139 156 169 182
0.5 1 5 14 26 56 88 106 119 134 154 169 183 196
A 1.0 1 5 13 26 57 90 111 125 140 159 173 184 193
2.0 2 6 17 32 66 96 117 132 147 165 178 187 194
0 2 8 18 29 51 76 97 108 121 137 149 159 168
 B 0.5 2 9 19 31 55 80 104 120 135 152 164 174 184
1.0 3 12 24 37 61 87 110 126 141 158 170 181 191
2.0 2 9 20 32 56 81 105 123 139 156 169 180 190

From Table 3 we can conclude that first peak of 99/1 and 98/2 mixes is slightly accelerated
compared to reference for both sample. The same phenomenon is found for the second peak of
heat for sample B. First peak is supposed to be due to clinker fraction hydration and second peak
is attributed to slag hydration. However, sample A exhibits only one peak. These atypical results
indicate that, in this case, maximum hydration rate of both clinker and slag are simultaneous.
Acceleration of both clinker and slag fraction by using Na2SO4 as activator is confirmed by
results of total heat liberation listed on Table 4.

ACTIVATION WITH SODIUM SULFATE WASTE

The use of an activator is usually expensive and may impair its use in practice. Aiming the
reduction of the costs and trying to find an environmental solution for waste disposal an attempt
was made concerning the use of a waste as activator. So we replaced the Na2SO4 (Reagent
Grade) by a glass - industry waste rich in this component (27.1% SO3 and 47.5% Na2O). Similar
tests to those of compressive strength shown in Table 2 were carried out. Preliminary results are
listed on Table 5.

Table 5 - Results of sodium sulfate waste as an activator

Cement Waste Compressive Strength (MPa)
Content (%) 1 day 3 days 7 days 28 days
0 5.1 17.4 35.3 59.1
0.5 3.0 16.0 30.9 55.5
1 1.0 2.4 16.3 30.6 50.5
2.0 1.1 16.7 28.5 43.8
0 4.3 13.1 20.0 32.8
2 0.5 3.7 10.8 17.3 28.9
1.0 5.1 13.2 18.6 29.5
2.0 1.1 10.0 15.3 26.1

In spite of bad results for cement 1, the use of waste brought up some advantages to cement 2,
mainly with 1% Na2SO4. This fact stimulates further studies to a better understanding of the
behaviour of waste activated cement as a contribution for waste elimination.

DISCUSSION AND CONCLUSION

• Sodium silicate is the most used activator for alkali activated slag but its behaviour was not
good in presence of Ca(OH)2 liberated from clinker hydration.

• At 1% levels, Na2SO4 seems to be the most suitable activator among those used in this study.
• Unique heat peak found in cement 1 is probably not due to influence of activator because it
also occurs in reference sample. In this case a higher specific surface area of slag and a poorer
reactivity of clinker compared to sample 2 accelerated slag hydration and retarded clinker
hydration.
• Compared to cement 1, cement 2 presented a higher heat liberation at first 12 hours probably
due to its lower slag content in spite of being coarser than sample 1. At 24h and beyond (72 h)
heat liberation was higher for sample 1. Results are in agreement with compressive strength
results. Setting time is accelerated with the increase of Na2SO4 contents and unsoundness due
to its use was not detected.
• At 1 and 3 days the behaviour of both samples activated with Na2SO4 was similar, with a
strength gain of aproximately 100% and 25-30% respectively for 2% Na2SO4. However, a
different behaviour was found after 7 days, with a harmful influence of Na2SO4 on the cement
of better performance (sample 1). On the other hand, long term strength was little affected in
cement of worse performance.
• Optimum contents of Na2SO4 depends on characteristics of both cement and activator and
further studies will be necessary for supplementary consideration about the potential use of
sodium sulfate-rich waste as activator.

REFERENCES
Jawed, I and Skalny, J. “The influence of alkali sulfates on the properties of cement and
concrete.” World Cement, 1983, Nov., p325.
Wang S.D. et alii, “Alkali-activated slag cement and concrete: a review of properties and
problems.” Advances in Cement Research, 1995, 7 no 27, july, 93-102.