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CEMENT and CONCRETE RESEARCH. VoL 21, pp. 101-108, 1991. Printed in the USA.

0008-8846D1. $3.00+00. Pergamon Press pie.

ALKALI A C T I V A T E D GROUND G R A N U L A T E D B L A S T - F U R N A C E
SLAG CONCRETE:
PRELIMINARY I N V E S T I G A T I O N

E. Douglas*, A. Bilodeau**, J. B r a n d s t e t r
and V.M. Malhotra***
*Research Scientist
**Engineer
***Head, Concrete T e c h n o l o g y Section
Mineral Sciences Laboratories, CANMET
Ottawa, Ontario, Canada, KIA 0GI

+Professor, Technical University,


Department of Technology,
Brno, C z e c h o s l o v a k i a
(Communicated by D.M. Roy)
(Received May 3; in final form Nov. 9, 1990)

ABSTRACT

This report presents results of a preliminary investigation


dealing with the compressive strength development of alkali
activated ground granulated blast-furnace slag concretes.
These concretes incorporated sodium silicate as an activator
but did not contain any portland cement.
The five concrete
mixtures studied were proportioned using sodium silicate and
small amounts of hydrated lime.
The water-to-binder ratio
of the mixtures ranged from 0.34 to 0.50.
The air-entrained
concrete produced satisfactory workability.
The 1-day and
28-day compressive strengths of the concretes ranged from
20.4 to 38.9 MPa and from 45.5 to 59.6 MPa, respectively.
The 7- and 14-day flexural strengths were of the order of
5 MPa.
Introduction

Ground granulated blast-furnace slags possess some hydraulic


properties; therefore when slag mortars are made according to
current standards, strength development occurs but at a lower
rate than in portland cement mortars (i).
It has been established that ground granulated blast-furnace slag
mortars and concretes can be activated with alkaline reagents
(NaOH, Ca(OH)2, sodium or potassium silicates), yielding
compressive strengths comparable to or higher than those made
with portland cement alone (2,3,4,5).
This opens the possibility
101

102

E. Douglas, et al.

Vol. 21, No. 1

of f o r m u l a t i n g s l a g c o n c r e t e s w i t h o u t p o r t l a n d c e m e n t and p o s s ibly w i t h i m p r o v e d p r o p e r t i e s such as h i g h e r r e s i s t a n c e to


c h e m i c a l a t t a c k (6,7,8,9).
This p r e l i m i n a r y s t u d y p r e s e n t s the
p r o p o r t i o n i n g and the p r o p e r t i e s of five slag c o n c r e t e m i x t u r e s
a c t i v a t e d w i t h s o d i u m silicate.
T h e w o r k w a s p e r f o r m e d at C A N M E T
l a b o r a t o r i e s in O c t o b e r 1989.

scope of Investiqation
F i v e a l k a l i a c t i v a t e d slag c o n c r e t e m i x t u r e s w e r e made.
The
first t h r e e m i x t u r e s w e r e m a d e u s i n g a s o d i u m s i l i c a t e s o l u t i o n
h a v i n g a s i l i c a t e m o d u l u s Ms = 1.47 and low w a t e r - t o - b i n d e r *
r a t i o s r a n g i n g from 0.34 to 0.39.
Two o t h e r m i x t u r e s i n c o r p o r a t e d a s o d i u m s i l i c a t e s o l u t i o n of Ms = 1.36 and h a d h i g h e r
w a t e r - t o - b i n d e r r a t i o s of 0.50 and 0.46.
One of t h e s e m i x t u r e s
was a i r - e n t r a i n e d .
A n u m b e r of 102 x 2 0 3 - m m c y l i n d e r s and 76 x 102 x 4 0 6 - m m p r i s m s
w e r e c a s t for c o m p r e s s i v e and f l e x u r a l s t r e n g t h t e s t i n g at
v a r i o u s ages.

Concrete Mixtures
Materials
The c o n c r e t e m i x t u r e s w e r e m a d e in the C A N M E T
O c t o b e r 1989 u s i n g the f o l l o w i n g m a t e r i a l s :

laboratory

in

S l a g -- A g r o u n d g r a n u l a t e d b l a s t - f u r n a c e s l a g f r o m n o r t h e r n
O n t a r i o w a s u s e d in all the m i x t u r e s .
The chemical composition,
g l a s s c o n t e n t and f i n e n e s s of the s l a g are s h o w n in T a b l e i.

sodium silicate -teristics was used


mixtures:
specific
1 0 . 7 8 % and s i l i c a t e
Lime -- H y d r a t e d
t u r e s to c o n t r o l

S o d i u m s i l i c a t e w i t h the f o l l o w i n g c h a r a c to p r e p a r e the s o l u t i s n s a d d e d to t h e c o n c r e t e
g r a v i t y = 1.460 k g / m ~ SiO 2 = 29.73%, Ha20 =
m o d u l u s Ms = 2.85.

lime of c o m m e r c i a l
the setting.

grade was used

in all m i x -

Aggregates -- The c o a r s e a g g r e g a t e u s e d w a s c r u s h e d l i m e s t o n e
w i t h a m a x i m u m s i z e of 1 9 - m m and the fine a g g r e g a t e w a s n a t u r a l
sand.
T h e g r a d i n g and p h y s i c a l p r o p e r t i e s of b o t h t h e fine and
c o a r s e a g g r e g a t e s are s h o w n in T a b l e s 2 and 3.

Air-entraining admixture -- A s u l p h o n a t e d h y d r o c a r b o n t y p e airentraining

a d m i x t u r e was u s e d

in one m i x t u r e .

Mixture Proportioning
In all t h e m i x t u r e s the dry a g g r e g a t e s , the slag, the l i m e s l u r r y
and the w a t e r w e r e m i x e d for two m i n u t e s b e f o r e a d d i n g t h e s o d i u m
*The b i n d e r
the s o d i u m

i n c l u d e s g r o u n d g r a n u l a t e d slag, s o l i d c o m p o n e n t s
s i l i c a t e s o l u t i o n and c a l c i u m h y d r o x i d e .

of

Vol. 21, No. 1

ALKALI-ACTIVATEDSLAG,CONCRETE

103

TABLE 1
Physical Properties and Chemical Analysis
of the Granulated Blast-furnace Slag
Description

of T e s t

Fineness
Passing, 45 #m
S u r f a c e area, Blaine,

Slag

m2/kg

97
460

Chemical analysis
SiO 2
AI203
Fe203
CaO
MgO
SO 3
K20
Na20
Loss on i g n i t i o n

38.00
8.74
0.55
32.00
18.60
2.45
0.76
0.22
1.98

Glass

90.3

content

Compressive strength
m o r t a r s (50% PC)
A S T M C 989

of

S l a g a c t i v i t y index,
% (ASTM C 989)

7 days
28 days

18.7
31.4

7 days
28 days

69.8
i00.0

s i l i c a t e solution.
The lime s l u r r y was c o n s t i t u t e d by e q u a ~
p a r t s of h y d r a t e d lime and water.
The s o d i u m s i l i c a t e s o l u t i o n
of Ms = 1.47 u s e d in m i x t u r e s i, 2 and 3 was p r e p a r e d w i t h the
s o d i u m s i l i c a t e of Ms = 2.85 of c o m m e r c i a l g r a d e by a d d i n g a
s o l u t i o n of 50% N a O H and w a t e r (Table 4).
The s o d i u m s i l i c a t e

TABLE 2
Grading of Aggregates
Coarse

Sieve

19.0
12.7
9.5
4.75

Size

mm
mm
mm
mm

Aggregate

Cumulative
Percentage
Retained

0.0
35.0
60.0
i00.0

Fine A g g r e g a t e
Cumulative Percentage
Retained
Sieve

Size

4.75 mm (No. 4)
2.36 mm (No. 8)
1.18 mm (No. 16)
600 ~m (No. 30)
300 ~m (No. 50)
150 ~m (No. i00)
pan

Mix
i, 2 and 3

Mix
4 and 5

0.0
i0.0
32.5
57.5
80.0
94.0
i00.0

0.0
8.5
28.0
49.5
68.5
80.5
i00.0

104

E. Douglas, et al.

TABLE
Physical

Properties

Coarse
Specific Gravity
Absorption, %
*Crushed
**Natural

Vol. 21, No. 1

3
of A g g r e g a t e s

Aggregate*
2.69
0.82

Fine A g g r e g a t e * *
2.70
i.i

limestone
sand

s o l u t i o n o b t a i n e d c o n t a i n e d 14.77% SiO 2 and 10.48% Na20.


The SiO 2
and Na20 c o n t e n t in the s o d i u m s i l i c a t e s o l u t i o n s was d e t e r m i n e d
by t i t r a t i o n w i t h 2N HCl u s i n g m e t h y l red as indicator.
The p e r c e n t a g e of Na20 w i t h r e s p e c t to the slag in the c o n c r e t e
m i x t u r e s 1 and 2 was 3.63% and the b i n d e r - t o - a g g r e g a t e ratio was
1:3.
To m a k e the c o n c r e t e m o r e cost effective, m i x t u r e 3 was
p r o p o r t i o n e d w i t h a b i n d e r to a g g r e g a t e r a t i o of 1:6.
The
p e r c e n t a g e of Na20 w i t h r e s p e c t to the slag in the c o n c r e t e
m i x t u r e was 3.41%.
To i m p r o v e w o r k a b i l i t y in the l e a n e r m i x t u r e s 4 and 5, a s o d i u m
s i l i c a t e s o l u t i o n of Ms = 1.36 was p r e p a r e d w i t h the s o d i u m
TABLE

M i x t u r e P r o p o r t i o n s and P r o p e r t i e s
of F r e s h C o n c r e t e - M i x t u r e s i, 2 and 3

M i x No.

Mix
Proportions
per m 3

Properties
of F r e s h
Concrete

Fine Agg.
C o a r s e Agg.
Water
Lime slurry*
Slag
N a - S i l i c a t e sol.**
Water/binder
Slump

(mm)

523 kg
1042 kg
63 kg
26 kg
517 kg
201 kg
0.39

530 kg
1057 kg
40 kg
33 kg
524 kg
203 kg
0.34

165

*Lime slurry:
50% lime, 50% w a t e r by w e i g h t
* * S p e c i f i c g r a v i t y of s o l u t i o n = 1.34
For 1 L i t e r of solution:
449 mL of s o d i u m s i l i c a t e
of Ms = 2.85
143 m L of N a O H 50%
408 m L of w a t e r
A n a l y s i s of s o d i u m s i l i c a t e solution:
14.77% sio 2
10.48% Na20
Ms = 1.47

819 kg
1143 kg
28 kg
23 kg
324 kg
128 kg
0.35

Vol. 21, No. 1

AIKALI-ACTIVATED SLAG, CONCRETE

TABLE
Mixture
of F r e s h

Properties
of Fresh
Concrete

P r o p o r t i o n s and P r o p e r t i e s
C o n c r e t e - M i x t u r e s 4 and 5

Mix No.

Mix
Proportions
per m 3

105

Sand
Coarse Agg.
Fine sand (filler)
Water
Lime slurry*
Slag
Na-silicate sol.**
Air-entr. agent
Water/binder

747 kg
1044 kg
125 kg
58 kg
23 kg
271 kg
129 kg
0
0.50

745 kg
1038 kg
124 kg
43 kg
23 kg
269 kg
129 kg
245 m L
0.46

Unit Weight
Slump
Air

2395 kg/m 3
140 mm
2.2%

2370 kg/m 3
140 m m
4.2%

*Lime slurry:
11.5 kg of Lime + 11.5 kg of w a t e r
*,129 kg of sodium silicate solution = 97.5 litres
For 97.5 L of sodium silicate sol.:
54.3 L of sodium
silicate sol. of
Ms = 2.85
18.5 L of NaOH 50%
24.7 L of w a t e r
A n a l y s i s of sodium silicate sol.:
12.77% Na20 , 16.82%
Si02, Ms = 1.36
silicate of commercial grade by addition of 50% NaOH solution and
w a t e r (Table 5).
The b i n d e r to aggregate ratio in these mixtures
was a p p r o x i m a t e l y 1:6 and the p e r c e n t a g e of NazO with respect to
the slag was 6% in both mixtures.
The effect of h i g h e r contents
of Na20 w i t h respect to the slag in earlier h y d r a t i o n and h i g h e r
c o m p r e s s i v e strengths has been discussed elsewhere (2). Nevertheless, in the concrete mixtures studied, the h i g h e r w a t e r - t o b i n d e r ratios in m i x t u r e s 4 and 5 results in lower strengths than
in m i x t u r e s i, 2 and 3 in spite of the h i g h e r Na20 to slag ratio.
The g r a d i n g of the aggregate was the same as the one used for
m i x t u r e s i, 2 and 3 but 6.5% of the total aggregate was fine sand
p a s s i n g 150 ~m and added as a filler (Table 2).
The p r o p o r t i o n s of mixtures i, 2 and 3 are shown in Table 4 and
those of m i x t u r e s 4 and 5 are shown in Table 5. An
a i r - e n t r a i n i n g admixture was added in mixture 5.
Preparation

and C a s t i n g

of T e s t

Specimens

A n u m b e r of 102 x 203-mm cylinders were cast to


c o m p r e s s i v e strengths up to one year and prisms
t e s t i n g in flexure at 7 and 14 days in mixtures
14 days in m i x t u r e s 4 and 5. All cylinders and

determine
were cast for
1 and 2, and at
prisms were cast

2373
2387
2464
2435
2415

W/binder

0.39
0.34
0.35
0.50
0.46

Mix
No.

1
2
3
4
5

vs.

43.4
48.3

41.6
44.6
54.5
41.0
41.5
38.2
41.8
49.4
33.7
35.0

28.1
37.5
38.9
23.2
20.4

43.1
44.3

14d

7d

3d

Strength

Concretes

added

Id

Compressive

Hardened

solution

was

(min)

the

46.3
51.0
59.6
45.4
46.8

28d

(MPa)

to

140
120
70
75
5O
45
25

(mm)

Mixing

Slump

After

Concrete

Time

0*
5
15
30
50
75
105
125

Time

TABLE
of

silicate

140
115
i00
95
30
20

(mm)

Concrete

Properties

Density
of Cylinders
(kg/m 3 )

= when

of

Slump

sodium

(min)

0*
13
23
43
65
103
138

Time

Concrete

Workability

TABLE

- -

6.3

6.3

5.3
5.8

48.5
52.6
62.8
50.2
51.0

4.8
5.5

7d

14d

Flexural
Strength
(MPa)
91d

mix

Vol. 21, No. 1

ALKALI-ACTIVATED SLAG, CONCRETE

in two layers,
table.

107

each layer being compacted using a v i b r a t i n g

A f t e r casting, all the m o u l d e d specimens w e r e covered w i t h water


s a t u r a t e d burlap and left in the casting room at 23 1.7C for
24 h.
The cylinders were then d e m o u l d e d and after density
m e a s u r e m e n t s they were transferred to the moist curing room until
required for testing.
Test

Results

Properties of freshly-mixed concrete are given in Table 4 for


m i x t u r e s i, 2 and 3, and in Table 5 for m i x t u r e s 4 and 5.
The
slump of concrete as a function of time after m i x i n g for m i x t u r e s
4 and 5 is shown in Table 6.
Compressive
Table 7.

and flexural

strengths

Discussion

test results

of T e s t

are given

in

Results

As shown in Table 4, m i x t u r e s 1 and 2 with a b i n d e r to a g g r e g a t e


ratio of 1:3 had a higher content of ground g r a n u l a t e d blastfurnace slag requiring the addition of high amounts of sodium
silicate and thus rendering the mixtures too costly.
It has to
be noted that m i x t u r e I, w i t h a w a t e r / b i n d e r = 0.39 had a slump
of 165 mm, while m i x t u r e 2, with a w a t e r / b i n d e r = 0.34 was not
workable.
The leaner mixture 3, w i t h a binder to a g g r e g a t e ratio
of 1:6 and a w a t e r / b i n d e r = 0.35 also had no slump.
The lack of
w o r k a b i l i t y in m i x t u r e s 2 and 3 was p r o b a b l y due to the lower
w a t e r - t o - b i n d e r ratios.
High c o m p r e s s i v e strengths were obtained at all ages in concrete
m i x t u r e s 1 and 2.
The leaner concrete m i x t u r e 3 p e r f o r m e d better
than concretes from mixtures 1 and 2 although the Na20 to slag
ratio was slightly lower.
This fact cannot be easily explained.
The flexural strengths of concretes from m i x t u r e s 1 and 2 at 14
days w e r e slightly lower than at 7 days.
An a i r - e n t r a i n i n g
admixture was incorporated in mixture 5 to obtain an air content
of 4.2 per cent.
Slump was m e a s u r e d in mixtures 4 and 5 as a
function of time and, as shown in Table 6; the slump retention
was good even after 45 minutes, that is, the slump at 45 minutes
was I00 m m and 70 mm for mixtures 4 and 5, respectively, compared
to a slump of 140 mm m e a s u r e d 13 minutes after adding the sodium
silicate to the mix.
Table 8 shows that c o m p r e s s i v e strengths
a p p r o a c h i n g 45 MPa at 28 days were obtained for both concretes.
The values of c o m p r e s s i v e and flexural strengths of concretes
from m i x t u r e s 4 and 5 were similar regardless of the d i f f e r e n c e
in w a t e r to b i n d e r ratios.
This may be e x p l a i n e d p a r t l y by the
h i g h e r air content of mixture 5.
Concludinq
i.

Remarks

Ground g r a n u l a t e d b l a s t - f u r n a c e slag a c t i v a t e d w i t h sodium


silicate can be used to make slag concretes w i t h s a t i s f a c t o r y
w o r k a b i l i t y and strength properties as m e a s u r e d at ages up to
91 days.

108

E. Douglas, et al.

Vol. 21, No. 1

2.

For the b i n d e r - t o - a g g r e g a t e ratios of a p p r o x i m a t e l y 1:6, the


amount of sodium silicate of Ms = 1.36 added should be such
to m a i n t a i n a percentage of Na20 with respect to the slag of
a p p r o x i m a t e l y 6%.

3.

A l:l lime slurry should be added as a retarder in a proportion of approximately 4% Ca(OH)2 with respect to the slag.

4.

Air can be entrained in activated slag concrete in order to


improve w o r k a b i l i t y and durability.

Referemces

i.

Douglas, E., Elola, A. and Malhotra, V.M., A S T M Cement,


Concrete and Aggregates, Vol. 12, No. 2, Summer 1990.

2.

Puzhanov, G.T., Tr. Kazakhsk. Filiala Akad. Stroit.


Arkhitekt. SSSR, Sb, 2. pp. 125-133.

3.

Glukhovsky,
1978.

4.

Forss, B., Proceedings,


Concretes, pp. 101-104,

5.

Douglas, E. and Brandstetr, J., Cement and Concrete Research,


Vol. 20, pp. 746-756, 1990.

6.

Glukhovsky, V.D., Krivenko, P.V., Rostovskaya, G.S.,


Timkovich, V.J. and Pankratov, V.L.
U.S. Patent No. 4, 410,
365; 1983.

7.

Voinovitch, J.A. and Dron, R., Silicates Industriels


41:209-212; 1976.

8.

Talling, B. and Brandstetr, J., Proceedings of the Third


International Conference on Fly Ash, Silica Fume, Slag and
Natural Pozzolans in Concrete; Trondheim, Norway, June 18-23,
1989; pp. 1519-1545; ACI SP-II4, V 2, V.M. Malhotra, Editor,
1989.

9.

Glukhovsky, V.D. et al., Seventh International Congress on


the Chemistry of Cement V/164-168; Paris; 1980.

V.D. and Pakhonov, V.A., Budivelnik,

Kiev, USSR,

6th International Conference Alkali


Denmark, 1983.