Construction

and Building

Construction and Building Materials 21 (2007) 1576–1582

MATERIALS
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The effect of slaked lime, anhydrous gypsum and limestone powder

on properties of blast furnace slag cement mortar and concrete
a,*
K.J. Mun , S.Y. So b, Y.S. Soh b

a
R&D Center, Hanil Co., Ltd, Iksan, 570-946, South Korea
b
Research Center of Industrial Technology, Chonbuk National University, Jeonju, 561-756, South Korea

Received 15 April 2005; received in revised form 11 September 2005; accepted 22 September 2005
Available online 28 August 2006

Abstract

Basic properties of blast furnace slag cement mortar and concrete are investigated by adding inorganic activators. The result of this
research concludes that slag cement mixed with suitable activator agents such as lime, gypsum and limestone powder could accelerate the
compressive strength and tighten pore structure at early age. The addition of activator into mortar and concrete containing slag cement
produces superior properties, reduced shrinkage and less carbonation compared to mortar and concrete containing slag cement without
the addition of activator. Consequently, there are possibilities for manufacturing blast furnace slag cement, which could compensate the
weak properties at early curing age. When compared with ordinary Portland cement, this cement has superior characteristics for long
curing age.
 2006 Elsevier Ltd. All rights reserved.

Keywords: Granulated blast-furnace slag; Pore size distribution; Drying shrinkage, Carbonation

1. Introduction cally and experimentally reviewing the low compressive

Although blast furnace slag cement has such good
qualities as low heat of hydration, high strength
obtained after long curing age, and excellent durability
in an aggressive environment, etc., it continues to present
such problems as setting retardation, decreased early
strength, increased drying shrinkage and carbonation
[1]. In the case of adding activator, the hydrate reaction
of granulated blast furnace slag (GBFS) exhibits different
characteristics, which are variation in velocity of hydra-
tion reaction, various types of crystal hydrate, pore vol-
ume and pore distribution depending on the type of
activator [2]. The purpose of this work is to investigate
a means to increase the various beneficial physical char-
acteristics of blended cement with GBFS. By theoreti-
*
Corresponding author. Tel.: +82 63 270 4273; fax: +82 63 270 2285.
E-mail address: mun7890@hanmail.net (K.J. Mun).
strength obtained at early curing age, drying shrinkage,
and carbonation, various kinds of activator are attempted
to be added.
2. Experimental program
2.1. Materials
Ordinary Portland Cement (OPC) manufactured by S-
company in Korea and GBFS (a by product) of K-Iron
manufactured in Korea were used. A small quantity of
commercial slacked lime, anhydrous gypsum, and lime-
stone powder were applied as activators and filler. Their
chemical and physical properties are shown in Table 1.
Crushed stone 20 mm (specific gravity = 2.60 g/cm3,
F.M. = 6.68) was used as coarse aggregate, and river
sand was used as fine aggregate for the physical concrete
test. AE water-reducing admixture of naphthalene type
was used to secure the fluidity and air content.

0950-0618/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.conbuildmat.2005.09.010
 K.J. Mun et al. / Construction and Building Materials 21 (2007) 1576–1582 1577

Table 1
Chemical and physical properties of materials used
Materials Properties
Chemical components (%) Blain (cm2/g) Specific gravity
SiO2 Al2O3 Fe2O3 CaO MgO SO3 Ig-loss In-R
GBFS 34.51 17.04 0.30 42.65 6.87 0.06 – – 4600 2.91
Limestone powder 0.7 0.07 0.19 54.5 1.12 0.1 43.24 0.08 8000 2.73
Anhydrate gypsum 0.16 0.1 0.04 39.07 – 53.83 6.71 0.09 4600 2.40
Ca(OH)2 1.20 0.70 0.40 60.50 1.40 0.30 24.38 0.22 6000 2.27
OPC 19.88 5.39 3.21 62.39 3.84 0.04 2.15 0.81 3300 3.15

2.2. Mixture proportion tar mixture was 48.5%, and the proportions of cement:
sand was 1:2.45. Table 3 shows the mixture proportion
Table 2 shows the mix proportion for blended cement for evaluating the carbonation properties of concrete con-
used to compare and to evaluate the single or complex taining blended cement.
actions of each activator. The W/C of blended cement mor-
2.3. Experimental method
Table 2
All tests were carried out based on Korean Standards
Proportions of the blended cement mixture
(KS). Molds of dimensions 50 · 50 · 50 mm for compres-
Mix no. Mix proportion (%) sive strength, 40 · 40 · 160 mm for drying shrinkage, and
OPC BFS A.G H.L L.S.P 80 · 100 · 200 mm for carbonation were prepared. The
A 100 0 0 0 0 samples were cured at 20 ± 2 C in water after 1-day stan-
B 70 30 dard room and kept cured until the time of testing. The
C 50 50 paste of OPC and slag cement were hardened to measure
D 30 70
E 47.5 2.5 0 0 the differential thermal analysis (DTA) and pore structure.
F 49.5 0 0.5 0
G 47.5 50 0 0 2.5 3. Results and discussion
H 47 2.5 0.5 0
I 44.5 2.5 0.5 2.5
3.1. Pore volume

Table 3 Fig. 1 shows comparative results of pore distribution

Proportions of the concrete mixture for testing of carbonation and pore volume for all mixtures A–I. The pore diameters
W/C (%) S/a (%) Weight unite materials (kg/m3) AE water-reducing are ranged from 3 to 10 000 nm. The total pore volumes
W C S G
admixture (C · %) show no differences on substitution ratios of GBFS, even
when the activator is added. However, remarkable differ-
50 36 180 360 620 1122 0.5
ences are observed in distribution of pore diameters.

4000 1000~10000nm
100~1000nm
10~100nm
3~10nm
/g)

3000
3
Cm
-4
Pore volume( × 10

2000

1000

0
A B C D E F G H I
Type of cement

Fig. 1. Pore distribution and pore volume according to mix type of cement (7 days).
1578 K.J. Mun et al. / Construction and Building Materials 21 (2007) 1576–1582

On the whole, the pore diameters of paste with the addi-

tion of activator reveal that the distribution ratio of pore
diameters below 100 mm is larger and tended to be smaller
than OPC. Paste without the addition of activator has pore
diameters exceeding 100 nm diameter.
According to reaction and movement of Ca, Si, Al and
Mg, the inner-structure of GBFS particle is composed of a
non-hydration layer, a leaching layer, an inner hydration
layer and an exterior hydration layer from the center of
the particle. Approaching the surface of the GBFS particle,
CaO/SiO2 tends to increase, Al2O3/SiO2 decreases, and
MgO/SiO2 increasingly appears in the leaching layer [2–
4]. Thus, it is evident that the dissolution of Ca2+ and
Al3+ which are ionic bonding materials depends on the
composition of GBFS particle structure [4,5]. Silicate
hydrate has a high degree of polymerization, and restrains
from spreading due to the encirclement of a dense inner
hydrate layer.
As a result, the pore diameter formed during early
hydration increases comparatively. In this case, if activator
of as alkali or sulfate is added, the degree of polymerization
of CaO/SiO2 decreases spontaneously due to hydration on
the surface of GBFS particle, and many trapped silicate
hydrate are emitted. Then, capillary pores formed by com-
binative water and evaporative water are spontaneously
filled up densely [5,6].
The total pore volume obtained by increasing various
kinds of activators reflects nearly similar properties to A
(OPC) or C specimen without activator. In the case of
the specimen with activator, in contrast, the higher distri-
bution ratio of pore diameters below 100 nm is measured
than the OPC and C specimen without activator. The pore
volume and distribution of blast furnace slag cement are
controlled by the artificial addition of activator. Accord-
ingly, defects of blast furnace slag cement as low compres- Fig. 2. Compressive strength of all mix types of cement.
sive strength at early ages could be improved.

3.2. Compressive strength of cement mortars
Fig. 2 shows compressive strengths according to the
type of cement used for mixture proportion. It is evident
that the 3-day and 7-day compressive strengths of 30%
(B) with GBFS increase more than 50% (C), and more
than 70% (D), respectively. In Fig. 2, E–G specimens
present compressive strengths when gypsum, slacked
lime, and limestone powder are used separately. As for
the 3-day compressive strengths, there exist 30% increase
in the compressive strength of E specimen containing a
2.5% addition of gypsum, 24% increase in compressive
strength for F specimen with 0.5% of slacked lime addi-
tion, and 13% increase for G specimen containing 2.5%
limestone powder addition. These results indicate an
improvement compared to cases where no activator is
added. The result obtained with the addition of slacked
lime restrains the film formation of GBFS particle sur-
face by producing alkali from early hydration, rapidly
destroying the early formed acid film, and promoting
hydration formations such as C–S–H, and C4AH13.
The gypsum forms a dense ettringite structure through
hydration with Al2O3, and limestone powder does not
only increase density by filling up pore formed in the
process of hydration of cement but also contributes to
the increase of compressive strength, when forming a
carbonate crystal by substituting sulfate for ettringite.
The substituted sulfate is thought to promote hydration
in blast furnace slag [4,5].
In the case of using an activator alone, a stimulative
action is observed as gypsum tends to be larger than slaked
lime and to be higher than limestone powder. It is reported
that the addition of activators is a very effective way to
increase early strength of blast furnace slag cement. H
and I specimens represent the compressive strengths with
the increase in various kinds of activators. The early com-
pressive strength of blast furnace slag cement (I) with
added gypsum, slaked lime, and limestone at fixed propor-
tions is higher than the others. This can be attributed to the
compound actions of activators.
 K.J. Mun et al. / Construction and Building Materials 21 (2007) 1576–1582
Fig. 3. Comparison of compressive strength with added activators (I),
without activator (A) and with OPC (C).
In order to completely evaluate the experimental results
obtained (Fig. 3), the mixing proportion (I) which shows
the highest early compressive strength after adding activa-
tor under the same conditions is selected and compared to
A (OPC) and C specimen with no activator. Compressive
strength of cement mortar with added activator increases
about 50% for 3 days and 35% for 7 days more than the
case of no activator. However, at longer curing ages (after
28 days) the compressive strengths are nearly the same.
Also, they show early age properties 6% lower at 3 days,
7% higher at 7 days, long age properties 16%, 23%, 27%
higher at 28, 56 and 90 days than the compressive strength
of OPC.
Laboratory investigations on a series of these mixtures
have revealed the possession of positive early age proper-
ties and at the same time fairly comparable strengths at
later ages, by using the proper amount of activators.
3.3. Drying shrinkage
Fig. 4 shows the drying shrinkage ratio of cement mor-
tar of a total mix type. As the substitution ratio of GBFS is
higher, the shrinkage tends to increase. In the case without
activator, the hydration of GBFS progresses at a very slow
rate. As the substitution ratio of blast furnace slag to OPC
is high, the hydrate formed in the same curing age is
reduced and the inner structure of cement mortar is easily
transformed by capillary force due to water evaporation. It
is therefore considered that the shrinkage ratio is higher.
The drying shrinkage ratio of cement mortar from E and
to I specimens, and the drying shrinkage ratio of cement
mortar with only the addition of slaked lime is a little
1579
Fig. 4. Drying shrinkage of cement by all mix types.
higher than cement mortar with added limestone powder
and anhydrous gypsum. Meanwhile, the shrinkage ratio
of cement mortar with added limestone powder is the low-
est. This results from the phenomenon of Ca(OH)2 in
cement mortar whereby the inner structure has no harden-
ing force and is subjected to easy movement or melting by
capillary contractile force, causing water evaporation,
therefore transpiring to cement mortar surface with water
evaporation [3,4]. In the case of limestone powder, it is
explained that total pore volume decreases by its tamping
action and isolation of parts of the capillary pore restrains
from water evaporation. I and H specimens have nearly
similar drying shrinkage ratios with an increase in the kinds
of activators until 14-days of drying age. However, after
the 14-days period, it is observed that the drying shrinkage
ratio of I specimen added gypsum, slaked lime and lime-
stone powder is the lowest.
For the purpose of evaluating the experimental results
in Fig. 5, the mix proportion for I specimen, which shows
the most superior property of drying shrinkage by adding
activator under the same conditions, is selected and com-
pared to A (OPC) and C with no activator in drying
shrinkage ratio.
1580 K.J. Mun et al. / Construction and Building Materials 21 (2007) 1576–1582

-1

-2

-3

-
-4
3D
-5
7D
-6 28 D

-7
0 100 200 300 400 500 600 700 800

Fig. 6. DTA curve of A(OPC) with curing ages.

Fig. 5. Comparison of compressive strength with added activators (I),

without activator (A) and with OPC (C). 1

0
It is certain that the drying shrinkage ratio of cement
-1
mortar with an activator addition has a similar tendency
to cement mortar without activator for 1 day of curing per- -2
iod, but changes with a distinct difference after 3 days.
-3
Also, when comparing the drying shrinkage of I specimen
with that of A specimen (OPC), there is no significant dif- -4 28 D
ference in the shrinkage ratio for 56 days of drying period, 7D
-5
but after 90 days, I specimen shows a slightly higher ten- 3D
dency than A (OPC). This proves that if a small quantity -6
of activator agent is mixed or added to blast furnace slag
-7
cement in the definite ratio, it could effectively reduce
defects, as drying shrinkage at early curing age of blast fur- -8
0 100 200 300 400 500 600 700 800
nace slag cement.

3.4. DTA Fig. 7. DTA curve of I with curing ages.

Figs. 6 and 7 show results of DTA for A and I paste

specimen which are cured at 3, 7, and 28 days. In the case
of I specimen, the quantity of Ca(OH)2 which is formed by
hydration of OPC shows a tendency to decrease with an
increase in curing days. This phenomenon shows that
Ca(OH)2 which is formed in OPC hydration produces
many hydrate materials through hydration with mineral
elements in GBFS, and that it can increase consolidation
between aggregate and paste or between pastes with a den-
sity of crystal structure [3,4].
Conversely, paste of A specimen (OPC) exhibits an
increase in Ca(OH)2 quantity with an increase in curing
age.
3.5. Carbonation
The depths of carbonation for the manufactured speci-
mens of concrete are measured using a carbonation exper-
iment under curing conditions of carbonate at 10% gas
density, 20 C temperature, and 60% humidity.
Fig. 8 shows the carbonation depth by substitution ratio
of blast furnace slag. It is evident that at the same curing
age, the carbonation ratio increases according to increasing
substitution ratio.
Fig. 9 shows the carbonation depth of the concrete
made by increasing activators to blast furnace slag
cement. It is evident that the carbonation depth of adding
gypsum alone (E) is the highest, gypsum and slacked lime
(H) are intermediate, and gypsum, slacked lime and lime-
stone (I) are the lowest. That is to say, under similar con-
ditions, the substitution ratio of GBFS is the same, and
the increase of hydrate by stimulant action of gypsum,
slacked lime and dense structure is formed by the filling
action of limestone powder greatly reduces the permeabil-
ity of carbon dioxide.
Fig. 10 shows a comparison between the carbonation
depths of A (OPC), C, and I specimen. Carbonation depth
of concrete with activator addition decreases relative to
curing time, where a decrease is observed for concrete with-
 K.J. Mun et al. / Construction and Building Materials 21 (2007) 1576–1582 1581

Fig. 8. Carbonation depths by substitution ratio of GBFS.

Fig. 9. Carbonation depths by adding activators.

Fig. 10. Comparison of carbonation depths with added activators (I), without activator (A) and with OPC (C).
1582 K.J. Mun et al. / Construction and Building Materials 21 (2007) 1576–1582
out activator addition. It is confirmed that at 180-day of
curing period, the carbonation depth is reduced to about
20%.
Also, comparing the carbonation depth of I and A (OPC)
specimen, I specimen is higher than A (OPC) specimen from
early to later duration of carbonation. The main reason is
that the continuous hydration of GBFS partly uses up the
Ca(OH)2 and then self-carbonation generated in the process
of diminishing potential of hydrogen (pH) occurs.
4. Conclusion
In order to investigate the effects of gypsum, slacked
lime, and limestone powder as activators on properties of
blast furnace slag cement mortar and concrete, experiments
are conducted, and results are summarized as follows:
(1) The results of experiments on pore structure proper-
ties, show no considerable difference for total pore
volumes by cement mixing ratio, but show a large
distinction in the distribution of pore diameter. In
the case of the specimen with activator, the higher
distribution ratio of pore diameters below 100 nm
is measured than the OPC and C specimen without
activator.
(2) Promoting hydration of GBFS by adding activator
sharply increases early compressive strength than
that without activator added. Also, it is confirmed
that blast furnace slag cement of approximately
the same early strength with OPC is feasible to
be manufactured.
(3) In the case of mixing or adding a small quantity of
activator to blast furnace slag cement, a great reduc-
tion of drying shrinkage at early curing period and a
decrease in carbonation depth are confirmed.
Acknowledgement
The authors thank the Ministry of Environment in
Korea for the financial support.
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