Cement and Concrete Composites 114 (2020) 103734

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Cement and Concrete Composites

journal homepage: http://www.elsevier.com/locate/cemconcomp

Hydration reactivity of calcium-aluminate-based ladle furnace slag powder

according to various cooling conditions
Sunmi Choi a, Jinman Kim b, *
a
Eco-friendly Concrete Research Center, Kongju National University, South Korea
b
Department of Architectural Engineering, Kongju National University, South Korea

A R T I C L E I N F O A B S T R A C T

Keywords: Ladle furnace slag (LFS) is a reduction slag discharged from a secondary metallurgical process, and its cooling
Slow cooled LFS methods in the discharging process are classified into a rapid or slow method. While the former is only an hour
Rapid cooled LFS consuming process by water quenching or air spraying which is needed heavy equipment, the latter is several
Ladle furnace slag
days consuming process by self-cooling of slag containing intermittent water spraying without special equip­
C12A7, high early strength
Up-cycling
ment. The objective of this study is to investigate the binder characteristics of slowly cooled LFS, which is
experimentally evaluated in the two viewpoints. The one is the material level evaluation focused on the
mineralogical properties such as mineral composition and vitrification ratio, the other is the mixtures level
evaluation focused on the hydration properties of LFS powder such as setting time and strength development.
From this experiments, the calcium–aluminate-based LFS powder, though it is slowly cooled, shows a high
content of reactive mineral of C12A7 and low vitrification of 19% in the material stage. Also, if it does not make
contact with water during cooling, its mortar mixture shows a very short setting time of 8 min and high
compressive strength of 15 MPa at 3 h age and over 30 MPa at 28 day age. Therefore, this study suggests that the
calcium–aluminate-based LFS powder is a very good cementitious material, having comparatively high activity
at early age.

1. Introduction
World crude steel production reached 1816 million tons in 2018 and
is steadily increasing [1]. Because the steel industry produces a large
amount of by-products, carefully coping with natural destruction and
environmental pollution resulting from industrial development is
necessary.
Steel slag of steel industry by-product can be classified into two
types. The first one is called the blast furnace slag, which is produced
during the manufacturing of pig iron. The second one is the steel-making
slag, which is produced during steel production. Almost all of the blast
furnace slag, being quenched with water and pulverized, has been used
as a cementitious material. This method is very valuable because of
making a dual effect not only increasing the value of steel slag but also
improving the environmental characteristics of concrete. However, most
steel-making slag, which accounts for 45% of the steel slag, is used as
aggregate for roads and fills, and some of them are used as cemented raw
materials and fertilizers; thus, it has a little value [2–4].
Steel-making slag can be classified into converter slag, electric arc
furnace (EAF) primary slag (also called EAF oxidation slag), and
secondary-metallurgical slag (also called ladle furnace slag). Ladle
furnace slag (LFS), is also called reduction slag because it is discharged
from a secondary metallurgical process of reduction. In the secondary-
metallurgical process, the deoxidizer has been used two types of Si
and Al-based materials. Although Al-based deoxidizer shows compara­
tively higher reduction efficiency, it is only used in processes that
require high-purity products due to its high cost, and then Si-based
deoxidizer is more commonly used in the real process. Naturally, in
the Si-based reduction process generates a calcium-silicate rich slag, and
the Al-based reduction process generates a calcium-aluminate rich slag
[5]. Even though there are many pieces of research for recycling the
steel slag, researches for recycling these two types of reduction slag is
quite rare.
The present study deals with the utilization of ladle furnace slag,
especially focused on the calcium–aluminate rich slag, which is very
difficult to recycle because of its high humidity powder state. This slag is
originally a large upside-down bell shape and has a high temperature up
to 1000 ◦ C, when it is dumped from slag pot in the slag processing area.

* Corresponding author.
E-mail address: jinman0223@hotmail.com (J. Kim).

https://doi.org/10.1016/j.cemconcomp.2020.103734
Received 11 November 2019; Received in revised form 9 June 2020; Accepted 6 July 2020
Available online 19 July 2020
0958-9465/© 2020 Published by Elsevier Ltd.
S. Choi and J. Kim
It has been slowly self-divided into powder as time goes on, so-called
self-differentiation. To increase process efficiency, it is showered by
water and increase the self-differentiation speed, and it is turned into a
high humidity powder state containing some of the sludge. Therefore, by
this conventional slag discharging process, the LFS changes to be a type
of useless by-product. While it was once thought that the cause of self-
differentiation of the LFS is volume expansion by internal free-CaO or
free-MgO, from the recent findings it has shown that the cause might be
mixed with the expansion due to the phase change of C2S near 680 ◦ C
during the cooling process of the LFS [6].
Authors reported a case of producing a regulated set cement from
this calcium-aluminate rich slag, based on the idea that it has a quick-
setting characteristic when it is rapidly cooled [7]. This technique is
very valuable in the up-cycling aspect of steel industry by-products.
However, the rapidly cooling system suffers from the limitation in that
it should be applied to the melting slag. Because the ladle furnace used in
the secondary-refining process has a comparatively small volume
comparing other furnaces, so the volume of 1 batch slag is very small
comparing the volume of slag pot of a container for transporting slag,
which is decided from a general capacity of the furnace. Therefore slag
pot is loaded with diversely charged LFS. When a slag pot is transferred
to a slag-treatment facility, the previously loaded slag at the bottom is
supercooled and formed into a massive solid state. In this respect, the
proportion of the melted slag in the actual process is not high. Hence, the
secondary-refining slag that is massively produced still needs to be
treated by conventional method.
In the container for transporting slag, water spraying causes a hy­
dration reaction in the slag, and it is the main reason for the decrease in
the slag activity. When it contacts with water, the CA-based mineral
loses its reactivity as a cement-based material, because it forms a stable
C-A-H mineral during water spraying and does not cause reactions
anymore. Therefore, slag recycling value is reduced by water spraying.
To use the slag that contains a sufficiently reactive mineral of calcium
aluminate system by the high temperature in the furnace, we need to
avoid the use of water in the cooling process. However, slag-treatment
facilities still stick to the water-spraying method despite the many is­
sues involved. Maybe it is because the characteristics of cool slag
without water spraying are not clearly understood.
The objective of this study is to examine the binder characteristics of
slow-cooled LFS slag, which is not cooled by water spraying. Every result
of this study simultaneously has relatively evaluated with those of rapid
air- and water-spray-cooled samples. The results of this study are ex­
pected to provide an important technological role to make the envi­
ronment to change from the current water-spray-cooling method to the
air slow-cooling method.
2. Materials and experimental methods
2.1. Material
The materials used in this study were calcium–aluminate-based LFS
generated by the Korean “S” steel company. Slag from the same process
was subjected to different cooling conditions. Slowly cooled LFS slag
(SC-LFS) was cooled for two days in the ambient air condition without
contacting water, which was discharged to the slag processing area in a
molten state. Slowly cooled water-sprayed LFS(SC(W)-LFS) was sprayed
a little water during the slow cooling process. So, the cooling speed of SC
(W)-LFS was a little more quickly than that of SC-LFS. Furthermore, the
slag that was cooled rapidly (RC-LFS) was scattered to the air by the
high-pressure gas, formed into beads of spherical forms with a size of 5
mm under, and cooled rapidly under 100 ◦ C within 1 h, whose high
reactivity was already proven by previous studies [7,8]. Thus, three
types of reduction slag were investigated.
The shape of the particles of the three types of reduction slag is
shown in Fig. 1, and the particle-size distributions of every sample are
shown in Fig. 2, which shows that the RC-LFS is the fine aggregates with
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Cement and Concrete Composites 114 (2020) 103734
90% or more having a spherical shape. Meanwhile, because 80% or
more of the SC(W)-LFS exhibited a chunk shape of 5 mm or more, it is
significantly deviated from the standard particle size curve of fine
aggregate. Also, because the SC-LFS is largely classified into two phases,
such as aggregate and fine powder, and the two shapes would show
differences in their hydration properties, the SC-LFS was used in the
experiments after being divided into the aggregate and fine powder
phases, based on the using a standard 1.2-mm sieve, which was set as the
criterion for 50% classification of the particle-size distribution. Even
though the size of the samples is different, when it was used as a binding
material, every sample was pulverized as a fine powder.
Table 1 lists the physical–chemical composition of the four types of
reduction slag, which were classified according to the cooling methods
and sizes, including those of two types of commercialized RSC for
comparison. Furthermore, based on a previous study that the long-term
strength and volume stability was improved when gypsum was used
with LFS fine powder [8], gypsum was used as a material for the
compressive strength test in this study.
The reduction slag rapidly cooled by air exhibited a higher content of
Al2O3, compared with the domestic commercial RSC, and mostly
showed similar values in other major compositions such as CaO and
SiO2. Theoretically, LFS originated by the same process should not differ
in terms of oxide the composition according to the cooling conditions.
However, they showed differences in the contents of CaO, Al2O3, Fe2O3,
MgO, and SO3. Accordingly, they also displayed differences in their
specific gravity. Maybe the real content of each oxide component of LFS
would be the average value of SC-LFS of 1.2 mm undersize and SC-LFS of
1.2 oversize, because SC-LFS was not lost during sampling at all. The
difference between the two samples shows that the comparatively
smaller particles have a higher content of CaO and a lower content of
Fe2O3. However other samples were lost certain components or
collected certain components during sampling due to the intrinsic pro­
cess. RC-LFS showed comparatively low content of Fe2O3 because
heavyweight of metal oxides was not dispersed into the air in the
atomizing process. SC(W)-LFS showed comparatively low content of
CaO and high content of MgO. The former would be because CaO was to
be swept out by water spray and then was not collected when sampling.
The later would be because of the heterogeneity of the MgO particle.
Even though we tried to get the proper sample representing well the
properties of the whole slag, sampling was very difficult due to the harsh
environment in the slag processing area. Each slag was pulverized into
powder with fineness of 6500 ± 300 cm2/g using a ball mill to evaluate
their hydration properties under the same conditions. We found that the
pulverization time required for the target fineness increased in the
following order: SC-LFS, RC-LFS, and SC(W)-LFS.
2.2. Experimental methods
The secondary-refining slag was qualitatively analyzed using the X-
ray diffraction (XRD) method (miniflex600, Rigaku) to evaluate its
mineral composition as a binder. The analyzed angle of region 2θ was
5◦ –60◦ , and the step size was 0.02◦ .
Ignition loss was determined using thermogravimetric analysis
(TGA) in a nitrogen atmosphere to evaluate the degree of hydration of
the secondary-refining slag. The TGA equipment used in the experiment
was Q50 of TA Instrument Company. The ignition loss was measured
using the heating slag powder from 20 to 800 ◦ C at a rate of 10 ◦ C/min.
The amount of reacted minerals was quantified in each decomposition
period.
The slag showed different vitrification ratios in the XRD, and thus,
their vitrification ratios were evaluated using an optical microscope [9].
The vitrification-ratio measurement using the microscope evaluated the
crystallinity and amorphism by measuring the gray level of light in the
particles transmitted to produce a specific size using an optical or
polarizing microscope. The gray levels were divided into 0–250, and the
standard gray level that distinguished between the crystallinity and
S. Choi and J. Kim
Fig. 1. Shape of LFS cooled in the different condition.
Fig. 2. Particle size distribution of SC-LFS and RC-LFS.
amorphism was set to 100 using the vitrification-ratio values measured
by the Rietveld method. The samples used in the experiment were
collected after pulverizing each slag and classifying the particles with
sizes between 45 and 75 μm. To increase accuracy, more than 200
samples were measured. Each sample was magnified by 100 times by the
optical microscope and computed using an image-analyzing program.
The vitrification ratio was evaluated using the percentage of particles
that satisfied the standard gray value of 100.
To evaluate the hydration characteristics of the slag, it was dried and
pulverized into similar fineness using a ball mill, and the pulverized
powder was used as materials to measure the setting time and
compressive strength. A setting-time test was carried out by measuring
the time in 1-min intervals using a Vicat test according to ISO 9597, and
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Cement and Concrete Composites 114 (2020) 103734
the times to reach penetration depths of 36 ± 1 and 0.5 mm were defined
as the initial and final settings, respectively [10]. A standard was spec­
ified to change the water content according to a standard flow. However,
ensuring the measurement time was not possible because the RSC and
RC-LFS powder have a quick setting time. Therefore, the experiment was
conducted by applying W/B 40% constant water content.
A compressive strength test was performed on the mortar specimen
made at W/B 50% and a mixing-design ratio of binder: sand = 1 : 3 at a
size of 4 × 4 × 16 cm according to ISO 679 [11]. Because the
strength-development characteristics of the CA-based compounds
greatly vary depending on the presence of gypsum, gypsum was
considered as a factor in the strength test, and the mixing ratio of gyp­
sum to the total amount of binder was 25%. In addition, considering the
quick setting characteristic, the age of the compressive strength mea­
surement was set to 3 h, 1 day, 7 days, and 28 days.
3. Results and discussion
3.1. Mineral analysis
Fig. 3 shows the analysis results of the mineral in the powder using
XRD for RC-LFS that was rapidly cooled by the strong air brow and SC-
LFS that was slowly cooled in air. In accordance with the findings from
previous studies [7,8], the XRD graph of the RC-LFS illustrated that the
major minerals were C12A7 (a quick-setting mineral), β-C2S (a long-term
strength development mineral), and periclase. The SC-LFS also con­
tained C12A7; however, C2S was found to have been transformed into a γ
type with low reactivity during the slow-cooling process. The change in
C2S from the β phase to the γ phase caused volume expansion, which was
considered to be an important reason for the self-differentiation of the
reduction slag. However, in the slow-cooled LFS, although the reactivity
S. Choi and J. Kim Cement and Concrete Composites 114 (2020) 103734

Table 1
Physical and chemical properties of LFS, compared with RSC and gypsum.
Cooling conditions Physical properties Chemical Properties
2
Cooling conditions Fineness (blaine, cm /g) Time for pulverization (H:M) Oxide composition (%)
Specific gravity (g/cm3)
Cooling conditions Al2O3 SiO2 Fe2O3 MgO SO3
Specific gravity
(g/cm3)
Fineness
(blaine, cm2/g)
Time for pulverization
(H:M)
CaO

RC-LFS 2.97 6300 1:00 52.1 26.5 8.9 1.2 6.6 3.0
SC(W)-LFS 3.16 6719 2:50 38.7 15.1 8.2 9.3 17.9 1.2
SC-LFS↓ 2.99 6428 0:30 56.2 19.2 11.4 3.1 5.3 1.8
SC-LFS↑ 3.32 6215 0:50 40.6 20.0 12.1 14.5 6.3 1.9
RSC(U) 2.99 5000 – 54.9 17.7 8.36 2.14 1.36 12.4
RSC(S) 3.02 4800 – 58.4 14.0 9.80 2.79 1.65 11.1
HG 2.67 1400 – 40.0 0.9 2.6 0.4 0.3 55.8

* LFS: Ladle furnac slag, RC: Rapidly cooled, SC(W): Slowly cooled(water).
↓: 1.2 mm under size, ↑: 1.2 mm over size, RSC: Regulated set cement, HG: α-type hemihydrate gypsum.

Fig. 3. XRD patterns of RC-LFS and SC-LFS(1.2 mm under).

Fig. 4. XRD patterns of SC-LFS classified according to particle size.

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S. Choi and J. Kim Cement and Concrete Composites 114 (2020) 103734

of C2S decreased, it was expected to be potentially used as a reactive

material because C12A7 which is a quick setting mineral was also existed
richly.
The SC-LFS was divided into aggregate and powder shapes using a
1.2-mm sieve, and measured by XRD (Fig. 4). We could possibly see the
higher and the clearer crystal peak in the powder shape (<1.2 mm) than
that in the aggregate shape (>1.2 mm). In particular, γ-type C2S peaks
were higher in the 1.2 mm sieve under particles, and β-type C2S peak
was higher in 1.2 mm over particles. These results suggest that the
powderization of the secondary-refining slag during the slow cooling
was mainly due to the phase change of C2S.
On the other hand, in the XRD graph of the SC(W)-LFS, we could
observe that the peak of C12A7 was relatively reduced, because C12A7
reacted with water during the water contacted and generated the
hydrogarnet (C3AH6) which is a hydrate (Fig. 5). In addition, the scan­
ning electron microscope (SEM) image showed that the slowly cooled
slag came into contact with water during the cooling process, as shown
in Fig. 6. Further, identifying hydrates such as hydrogarnet and ettrin­
gite [12] became possible. In this regard, contact with water during the
cooling process was a major cause of the reduction in the reactivity of
the slowly cooled reduction slag. Thus, the hydrate generated would
become a major cause for reducing efficiency during pulverization. Fig. 6. SEM image of SC(W)-LFS.
A TGA test was conducted to evaluate the hydration degree of the SC
(W)-LFS, and the results are shown in Fig. 7. The ignition-loss value was are listed in Table 2. The SC(W)-LFS contained 6.20%, 1.92%, and
zero for the RC-LFS, but they were 2.2% and 7.3% for the SC-LFS and SC 2.95% of C3AH6(3CaO⋅Al2O3⋅6H2O), Al(OH)3, and Ca(OH)2, respec­
(W)-LFS, respectively. The sections in the graph are divided into the tively, which are hydrates of C12A7 and CaO formed by contacting with
following: (a) H2O decay section of C3AH6 and Al(OH)3 hydrates, (b) Ca water during the cooling process. The results show that 11.07% of the
(OH)2 decay section due to the reaction between the leached Ca+ ion hydrates were already formed during the slow-cooling process (corre­
and water, and (c) decarbonization section of CaCO3. The reaction sponding numbers in Table 2). Moreover, the amount of CaCO3 gener­
amount of C12A7 and CaO in each section was calculated using the ated by their action with CO2 in air was 3.41%.
weight loss in the 200–650 ◦ C section of the SC(W)-LFS, and the results Meanwhile, the SC-LFS also contained 1.84%, 0.57%, and 0.81% of

Fig. 5. XRD patterns of SC(W)-LFS.

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S. Choi and J. Kim Cement and Concrete Composites 114 (2020) 103734

Fig. 7. TGA curve of RC LFS, SC-LFS and SC(W)-LFS.

Table 2
Minerals with Ig.loss of SC-LFS and SC(W)-LFS.
Range Temp. (◦ C) Mineral types Hydrates or Carbonate Ig.loss (wt.%) Hydrates (wt.%)

Range SC SC(W) SC
Temp.
(◦ C)
Mineral types
Hydrates or Carbonate
SC(W)

(a) 200–350 C12A7 C3AH6/Al(OH)3 2.43 0.72 8.12 (6.20/1.92) 2.41

(b) 350–450 CaO Ca(OH)2 0.72 0.20 2.95 0.80
(c) 450–650 CaO CaCO3 1.50 0.47 3.41 1.07
Sum 200–650 – 4.65 1.39 14.48 4.28

C3AH6, Al(OH)3, and Ca(OH)2, respectively. The results indicate that it
generated hydrates even with slow air cooling because it reacted with
moisture in the air.
The slowly cooled slag [SC(W)-LFS] contacted with moisture during
the cooling process; thus, the hydration reaction partially progressed.
Therefore, a relatively lower hydration index was exhibited when the
slag mixed with water at the later stage.
3.2. Vitrification ratio
In the blast furnace slag, which is a representative slag used as an
admixture for cement among the steel by-products, the reactivity largely
depends on the number of amorphous particles. In the reduction slag,
the difference in the vitrification ratios is an important indicator that
determines its value as a reactive material. The optical microscopic
images and measurement results are shown in Figs. 8 and 9,

Fig. 8. Vitrification image of RC LFS and SC-LFS.

6
S. Choi and J. Kim
respectively, to evaluate the vitrification ratios of the reduction slag
under different cooling conditions using a microscope.
When light is transmitted, amorphous particles appear transparent
with high gray levels, whereas crystalline particles are opaque and have
low gray levels [13,14]. Whereas the bulk of the reduction slag that was
rapidly cooled by air showed a high vitrification ratio of 92%, the slag
that was slowly cooled in air and that slowly cooled by water spraying
displayed low vitrification ratios of 19% and 6%, respectively. Thus, the
cooling rate could be considered as an important factor that determines
the vitrification ratio.
C12A7, which is a major mineral in the reduction slag, reacts well,
when in contact water, although it may have a crystalline phase
[15–17]. As mentioned earlier, because C2S in the slowly cooled
reduction slag changed into the γ phase with low reactivity, the reaction
of the slowly cooled reduction slag depends on C12A7, and the reaction
rate will be reduced depending on the degree of crystallization. On the
other hand, the reduction slag rapidly cooled by air exhibited a rela­
tively rapid hydration reactivity because it contained the C12A7 and
β–C2S phase with a high vitrification ratio.
Thus, concerning the vitrification ratio based on the particle size, the
smaller the size is, the larger is the vitrification ratio that can be pre­
dicted. This result could be attributed to the fact that small-size particles
lead to relatively fast cooling because a small particle has a higher
surface-area ratio (an indicator of cooling) than a volume ratio (an in­
dicator of heat capacity) compared with a large particle.
3.3. Hydration properties
3.3.1. Setting time
The results of the setting-time test, which was conducted to deter­
mine the initial hydration-reaction properties of the different reduction-
slag types, are shown in Fig. 10.
The reduction slag rapidly cooled by the air was set very rapidly that
measuring the setting time was not possible after contact with water,
and thus, the setting time in the Vicat test was found to be “0” min. The
rapid setting was indisputably attributed to the hydration reaction of
C12A7, which has a high vitrification ratio, because the reaction of C2S (a
major component mineral), was relatively slow, although it maintained
the β phase that exhibited a hydration reaction.
The slag that was slowly cooled in air was also found to set very fast;
thus, it indicated an initial setting time that was not longer than 3 min
and a final setting time that was not longer than 7 min. In particular, in
contrast to the original expectation, particles with sizes of 1.2 mm or
above, which have relatively low vitrification ratios due to their large
size, were set more rapidly. Fig. 9 shows that whereas the mean amor­
phous rate of small particles with sizes of 1.2 mm or below was 30%, that
of particles larger than 1.2 was merely 17%. This result was
Fig. 9. Vitrification ratio of RC LFS and SC-LFS.
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Cement and Concrete Composites 114 (2020) 103734
Fig. 10. Setting time of RC LFS and SC-LFS by vicat test.
contradictory to the general theory that the higher the amorphous rate
of the slag is, the higher is its hydration reaction [17]. As mentioned
earlier, the initial setting of the reduction slag slowly cooled by air could
be attributed to the hydration reaction of C12A7 because C2S was con­
verted to the γ phase with a low reactivity. The studies by Company S
and Company U in South Korea, which investigated the initial reactivity
of pure C12A7, reported that the crystalline phase exhibited more
excellent initial reactivity than the amorphous phase, which was
consistent with the findings of the present study [15]. The report sug­
gests that the crystalline phase, which had clear particle boundaries,
started earlier than the amorphous phase. This result was assumed to be
a phenomenon that occurred because the crystalline phase has a larger
dissolution surface than the amorphous phase during the
liquid-reaction-dominated initial hydration. However, proceeding with
more in-depth research on this aspect is necessary.
As predicted, the reduction slag that made contact with water during
cooling exhibited relatively late setting. However, its initial setting time
was 13 min, and its final setting time was 34 min. Thus, it displayed very
fast setting compared with Ordinary Portland Cement (OPC). Presum­
ably, this result was because C12A7 of the fast hydration reaction still
remained, which has not hydrated yet although some hydrates were
formed by contact with water.
The abovementioned results show the quick setting property of the
reduction slag cooled in air, which developed a very fast setting property
although not comparable with that of the reduction slag rapidly cooled
by air. Therefore, we deemed it necessary to conduct research on its
utilization as an accelerator by taking advantage of this property.
3.3.2. Development of the compressive strength of the LFS powder
Fig. 11 shows the results of the compressive-strength test of a single
binder mortar using the reduction slag cooled under different condi­
tions. In the case of the hydrated-slag powder alone, the RC-LFS devel­
oped strengths of 14 MPa even at a very short age of 3 h and 24 MPa at
the age of 28 days. However, the slowly cooled slag that did not make
contact with water (SC-LFS) as well as the slowly cooled slag that made
contact with water [SC(W)-LFS] exhibited a comparatively low strength.
As mentioned earlier, the main minerals in the reduction slag are
C12A7 and C2S. C12A7 reacts with water to produce hydrogarnet (C3AH6)
via an intermediate hydrate within a short time [ (Eq. (1)] [18,19].
Meanwhile, C2S also produces a C–S–H gel in reaction with water when
the β phase is maintained. It does not contribute to the hydration reac­
tion in the case of the slowly cooled reduction slag because of its con­
version into the γ phase. Therefore, the strength development of the
reduction-slag powder was caused by the hydration of C12A7. The SEM
photograph of the hydrated slowly cooled slag (Fig. 12) also revealed a
large quantity of hydrogarnet even though the age was only 3 h.
S. Choi and J. Kim
Fig. 11. Compressive strength of mortar using only LFS power as binder.
In the rapidly cooled slag, C12A7, which displayed a high vitrification
ratio, exhibited an excellent reactivity, whereas in the slowly cooled
slag, C12A7 was crystallized regardless of the contact with water and
particle size. Therefore, it lost reaction energy, which led to the devel­
opment of a very low strength.
C12A7 + 51H2O → 6C2AH8 + 2Al(OH)3 → 4C3AH6 + 6Al(OH)3 + 18H2O(1)
In the formation of hydrogarnet from the intermediate hydrate
during the hydration of C12A7, surplus water was generated, and the
volume was reduced. Also, hydrogarnet, which was the final hydrate,
Fig. 12. SEM image of hydrated SC-LFS at 3 h after mixing.
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Cement and Concrete Composites 114 (2020) 103734
also generated a thin film on the unhydrated particle surface, which
interfered with the water supply [15,16,20]. Accordingly, the effects of
the long-term strength enhancement could not be expected. We pre­
sumed that the insignificant strength development after seven days in
the rapidly and slowly cooled slag was a phenomenon that resulted from
the combination of these factors.
The slowly cooled slag did not develop a 3 h strength regardless of
the particle size but slightly developed a one-day strength. Concerning
the particle size, the small particles of 1.2 mm or below showed lower
than a one day strength than the large particles but exhibited even
higher strength values after seven days. The results for the initial
strength within one day are the same as those of the slightly slow setting
time of the small particles compared with the large particles.
Therefore, we can see that high crystalline ratios are relatively ad­
vantageous for the initial hydration, and we presumed that this phe­
nomenon occurred because the crystalline phase had a larger dissolution
surface than the amorphous phase during the liquid-reaction-dominated
initial hydration. Once water was lost after hydration, hydration pro­
gressed to a certain extent due to topochemical reaction, which
contributed more to the strength development. In this condition, higher
vitrification ratios are more advantageous for strength development.
3.3.3. Development of the compressive strength of LFS powder with gypsum
The strength development was generally weak in the SC-LFS.
Therefore, because of the mixing of gypsum, C12A7 induced the forma­
tion of ettringite [Eq. (2)]. Observing the production of ettringite hy­
drates from the slowly cooled reduction slag became possible after
mixing with gypsum (Fig. 13).
C12A7 + 12CaSO4 + 137H2O → 4(C3A⋅3CaSO4⋅32H2O) + 6Al(OH)3 (2)
The RC-LFS achieved 2–15 MPa more strength when gypsum was
mixed in each measurement age compared with that without gypsum
(Figs. 11 and 14). These results were similar to the ultra-quick-setting
S. Choi and J. Kim
Fig. 13. SEM image of hydrated SC-LFS with gypsum at 3 h after mixing.
cement [RSC(U) of U Company in South Korea] and slightly lower than
the ultra-quick-setting cement [RSC(S) of S Company in South Korea].
The SC-LFS also showed a big difference between that with and
without gypsum and revealed a high strength-development rate.
Regardless of the particle size, the SC-LFS showed strengths 15 MPa
range in the initial 3 h, which was higher than that of OPC in one day. It
exhibited excellent expression rates of 82% for the RC-LFS and 75% for
the OPC at 28 days. Moreover, the strength was not much lower than
that in the ultra-quick-setting cement of U Company, which is commonly
used in South Korea. However, the SC(W)-LFS showed a low strength.
The strength of the SC(W)-LFS at the seventh day was equal to that of the
SC-LFS at 3 h. Moreover, that of the SC(W)-LFS at age 28 days was less
Fig. 14. Compressive strength of mortar using LFS power with gypsu.
9
Cement and Concrete Composites 114 (2020) 103734
than that of the SC-LFS at one day. The results showed that even if C2S of
the SC-LFS had a low activity, mixing of the gypsum activated the
ettringite-formation reaction of C12A7 to realize a high strength. How­
ever, the water-sprayed SC-LFS had a low value as a cementitious ma­
terial because it has a low strength-development rate as the minerals
already reacted with water in the water-spraying process.
The results of the slowly cooled slag particle size indicated that a
small particle size realized a relatively lower strength within a one-day
age when it was not mixed with gypsum. However, it did not show the
same phenomenon when it was mixed with gypsum and realized a
similar strength regardless of age.
4. Conclusions
The following conclusions were deduced from the experiments
conducted to confirm the characteristics of the cementitious binder
without spraying water to the CA-based SC-LFS, which has not been
implemented because of its absence of reactivity.
1) The mineral analysis revealed that whereas C12A7 and β–C2S were
present in the RC-LFS, which is a rapidly cooled CA reduction slag,
C2S lost its reactivity during the slow-cooling process, and C12A7 lost
its importance as a reactive material because it reacted with water
during the water-spraying process.
2) We concluded that more than 3.45% of the effective cementitious
minerals reacted during the water spray in the slag processing area
because we analyzed that 5.68% and 2.23% of the minerals of the SC
(W)-LFS and SC-LFS, respectively, were hydrated.
3) The RC-LFS, SC-LFS, and SC(W)-LFS exhibited vitrification ratios of
92%, 19%, and 6%, respectively. Thus, we found that the cooling
rate greatly affected the vitrification ratio, which is a index to
determine the reactivity. Also, we found that the slag with smaller
particle size exhibited higher vitrification ratio even when cooled in
the same manner. It is originated that the smaller particle shows
higher cooling speed due to comparative higher specific surface area.
S. Choi and J. Kim
4) The setting-test results revealed that even the slowly cooled reduc­
tion slag (SC-LFS) exhibited a fast reactivity regardless of its gener­
ating size, when it is not contacted with water and used with gypsum.
5) The compressive-strength test revealed that whereas the RC-LFS
exhibited a high reactivity of 13.6 MPa in the compressive strength
even at the initial 3 h due to C12A7 and developed a long-term
strength partly due to the reaction of C2S, the SC(W)-LFS exhibited
a conspicuously low strength in both initial and long-term periods.
However, when gypsum was used with the SC-LFS, good initial and
long-term strengths were realized owing to the strength enhance­
ment due to the production effect of ettringite. Moreover, at the age
of 28 days, it exhibited strength equal to 75% of OPC and 84% of the
commercialized product RSC.
6) These results suggest that the CA-based secondary-refining slag can
be used as cementitious materials, if it does not make contact with
water, even in the secondary-refining slag that is discharged through
the slow-cooling process. Therefore, we believe that it can contribute
to the increase in the utilization of steel by-products when the cur­
rent water-spray- cooling method is changed to the slow air-cooling
method.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
The research reported in this paper was supported by the Korea
Science and Engineering Foundation (KOSEF) grant funded by the
Korean Ministry of Education, Science and Technology (MEST) (No.
2017R1A6A3A11035291). And The research was supported by the In­
ternational Science and Business Belt Program through the Ministry of
Science, ICT and Future Planning (2015-DD-RD-0068-06).
References
[1] www.worldsteel.org, 2016.
10
Cement and Concrete Composites 114 (2020) 103734
[2] M. Pasetto, N. Baldo, Recycling of steel slags in road foundations, Environ. Eng.
Manag. J. 9 (6) (2011) 773–777.
[3] Hyung-Seok Kim, Kee-Seok Kim, Sung Suk Jung, Jin Ill Hwang, Valorization of
electric arc furnace primary steelmaking slags for cement applications, Waste
Manag. 41 (2015) 85–93.
[4] Yi Huang, Guoping Xu, Huigao Cheng, Junshi Wang, An overview of utilization of
steel slag, Procedia Environ. Sci. 16 (2012) 791–801.
[5] Jérôme Berjonneau, Pascal Prigent, Jacques Poirier, The development of a
thermodynamic model for Al2O3–MgO refractory castable corrosion by secondary
metallurgy steel ladle slags, Ceram. Int. 35 (2) (2009) 623–635.
[6] Jubica Kriskova, et al., Effect of mechanical activation on the hydraulic properties
of stainless steel slag, Cement Concr. Res. 42 (2012) 778–788.
[7] Sunmi Choi, Jinman Kim, Dongyeop Han, Jiho Kim, Hydration properties of ladle
furnace slag powder rapidly cooled by air, Construct. Build. Mater. 113 (2016)
682–690.
[8] Jinman Kim, Sunmi Choi, Dongyeop Han, Improving the mechanical properties of
rapid air cooled ladle furnace slag powder by gypsum, Construct. Build. Mater. 127
(2016) 93–101.
[9] Yasumi Kasai, Naohiro Ikeda Edited, Test Method of Concrete, Technical Institute,
1993, pp. 76–78.
[10] ISO 9597, Determination of Setting Time and Soundness of Cements, 2014.
[11] ISO 679, Methods of Testing Cements – Determination of Strength, 2011.
[12] Carlos A. Rios, Craig D. Williams, Michael A. Fullen, Hydrothermal synthesis of
hydrogarnet and tobermorite at 175◦ C from kaolinite and metakaolinite in the
CaO-Al2O3-SiO2-H2O) system, Appl. Clay Sci. 43 (2009) 228–237.
[13] Bin Lin, Hong Wang, Xun Zhu, Qiang Liao, Bin Ding, Crystallization properties of
molten blast furnace slag at different cooling rates, Appl. Themal Eng. 96 (5)
(2016) 432–440.
[14] Jinman Kim, Sunmi Choi, Youngjea Bok, SangYoon Oh, Evaluation of vitrification
rate of CaO-Al2O3 based steel slag according to cooling speed, Proceedings of the
Korea Concrete Institute 25 (1) (2013) 153–154.
[15] Samsung C&T Co, Ltd, Union Co, Ltd, Wet shotcrete method using the casting
equipment consisting of a complex air injection system and mineral accelerator
with the amorphous C12A7 system cement made by water-cooling, Specify new
technologies (2004) 441.
[16] B. Raab, H. Poellmann, Heat flow calorimetry and SEM investigations to
characterize the hydration at different temperatures of different
12CaO⋅Al2O3(C12A7) samples synthesized by solid state reaction, polymer
precursor process and glycine nitrate process, Thermochim. Acta 513 (2011)
106–111.
[17] Chul-Woo Chung, Laura A. Turo, Jeseph V. Ryan, Bradley R. Johnson, John S. Mc
Cloy, The effect of concentration on the structure and crystallinity of a
cementitious waste form for caustic wastes, J. Nucl. Mater. 437 (2013) 332–340.
[18] J. Setien, D. Hernandez, J.J. Gonzalez, Characterization of ladle furnace basic slag
for use as a construction material, Construct. Build. Mater. 23 (2009) 1788–1794.
[19] Caijun Shi, Characteristics and cementitious properties of ladle slag fines from steel
production, Cement Concr. Res. 32 (2002) 459–462.
[20] D. Adolfsson, R. Robinson, F. Engström, B. Björkman, Influence of mineralogy on
the hydraulic properties of ladle slag, Cement Concr. Res. 41 (2011) 865–871.