Cement and Concrete Research 32 (2002) 459 – 462

Characteristics and cementitious properties of ladle slag fines

from steel production
Caijun Shi*
CJS Technology Inc., 2116 Upland Drive, Burlington, Ontario, Canada L7M 2Z2
Received 18 June 2001; accepted 5 October 2001

Abstract

Ladle slag is a by-product from further refining molten steel after coming out of a basic oxygen furnace (BOF) or an electric arc furnace
(EAF). Air-cooled ladle slag has a very large portion of fine particles due to the conversion of b-C2S to g-C2S during the cooling process.
X-ray diffraction (XRD) analysis of three ladle slag fine samples passing 100, 200 and 325 mesh indicates that the major mineral in ladle
slag fines is g-C2S, which does not show cementitious property in water. Experimental results have indicated that ladle slag fines show
significant cementitious property in the presence of an alkaline activator. The finer the ladle slag is, the better the cementitious property of
the slag is. D 2002 Elsevier Science Ltd. All rights reserved.

Keywords: Ladle slag; Mineralogical composition; Cementitious property; X-ray diffraction; Activator

1. Introduction under the action of chemical activators [2]. Also, cement

containing steel slag has much better corrosion resistance
Steel slag is a by-product from either the conversion of than conventional Portland cement [3].
iron to steel in a basic oxygen furnace (BOF), or the melting To further refine the steel after coming out of the BOF or
of scrap to make steel in an electric arc furnace (EAF). The EAF, fluxes are added to the molten steel while in a ladle.
chemical composition of steel slag is highly variable, thus, The slag from this process is usually called ladle slag. The
the mineral composition of steel slag also varies. Olivine, chemical composition of ladle slag is significantly different
merwinite, C3S, b-C2S, C4AF, C2F, RO phase (CaO – FeO – from that of steel furnace slag in that the former has a very
MnO – MgO solid solution) and free-CaO are common low FeO content, a higher Al2O3 content. The difference in
minerals in steel slag. Steel slag is used as asphalt concrete chemical composition results in different mineral composi-
aggregate in most countries that have steel plants. High free- tion. Ladle slag has a CaO/SiO2 ratio of around 2 and
CaO content in steel slag may cause volume expansion consists mainly of C2S.
problems. The Ministry of Transportation of Ontario, C2S exists in four well-established polymorphs: a, a0,
Canada banned the use of steel slag in asphalt concrete b and g. On cooling from elevated temperatures, a-C2S
several years ago due to the expansion problem. transforms to b-C2S at 630 C, then transforms to g-C2S at
The presence of C3S, b-C2S, C4AF and C2F endorses lower temperature. The conversion of b-C2S to g-C2S is
steel slag cementitious properties. It is generally agreed that accompanied by an increase in volume of nearly 10% and
the cementitious properties of steel slag increases with its results in the shattering of the crystals into dust because of
basicity. However, free-CaO content also increases with the their different crystal structures and densities [4]. Since the
basicity of steel slag. The C3S and b-C2S contents in steel major mineral in ladle slag is C2S, ladle slag from a slow
slag are much lower than those in Portland cement. Thus, cooling process has a very high percentage of fine powder,
steel slag can be regarded as a weak Portland cement clinker which makes materials handling more difficult and makes it
[1]. Steel slag exhibits very good cementitious property unsuitable for use as aggregates. For example, the limit for
less than 200 mesh is about 5% for asphalt concrete aggre-
* Tel.: +1-716-649-6780; fax: +1-716-649-7389. gate in most places, while the fines less than 200 mesh in
E-mail address: caijun105@hotmai.com (C. Shi). ladle slag can be up to 20– 35%.

0008-8846/02/$ – see front matter D 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 8 - 8 8 4 6 ( 0 1 ) 0 0 7 0 7 - 4
460 C. Shi / Cement and Concrete Research 32 (2002) 459–462

Table 1 2.3. Chemical activation of cementitious property of ladle

Chemical analysis of ladle slag samples
slag fines
Slag
sample CaO SiO2 Al2O3 MgO F SO3 Fe2O3 MnO TiO2 ZrO2 Total
Since ladle slag fines contain a high content of free
LS100 57.0 26.8 5.2 3.2 3.0 1.7 1.60 1.0 0.3 0.2 100.0 CaO, they cannot be used to replace Portland cement due
LS200 56.6 26.9 4.3 3.9 3.9 2.4 1.0 0.5 0.3 0.3 100.1
to potential soundness problems. In this study, 40% of
LS325 55.9 26.4 4.7 4.2 4.4 2.3 1.0 0.5 0.3 0.3 100.0
ground blast furnace slag by mass was blended with 60%
of those ladle slag fines samples to make blended cements.
Cementitious property of such a blended cement was
evaluated by using Na2SiO3 as an activator. Na2SiO3 was
In this study, characteristics and cementitious properties dissolved into mixing water then added into the blended
of ladle slag with different finesses from an EAF produc- cement. One part ladle slag-based cementing material or
tion was investigated. The purpose of the work is to ex- Portland cement was mixed with 2.75 parts standard
plore potential applications for ladle slag fines in cement Ottawa sand and sufficient mixing water to produce mor-
and concrete production. tars with specified flowability. The water requirement for
ladle slag-based cementing material ratio was found to
be 0.58 instead of 0.485 that is specified for Portland
2. Experimentation cement. Then these mortars were cast into 5  5  5 cm
(2  2  2 in.) cubic moulds and cured in a moist chamber
2.1. Raw materials with a relative humidity over than 95%. After in moulds
for 3 days, these cubes were demoulded and then cured in
The ladle slag in this study was from an EAF steel sealed plastic bags. At 3, 7 and 28 days, three cubes were
production. Three slag fine samples designated as LS100, tested in compression and presented results are averages of
LS200 and LS325 were obtained by screening to pass #100, the three replicates.
#200 and #325 sieves, and were analysed for their chemical
composition, as listed in Table 1. The three samples have
very similar chemical composition regardless of differences 3. Experimental results and discussion
in their finenesses. However, their CaO content slightly
decreases with the fineness, and their MgO, F and SO3 3.1. Mineral composition of ladle slag
contents slightly increase with the fineness of slag samples.
A commercial ASTM Type I Portland cement (PC) was XRD patterns of the three ladle slag samples are shown
used as reference cement. A ground pelletized blast furnace in Fig. 1. The identified minerals and their quantity are
slag (BFS) was used to blend with ladle slag to make a summarized in Table 3, which include C 3 S, b-C 2 S,
blended cement. Their chemical composition and some 54CaOMgOAl2O316SiO2, 11CaO7Al2O3CaF2, g-C2S,
physical properties are show in Table 2. Chemical reagent 3CaOMgO3SiO2, CaMg(CO3)2, CaF2 and Ca(OH)2. The
Na2SiO3 was used a chemical activator to activate the three slag samples have very similar XRD patterns and
potential cementitious property of the ladle slag. g-C2S is the major phase in all three samples. The only
difference is that LS200 sample contains more C3S and
2.2. Powder X-ray diffraction (XRD) analysis of ladle 54CaOMgOAl 2 O 3 16SiO 2 than samples LS100 and
slag fines LS325. 54CaOMgOAl2O316SiO2 and C3S have the same
structure but in the former compound where two moles of
Ladle slag fines were ground to powder with a manual SiO2 are replaced by one mole of MgO and one mole of
mortar for Powder XRD analysis using a Philips PW 1139 Al2O3, respectively.
Diffractometer. Minerals in ladle slag were identified by a Although free CaO is always present in ladle slag, it could
computer from the characteristic peak database of the not be clearly identified by XRD here. This may be due to
Powder Diffraction File of the Joint Committee on Powder the content of CaO, which is not sensitive to XRD. However,
Diffraction Standards. Ca(OH)2 was identified in all the three samples.

Table 2
Chemical composition (mass %) and some physical properties of Portland cement (PC) and blast furnace slag (BFS)
Item SiO2 Al2O3 Fe2O3 CaO MgO SO3 Na2O K2O LOI Total Density (kg/m3) Blaine fineness (m2/kg)
PC 20.7 3.7 3.0 62.9 4.2 2.6 0.1 0.6 0.3 98.1 3140 340
BFS 35.3 9.9 0.6 34.7 14.6 4.0 0.3 0.4 0 99.8 2920 495
 C. Shi / Cement and Concrete Research 32 (2002) 459–462 461

Fig. 1. XRD patterns of ladle slag samples.

Based on the chemical analysis in Table 1, C2S should be tities are very small, it can be expected that the cementitious
the major mineral in the ladle slag. b-C2S exists at tempera- property of these ladle slag fines is very weak under normal
tures over 1000 C. Since the molten ladle slag was poured hydration conditions.
onto ground and cooled down slowly, b-C2S converts to
g-C2S when the temperature drops down about 960 C. 3.2. Cementitious property of ladle slag in the presence of
Since b-C2S and g-C2S have different crystal structure and chemical activators
density, the conversion of b-C2S to g-C2S is accompanied
by an increase in volume of nearly 10% and results in the When ladle slag fines are mixed with water, they exhibit
shattering of the crystals into dust. little cementitious property. Fig. 2 shows the mortar strength
Among the identified minerals, only C3S, b-C2S and
54CaOMgOAl2O316SiO2 can exhibit cementitious prop-
erty under normal hydration conditions. However, their quan-

Table 3
Identified minerals in ladle slag fines
Quantity of minerals in ladle slag fines
No. Mineral compound LS100 LS200 LS325
1 3CaOSiO2 minor minor minor
2 b-2CaOSiO2 minor trace trace
3 54CaOMgOAl2O3 trace minor trace
16SiO2
4 11CaO7Al2O3CaF2 trace trace trace
5 g-2CaOSiO2 major major major
6 3CaOMgO3SiO2 trace trace trace
7 CaMg(CO3)2 trace trace trace
8 CaF2 trace trace trace
9 Ca(OH)2 trace trace trace Fig. 2. Strength development of ladle slag-based cement mortars.
462 C. Shi / Cement and Concrete Research 32 (2002) 459–462

has a low early strength but a high later strength. Activation

of b-C2S can significantly increase its early strength and does
not show an obvious effect on later strength. g-C2S shows
little cementing properties itself. The activation of g-C2 S
increases its early and later strength significantly, however,
its strength is still lower than that of the activated b-C2S.

4. Conclusions

The major mineral in ladle slag fines is g-C2S regardless

of their fineness. The other identified minerals include C3S,
b-C2S, 54CaOMgOAl2O316SiO2, 11CaO7Al2O3CaF2,
g-C2S, 3CaOMgO3SiO2, CaMg(CO3)2, CaF2 and Ca(OH)2.
Since the quantity of cementitious minerals such as C3S,
Fig. 3. Effect of chemical activator on strength development of b-C2S and b-C2S, and 54CaOMgOAl2O316SiO2 is very limited, the
g-C2S minerals[6]. cementitious property of ladle slag fines is very weak under
normal hydration conditions. Ladle slag fines show sig-
nificant cementitious property in the presence of a chemical
of ladle slag based cementing materials with ground blast
activator at room temperature. The potential cementitious
furnace slag and a chemical activator cured at room tempera-
property of ladle slag fines significantly increases with
ture. Blast furnace slag itself exhibits very high strength
their fineness regardless of some differences in their min-
under the action of proper chemical activators [5]. One
eral composition.
obvious feature of these results is that the strength increases
with the fineness of ladle slag. Although, there are some
differences in mineral composition of these sample, for
References
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