Optimization of Mineralogy and Microstructure

of Solidified Basic Oxygen Furnace Slag Through

SiO2 Addition or Atmosphere Control During
Hot-Stage Slag Treatment
CHUNWEI LIU, SHUIGEN HUANG, BART BLANPAIN, and MUXING GUO

Valorization of basic oxygen furnace (BOF) slag is of significant importance for mitigation of
the steel production’s environmental impact. The present work aims to investigate the influence
of SiO2 addition and oxygen partial pressure on the mineralogical modification of a typical
industrial BOF slag. The slag basicity (mass ratio of CaO/SiO2) was varied from 1.8 to 4.4 by
mixing specific amounts of SiO2 with the master BOF slag. The original and modified slags were
remelted and solidified under argon or air atmosphere followed by slow cooling. The
experimental observations were then compared with the results of thermodynamic modeling to
achieve a thorough understanding. With decreasing the basicity, free lime was eliminated, as it
forms dicalcium silicate (Ca2SiO4). With increasing oxygen partial pressure, wustite was
oxidized to hematite, which combined with free lime to form calcium aluminoferrite (C2AF).
The effects of SiO2 addition and oxygen partial pressure were finally evaluated with respect to
the energy consumption for the BOF slag valorization. The modified slag is suitable as a
precursor for construction applications as binders.

https://doi.org/10.1007/s11663-018-1444-z
Ó The Minerals, Metals & Materials Society and ASM International 2018

I. INTRODUCTION In the past decades, metallurgical slag valorization

has been intensively explored to apply the slag in various
STEEL slag, generated during the steelmaking pro- fields, such as landfill liner,[4,5] hydraulic binder,[6–8] and
cess, is a main by-product in the steel industry. fertilizer.[9] Among these, hydraulic binders that can be
Depending on the steel grade, 100- to 150-kg slag is used for constructional application appear to be more
discharged for producing 1 tonne of steel.[1] About 20 interesting, as they create higher value. However,
million tonnes of steel slag are produced annually in application of BOF slag for constructional materials is
Europe,[2] of which basic oxygen furnace (BOF) slag limited by its volume expansion during natural
accounts for almost half of the volume.[3] Storage of the aging.[10–12] This dimensional instability is induced by
huge amount of slag burdens the environment and is an the hydration of free lime and free magnesia in the
economic liability to the steel industry. Recycling and slag.[11] During the hydration, free lime and magnesia
reuse of slags toward added-value applications are, exhibit around 10 pct swelling,[13] leading to the disin-
therefore, of significant importance for the sustainability tegration of bulk slags. Typically, the lime content in the
of the steel industry. BOF slag is markedly higher than that of magnesia;
thus, lime is the main concern for volume instability.[10]
Recent research addressed that 4 wt pct free lime in
BOF slag is the limit for applying the slag as a
construction material.[10] Different methods have been
investigated to stabilize free lime in BOF slag, among
CHUNWEI LIU is with the Department of Materials Engineering, which SiO2 and Al2O3 were reported as effective
KU Leuven, 3000 Leuven, Belgium, and also with the National additions to eliminate the free lime.[14,15] The addition
Engineering Laboratory for Hydrometallurgical Cleaner Production
Technology, Institute of Process Engineering, Chinese Academy of of SiO2 results in more silicate after solidification, which
Sciences, 1 North 2nd Street, Zhongguancun, Haidian District, Beijing accommodates the extra CaO and, therefore, eliminates
100190, P.R. China. Contact e-mail: [email protected] the free lime, while the addition of Al2O3 produces more
SHUIGEN HUANG, BART BLANPAIN, and MUXING GUO C2AF as it combines with free lime.[14] Also, Gautier
are with the Department of Materials Engineering, KU Leuven,
Kasteelpark Arenberg 44, Box 2450, 3001 Leuven, Belgium.
et al. studied the effect of the cooling method on slag
Manuscript submitted July 18, 2017. microstructure and mineralogy in air and found that the
free lime content was decreased in the solidified slag.[16]

METALLURGICAL AND MATERIALS TRANSACTIONS B

The elimination of free lime was tentatively attributed to (15-mm inner diameter, 40-mm height) and melted in a
the suppression of the decomposition of tricalcium graphite heating furnace [W100/150-2200-50 LAX, FCT
silicate by rapid cooling. Additionally, hot-stage car- Systeme (Rauenstein, Germany)] under vacuum atmo-
bonation of the free lime has been investigated in recent sphere at 1873 K (1600 °C) for 1 hour to homogenize
years.[3,11,17] The mechanism is to stabilize the free lime the slag composition; afterward, the slag was cooled to
by forming geochemically stable calcium carbonate. room temperature inside the furnace at a cooling rate of
However, size reduction of BOF slag is needed to 5 K min1.
perform an effective carbonation, which inhibits the To study the effect of oxygen partial pressure, 20 g of
application of this method.[11,17] From previous studies, master slag were loaded in MgO crucibles (32-mm inner
the following can be concluded: (1) recycling BOF slag diameter, 70-mm height). For the tests under Ar, the
has high value-added application, but it is limited due to sample was placed in a vertical tube furnace [HTRV
the presence of free lime; (2) SiO2 addition effectively 100-250/18, GERO (Germany)] under Mg-purified Ar
combines with free lime, yet quantitative knowledge on atmosphere with a flow rate of 0.4 L min1. After
the mineralogical evolution is needed; and (3) although maintaining at 1673 K (1400 °C) for 1 hour, the slag
a previous study provided evidence that an oxidizing was cooled to room temperature in the furnace at
atmosphere may facilitate a ferrite to combine with free 5 K min1. The oxygen partial pressure was measured
lime, the underlying mechanisms remain unclear. by an oxygen sensor [Rapidox 2100, Cambridge Sen-
The present study aims to provide a fundamental sotec (United Kingdom)] and was maintained below
understanding of the effects of SiO2 addition and oxygen 1018 atm. For the tests in air, the slag was melted at
partial pressure on BOF slag microstructure and 1673 K (1400 °C) for 1 hour in a bottom loading
minerology after solidification, targeting a quantitative furnace (AGNI-ELT 160-02, Spring type) and then
and effective control of the slag product that is cooled to room temperature in the furnace at
microstructurally and mineralogically tailored to 5 K min1.
achieve better hydraulic properties. Experiments were
carried out to assess the influence of basicity by mixing
B. Characterization of the Slag Samples
specific amounts of SiO2 with the master BOF slag.
Also, the original and modified BOF slags were remelted The slag specimens were mounted in a low viscosity
and solidified under argon or air atmosphere followed resin (Epofix), ground by silicon carbide papers, and
by slow cooling. Experimental results were compared polished with diamond paste. The polished specimens
with the thermodynamic calculation using FactSage to
explain the phase formation. Thereafter, the promising
methods were evaluated from the perspective of energy *JEOL is a trademark of Japan Electron Optics Ltd., Tokyo.
consumption. The findings of this work suggest an
approach to optimize the microstructure/mineralogy of were coated with carbon for compositional and
the solidified slag through hot-stage slag engineering, microstructural analysis, which was achieved by electron
providing a precursor for construction applications as probe microanalysis (FE-EPMA, JXA-8530F, JEOL*)
binders. equipped with wavelength dispersive spectroscopy
(WDS) that allows fully quantitative chemical compo-
sition analysis. The beam current and accelerating
II. EXPERIMENTS AND THERMODYNAMIC voltage were set as 15 nA and 15 kV, respectively. After
MODELING crushing the slags to powder with size below 100 lm,
X-ray fluorescence (XRF, Panalytical PW 2400) was
A. Materials Preparation and Experimental Procedure used to measure the composition while X-ray diffraction
A typical BOF slag was used as the starting material, [XRD, 3003-TT, Seifert (Ahrensburg, Germany)] was
which was sampled from a slag yard at different used to identify the minerals. Quantitative analysis of
locations and depth from the surface. The slag was then the XRD pattern was achieved with the aid of the
mixed, ground, and milled to powder below 200 lm. Rietveld refinement method.
The typical chemical composition and mineral constitu-
tion of the BOF slag are listed in Tables I and II, C. Thermodynamic Modeling
respectively. The basicity (mass ratio of CaO to SiO2) of
the master slag is 4.4. Thermodynamic modeling of the phase evolution
To investigate the effect of basicity on the solidifica- during solidification was performed by using FactSage
tion microstructure and mineralogy, 100 g of master 7.0 associated with FactPS and FToxid databases. The
slag was individually mixed with 5, 10, and 15 g of SiO2 FactSage software has been successfully used in mod-
in ethanol for 24 hours by using a multidirectional mixer eling the slag system in recent years.[18–21] Experimental
(Turbula type). The mixtures were dried in a rotating observation was integrated with the simulation to
evaporator at 338 K (65 °C). Ten grams of the mixture understand the effect of oxygen partial pressure on the
with different basicity were loaded in a MgO crucible BOF slag mineralogy.

METALLURGICAL AND MATERIALS TRANSACTIONS B

 Table I. Chemical Composition of the Master Slag (Weight Percent)

CaO TÆFe* SiO2 MnO MgO Al2O3 P2O5 TiO2 Basicity

44.54 23.59 10.14 4.78 2.18 2.05 2.43 0.89 4.4
*Fe is given as the total iron, measured by XRF (Panalytical PW 2400).

Table II. Mineral Composition of the Master Slag

Mineral Phase Free Lime Monoxide Aluminateferrite Beta Dicalcium Silicate Magnetite
Chemical Formula CaO RO (FeO-MgO-MnO) 2CaOÆ(Al, Fe)2O3 b-C2S (Ca2SiO4) Fe3O4
Wt pct 18 5 32.3 29.4 15.3

was less than the critical limit (4 wt pct) for the slag
application as construction materials,[10] while in the
slags with basicity of 2.4 and 1.8, free lime is eliminated
completely. In contrast, the content of C2AF phase is
decreased with the addition of SiO2 due to the strong
affinity of SiO2 with CaO at high temperature. In the
slag with a basicity of 1.8, bredigite (formula
Ca1.75Mg0.25SiO4; in short, CMS) indicated by the
dashed line becomes a major phase, and accordingly,
b-C2S phase is decreased drastically compared to other
minerals. Chemical reactions of the free lime stabiliza-
tion and bredigite formation are, respectively, given in
Reactions [1] and [2]. According to the mass balance
calculation with Reaction [1], 0.54 wt pct SiO2 is con-
sumed to stabilize 1 wt pct free lime. Thus, stabilization
of 20 wt pct free lime in the present study consumes
10.7 wt pct SiO2. In practice, however, the actual
consumption of SiO2 should be less than 10.7 wt pct
Fig. 1—Quantitative XRD analysis of mineral content in the slag
treated at 1873 K (1600 °C) for 1 h and cooled at 5 K min1 in Ar.
because CaO can also react with FeO, MnO, and MgO
and form RO. For this reason, free lime was completely
eliminated even in the test with 10 wt pct SiO2 addition
III. RESULTS AND DISCUSSION (basicity of 2.4).
A. Influence of SiO2 Addition 2CaO þ SiO2 ¼ Ca2 SiO4 ½1
Figure 1 presents the quantitative XRD analysis of
the slags with different SiO2 additions treated at 1873 K
(1600 °C) under Ar atmosphere by means of Rietveld 1:75CaO þ SiO2 þ 0:25MgO ¼ Ca1:75 Mg0:25 SiO4 ½2
refinement. The major phases in these slags were calcium
aluminoferrite, beta dicalcium silicate (b-C2S), wustite- To have a quantitative understanding of the chemical
based solid solution (RO), and free lime (formula CaO). composition of each phase, the microstructure of the
The formula of calcium aluminoferrite is Ca2(Alx solidified slag was analyzed using EPMA-WDS.
Fe1–x)2O5 (in short, C2AF), with x in the range of 0 to Figure 2 shows the typical microstructures of the slags
0.7.[22] There is free lime of 20 wt pct detected in the with different SiO2 additions. The microstructure of the
master slag with a basicity of 4.4. With SiO2 addition of original slag is shown in Figure 2(a). WDS analysis
5, 10, and 15 wt pct, the basicity was accordingly confirms that free lime is a CaO-based solid solution
decreased to 2.8, 2.4, and 1.8, respectively. It should that also incorporates FeO, MgO, and MnO in Ar. The
be noted that FeO is more basic than Fe2O3 and Fe3O4, typical CaO content in the lime phase is above
and Fe2O3 can react with free lime to form CaO-FeO 68 wt pct. b-C2S crystal can be observed and constitutes
solid solutions. In the high basicity slag (basicity of 4.4), one of the major phases in the slags, except for the one
FeO might be dominant in RO, while Fe2O3 and Fe3O4 with a basicity of 1.8 (Figure 2(d)). WDS analysis
might be dominant in RO in the relatively lower basicity suggests that the b-C2S phase is typically associated with
slag. The content of free lime was significantly lowered P2O5 (> 2 wt pct), forming a solid solution of Ca2SiO4-
with the decrease of basicity, as indicated by the solid Ca3PO4 (in short, C2S-C3P).[23–25] It has been reported
line in Figure 1. In the slags with basicity of 2.8, the that [PO4]3– acts as a substitution of [SiO4]4 anion
content of free lime was decreased to 1.9 wt pct, which groups in the C2S-C3P solid solution.[23] According to

METALLURGICAL AND MATERIALS TRANSACTIONS B

Fig. 2—Microstructures of slags treated at 1873 K (1600 °C) for 1 h and cooled at 5 K min1 in Ar: (a) R = 4.4 (matrix slag), (b) R = 2.8, (c)
R = 2.4, and (d) R = 1.8.

previous studies, incorporation of 0.5 wt pct P2O5 can bredigite. Free MgO can cause slag instability by its
stabilize b-C2S, and this phase is crucial to prepare hydration; thus, it is preferred to avoid free MgO for
Portland cement.[26,27] RO (a bright phase in Figure 2) is preparing binder materials.
another main phase in all the cases. The RO phase is a Based on the preceding findings, it is confirmed that
FeO-based solid solution with a typical FeO content free lime is effectively eliminated by forming C2S or
over 60 wt pct, and other oxides found in RO are MgO, CMS through SiO2 additions. In the current study, by
MnO, and CaO. This phase has also been reported by decreasing the basicity to 2.8, the free lime has been
other researchers.[10,28–30] It is noteworthy that two lowered to a level (1.9 wt pct) that satisfies the require-
typical morphologies of RO can be found: small ment of the volume stability for constructional applica-
(< 10 lm) grains dispersed in C2S-C3P and free lime tion. Decreasing the basicity to 1.8, however, leads to a
(indicated by circles in Figure 2) and larger (> 20 lm) precipitation of CMS phase with poor cementitious
RO grains that were separated from other phases. In the property. Therefore, to stabilize free lime and obtain a
slag with basicity of 1.8, a large amount of bredigite better cementitious property of the BOF slag, the slag
(CMS) was formed (Figure 2(d)). The chemical formula should be modified at hot stage toward a basicity
of CMS (Ca1.75Mg0.25SiO4) is close to the C2S ranging from 1.8 to 2.8.
(Ca2SiO4), with a few CaO substituted by MgO.
However, CMS has a distinct structure compared to
B. Influence of Oxygen Partial Pressure
the C2S, and the impurities in the slag, such as Mn, can
partially replace Mg.[31,32] It has been reported that the The original BOF slag was treated at 1673 K
bredigite reacts slowly with water, and the compressive (1400 °C) for 1 hour under a controlled atmosphere,
strength of lime-activated bredigite cubes is too low to followed by furnace cooling at 5 K min1. Figure 3(a)
be of use for a cementitious material.[32] Therefore, it shows the XRD patterns of the air- and Ar-treated slags.
should be avoided to generate CMS for using the slag as The characteristic 2h values of free lime are 37.34 and
a binder in constructional application. Furthermore, 53.86 deg using Cu Ka radiation. In this work, the 2h
both the mineralogical and microstructural analysis positions of free lime shifted to the diffraction angles of
show that no free MgO exists in the slag. WDS analysis 37.51 and 54.16 deg (dashed lines in Figure 3(a)). This is
confirms that Mg incorporates with RO and C2S phases probably due to the incorporation of MgO and FeO in
in the slags with R = 2.4, 2.8, and 4.4. In the case of the lime phase, which is commonly observed in BOF
R = 1.8, however, Mg concentrates in RO, C2S, and slag.[28] In the present study, 1.60 and 18.98 wt pct MgO

METALLURGICAL AND MATERIALS TRANSACTIONS B

Fig. 3—(a) XRD spectra of the slags treated under Ar (top) and air atmosphere (bottom). Dashed lines represent the characteristic position of
free lime. (b) Comparison of the minerals in the air-treated and Ar-treated slags, as quantified by Rietveld refinement of XRD spectra.

Fig. 4—Microstructures of the master slag treated under (a) air and (b) Ar atmosphere. Green circles represent the dispersed RO in lime matrix.
The yellow rectangles represent local magnification. (1) C2AF, (2) b-C2S, (3) RO (the shining points), (4) CaO (the gray matrix), and (5) MgO
(the black matrix). Scale bar is 10 lm (Color figure online).

and FeO were identified in the lime phase. The inter- solutions. In the air-treated slag, only small RO grains
planar distances of MgO and FeO are relatively smaller are observed and those grains are dispersed in the
than that of CaO so that the peaks shift to larger 2h periclase, as shown in Figure 4(a). The RO phase in the
positions.[33] Free lime was detected in the Ar-treated Ar-treated slag, as shown in Figure 4(b), appears in two
slag but was eliminated completely in the air-treated different morphologies, e.g., big RO grains as a sepa-
slag. The other major phases, i.e., C2AF, b-C2S, and RO rated crystal and tiny grains dispersed inside the lime
are observed in both the Ar- and air-treated slags. solid solution (indicated by the circles in Figure 4(b)).
Quantitative analysis of the mineralogical composition To provide a better understanding of the precipitation
was achieved by using the Rietveld refinement method, of FeOx from lime-rich CaO-FeOx solid solution, the
and the result is shown in Figure 3(b). The predominant phase diagram of the CaO-FeOx system in contact with
phase in the Ar-treated slag is b-C2S (> 40 wt pct). iron is shown in Figure 5, as calculated by FactSage.
However, C2AF becomes the predominant phase The phase diagram is mainly based on the work of Allen
(> 65 wt pct) in the air-treated slag. Consequently, the and Snow,[34] Abbattista et al.,[35] and Schürmann and
amount of RO and b-C2S phases in the air-treated slag is Kraume.[36] The system is under a low oxygen partial
considerably lower than in the Ar-treated slag. Addi- pressure that is comparable to the present study. The
tionally, 3.8 wt pct MgO was found in the air-treated maximum solubility of FeOx in the lime solid solution is
slag. 12 wt pct when the system is equilibrated at 1403 K
The microstructure of the air- and Ar-treated slag is (1130 °C).[37] WDS analysis indicates that 19 wt pct
shown in Figure 4. The size of C2AF crystal is much FeOx was incorporated in the overall lime phase,
larger in the air treatment condition. The WDS analysis resulting in the precipitation of FeOx (RO). According
confirms that the free lime, RO, and periclase are solid to Figure 5, FeOx precipitates from the lime-rich

METALLURGICAL AND MATERIALS TRANSACTIONS B

CaO-FeOx solid solution in the temperature range of crystal precipitation sequence. C2S is the first crystal
1403 K to 1333 K (1130 °C to 1060 °C). The periclase is precipitated in the air-treated slag (at 1878 K), followed
a MgO-based solid solution with a typical MgO content by C3S (at 1708 K) and C2AF (at 1638 K). In the
over 70 wt pct. WDS results indicate that the overall Ar-treated slag, however, CaO will first precipitate at
MgO content in the slag treated in air is higher than that 1963 K, followed by C3S (at 1773 K), MgO (1713 K),
in Ar (5.61 to 3.79 wt pct), implying a slight dissolution and C2S (1625 K), respectively. Durinck et al. have
of the MgO crucible into the air-treated slag. This is reported on the influence of the oxygen partial pressure
probably due to the increase of Fe2O3 (oxidation of FeO on the crystallization sequence in the EAF slag[38] and
under air treatment condition), which behaves as an found that the C2S precipitation temperature in air-
acidic substance and facilitates the dissolution of MgO. cooled slag is higher than that in Ar-cooled slag. In the
In industrial practice, there will be less MgO pickup present work, above 1773 K, 23.1 wt pct C2S is gener-
because of the lower surface-to-volume ratio and ated in the air-treated slag, but no C2S precipitated from
relatively short duration of the treatment. the slag melted in Ar until 1625 K. According to the
Figures 6(a) and (b) present the phase evolution, calculation, a large amount of free lime is formed by the
respectively, for air- and Ar-treated slags, as predicted decomposition of C3S between 1673 K (1400 °C) and
by FactSage equilibrium calculations. The C2S trans- 1573 K (1300 °C), as expressed by Reaction [3]:
forms from b to c type in the FactSage calculation since
the stabilization of b-C2S by phosphorus is not consid- Ca3 SiO5 ¼ CaO þ Ca2 SiO4 : ½3
ered. To avoid such a discrepancy, all the C2S is given in The amount of C3S generated in the air-treated slag is
the form of b-C2S in Figure 6. Figure 6(c) indicates that decreased markedly due to the decrease in basicity
the calculated quantities of major phases agree well with after the formation and precipitation of C2S; therefore,
the experimental results. According to the calculation, the CaO formed by C3S decomposition is also
the change of the oxygen partial pressure affects the decreased. Additionally, as indicated by the circles in
Figures 6(a) and (b), C2AF starts precipitating at a
much higher temperature in air [1643 K (1370 °C)]
than in Ar [1453 K (1180 °C)]. This means in the case
of slag treatment under air that C2AF has more time
to grow after its precipitation during cooling, which
explains the larger C2AF crystals observed in
Figure 4(b) than in Ar-treated slag. Also, the calcu-
lated amount of C2AF is much higher in air than in
Ar condition, which agrees with the experimental data.
The large amount of C2AF generated under air condi-
tion consumes more Ca2+ and contributes to the
removal of free lime in the slag. In addition, due to
the different contents of FeO in the slags, the melting
point decreased from 1533 K (1260 °C) of the air-
treated slag to 1328 K (1055 °C) of the Ar-treated
slag. This is in agreement with Bodsworth and Bell’s
results.[39] Notably, in the Ar-treated slag, FeO precipi-
tates from 1448 K (1175 °C) and finally increases to
17.1 wt pct of the total slag, whereas the formation of
Fig. 5—Phase diagram of CaO-FeOx system in contact with iron, as FeO in the air-treated slag is not significant due to the
calculated by FactSage. L—liquid; ss—solid solution. presence of oxygen.

Fig. 6—Phase evolution during solidification as calculated by FactSage under (a) air and (b) Ar atmosphere. (c) Comparison between the
experimental and calculated results.

METALLURGICAL AND MATERIALS TRANSACTIONS B

 The elimination of CaO, the decrease of the FeO 2.5 m, and height 3.5 m; (3) the treatment time is
content, and the concurrent increase in C2AF content 10 min; and (4) heat transfer during introduction of
for the air-treated slag can be better understood from additives or oxygen is neglected.
Reactions [4] and [5]. When the slag is heated in air,
Fe2+ in the slag (FeO) is oxidized to Fe3+ (Fe2O3), as 1. Energy consumed during the stabilization by lower-
expressed by Reaction [4]: ing the slag basicity (through SiO2 addition)
Stabilization of BOF slag by adding SiO2 can effec-
2FeO þ 0:5O2 ¼ Fe2 O3 ½4 tively decrease the basicity, as a subsequence to elimi-
Fe2O3 then reacts with CaO at around 1643 K nate free lime by forming C2S. As suggested in the
(1370 °C) to produce C2AF through Reaction [5] dur- present study, 5 wt pct SiO2 addition is sufficient to
ing the solidification process: stabilize the free lime. To stabilize 20-tonne slag, 1-tonne
SiO2 is injected for the treatment in 10 minutes. The
2CaO þ xAl2 O3 þ ð1xÞFe2 O3 ¼ Ca2 ðAlx ; Fe1x Þ2 O5 energy required for heating the SiO2 from 295 K to
½5 1873 K (°C to 1600 °C) can be calculated by Eq. [6]:

Due to the fact that FeO is more basic than Fe2O3, the Q1 ¼ CsPi  msi  DT; ½6
basicity of the air-treated slag is believed to be decreased where CsPi is the heat capacity of SiO2
after the oxidation. In addition, Fe2O3 consumes free (0.719 J g1 K1)[41] and msi is the mass of SiO2 (kg).
lime by Reaction [5] and the basicity can also be The enthalpy changed ðDH1600 C Þ by the formation of
decreased. Assuming that the contribution of Al2O3 in C2S through the reaction of CaO with SiO2 (Reaction
Reaction [5] was negligible and FeO can be oxidized [1]) is –1.76 9 104 J mol1, as calculated by FactSage.
completely during the treatment, stabilization of 1 mole The negative sign indicates that the reaction is
CaO consumes 1 mole FeO, i.e., stabilizing 1 wt pct exothermic.
CaO needs 1.28 wt pct FeO. Therefore, 25.6 wt pct FeO Thus, energy released during the reaction is
is needed to completely remove 20 wt pct of the free
lime in the original BOF slag. In the BOF slag, however, Q2 ¼ H1600 C  nSiO2 ; ½7
due to the presence of Al2O3 and Mn2O3 (respectively,
5.49 and 3.76 wt pct in our study), and the presence of where nSiO2 is the molar number of SiO2.
FeO in the lime phase, stabilization of 1 wt pct free lime The energy loss due to the radiation can be calculated
may require less than 1.28 wt pct FeO. by Eq. [8]:
To summarize, the high oxygen partial pressure at the Q3 ¼ E  S  t; ½8
hot-stage slag treatment is critical to eliminate free lime
and to decrease FeO by forming C2AF. The mechanism where S is the surface area of the slag pot (top and
is attributed to the oxidation of FeO to Fe2O3 in an inclined surface, m2); t is the processing time (seconds);
oxidizing atmosphere and formation of C2AF. The E = r Æ (T4 - 3004) is the radiation of the slag (W/
formation of C2AF consumes free lime and RO, leading m2),[42] where r= 5.67 9 108 W/(m2Æ K4) is the Ste-
to the elimination of free lime. It is concluded that no fan–Boltzmann constant[43]; and T is the absolute tem-
more than 1.28 wt pct FeO is needed to stabilize perature (Kelvin).
1 wt pct CaO in slags in an oxidizing atmosphere. The convective contribution to the heat loss is
Furthermore, the cementitious property of the slag is
expected to be enhanced by the replacement of poor-hy- Q4 ¼ a  S  t; ½9
draulic FeO and instable free lime by the C2AF.[40] where a ¼ 50W=ðm2  KÞ (as a first estimate) is the
convective coefficient of the air.[44]
C. Evaluation for Lime Stabilization of BOF Slag By substituting values of parameters into Eqs. [6]
with Respect to Energy Consumption through [9], the total energy exchangeQ during the slag
treatment is obtained:
The current BOF slag stabilization treatment lies in
the introduction of additives or increasing oxygen Q ¼ Q1 þ Q2 þ Q3 þ Q4 ¼ 1:79  1010 J ½10
partial pressure to remove the free CaO by different
reactions toward a stable matrix of calcium silicates or
calcium aluminoferrite. Based on the results we obtained 2. Energy consumed during the stabilization by oxidiz-
in the aforementioned sections, the effective stabilization ing the slag (through oxygen partial pressure control)
methods are evaluated with respect to energy consump- By increasing the oxygen partial pressure, the wustite
tion. The energy consumption during hot-stage engi- is oxidized to hematite and then stabilizes the free lime
neering is estimated under the following assumptions: by forming C2AF. Similarly, 20-tonne slag (with
(1) during treatment, the melt temperature is fixed at 15 wt pct FeO) is assumed to be charged in a slag pot
1873 K (1600 °C) (i.e., the energy needed to maintain at 1873 K (1600 °C). The energy required for heating
such a temperature during the treatment is calculated); the oxygen is negligible compared to other energy
(2) 20-tonne slag is charged to a slag pot at 1873 K consumptions. The enthalpy change during the oxida-
(1600 °C), which can be simplified to a circular trun- tion from FeO to Fe2O3 can be calculated by FactSage:
cated cone with upper diameter 3.5 m, lower diameter DH01600 C ¼ 1:46  105 J=mol: ½11

METALLURGICAL AND MATERIALS TRANSACTIONS B

 Therefore, the energy released during the oxidation stabilizing the slag. Finally, the methods of SiO2 or
can be calculated as oxidizing treatments were evaluated by comparing the
nFeO energy consumption during hot-stage engineering. The
Q01 ¼ DH01600 C  ; ½12 main conclusions are summarized as follows.
2
1. Free lime can be transformed to C2S or CMS by
where nFeO is the molar number of FeO. Due to the
lowering basicity through SiO2 addition. At the
Al2O3 content in the slag being much lower than that
basicity of 2.8, free lime can be controlled in a sat-
of FeO and Fe2O3, v = 0.1 is assumed in the Ca2(Alx,
isfied level to reuse the slag in constructional appli-
Fe1–x)2O5. Thus, the enthalpy change of Reaction [5]
cation. With too low basicity (R < 1.8 for current
can be calculated by FactSage:
case), however, a large amount of CMS with poor
DH001600 C ¼ 1:23  105 J=mol ½13 cementitious property is formed. Based on the results
of this work, an optimized basicity is suggested in the
Thereby, the energy change of stabilizing all the free range from 1.8 to 2.8.
lime becomes 2. Laboratory experiment and FactSage calculation
nCaO demonstrate that free lime can be removed during
Q02 ¼ DH1600 C  ½14 hot-stage treatment under a high oxygen partial
2
pressure condition. The reason is attributed to the
where nCaO is the molar number of the free lime. Con- fact that, under high oxygen partial pressure (‘‘air’’ in
sidering heat loss due to the radiation and convection, current study), FeO can be oxidized to Fe2O3 and
which can be estimated by Eqs. [8] and [9], respec- further consumes free lime to form C2AF. To elimi-
tively, the total energy change Q, in the slag stabiliza- nate free lime completely, the theoretical mass ratio
tion treatment can be calculated in Eq. [15]: of free lime to FeO should be less than 1.28, which is
satisfied in the as-delivered BOF slag.
Q0 ¼ Q01 þ Q02 þ Q3 þ Q4 ¼ 1:34  1010 J ½15 3. Energy efficiency for hot-stage slag stabilization by
Compared with SiO2 addition, energy consumption SiO2 addition and slag oxidation was evaluated. The
during the stabilization treatment by oxidizing slag calculation of energy consumption of the slag treat-
under high oxygen partial pressure is lower (1.34 9 1010 ment indicates that stabilization of the free lime
to 1.79 9 1010 J). To have a thorough evaluation, the through the slag oxidation is more energy effective. A
following aspects should also be considered. comprehensive understanding is still needed to fur-
ther evaluate the stabilization approaches, e.g., the
1. From the materials consumption point of view, effect of slag viscosity and temperature on the reac-
reducing the basicity of the BOF slag consumes SiO2 tion kinetics of the two methods: comparison of
(5 wt pct in the present study), while changing the volume stability and cementitious property of the
oxygen partial pressure consumes only air, so that slags stabilized by the two methods.
stabilization of the BOF slag by oxidation could be
more material effective.
2. In view of the practical operation, injection of SiO2
or air during hot-stage treatment may increase the
viscosity due to the temperature drop, as it subse- ACKNOWLEDGMENTS
quently interferes in the reaction kinetics and dete-
riorates the operation. The dependence of reaction Financial support from the Agency for Innovation
kinetics on the slag viscosity and temperature should by Science and Technology of Belgium (IWT, Grant
be further investigated, i.e., dissolution of SiO2 and No. 140514) is appreciated. One of the authors (CL)
reaction between SiO2 and free lime vs oxidation of acknowledges the support of the China Scholarship
FeOx and reaction between Fe2O3 and free lime. Council (CSC, Grant No. 201306080002).
3. SiO2 addition results in more C2S, while air atmo-
sphere generates more C2AF. Both C2S and C2AF
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