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Resources, Conservation & Recycling 136 (2018) 187–197

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Resources, Conservation & Recycling


journal homepage: www.elsevier.com/locate/resconrec

Review

Characteristics of steel slags and their use in cement and concrete—A review T
a a,⁎ a b
Yi Jiang , Tung-Chai Ling , Caijun Shi , Shu-Yuan Pan
a
Key Laboratory for Green & Advanced Civil Engineering Materials and Application Technology of Hunan Province, College of Civil Engineering, Hunan University,
Changsha 410082, Hunan, China
b
Carbon Cycle Research Center, National Taiwan University, Taipei 10672, Taiwan, ROC

A R T I C LE I N FO A B S T R A C T

Keywords: Steel slags are industrial by-products of steel manufacturing, characterized as highly calcareous, siliceous and
Steel slag ferrous. They can be categorized into basic oxygen furnace (BOF) slag, electric arc furnace (EAF) slag, and ladle
Waste recycling furnace (LF) slag. They are found to be useful in many fields, such as road construction, asphalt concrete,
Concrete properties agricultural fertilizer, and soil improvement. However, better utilization for value-added purposes in cement and
Aggregate replacement
concrete products can be achieved. In this paper, an overview of the recent achievements and challenges of using
Cement replacement
steel slags (BOF, EAF and LF slag) as cement replacement (usually ground into powder form with the size of
Cement production
400–500 m2/kg) and aggregate in cement concrete is presented. The results suggest that the cementitious ability
of all steel slags in concrete is low and requires activation. For the incorporation of steel slags as aggregate in
concrete, special attention needs to be paid due to the potential volumetric instability associated with the hy-
dration of free CaO and/or MgO in the slags. Studies have indicated that adequate aging/weathering and
treatments can enhance the hydrolyses of free-CaO and -MgO to mitigate the instability. Considering the en-
vironmental and economic aspects, steel slags are also considered to have a potential use as the raw meal in
cement clinker production.

1. Introduction upgrading since they usually encounter several technological barriers to


valorization such as volume instability (Pan et al., 2016). More than
Recently, the green supply chain (e.g., waste-to-resources) has been 400 million tons of steel slags have been deposited in China, with an
aggressively established in industrial parks around the world to realize annual accumulation rate of 100 million tons, leading to occupation of
a circular economy (Li et al., 2015). Steel slags, industrial by-products lands and potential pollution of water and soil due to the alkaline
of steel manufacturing, are annually produced in a huge quantity, leachates from steel slags (Mayes et al., 2008; Shi and Qian, 2000;
which should be considered as a green resource. Modern steels can be Zhang et al., 2011). Currently, steel slags can be recycled for internal
broadly categorized into four types, i.e., carbon, alloy, stainless and tool metallurgical purposes (Yi et al., 2012) or used in road construction
steels. Carbon steel is produced either in a basic oxygen furnace (BOF) (Pasetto and Baldo, 2010a,b, 2015, 2016), cement and concrete
or an electric arc furnace (EAF), and then refined in a ladle furnace (LF) (Carvalho et al., 2017; Yi et al., 2012), bituminous mixes (Skaf et al.,
to achieve a better quality. As for stainless steel, it can be produced in 2017), fertilizer (Yi et al., 2012) and soil improvement (Poh et al.,
an EAF, an LF, or an argon oxygen decarburization (AOD) furnace 2006). Several studies have also evaluated the feasibility of steel slags
(Iacobescu et al., 2016; Kriskova et al., 2012; Zhang and Xin, 2011). for CO2 mineralization (Pan et al., 2017; Yu and Wang, 2011) and water
During the manufacturing of carbon and stainless steels, a significant pollution control (Drizo et al., 2006). In the US, about 60.3% of the
amount of by-product steel-slag is produced, accounting for about total steel slag production is directly used as road base, while the re-
15–20 wt.% of the total steel output (Han et al., 2015; Shi, 2004). The mainder is used for asphaltic concrete (10.9%), fill (10.8%) and cement
compositions of the generated steel slags are highly variable and basi- clinker production (5.0%) (Ilyushechkin et al., 2012). In China, the
cally, they can be classified into BOF slag, EAF slag and LF slag. utilization ratio of steel slags is less than 30%, found in cement pro-
The annual production of steel slags is about 14 million tons in duction, chemical admixture for concrete, brick and block manu-
Japan (NSA, 2017), 21 million tons in Europe (Euroslag, 2012) and facturing (NDRC, 2014; Yi et al., 2012).
over a hundred million tons in China (Zhang et al., 2011). Compared Due to the high demand for cement and concrete production
with the widespread use of blast furnace slag, steel slags undergo less worldwide, the cement and concrete industries have an increasing


Corresponding author.
E-mail address: tcling@hnu.edu.cn (T.-C. Ling).

https://doi.org/10.1016/j.resconrec.2018.04.023
Received 21 December 2017; Received in revised form 22 April 2018; Accepted 29 April 2018
Available online 03 May 2018
0921-3449/ © 2018 Elsevier B.V. All rights reserved.
Y. Jiang et al. Resources, Conservation & Recycling 136 (2018) 187–197

oxygen flow is applied at supersonic speed through a lance to initiate


intense oxidation reactions at a temperature of 1600–1650 °C. Once the
desired chemical composition is achieved, the oxygen supply is stopped
and the slag, composed of the impurities combined with burnt lime or
dolomite, floats on top of the molten steel (Yildirim and Prezzi, 2011).
There are numerous available methods for cooling steel slags, in-
cluding natural air cooling, water spraying, air quenching, and shallow
box chilling (Shi, 2004). The cooling medium and cooling rate of the
above methods are quite different, thereby resulting in variable com-
positions, morphology, hydration properties and leaching character-
istics of the steel slag produced. Prior to valorization, steel slags may
also undergo metal recovery processes (e.g. crushing, screening and
magnetic separation) to recover valuable components such as iron
(Shen and Forssberg, 2003; Zhang et al., 2011).

2.2. Physico-chemical characteristics

The chemical compositions of BOF slag are highly variable because


of the diversity of iron ores, admixtures, steel-making methods and
cooling processes. Table 1 summarizes the chemical properties of BOF
slag used from the literature. BOF slag is composed mainly of 40–60%
CaO, 10-20% SiO2, 20–30% Fe2O3 (FeO/Fe), 1–6% Al2O3 and 2–10%
MgO and the remaining minor oxides are MnO, P2O5, Na2O, SO3, etc.
The presence of a high content of CaO and MgO in BOF slag is mainly
attributed to the high fluxes dosage for minimizing the impurities,
while the iron oxides come from the iron residue that was not reclaimed
Fig. 1. Schematic representation of a basic oxygen furnace process (Yildirim during the conversion of molten iron to steel (Geiseler, 1996; Yildirim
and Prezzi, 2011). and Prezzi, 2011).
BOF slag usually possesses relatively high basicity (ratio of alkaline
interest in finding alternative materials to replace the use of natural oxides to acidic oxides) and presents in different mineral phases, in-
resources. Thus, extensive studies have been carried out to explore the cluding tricalcium silicate (C3S), dicalcium silicate (C2S), dicalcium
possibility of utilizing steel slags as cement and concrete materials. ferrite (C2F), MgO, CaO and RO phase (CaO, MgO, MnO and FeO solid
Alternatively, they are involved in cement clinker production, which in solution) (Belhadj et al., 2012; Han et al., 2015; Wang et al., 2013a;
turn reduces CO2 emissions and the total cost of the materials used Yildirim and Prezzi, 2011). Shi and Qian (2000) reported that the
(Reddy et al., 2006). This paper provides a critical review of the va- content of lime (f-CaO) increases with the basicity of steel slag and thus
lorization of steel slags in cement, concrete and clinker production. The the f-CaO content in BOF slag could be as high as 10%. This is relatively
challenges and opportunities of using BOF, EAF and LF slags as sup- higher than that of other steel slags (Geiseler, 1996; Reddy et al., 2006).
plementary cementitious materials and/or aggregates in cement and The iron may exist in forms such as wustite and magnetite, compounds
concrete are illustrated. The use of steel slags for cement clinker pro- that have a negligible cementitious capability (Lizarazo-Marriaga et al.,
duction is also discussed. 2011).
BOF slag is a rock-like and dark (due to the high content of iron)
2. Basic oxygen furnace (BOF) slag material with an angular surface and cavernous inside (Fig. 2). Table 2
summarizes the physical properties of BOF slag used from the literature.
2.1. Generation processes It is found that the average specific gravity of the slag is around 3.4,
which is ∼30% higher than normal aggregate. It also possesses low
In China, BOF slag accounts for about 70% of the annual steel slag crushing value (i.e., high hardness) and contains highly porous struc-
production (Cheng and Yang, 2010). In the BOF process (Fig. 1), minor tures (Pang et al., 2015; Adegoloye et al., 2015).
steel scrap and a large amount of molten iron from ironmaking as well
as fluxes (lime/dolomite) are added into the furnace, and a 99% pure

Table 1
Chemical compositions of BOF slags (wt.%) used from the literature.
References Sources SiO2 Al2O3 Fe/FeO/Fe2O3 CaO MgO SO3 MnO P2O5 f-CaO Others LOI Treatment

Palankar et al. (2016) India 15.0 4.1 22.5 (Fe2O3) 41.5 6.2 0.1 – – 5.3 0.14(Na2O)/0.05(K2O) 0.25 Before weathering
Pang et al. (2016b) China 14.8 5.5 18.4 (Fe2O3) 46.7 6.3 – 2.8 1.7 7.5 – 3.04 –
Wang et al. (2013a) China 15.5 5.4 25.5 (Fe2O3) 38.6 7.7 0.2 1.9 1.6 – – – –
Liu et al. (2016) China 11.0 1.4 12.7 (Fe2O3)/12.7 41.4 8.6 – – – – – – Cooled by hot stuffy
(FeO) method
Li et al. (2013) China 18.9 2.9 8.9(Fe2O3)/ 40.0 5.4 0.9 2.8 1.3 – – – –
13.5(FeO)/1.22(Fe)
Lizarazo-Marriaga U.K. 11.5 2.3 27.3(Fe2O3) 37.4 9.3 0.3 3.7 1.3 – 0.37(TiO2)/0.03(Na2O)/ 3.12 Weathered
et al. (2011) 0.01(K2O)
Monshi and Asgarani Iran 10.4 2.0 21.0(Fe2O3) 56.4 1.7 – 2.5 – – 3.1(TiO2)/0.2(S)/2.4(V2O5)/ – Magnetic separated
(1999) 0.3(Na2O+K2O)

Remark: – means not detected or clarified, LOI = Loss on ignition. Hot stuffy, a heat pyrolytic pulverization technology.

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Y. Jiang et al. Resources, Conservation & Recycling 136 (2018) 187–197

Han et al. (2015), the hydration process of BOF slag can be divided into
five stages, which is similar to that of pure cement. In the initial hy-
dration period (0–1 h) of blended cement with BOF slag, the hydration
heat evolution rate and cumulative hydration heat increased with an
increase of slag substitution ratio (Fig. 3a and c). This is due to the low
reactivity of BOF slag which leads to the higher effective water to ce-
ment ratio and promotes the hydration of cement particles, whereas as
the hydration went on, both the hydration rate and cumulative hy-
dration heat decreased significantly (Fig. 3b and d). Compared to pure
cement, the addition of BOF slag lowered the calcium ion concentra-
tion, resulting in a prolonged dormant period and retardation of the
setting time. Hydration can be enhanced by elevated temperature,
which can be used to compensate the prolonged setting (Belhadj et al.,
2014; Han et al., 2015; Wang et al., 2012). Other studies reported that
the addition of alkalis such as NaOH solution or slaked lime can im-
Fig. 2. Basic oxygen furnace slag (Palankar et al., 2016).
prove and enhance the hydration of BOF slag powder as well (Cao and
Yang, 2015; Han et al., 2015; Wang et al., 2011; Zhao et al., 2016).

2.3. Use of BOF slag powder as supplementary cementitious materials


2.3.2. Workability and mechanical properties
The calcium silicate phases in BOF slag could provide potential In general, the addition of fine BOF slag as supplementary ce-
cementitious properties. However, the reactivity of C3S and β-C2S in mentitious material in blended cement is beneficial to the improvement
BOF slag is relatively low, probably due to the dense structure and large of workability (Diao et al., 2016; Wang et al., 2012). However, several
crystal size formed at a higher temperature (∼1600 °C). The presence studies have shown opposite results probably due to the different sur-
of non-hydraulic γ-C2S associated with the polymorphic transformation face roughness and particle size distributions of BOF slag (Roslan et al.,
from β-C2S under a slow cooling process also contributes to the low 2016; Guo et al., 2014). In this case, extra water may be needed to
reactivity of BOF slag (Cheng and Yang, 2010; Lizarazo-Marriaga et al., compensate for the reduction of workability. In general, no segregation
2011; Xu et al., 2004; Zhang et al., 2011). or bleeding was observed for blended cementitious material in-
Reddy et al. (2006) used a rapid cooling method (i.e., high-pressure corporating fine BOF slag.
water jets) and metallothermic reduction to accelerate the cooling rate The use of BOF slag powder as supplementary cementitious material
and reduce the FeO and P2O5, respectively. The mineralogical compo- directly impacts the compressive strength of concrete (Wang et al.,
sition of the treated slag was greatly changed, which enhanced the 2013a, 2013b). In Fig. 4, the strength of concrete is shown to decrease
cementitious properties (Reddy et al., 2006). Jiang et al. (2017) also as the substitution ratio of BOF slag increases, especially at a high
indicated that the quick cooling and slag oxidation largely enhanced the water-to-binder (W/B) ratio of 0.5 (Wang et al., 2013a). Therefore, the
stabilization effect of Fe3+ ions on C2S crystal structures, leading to the use of superplasticizer in blended cement is essential to maintain the
retention of α’-C2S phase in the slag samples. Additionally, BOF slag required compressive strength (Wang et al., 2013a). Sun (2003) found
modified by quicklime and iron tailings under high temperature was that, with the increase of the substitution ratio from 0% to 60%, the 3-
reported by Zhang et al. (2015). The contents of C2S and C3S in mod- day compressive strength of concrete significantly decreased from
ified slag were improved, while the FeO and MgO in RO phase were 100% to ∼28%. However, the increment of compressive strength from
transferred into Fe3O4 and MgFe2O4, respectively. 28 days to 90 days was about 34% for 50% steel slag concrete and only
Both the fineness and specific surface area of BOF slag exhibit sig- 6% for normal concrete (Fig. 5), giving an indication that BOF slag
nificant effects on mechanical properties and durability of blended ce- concrete may have a lower early-age strength but could undergo a
ment mortars. Wang et al. (2013b) found that the reactivity of BOF slag higher improvement in strength as it ages. The pore structure analysis is
powder at early and middle ages could be improved through mechan- in good agreement with the mechanical test results, showing that the
ical grinding. Several studies also indicated that the specific surface porosity of cement-slag paste at 3 days was higher than the control
area of steel slag should be controlled within 400–500 m2/kg to group (Fig. 6), but both the pore size distribution and porosity im-
maintain their cementitious properties in blended cement (Han et al., proved with age (Li and Chen, 2006; Wang and Yan, 2008). To achieve
2015; Li, 2003). comparable performance with that of normal concrete, Sun (2003) re-
commended the optimum percentage of BOF slag at about 10–20% of
2.3.1. Hydration reactions the binder mass.
Due to the dominant production and stock, the hydration char-
acteristics of BOF slag powder have been widely reported. According to

Table 2
Physical properties of BOF slags and other natural aggregates.
BOF slag Crushed Lime stone Gravel Sand
granite

Specific gravity 3.35–3.42 2.69 2.47–2.69 2.73 2.55–2.72


Water absorption 2.0–3.31 0.5 0.3–1.67 0.75 0.4–3.99
(%)
Crushing value (%) 21 24 – – –
Impact value (%) 16 21 – – –
Los-Angeles test (%) 11–18 20 24–25 18 –
References Chen and Wei (2016), Palankar et al. Chen and Wei (2016), Liu et al. (2011), Pellegrino et al. Palankar et al. (2016), Pang et al.
Palankar et al. (2016) and (2016) Maslehuddin et al. (2003), Qasrawi (2014) (2013) (2016a), Pellegrino et al. (2013) and
Pang et al. (2016a) and Sezer and Gülderen (2015) Qasrawi (2014)

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Y. Jiang et al. Resources, Conservation & Recycling 136 (2018) 187–197

Fig. 3. Hydration heat evolution rate of blended cement containing steel slag at 25 °C (a) the first peak and (b) hydration within 168 h. Cumulative hydration heat of
blended cement containing steel slag at 25 °C (c) the initial hydration time and (d) hydration within 168 h.
Adapted from Han et al. (2015) with permission from Elsevier.

2.3.3. Durability also enhanced the connectivity of pores, and 2) at constant 28 days’
By replacing part of the cement with BOF slag powder, it is found to compressive strength, the concrete with BOF slag could achieve sa-
increase chloride ion penetration of concrete. Wang et al. (2013a) ob- tisfactory permeability similar to that of pure cement concrete by de-
served that 1) at the same W/B ratio, the chloride ion penetration of creasing the W/B ratio. In contrast, Fei et al. (2016) found a positive
concrete with BOF powder was higher than that of pure cement con- effect on chloride impermeability by a composite admixture containing
crete, even though their compressive strength after 90 days was similar, BOF slag powder and ground granulated blast furnace slag (GGBFS).
and it was probable that BOF slag not only induced high porosity, but The chloride diffusion coefficients of concrete with 30%–50%

Fig. 4. (a) Compressive strength of concrete with W/B of 0.5 and (b) Compressive strength of concrete with W/B of 0.35 (Wang et al., 2013a).

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Y. Jiang et al. Resources, Conservation & Recycling 136 (2018) 187–197

Fig. 5. The strength development of concrete with an increasing replacement


ratio of steel slag (Sun, 2003).

Fig. 7. Carbonation depth of the concrete with 3 days’ initial standard curing
composite admixture were decreased by 10%–40% at different ages. (Wang et al., 2013a).
The minimum value of chloride diffusion coefficient was recorded for
concrete with 30% GGBFS and 20% BOF slag composite powder at the 2.4. Use of BOF slag as aggregates in concrete
age of 120 days. Fei et al. (2016) attributed the positive effect to two
reasons. First, a secondary hydration reaction occurs between the In general, concrete with BOF slag aggregate was found to have
amorphous SiO2 in mineral admixtures and the calcium hydroxide (CH) poor workability (Pang et al., 2015; Qasrawi, 2014; Wang et al., 2015).
generated after the hydration of cement, which improves the pore In some cases, the slump could decrease by up to 80% when natural
structure and the interfacial transition zone. Second, the secondary coarse aggregate was fully replaced by BOF slag (Qasrawi, 2014). This
hydration reaction generates more calcium silicate hydrate (C–S–H) gel is attributed to the increase in water demand and the angular shape of
with relatively low alkalinity, which can better solidify chloride ions. steel slag particles, which decrease the flowability of concrete (Qasrawi,
A similar conclusion in terms of resistance to the diffusion of CO2 2014). A significant reduction of workability was observed at a lower
has been drawn by Wang et al. (2013a). As shown in Fig. 7, the car- W/B ratio or when using a smaller particle size of steel slag (Pang et al.,
bonation depth increases significantly with the increasing BOF re- 2015; Wang et al., 2015). Rapid slump loss with time and a fast setting
placement fraction. This is due to the deterioration of the pore structure time were also found in the work of Wang et al. (2015), imposing a
of concrete, whereas the deterioration can be reduced by increasing the negative influence on the transportation of slag aggregate concrete. It is
curing time and lowering the W/B ratio. Several studies (Wang et al., noteworthy that in previous studies (Pang et al., 2015; Sezer and
2016; Zhang et al., 2012) also indicated that drying shrinkage caused Gülderen, 2015), bleeding and segregation also were observed when
by the loss of moisture is likely to be related to the porosity of concrete. BOF slag was used to fully replace both coarse and fine aggregate in the
The loss rate of the moisture of BOF slag concrete is faster due to the concrete mix.
greater porosity. As a result, the amount of drying shrinkage increases As mentioned earlier, BOF slag can possess up to 10% f-CaO, and the
with higher proportions of BOF slag in the mixture. However, the ad- hydration of f-CaO can increase the volume expansion by 98%, re-
dition of fly ash (Zhang et al., 2012) or high-alumina cement (Wu et al., sulting in a higher internal pressure and thus damage to the concrete.
1999) may help to mitigate the shrinkage issue. Free MgO (f-MgO) is another unstable factor in the slag, potentially
Li et al. (2009) assessed the effectiveness of BOF slag powder in causing a 148% increase in volume. However, when comparing with f-
suppressing the alkali-aggregate reaction (AAR) expansion by means of CaO, the soundness issue associated with the presence of f-MgO is less
the ASTM C441 test and accelerated mortar bar test. They concluded significant due to the slow hydration rate (Wang et al., 2017).
that the combined use of BOF slag powder and GGBFS is an effective Several studies have reported that natural weathering is an effective
way to control the AAR expansion with capability to reduce the ex- approach to mitigating the volume expansion of BOF slag (Adegoloye
pansion rate by 50%. et al., 2016; Pellegrino et al., 2013). The content of f-CaO was reduced

Fig. 6. Pore size distribution of hardened paste with (S0) pure cement and (S1) 55% cement and 45% steel slag powder at 3 days with the common W/B ratio of 0.42
(Wang and Yan, 2008).

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Y. Jiang et al. Resources, Conservation & Recycling 136 (2018) 187–197

Fig. 8. Images showing the deterioration of steel slag ag-


gregate in the concrete mixes. (a) Cube sample after aggregate
undergoes expansion leading to pop-out of surface, (b) Pop-out
of the surface due to internal pressure exerted by the ag-
gregate, (c) Loss of cover due to expansion of the aggregate
and exposure of white paste-like formation, (d) Image showing
deteriorated steel slag aggregate (Palankar et al., 2016).

from 5.33% to 0.16% after weathering and spraying water at regular presence of BOF slag in clinker manufacturing processes permits a
intervals for nine months (Palankar et al., 2016). Other available lower firing temperature and conserves natural resources (Geiseler,
methods for controlling the f-CaO content in slag include water 1996). It was found that the magnetic separated BOF slag with low MgO
quenching (Reddy et al., 2006), slag oxidation and air cooling (Jiang and alkali contents should be used as clinker raw materials along with
et al., 2017), hot stuffy (Huang et al., 2016; Zhao et al., 2016), the blast furnace slag and lime stone. Blended cement made with 6% BOF
modified free lime slaking procedure (Belhadj et al., 2014), attrition slag, 37% iron slag, 57% limestone and 3% gypsum exhibited sa-
and chelation (Ding et al., 2017) and accelerated carbonation (Pan tisfactory performance, as compared with ordinary Portland cement
et al., 2012). The f-CaO content of carbonated BOF slag aggregate was (Monshi and Asgarani, 1999).
found to decrease from about 7 wt.% to less than 1 wt.% after 3 h of
accelerated carbonation. The performance of concrete prepared with 3. Electric arc furnace (EAF) slag
carbonated BOF slag as aggregate can be greatly improved, in terms of
pore structure, mechanical strength, and freezing-thawing resistance 3.1. Generation processes
(Pang et al., 2015, 2016a). Carbonation of BOF slag aggregate can
slightly improve the compressive strength of concrete, probably due to EAF slag is the steel-making slag generated from the EAF. It is re-
the stronger interfacial transition zone between the cement matrix and ported that the EAF process is dominating the steel industry of the US
the aggregate. The presence of a calcite layer covering carbonated BOF with a 55% share of the total steel output in 2006. An EAF is different
slag can also degrade the resistance of sulfuric acid attack (see Fig. 8) from a BOF, for example, in the way of energy supply where the former
(Palankar et al., 2016). For steel slags, carbonation is an interesting uses high-power electric arcs instead of gaseous fuels (as shown in
topic. The high calcium content and alkalinity would favor the se- Fig. 9). Also, steel scrap has become the major feed material in the EAF
questration of CO2 and it will subsequently change the chemistry and process together with limited iron scrap, pig iron and direct reduced
properties of steel slags (Huijgen et al., 2005; Salman et al., 2014c). To iron rather than a large amount of melted iron (Shi, 2004; Yildirim and
promote the development of sustainable industrial solutions that con- Prezzi, 2011). During the melting process, optional metals are also
vert CO2 into valuable products, new associations, for example CO2 added to obtain the desired chemical composition, and oxygen is blown
Value Europe, were established globally which may boost the carbo- to oxidize the impurities and purify the steel. Two types of steel slags
nation industry and the carbonated steel slag products (Euractiv, 2017). can be generated accordingly in the EAF process, including (i) EAF-C
slag from carbon steel production, and (ii) EAF-S slag from stainless
2.5. Use of BOF slag for cement clinker production steel production (Euroslag, 2017; Shi, 2004; Yildirim and Prezzi, 2011).

The manufacture of cement is an energy-intensive process with high 3.2. Physico-chemical characteristics
CO2 emissions. With regard to economic and environmental con-
siderations, BOF slag has been applied in the production of cement Using steel scrap instead of melted iron as feed material, the EAF
clinker to reduce the consumption of energy and resources. The process is actually a steel scrap recycling process and the chemical

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Y. Jiang et al. Resources, Conservation & Recycling 136 (2018) 187–197

Fig. 9. Schematic representation of electric-arc-furnace (EAF) steelmaking and ladle refining (LF) processes (Yildirim and Prezzi, 2011).

composition of EAF slag can vary over a wider range than BOF slag. Manso et al., 2006). In terms of volume stability, evaluations were
EAF-C slag shares many things in common with BOF slag such as the conducted through natural aging for 365 days (Adegoloye et al., 2015;
primary oxides (Table 3), mineral phases and physical appearance (e.g. Adegoloye et al., 2016), accelerated aging (Pellegrino et al., 2013;
color and morphology). However, EAF-S slag from stainless steel pro- Pellegrino and Gaddo, 2009; Santamaría et al., 2016) and autoclave
duction contains a lower FeO content but a higher Cr content (Shi, exposure (Manso et al., 2006). The results were generally positive, al-
2004; Yildirim and Prezzi, 2011). The mineral phases identified for EAF lowing the use of EAF slag as aggregates in concrete. However, further
slag include merwinite (3CaO·MgO·2SiO2), wustite (solid solutions of care is needed to ascertain the safe, security and sustainability for the
FeO), olivine, C2S and C3S (Adegoloye et al., 2016; Muhmood et al., use of 100% EAF slag as aggregates in concrete (Sheen et al., 2015a).
2009; Santamaría et al., 2016; Yildirim and Prezzi, 2011; Piatak et al.,
2015). 3.5. Use of EAF slag for cement clinker production

3.3. Use of EAF slag powder as supplementary cementitious materials Tsakiridis et al. (2008) have successfully introduced EAF slag into
the production of cement clinker. No negative effect was observed on
Due to its high surface roughness, EAF slag (with a mean particle the quality of the produced cement with a substitution ratio of up to
size of ∼45 μm) would decrease the workability of the concrete mixture 10.5% EAF slag. Iacobescu et al. (2011) also incorporated 10% EAF slag
(Roslan et al. 2016). Similar to that of BOF slag, the compressive with clinker production to lower the clinkering temperature down to
strength decreases with an increased content of EAF slag powder (Amin 1380 °C. High content of belite (mainly in α’ polymorph) was observed
et al., 2015; Hekal et al., 2013; Roslan et al., 2016). However, a mix in the produced cement. Similarly, Iacobescu et al. (2013) used 17%
with 10% EAF slag was found to exhibit a strength comparable to that EAF slag to produce calcium ferroaluminate belite cement at the tem-
of the control mix, and further improvement of mechanical properties perature of 1320 °C. It was observed that, due to its characteristics of
could be obtained by replacing 4% of EAF slag with silica fume (Amin low pH and porosity, the EAF belite cement could bind heavy metals
et al., 2015). Muhmood et al. (2009) also found that the water and limit their leaching behaviors, such as Cr leaching below 1 mg/L.
quenching method could improve the cementitious property of EAF
slag. A paste prepared with 20% treated EAF slag and 30% GGBFS 3.6. Use of EAF slag as a modifying agent
achieved 61 MPa at 28 days, only about 8% lower than the corre-
sponding control sample (Muhmood et al., 2009). EAF slag can be used as a modifying agent to increase the reactivity
of BOF slag. This can be achieved by adding EAF slag into molten BOF
3.4. Use of EAF slag as aggregates in concrete slag during the discharging process in steelworks. Li et al. (2011) re-
ported that an addition of 10–20% EAF slag can lead to a 7.3–12.7%
Compared with BOF slag, EAF slag has been suitably used as ag- increase in alite content and a decrease in the crystal size and the for-
gregates in blended concrete. Good workability can be obtained by mation of C6AF2. Also, Li et al. (2013) reported that EAF slag and coal
using a proper grading and water reducing agent (San-José et al., 2014; bottom ash can modify the mineralogical compositions of BOF slag, and
Liu et al., 2011). Enhancement of the mechanical strength was observed therefore the cementitious property of BOF slag.
due to the stronger bonding between the EAF slag and the cement paste
(San-José et al., 2014; Pellegrino and Gaddo, 2009; Maslehuddin et al., 4. Ladle furnace (LF) slag
2003). In addition, the EAF slag aggregate barely affects the freezing-
thawing (Arribas et al., 2014; Manso et al., 2006; Pellegrino and Gaddo, 4.1. Generation processes
2009), wetting-drying (Manso et al., 2006; Pellegrino and Gaddo,
2009), sulfate (Arribas et al., 2014; Manso et al., 2006) and fire attacks After primary steelmaking, the refining operations of both carbon
(Grubeša et al., 2016; Yu et al., 2016). Little to no expansion of volume and stainless steel can be performed in an LF (Fig. 9), producing the LF
was observed due to the alkali-aggregate reaction (Arribas et al., 2014; slag. The LF process is based on the principles of deoxidation and

193
Y. Jiang et al. Resources, Conservation & Recycling 136 (2018) 187–197

alloying, temperature and composition homogenization, desulfuriza-

Air cooled and water sprayed


tion, steel cleanliness improvement, inclusion flotation and the shape

Air cooled and weathered

Air cooled and weathered


control of sulfide and oxide (Pretorius, 2015; Yang et al., 2007). Due to
Water quenched the uses of fluxes (e.g., calcium aluminate or CaF2) in the LF process,
the compositions and properties of the produced LF slag are quite dif-
ferent to that of BOF and EAF slags (Pretorius, 2015; Shi, 2004; Shi and
Air cooled
Treatment

Hu, 2003). For the stainless steel process, refining operations are also
completed in an AOD furnace and generate AOD slag (Salman et al.,





2014a).
LOI

0.1

4.2. Physico-chemical characteristics









As shown in Table 4, the oxides in LF slag are primarily CaO, SiO2,


0.5(TiO2)/0.2(Na2O) /0.2(K2O)

MgO and Al2O3. The CaO content in LF slag (i.e., 44.5–58.4%) is higher
0.1-0.2(V2O5)/0.05-0.1(Ba)

0.05-0.4(V2O5)/0.1-0.5(Ba)

than that in BOF and EAF-C slags, while the contents of iron-bearing
constituents are much lower. TiO2 and Cr2O3 are present as a minority
0.14(SO3)/0.6(TiO2)

in LF slag, probably due to the alloying for desired compositions


(Kriskova et al., 2012). C2S is the primary mineral phase in LF slag due
0.15(Na2O)

1-2(V2O5)
0.15(SO3)

to the CaO/SiO2 ratio (about 2). The C2S phase exists in the form of a
0.9(TiO2)
0.7(TiO2)
Others

gamma polymorph (γ-C2S) (Shi and Hu, 2003). Other common miner-
alogies in LF slag include merwinite (Ca3Mg(SiO4)2), bredigite (Ca7Mg

(SiO4)4) and periclase (MgO) (Kriskova et al., 2012).


LF slag is usually a white powder (Fig. 10) as a result of self-pul-
Cr2O3

0.5-5
5-30
2-5

verization (or dusting) during the cooling process, where β-C2S is







transformed to γ-C2S with a volume increase of ∼10% (Salman et al.,


2014a; Shi, 2002). The self-pulverization of LF slag would lead to
f- CaO

several potential challenges, such as handling and storing difficulties


0.4
0.1







(Tossavainen et al., 2007). Thus, stabilizers, such as borates and


phosphates, can be used to prevent this technological issue (Pontikes
0.7(P2O3)

et al., 2010; Seki et al., 1986).


P2O5

0.05
0.6
0.5




4.3. Use of LF slag powder as supplementary cementitious materials


MnO/Mn2O3

LF slag, especially the γ-C2S-based type, exhibits limited cementi-


tious properties (Shi, 2002). Thus, activation via mechanical (Kriskova
2.66

4.18

et al., 2012), thermal (Shi and Hu, 2003) and chemical (Cao and Yang,
1.5
1.4

2.6




2015; Han et al., 2015; Salman et al., 2015; Shi, 2004; Shi and Hu,
2003) approaches is often used to increase the reactivity of LF slag.
MgO

5-15
21.4
1.86
7.26

5.03

12.8
2-5
1-3
4.3

Through mechanical grinding, the structure and reactivity of LF slag


12

can be improved (Kriskova et al., 2012). Also, deploying autoclave


curing at 175 °C (i.e., the thermal approach) or the combined use of
15-25
15-25
20-50
30.8
38.8
16.9
54.0
37.8

31.5
CaO

cement, hydrated lime and ground quartz (i.e., the chemical approach)
33

could improve the mechanical strength of blended cement (Shi and Hu,
2003). The incorporation of gypsum can further improve the perfor-
Fe/FeO/Fe2O3

mances of blended cement, in terms of mechanical strength and dur-


Chemical compositions of EAF slags (wt.%) used from the literature.

ability (Kim et al., 2016). Currently, alkali activators (e.g. NaOH and
Remark: – means not detected or clarified, LOI = Loss on ignition.
30-50
30-50
5-30
24.1

43.4
1.23
14.5
36.8

Na-silicate) have been focused on and optimized with steam curing to


1.2

accelerate the hydration reaction kinetics of LF slag and the subsequent


strength development of blended cement (Salman et al., 2015). Shi
10-15
Al2O3

5-15
4.84
4.89

5.51

2.43

(2002) and Shi and Qian (2000) reported that the cementitious prop-
1-3
6.1
5.9

20

erties of both β-C2S and γ-C2S could be activated by Na2SiO3 under


room temperature conditions.
15-20

10-40

The characteristics of modified LF slag by different cooling methods


5-25
SiO2

23.3
29.0
26.4
24.9
19.8
13.1

38.6

have also been investigated. Choi et al. (2016) reported that pulverized
LF slag, rapidly cooled by high-pressure air, possesses high hydration
Australia
Malaysia

reactivity with 91.9% glass content. Tossavainen et al. (2007) revealed


Sources

Taiwan
Europe
Europe
Europe
China

Egypt
India
India

that, after re-melting and water jet cooling, LF slag almost completely
became amorphous. Sheen et al. (2015a) used water-cooled LF slag to
produce self-compacting concrete with a good workability and quick
Muhmood et al. (2009)
Muhmood et al. (2009)

Mombelli et al. (2016)


Mombelli et al. (2016)
Mombelli et al. (2016)

setting time. However, the compressive strength and electrical re-


Sheen et al. (2015a)
Roslan et al. (2016)

Hekal et al. (2013)

sistance of self-compacting concrete were found to reduce by 11% and


Yu et al. (2016)

42%, respectively. The results were in good agreement with the finding
Li et al. (2013)

reported by Sheen et al. (2015b).


References

Regarding the durability and stability, the contents of f-CaO and f-


Table 3

MgO in LF slag may result in fatal volume expansion, thereby leading to


a disintegration of the slag pieces and a loss of strength. Water cooling

194
Y. Jiang et al. Resources, Conservation & Recycling 136 (2018) 187–197

Table 4
Chemical compositions of LF slags (wt.%) used from the literature.
References Sources SiO2 Al2O3 Fe/FeO/Fe2O3 CaO MgO SO3 MnO TiO2 Cr2O3 Others Treatment

Kriskova et al. (2012) Belgium 28.3 1.2 – 51.5 11.3 – – – 3.9 3.8(others) Before aging
Shi and Hu (2003) Canada 26.8 5.2 1.59 57.0 3.2 1.7 1.0 0.3 – 3.0(F)/0.2(ZrO2) –
Sheen et al. (2015a) Taiwan 23.5 4.1 0.08 50.6 8.2 – – 0.09 – – Rapidly water cooled and weathered
Salman et al. (2015) Belgium 30.31 1.31 – 58.4 7.41 – – 1.09 0.44 – –
Choi et al. (2016) South Korea 10.9 26.6 4.3 44.5 6.6 – 0.6 – – – Rapidly air cooled

Remark: – means not detected or clarified, LOI = Loss on ignition.

the leaching concentrations of all tested heavy metals and metalloids


(e.g. As, Cd, Co, Cu, Ni, Pb, Sb, Se, Ti) were within the permissible
limits, except for Cr which was about twice of the permissible limit.
This is because alkali tends to intensify Cr, V and Mo leaching, while
decreasing Ba leaching. It is also reported that water cooling could
reduce the leaching of Ca, Al, Ba, Se and increase the leaching of Si, Mg,
Mo and Cr, but all the potentially hazardous elements were found to
within the regulations (Barella et al., 2012; Loncnar et al., 2009).
Accelerated carbonation treatment can effectively decrease the re-
lease of Zn and Mo, while enhancing the release of Cr and V based on
the behavior of EAF-S and AOD slags (Baciocchi et al., 2015). Kühn
et al. (2006) gave an overview of different practical methods in Europe
to immobilize the Cr species in steel slags. These methods either reduce
the Cr content in slag during scorification or enhance the binding of Cr
in stable phases through the addition of spinel forming agents. Both of
them are expected to reduce Cr leaching and fulfill the environmental
Fig. 10. Ladle furnace slag from stainless steel production (Sheen et al., 2015a). demands.
Mombelli et al. (2016) reported that EAF-C slag featuring high MgO
and weathered LF slag was able to replace cement up to 30% without and CaO concentrations tends to increase Ba leaching. This is because
obvious volume expansion (Sheen et al., 2015a). However, cylinders MgO and CaO could enhance the dissolution of BaO species within
prepared with 100% LF slag were easily cracked under autoclaving calcium silicate lattices. The calcium silicate lattices would hydrate
curing. In other words, a high replacement ratio of cement by LF slag is with water and thus release Barium. The V-retaining ability is con-
not recommended, unless fly ash and/or ground quartz are used to trolled by CaO, SiO2, Al2O3 and MgO, where these oxides could im-
consume the f-CaO in LF slag. prove the V-retaining behaviors. For the Cr release, a high CaO/SiO2
ratio would enhance Cr leaching. Previous studies (Barella et al., 2012;
4.4. Use of LF slag for cement clinker production Manso et al., 2006) reported that a coarser size of steel slag produces
lower leaching concentrations of metals and the use of steel slag in
Vilaplana et al. (2015) prepared a special type of cement containing concrete can further prevent the potential toxicity of steel slag.
high alite content at a laboratory scale, where ∼39% LF slag, ∼45% Therefore, concrete blended with steel slags should be regarded as a
limestone, ∼14% shale, ∼1% mill sludge and 5% gypsum were used non-hazardous material, which is suitable for use in construction in-
for cement manufacturing. The produced cement could be classified as dustries.
the 42.5R Portland cement, as well as exhibiting excellent strength,
satisfactory dimensional stability and faster initial setting in accordance 6. Conclusions
with the EN 197-1 standard.
Iacobescu et al. (2016) used a fine fraction of LF slag, limestone, The valorization of BOF, EAF and LF slags is an important strategy
flysch and bauxite residue to produce cement, aiming to understand the on industrial waste management toward a circular economy. One of the
influence of LF slag on the characteristics of clinker. They found that valorization pathways with great potential is for cement and concrete
the addition of LF slag in the raw meal favors the formation of C3S and production. BOF slag is more alkaline and reactive than EAF and LF
C4AF, while restraining the formation of C3A. Thus, the final product of slags, which could be used as supplementary cementitious materials at
ordinary Portland cement made with 14% LF slag exhibited better a substitution ratio of 10–20 wt.% with satisfactory performance. The
mechanical strength but a longer setting time associated with the lower rock-like appearance of BOF slag also allows for its use as aggregates in
C3A content and the presence of Cr (acts as a retarder). From the en- concrete. However, special attention should be paid to the potential
vironmental perspective, a 12% reduction in CO2 emission could be volumetric instability associated with the presence of high f-CaO con-
achieved with the use of 14% LF slag in cement clinker production. tent. The volumetric instability could be properly reduced or even
eliminated by natural weathering and aging or other treatment methods
5. Environmental benefits from steel slag valorization such as accelerated carbonation. EAF slag has similar characteristics
and application foregrounds with BOF slag, but it is more recommended
Improper disposal of steel slags can have a deleterious impact on for use as aggregates instead of cement replacement in concrete. LF slag
surface- and ground-water through the release of trace elements and usually presents in a powdery form and is dominated by the γ-C2S
hyperalkaline drainage (Piatak et al., 2015). This may greatly threaten phase, thereby being considered as a non-hydraulic material.
the safety of humans and the environment, especially stainless steel slag Mechanical, thermal and chemical activations are typically adopted to
which contains different heavy metals (Pellegrino and Gaddo, 2009; enhance its reactivity prior to its use in concrete. In terms of cement
Xiang et al., 2016; Zhang and Xin, 2011). Salman et al. (2014b, 2015) clinker production, all three BOF, EAF and LF slags are found to be
studied the heavy metals and metalloids leaching from alkali-activated feasible for use in the raw material. Before steel slags can be widely
and un-activated pastes made with stainless LF slag. They found that introduced to cement and concrete industries, further studies are

195
Y. Jiang et al. Resources, Conservation & Recycling 136 (2018) 187–197

needed to ascertain the safety and sustainability regarding the potential cements. J. Hazard. Mater. 196 (1), 287–294.
expansion and soundness problem of f-CaO of steel slags. Iacobescu, R.I., Pontikes, Y., Koumpouri, D., Angelopoulos, G.N., 2013. Synthesis, char-
acterization and properties of calcium ferroaluminate belite cements produced with
electric arc furnace steel slag as raw material. Cem. Concr. Compos. 44 (93), 1–8.
Acknowledgments Ilyushechkin, A.Y., Roberts, D.G., French, D., Harris, D.J., 2012. IGCC Solids Disposal and
Utilisation, Final Report for ANLEC Project 5-0710-0065.
Jiang, L., Bao, Y., Yang, Q., Chen, Y., Liu, G., Han, F., Wei, J., Engström, F., Deng, J.,
The research funding from Hunan Provincial Science and 2017. Formation of spinel phases in oxidized BOF slag under different cooling con-
Technology Department (Hunan Province Key Research Project, ditions. Steel Res. Int. 88 (11) e201700066.
2017WK2090) and the National Natural Science Foundation of China Kühn, M., Mudersbach, D., Liberato, B.J.M., Angelis, V., Capodilupo, D., Fries, U., 2006.
Chrome Immobilisation in EAF Slags from High-Alloy Steelmaking: Development of a
(NSFC International (Regional) Cooperation and Exchange Program, Slag Treatment Process. Office for Official Publications of the European
51750110506) are gratefully acknowledged. Communities.
Kim, J.M., Choi, S.M., Han, D., 2016. Improving the mechanical properties of rapid air
cooled ladle furnace slag powder by gypsum. Constr. Build. Mater. 127, 93–101.
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