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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.
⁎
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
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).
Table 2
Physical properties of BOF slags and other natural aggregates.
BOF slag Crushed Lime stone Gravel Sand
granite
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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. 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
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
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
–
–
–
–
–
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)
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
–
0.5-5
5-30
2-5
0.05
0.6
0.5
–
–
–
–
–
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
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
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
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
10-40
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
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)
42%, respectively. The results were in good agreement with the finding
Li et al. (2013)
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
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.
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Technology Department (Hunan Province Key Research Project, ditions. Steel Res. Int. 88 (11) e201700066.
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