Resources, Conservation and Recycling 52 (2008) 1115–1120

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Resources, Conservation and Recycling

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Review

Utilization of copper slag in cement and concrete

Caijun Shi a , Christian Meyer b , Ali Behnood c,∗
a
College of Civil Engineering, Hunan University, Changsha, Hunan, China
b
Department of Civil Engineering, Columbia University, New York, NY 10027-6623, USA
c
Department of Civil Engineering, Iran University of Science and Technology, Tehran, Iran

a r t i c l e i n f o a b s t r a c t

Article history: Copper slag is a by-product obtained during matte smelting and refining of copper. The common man-
Received 3 February 2008 agement options for copper slag are recycling, recovering of metal, production of value added products
Received in revised form 25 June 2008 such as abrasive tools, roofing granules, cutting tools, abrasive, tiles, glass, road-base construction, rail-
Accepted 25 June 2008
road ballast, asphalt pavements. Despite increasing rate of reusing copper slag, the huge amount of its
annual production is disposed in dumps or stockpiles to date. One of the greatest potential applications
Keywords:
for reusing copper slag is in cement and concrete production. Many researchers have investigated the
Aggregate
use of copper slag in the production of cement, mortar and concrete as raw materials for clinker, cement
Copper slag
Clinker
replacement, coarse and fine aggregates. The use of copper slag in cement and concrete provides poten-
Cement tial environmental as well as economic benefits for all related industries, particularly in areas where a
Concrete considerable amount of copper slag is produced. This paper reviews the characteristics of copper slag and
Recycled materials its effects on the engineering properties of cement, mortars and concrete.
© 2008 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1115
2. Production of copper slag . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1116
3. Chemical composition of copper slag . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1116
4. Physical properties of copper slag . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1116
5. Use of copper slag in cement clinker production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1116
6. Use of copper slag in blended cement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1117
7. Use of copper slag in concrete . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1117
8. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1120
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1120

of copper slag is produced in Iran, Brazil and Oman, respectively

1. Introduction (Behnood, 2005; Moura et al., 1999; Taeb and Faghihi, 2002; Al-Jabri
et al., 2002). Current options for management of copper slag include
Production of industrial slag dates back to the beginning recycling, recovering of metal, production of value added products
of extracting of metals from ores through metallurgical pro- and disposal in slag dumps or stockpiles. Currently, copper slag
cesses. Copper slag is a by-product obtained during the matte has been widely used for abrasive tools, roofing granules, cutting
smelting and refining of copper (Biswas and Davenport, 2002). tools, abrasive, tiles, glass, road-base construction, railroad ballast,
Production of one ton of copper generates, approximately asphalt pavements, cement and concrete industries. The reports of
2.2–3 tons copper slag. In the United States, the amount of copper Portland Cement Association show that copper slag has been used
slag produced is about four million tons, and in Japan, it is about in full-scale cement manufacturing in different plants. Production
two million tons per year (Collins and Ciesielski, 1994; Ayano and of Portland cement includes the grinding of raw materials, the calci-
Sakata, 2000). Approximately 360,000, 244,000 and 60,000 tons nations of them at 1500 ◦ C and the grinding of cement clinker with
gypsum. The average energy input required to produce one ton of
cement is approximately 4.8 million Btu. As seen, it is an energy-
∗ Corresponding author. Tel.: +98 912309 8421; fax: +98 218802 4784. intensive process which releases significant amount of pollution
E-mail address: a behnoud@iust.ac.ir (A. Behnood). such as CO2 . Consequently, the production of Portland cement has

0921-3449/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.resconrec.2008.06.008
1116 C. Shi et al. / Resources, Conservation and Recycling 52 (2008) 1115–1120

Table 1
Chemical composition of copper slag from different sources by mass (%)

No. Fe2 O3 SiO2 , CaO MgO Al2 O3 SO3 CuO Country (Reference)

1 44.78 40.97 5.24 1.16 3.78 1.06 – Iran (Marghussian and Maghsoodipoor, 1999)
2 44.80 24.7 10.9 1.7 15.6 0.28 2.1 USA (Mobasher et al., 1996)
3 49.50 34.51 2.20 1.48 6.55 1.20 0.43 Canada (Douglas and Mainwaring, 1986)
4 45.3 36.0 9.30 3.24 3.45 0.49 0.33 Australia (Roper et al., 1983)
5 62 26 2.5 3.7 – – 1.4 Brazil (Moura et al., 1999)
6 52.0 35.5 2.11 1.06 5.90 0.14 0.88 Japan (Ayano and Sakata, 2000)
7 60.00 30.07 0.6 0.75 3.97 0.32 0.79 Spain (Sanchez de Rojas et al. (2004))
8 53.72 34.3 7.91 0.94 3.83 3.02 – Taiwan (Hwang and Laiw, 1989)
9 36 31 4 – 6 – 0.33–0.80 Malaysia (Zain et al., 2004)
10 41.53 37.13 – – – 0.11 0.79 Chile (Imris et al., 2000)
11 39.65 31.94 3.95 2.82 2.4 – 1.01 Turkey (Kiyak et al., 1999)

many environmental problems as well as economic considerations.
By using copper slag as a partial replacement of cement, substantial
amounts of energy required for production of cement will be saved
because its use needs only grinding. Furthermore, it will be pos-
sible to reuse a waste by-product material beneficially. Also, more
amounts of copper slag will be utilized by using it as fine and coarse
aggregates in concrete because more than 75% volume of concrete is
occupied by aggregates. Many researchers have investigated the use
of copper slag in cement clinker production, and the effects of cop-
per slag on the properties of Portland cement mortar and concrete
in the form of cement replacement, coarse and fine aggregate. The
use of copper slag in cement and concrete provides potential envi-
ronmental as well as economic benefits for all related industries,
particularly in areas where a considerable amount of copper slag is
produced. This paper reviews the characteristics of copper slag and
its effects on the properties of cement, mortars and concrete.
0.7–3.5%. The chemical compositions of copper slag obtained from
different regions are given in Table 1.
4. Physical properties of copper slag
The physical properties of copper slag are given in Table 2. As
seen, the density of copper slag varies between 3.16 and 3.87 g/cm3
based on the amount of iron content. The average specific gravity of
copper slag is about 3.5 g/cm3 that means copper slag is denser than
ordinary natural aggregates. In general, water absorption of copper
slag is very low. As stated previously, when liquid slag is cooled
slowly, it forms a dense, hard crystalline product whereas quick
solidification by pouring molten slag into water gives granulated
amorphous slag. The granulated copper slag has a higher water
absorption and less unit weight compared with air-cooled copper
slag due to its more porous texture.

5. Use of copper slag in cement clinker production

2. Production of copper slag
As shown in Table 1, copper slag has a high Fe content and has
Copper slag is a by-product obtained during the matte smelt- been used as an iron adjustment material during the cement clinker
ing and refining of copper (Biswas and Davenport, 2002). Major production (Huang, 2001). Since the main composition of copper
constituents of a smelting charge are sulphides and oxides of iron slag is vitreous FeSiO3 , it has low melting point and could reduce the
and copper. The charge also contains oxides such as SiO2 , Al2 O3 , calcination temperature for cement clinker. Thus, the use of copper
CaO and MgO, which are either present in the original concen- slag to replace iron powder as iron adjusting materials facilitates
trate or added as flux. It is iron, copper, sulphur, oxygen and their cement production, reduces or eliminates the need of mineralizer.
oxides which largely control the chemistry and the physical con- However, the use of iron powder does not show this advantage.
stitution of the smelting system. A further important factor is the The performance testing results indicated that cement produced
oxidation/reduction potential of the gases which are used to heat by using copper slag performed even better than using iron pow-
and melt the charge (Gorai et al., 2002). As a result of this pro- der. In another publication, it was reported that copper slag was
cess, copper-rich matte (sulphides) and copper slag (oxides) are successfully used as an iron adjustment material in cement clinker
formed as two separate liquid phases. The addition of silica during production (Guo, 2003). In another study, researchers used the tail-
smelting process forms strongly bonded silicate anions by com- ings from Mo ores and copper slag to produce cement clinker. In
bining with the oxides. This reaction produces copper slag phase, addition, CaF was used as a mineralizer. The performance of the
whereas sulphides form matte phase due to low tendency to form cement was even better than that produced using traditional clay,
the anion complexes. Silica is added directly for the most complete limestone and mill scale (Liu et al., 2007).
isolation of copper in the matte which occurs at near saturation
concentration with SiO2 (Shi and Qian, 2000). The slag structure
Table 2
is stabilized with the addition of lime and alumina. The molten
Physical properties of copper slag (Ayano and Sakata, 2000; Khanzadi and Behnood,
slag is discharged from the furnace at 1000–1300 ◦ C. When liquid 2007; Gorai et al., 2002; Hwang and Laiw, 1989; Moura et al., 1999; Shoya et al.,
slag is cooled slowly, it forms a dense, hard crystalline product, 2003, 1997)
while as quick solidification by pouring molten slag into water gives
Appearance Black, glassy, more vesicular when granulated
granulated amorphous slag (Gorai et al., 2002).
Particle shape Irregular
Density (g/cm3 ) 3.16–3.87
3. Chemical composition of copper slag Water absorption (%) 0.15–0.55
Hardness (mohs) 6–7
Water soluble chloride (ppm) <50
The composition of a specific slag depends on the type of fur- Soundness (%) 0.8–0.9
nace, the metallurgical process producing it and the composition of Aggregate crushing value (%) 10–21
the extracted ore. In general, the percentages of the main oxides of Aggregate impact value (%) 8.2–16
copper slag can be varied in the ranges as follows—Fe2 O3 : 35–60%, Abrasion loss (%) 24.1
Conductivity (␮s/cm) 500
SiO2 : 25–40%, CaO: 2–10%, Al2 O3 : 3–15%, CuO: 0.3–2.1%, MgO:
 C. Shi et al. / Resources, Conservation and Recycling 52 (2008) 1115–1120
Table 3
Regulatory limits for various heavy metals according to Malaysian Environmental
Quality Orders (MEQO) and United States Environmental Agency (USEPA)
Element (mg/l) MEQO
Standard A Standard B
Cu 0.20 1.00
Ni 0.20 1.00
Pb 0.20 0.50
Zn 1.00 1.00
As – –
Cr – –
Cd – –
The use of copper slag also results in lower required calcina-
tion temperature and improved grindability of the clinker although
the raw materials cost may or may not be reduced depending
on the local availability of copper slag (Tan et al., 2000; Huang,
2001).
6. Use of copper slag in blended cement
The use of copper slag as a pozzolanic material for a partial
substitute for ordinary Portland cement and its effects on the hydra-
tion reactions and properties of mortar and concrete have been
reported in several publications (Al-Jabri et al., 2006; Taha et al.,
2007; Malhotra, 1993; Tixier et al., 1997; Ariño and Mobasher,
1999; Douglas and Mainwaring, 1986; Deja and Malolepszy, 1989).
Roper et al. (1983) reported that copper slag does not need to be
completely glassy for significant hydration to occur. One poten-
tial concern for such materials is their heavy metal content and
the leaching characteristics. The leachability of copper, nickel, lead,
and zinc ions from copper slag was lower than the regulatory lim-
its. Table 3 shows the leachability limits imposed by the Malaysian
Environmental Quality Orders (MEQO) and United States Environ-
mental Protection Agency (USEPA). Standard A is the limit allowed
for the effluent to be safely released into any catchment area,
whereas Standard B is for the effluent to be released into any ter-
restrial water system. Zain et al. (2004) reported that the mortar
incorporating waste copper slag up to 10% replacement is safe
with respect to leachability of the above heavy metal based on
the mentioned standards. They used direct air-acetylene flame AAS
method to determine the concentration of the respective ions in
the leachability test. Furthermore, Sanchez de Rojas et al. (2004)
showed that the copper slag incorporation into the cement mortar
does not cause an increase in the leached elements. Another work
Fig. 1. Compressive strength of NaOH-activated copper slag and Portland cement mortars (Shi and Qian, 2000).
1117
showed that the amounts of leached elements of copper slag are
significantly lower than the regulatory levels determined by United
States Environmental Protection Agency (Alter, 2005). The United
USEPA Nations (UN) Basel Convention on the Transboundary Movement of
Hazardous Wastes and their Disposal considered such reports and
N/R
ultimately ruled that copper slag is not a hazardous waste.
– Moura et al. (1999) investigated the compressive and flexural
5.0 strength of concrete containing copper slag as 10% of the cement
N/R by mass. The results indicated that concrete with copper slag had
5.0
lower compressive strength than concrete without copper slag
5.0
1.0 admixture up to 91 days. The flexural strengths of concrete with
and without copper slag were similar for water to cement ratio of
0.4–0.5. Ariño and Mobasher (1999) prepared mortar specimens
containing up to 15% copper slag as a cement replacement with
constant water to cementitious solids ratio of 0.4. The compression-
test results indicated that copper slag concrete was significantly
stronger but more brittle than ordinary Portland cement concrete.
Fracture test results confirmed that the increased brittleness of con-
crete was due to the use of copper slag in the mentioned study.
Fig. 1 indicated that copper slag containing approximately 19% CaO
had good cementitious property under the activation of NaOH. The
NaOH-activated copper slag mortars had higher strength than that
of Portland cement mortars even after 4 h of curing at 80 ◦ C (Deja
and Malolepszy, 1989, 1994). In addition, they reported higher cor-
rosion resistance of copper slag mortars in comparison to plain
Portland cement mortars. Fig. 2 shows the compressive strength
of copper slag mortars as a function of replacement level (Zain et
al., 2004). Based on the results of this work, the strength of copper
slag mortar is generally lower than that of the control mortar. They
reported an optimum strength performance of the copper slag mor-
tars containing 5–7.5% copper slag by cement weight. In another
study, it was found that the replacement of 10–15% cement clinker
does not have a significant effect on compressive strength, but sig-
nificantly increases the abrasion resistance of the cement mortar
(Dai et al., 1998).
7. Use of copper slag in concrete
Several researchers have investigated the possible use of copper
slag as fine and coarse aggregates in concrete and its effects on the
different mechanical and long-term properties of mortar and con-
crete. With some benefits of using copper slag as fine and coarse
aggregates, some negative effects such as delaying of the setting
time, especially when only copper slag has been used as fine aggre-
gate have also been reported. Ayano and Sakata (2000) reported
1118 C. Shi et al. / Resources, Conservation and Recycling 52 (2008) 1115–1120
Fig. 2. Compressive strength of copper slag mortars as a function of replacement
level (Zain et al., 2004).
that the slag component was an insoluble residue of 0.15 mm size
that could be readily removed by washing. They concluded that
the effect of copper slag on the setting time was different with the
particle size of copper slag (that is, the smaller size of copper slag
causes the longer delay in the setting time). However, the effect of
copper slag on the setting time was decreased by increasing the
washing times. Since concrete floors and pavements are one of the
useful applications for copper slag aggregates due to high hard-
ness and good mechanical properties, it is important to know its
effects on the bleeding of such concrete. Bleeding is defined as the
movement of water in freshly placed concrete to its surface, and
is a form of settlement of heavier solids in the concrete while the
water travels to the surface. When bleeding is excessive, harmful
effects arise on concrete quality by producing defects such as the
formation of water channel, water pocket beneath the aggregates,
the increase of water to cement ratio near the top of surface and
finally, the formation of a weak top layer. These defects will result in
less durable concrete. Shoya et al. (1997) reported that the amount
and rate of bleeding increased by using copper slag fine aggregate
depending on the water to cement ratio, the volume fraction of slag
and air content. They recommended using less than 40% copper slag
as partial replacement of aggregate to control the amount of bleed-
ing to less than 5 l/m2 . Hwang and Laiw (1989) reported that the
amount of bleeding of mortar made with copper slag is compara-
tively less than that using natural sand. However, the heavy specific
Fig. 4. Compressive strength development of mortars containing copper slag sand with different water to cement ratios (Hwang and Laiw, 1989).
Fig. 3. Drying shrinkage strain using copper slag and river sand (Ayano and Sakata,
2000).
weight and the glass-like smooth surface properties of irregular
grain shape of copper slag aggregates are effective for character-
istics of bleeding. Hwang and Laiw (1989) and Ayano and Sakata
(2000) reported that the shrinkage of specimens containing cop-
per slag fine aggregate is similar or even less than that of specimens
without copper slag (Fig. 3).
Several works reported that the compressive and tensile
strengths of concrete specimens made with copper slag fine and
coarse aggregates are almost the same as that of normal con-
crete or even significantly more than control mixtures (Caliskan
and Behnood, 2004; Shoya et al., 1997; Ayano and Sakata, 2000;
Hwang and Laiw, 1989). It was noticed that the use of copper slag
as fine aggregate could greatly increase the abrasion resistance of
the cement mortar (Tang et al., 2000). Hwang and Laiw (1989)
evaluated the compressive strength development of mortars and
concrete containing fine copper slag aggregate with different water
to cement ratios (Figs. 4 and 5). Fig. 4 shows the mortars containing
the larger amounts of copper slag sand had lower early strengths
at w/c of 0.48. The strengths of mixtures with 20–80% substitu-
tion of copper slag were higher than that of the control specimens.
Fig. 5 indicates similar trends of compressive strength develop-
ment of concrete containing copper slag fine aggregate to those
of mortars. Li (1999) and Zong (2003) also reported that concrete
containing copper slag as fine aggregate exhibited similar mechan-
ical properties as that containing conventional sand and coarse
aggregates.
 C. Shi et al. / Resources, Conservation and Recycling 52 (2008) 1115–1120 1119

Fig. 5. Compressive strength development of concrete containing copper slag sand with different water to cement ratios (Hwang and Laiw, 1989).

Fig. 6. Resistance of sulfate attack of concrete using copper slag judged by (a) weight change, (b) relative dynamic young’s modulus (Ayano and Sakata, 2000).

Evaluation of the effects of copper slag aggregate on the sul-
fate attack resistance (Fig. 6) and the depth of carbonation (Fig. 7)
showed no significant attack and slower rate of carbonation by
using copper slag (Hwang and Laiw, 1989; Ayano and Sakata, 2000).
Some researchers reported the freezing–thawing resistance of con-
crete containing copper slag aggregate is lower than that of control
samples (Shoya et al., 1997, 2003), whereas others reported simi-
lar or higher resistance for specimens made with copper slag fine
aggregate (Li, 1999; Ayano and Sakata, 2000).
Caliskan and Behnood (2004) investigated the compressive
strength of normal-strength concrete containing copper slag coarse
aggregate (Fig. 8). As seen, the compressive strength of copper slag
coarse aggregate concrete was marginally higher than that of lime-
stone aggregate concrete.
Good performance of copper slag as fine and coarse aggregates
in normal concrete is the basis for researchers to evaluate its pos-
sible use in producing special concrete such as self-consolidating
concrete (Shoya et al., 2003), high-performance concrete (Al-Jabri,

Fig. 7. Carbonated thickness of concrete using copper slag and river sand (Ayano Fig. 8. Compressive strength development of concrete containing copper slag and
and Sakata, 2000). limestone coarse aggregates (Caliskan and Behnood, 2004).
1120 C. Shi et al. / Resources, Conservation and Recycling 52 (2008) 1115–1120
2006) and high-strength concrete (Khanzadi and Behnood, 2007).
One province in China published technical guidelines for the use of
copper slag as sand for mortars and concrete (SPCSA, 1999), some
other provinces are developing the specifications.
8. Conclusion
This paper reviews the engineering characteristics of copper slag
and its effects on the properties of cement and concrete. When
copper slag is used as a raw material for clinker production, it can
act as both iron adjusting and mineralizing component. Further, it
also improves the grindability of the clinker. When it is used as
a cement replacement or an aggregate replacement, the cement,
mortar and concrete containing different forms of copper slag have
good performance in comparison with ordinary Portland cement
having normal and even higher strength. Such studies will be more
important due to the fact that the production of Portland cement
is an energy-intensive process which releases significant amount
of pollution such as CO2 . Also, the production of cement has many
environmental problems as well as some economic considerations.
By using copper slag as a partial replacement of cement, substantial
amounts of energy required for production of cement will be saved
because its use needs only grinding. Furthermore, it will be pos-
sible to reuse a waste by-product material beneficially. Also, more
amounts of copper slag will be utilized by using it as fine and coarse
aggregates in concrete because more than 70% of concrete volume
is occupied by aggregates. From environmental point of view, cop-
per slag is a safe material based on the criteria of different standards
such as United States Environmental Protection Agency, so that the
United Nations (UN) Basel Convention on the Transboundary Move-
ment of Hazardous Wastes and their Disposal ruled that copper
slag is not a hazardous waste. The review of the results of other
works which were presented in this paper encourages increasing
the rate of reuse and recycling of properly prepared copper slag.
Furthermore, it can be concluded that the utilization of copper slag
in cement and concrete provides additional environmental as well
as technical benefits for all related industries, particularly in areas
where a considerable amount of copper slag is produced. However,
the economic considerations need further evaluations in different
areas.
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