REVI EW

Use of waste copper slag, a sustainable material

Krishna Murari

Rafat Siddique

K. K. Jain
Received: 18 February 2013 / Accepted: 30 March 2014
Springer Japan 2014
Abstract The utilization of solid waste is the challenge
for the civil and environmental engineers to utilize the
waste from different industry to excel the sustainable
development, and in the same time, it is matching with the
cost concern of the present materials. Copper slag is a by-
product obtained during smelting and rening of copper.
The waste copper slag can be used as abrasive tools, road
construction, and ballast. 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 for reusing copper slag is in cement
and concrete production. Many researchers have investi-
gated the use of copper slag in the production of cement,
mortar, and concrete as mixed with lime stone powder,
dust, cement replacement, use as partial replacement of
coarse, and ne aggregates. The use of copper slag in
cement and concrete provides potential environmental as
well as economic benets for all related industries, par-
ticularly in areas where a considerable amount of copper
slag is produced. This paper reviews the application area of
copper slag and its allowable use in different activities.
Keywords Copper slag Concrete Waste Cement
Introduction
Increasing urbanization and economical growth by indus-
trialization concept and technological innovations in the
different eld have contributed to an increase both in the
quantity and variety of wastes generated by industrial,
mining, domestic, and agricultural activities. Globally the
estimated quantity of wastes generation was 12 billion ton-
nes in the year 2002 of which 11 billion tonnes were indus-
trial wastes and 1.6 billion tonnes were municipal solid
wastes (MSW). About 19 billion tonnes of solid wastes are
expected to be generated annually by the year 2025. Annu-
ally, Asia alone generates 4.4 billion tonnes of solid wastes,
and MSW comprise 790 million tones (MT) of which about
48 MT (6 %) is generated in India. By the year 2047, MSW
generation in India is expected to reach 300 MT, and land
requirement for disposal of this waste would be 169.6 km
2
as
compared to 20.2 km
2
occupied in 1997 for management of
48 MT [12, 13]. It is a challenge for the civil and environ-
mental engineers to utilize the waste from different industry
to ensure the sustainable development and in a way that it is
matches with the cost concern of the present materials. The
waste generated from different industry can go for the
recycling or deposal mechanisms that will be lowering the
environmental impact. The status of solid waste generation
in India (MT/y) and composition of Municipal Solid Waste
in India as per NSWAI are shown in Figs. 1 and 2. Copper
slag is a massive metallurgical residue obtained from the
transformation of copper ore concentrates into metallic
copper in the smelters. Slags are deposited in landlls that
occupy large areas of land. Their chemical composition is
rich in iron, silicon, and aluminum oxides, and in their
mineralogical composition, the presence of fayalite and
magnetite among other compounds is common. The use of
supplementary cementitious materials (SCM), e.g., y ash
K. Murari (&) K. K. Jain
Department of Civil Engineering, Jaypee University of
Engineering & Technology, Guna, Madhya Pradesh, India
e-mail: melokrishna@yahoo.com
K. K. Jain
e-mail: kk.jain@juet.ac.in
R. Siddique
Department of Civil Engineering, Thaper University, Patiala,
India
e-mail: siddique_66@yahoo.com
1 3
J Mater Cycles Waste Manag
DOI 10.1007/s10163-014-0254-x
(FA), granulated blast furnace slag (GBFS), silica fume (SF),
and activated metakaolin (AM) can improve various prop-
erties in fresh and hardened state of concrete.
In particular, there is the use of metallurgical waste in the
construction industry, where one of the studied applications
is its use as a substitute for aggregates, both in cement mortar
and concrete [10, 14, 15, 22]. The global concern is to
making economic friendly material product at lower cost
with less harmful effect on environment. In this context,
various worldwide experiences point to the appropriate use
of the copper slag in the manufacture of concrete and cement
mortars, generating a recycling opportunity for what would
otherwise be massive metallurgical liabilities.
Addition of cost saving materials with replacement of
considerable amount of cement reduces CO
2
emission during
the manufacture of portland cement [6, 7, 21, 22]. Nonferrous
slags are produced during the recovery and processing of
nonferrous metal from natural ores. The slags are molten by-
products of hightemperature processes that are primarily used
to separate the metal and nonmetal constituents contained in
the bulk ore. When cooled, the molten slag converts to a
rocklike or granular material. In preparation for metal ion
reduction (designed to separate the metal from the nonmetal
constituents), some monoxide minerals are often converted to
oxides byheatingat air temperatures belowtheir meltingpoint
roasting. Sulde minerals, whenpresent incopper andnickel
ore, are converted to oxides in this process. The reduction of
the metal ion to the free metal is normally accomplished in a
process referred to as smelting. In this process, a reducing
agent, such as coke (impure carbon), along with carbon
monoxide and hydrogen, is combinedwiththe roastedproduct
and melted in a siliceous ux. The metal is subsequently
gravimetrically separated fromthe composite ux, leavingthe
residual slag. In general, the following nonferrous slags are
there: copper, nickel, phosphorus, lead, leadzinc, and zinc.
Copper and nickel slags are produced by(1) roasting, in which
sulfur in the ore is eliminated as sulfur dioxide (SO
2
); (2)
smelting, in which the roasted product is melted in a siliceous
ux and the metal is reduced; and (3) converting, where the
melt is de-sulfurized with lime ux, iron ore, or a basic slag
and then oxygen lanced to remove other impurities. Copper
and nickel slags have been used as granular base and
embankment materials, aggregate substitutes in hot mix
asphalt, mine backll materials, railway ballast materials, grit
blast abrasives, roong granule material, and in the manu-
facture of blended cements (granulated copper and nickel
slags). Scientists, technologists, environmentalists, and
researchers have to play their due role in managing such
wastes suitably and economically. This paper presents a
detailed review about waste copper slag as a material which
can be effectively used in different construction practices. It
can used inpavement constructionand can be usedin concrete
as a ne and coarse aggregate replacement and in cement
mortar as cement replacement. It is a positive effort to explore
its use in concrete/asphalt concrete.
Recent studies on solid waste generation and their
impact in India
A 1998 study by TERI (The Energy Resources Institute,
earlier Tata Energy Research Institute) titled Solid Waste
Fig. 1 Current status of solid
waste generation in India (Mt/y)
Fig. 2 Composition of municipal solid waste in India as per NSWAI
J Mater Cycles Waste Manag
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Management in India: options and opportunities calcu-
lated the amount of land that was occupied by waste dis-
posed post-independence, until 1997. The study estimated
the land occupied in multiples of the size of a football eld
and arrived at 71000 football elds of solid waste, stacked
9 m high. Based on a business as usual (BAU) scenario of
91 % land lling, the study estimated that the waste gen-
erated by 2001 would have occupied 240 sq.km or an area
half the size of Mumbai; waste generated by 2011 would
have occupied 380 sq.km or about 220000 football elds or
90 % of Chennai, the fourth biggest Indian city area-wise;
and waste generated by 2021 would need 590 sq.km which
is greater than the area of Hyderabad (583 sq.km), the
largest Indian city, area-wise [4]. A lot of effort is given to
utilize the coal combustion waste, ceramic industry waste,
foundry sand, etc. It is also essential to give a fair focus on
the initial waste from aluminum, zinc, copper, and other
metal industry waste for their proper economic and sus-
tainable utilization.
There are solutions for proper utilization of industrial
wastes viz. y ash (from thermal power plants), blast fur-
nace slag and steel slag (from iron and steel industries),
phospho-gypsum (from fertilizer plants), red mud (from
aluminum industries), lime sludges (from sugar, paper,
calcium carbide industries), leadzinc slag (from zinc
industries), and kimberlite (from mining) for manufacture
of cement and related building materials. A study con-
ducted by the Indian Institute of Soil Science (IISS),
Bhopal, found that compost produced from solid waste in
India is low grade, with high heavy metal concentrations
and low nutrient value. Figure 3 shows the range of con-
centration of heavy metals zinc (Zn), copper (Cu), cad-
mium (Cd), lead (Pb), nickel (Ni), and chromium (Cr) in
MSW composts from 29 cities. Compost from only two
cities out of twenty-nine passed the statutory guidelines by
European countries (except the Netherlands) for high
quality composts. The study also found that incidence of
heavy metals in solid waste compost from cities (population
\1 million) is less than half of that from bigger cities, but
the compost still does not clear the quality control stan-
dards in all instances. If all solid waste generated in India
in the next decade is composted as mixed waste and used
for agriculture, it would introduce 73000 tons of heavy
metals into agricultural soils as shown in Table 1. Heavy
metals concentration in mixed solid waste compost in
comparison with quality control standards as shown in
Fig. 4 can cause harm to public health and environment
and is the major concern leading to its restricted agricul-
tural use [11]. Mixed waste composting is therefore not an
option for sustainable waste management. In countries like
India where more than 91 % of solid waste is land lled
and there are no other alternatives available, mixed waste
composting is widely practiced and considered better (if
not the best) than land lling [8]. If all solid waste gen-
erated in India from 2011 to 2021 is treated in mechanical
biological treatment (MBT) facilities and the compost was
used for agriculture, it would introduce 73000 tons of
heavy metals into agricultural soils.
Industrial waste generated in India and their utilization
Industrial and mineral wastes from mineral processing
industries, such as metallurgy, petrochemicals, chemicals,
paper, and pulp account for nearly 150 million tonnes per
annum. The more important wastes from these industries
from the view point of building materials are y ash from
thermal power plants, slag from steel industry, press mud
Fig. 3 Heavy metal
concentrations beyond quality
control standards in mixed solid
waste compost from Indian
cities
J Mater Cycles Waste Manag
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from sugar industry, paper sludge from pulp and paper
industry, phospho- chalk and phospho-gypsum from fer-
tilizer industry, carbide sludge from the acetylene industry,
calcium carbonate sludge from soda ash and chrome sludge
from sodium chromate industry, red mud from aluminum
industry, and metallurgical slags from nonferrous industry
[21, 22]. Data on the availability of these wastes and their
areas of utilization are given in report of central pollution
control board, India.
Types of slag
SLAG is a broad term covering all nonmetallic coproducts
resulting from the separation of a metal from its ore. Its
Fig. 4 Heavy metals
concentration in mixed solid
waste compost in comparison
with quality control standards
Table 1 Potential hazard of
introducing heavy metals into
agricultural soils
Years Heavy metals
Zinc Copper Cadmium Lead Nickel Chromium Total
2011 1818.4 1625.1 10.1 1106.9 180.1 623.7 5364
2012 1894.2 1692.9 10.5 1153.0 187.6 649.7 5588
2013 1973.1 1763.4 11.0 1201.0 195.4 676.8 5821
2014 2055.3 1836.9 11.4 1251.1 203.5 705.0 6063
2015 2141.0 1913.4 11.9 1303.2 212.0 734.3 6316
2016 2230.2 1993.2 12.4 1357.5 220.9 764.9 6579
2017 2323.1 2076.2 12.9 1414.1 230.1 796.8 6853
2018 2420.0 2162.8 13.4 1473.0 239.7 830.0 7139
2019 2520.8 2252.9 14.0 1534.4 249.6 864.6 7436
2020 2625.8 2346.8 14.6 1598.3 260.0 900.7 7746
2021 2735.3 2444.6 15.2 1664.9 270.9 938.2 8069
Total 24737 22108 137 15057 2450 8485 72975
Fig. 5 General process diagram
for copper, nickel, and lead
zinc slag production
J Mater Cycles Waste Manag
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chemistry and morphology depend on the metal being pro-
duced and the solidication process used. Slags can be
broadly categorized as ferrous (iron/steel) and nonferrous
(copper, lead/zinc) depending on the industry from which
they come. Figure 5 presents a general schematic diagram
for the slag production process for copper, nickel, and lead
zinc slags. Nonferrous slags, which are only 12 % of the
total annual production and their types and uses, are
described below:
Ferrous slag products iron blast furnace slag (BFS)
This is the by-product from the reduction of iron ores to
produce molten iron and molten slag.
1. When allowed to cool slowly to a crystalline rock
form, it becomes a light gray vesicular rock known as
air-cooled blast furnace slag. Principle uses include
(a) uncrushedll and embankments (particularly
areas subject to severe loading such as mainline rail
systems), working platforms on difcult sites, pave-
ments, where binding nes are produced by rolling to
break the slag down to ll the voids. (b) Graded road
baseon its own or blended with other slags and/or
with other natural rocks and sands. (c) Crushed and
gradedfor concrete aggregates, concrete sand, glass
insulation wool, lter medium, and use under concrete
slabs as a platform.
2. By passing the molten slag through high volume high
pressure water sprays, a glassy, sand-type (granulated)
material is formed, known as granulated blast furnace
slag. The color of this product is very similar to normal
beach sand. (a) The principal use is as cement
replacement (when ground), replacing 3050 % of
portland cement in normal concrete, but can replace
up to 70 % in specialist applications such as marine
concrete. (b) Other uses include glassmaking, trace
elements in agriculture, concrete block manufacture,
sporting eld sub-base (for drainage), ltration med-
ium, reinforced earth embankments, and mine back-
lling and grit-blasting medium requiring ne etching.
Basic oxygen steelmaking slag (BOS or steel furnace
slag)
This slag is formed when molten iron, scrap metals, and
various uxes, such as lime, are oxidized by injecting
large amounts of pure oxygen into the molten iron mix to
create molten steel and molten slag. Slow cooling of the
molten slag produces a dense rock material. Principal
uses include a. blending with many other products such as
granulated slag, y ash, and lime to form pavement
material, and b. other uses include, skid resistant asphalt
aggregate, rail ballast, asphaltic concrete aggregate, soil
conditioner, hard stand areas, and unconned construc-
tion ll.
Electric arc furnace slag (EAF or steel furnace slag)
Produced when scrap metal and uxes are oxidized by the
use of an electric current, molten slag is generally placed
into ground bays for cooling. Both BOS and EAF slags are
somewhat heavier than blast furnace slag and most quar-
ried rock material. Uses include (a) blending with many
other products such as granulated slag, y ash, and lime to
form pavement material, skid resistant asphalt aggregate,
and unconned construction ll.
Copper/lead/zinc slag (CLZS)
Formed from the smelting of ores, it is generally granulated
to form a sand size product with a top size of about 5 mm,
with only a small quantity of material below 1 mm. It is
dark in color and has attracted the name of black sand.
Mostly spherical in nature, it has been used as concrete
sand.
Utilization of copper: historical prospective,
availability, and use
Copper is one of the basic chemical elements. In its nearly
pure state, copper is a reddish-orange metal known for its
high thermal and electrical conductivity. It is commonly
used to produce a wide variety of products, including
electrical wire, cooking pots and pans, pipes and tubes,
automobile radiators, and many others. Copper is also used
as a pigment and preservative for paper, paint, textiles, and
wood. It is combined with zinc to produce brass and with
tin to produce bronze. It is a ductile metal with excellent
electrical conductivity and nd extensive use as an elec-
trical conductor, as a heat conductor, as a building material,
and as a component of various alloys. Copper has played a
signicant part in the history of mankind, which has used
the easily accessible uncompounded metal for nearly
10000 years. A copper pendant from about 8700 B.C. was
found in what is now northern Iraq. There is evidence that
by about 6400 B.C., copper was being melted and cast into
objects in the area now known as Turkey. By 4500 B.C.,
this technology was being practiced in Egypt as well. Most
of the copper used before 4000 B.C. came from the random
discovery of isolated outcroppings of native copper or from
meteorites that had impacted Earth. The rst mention of the
systematic extraction of copper ore comes from about 3800
B.C. when an Egyptian reference describes mining opera-
tions on the Sinai Peninsula. During the Roman Empire,
copper was principally mined on Cyprus, hence the origin
J Mater Cycles Waste Manag
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of the name of the metal as cyprium, metal of Cyprus,
later shortened to Cuprum. Today, the USA and Chile are
the worlds top two copper producing countries, followed
by Russia, Canada, and China. Nevertheless, the price of
copper rose rapidly, increasing 500 % from a 60-year low
in 1999, largely due to increased demand. This metal has
come into the limelight on account of high volatility in
prices. The size of Indian Copper Industry is around four
lakh tons, which as percentage of world copper market is
three percent. Sterlite Industries, Hindalco, and Hindustan
Copper are three major producers of copper in India. The
Indian copper industry grew by nearly 50 % in 2011.
About a decade ago, the Indian copper industry consisted
of a single state-owned company, and now the copper
industry in India takes up about 3 % of the global market
for copper. In 2011, Indias copper demand is estimated to
grow by at least 7 %following a similar forecast in 2010,
fed by the power sector. According to Indias 11th 5 year
plan (20072012), the countrys power generation sector is
likely to make a huge investment with 150 power projects
for the various stages of installation. The most favorable
contributing factors for the growth of the Indian copper
industry include changes in global usage, industrial
development in India, domestic increases in the construc-
tion, power, telecommunications, and automobile sectors.
Copper is used broadly in the manufacture of electrical
machinery, building, cabling for power and telecommuni-
cations, and automobiles. Growing trend in the building
construction and automobile sector is expected to keep
demand of copper high. At the same time, the waste gen-
erated by the copper industry is also increasing at the same
percentage.
Properties of waste copper slag
Physical properties
Copper slag grains have a color of black glassy type and
a neness modulus of 3.5. The hardness is about 7
Mohs scale. Other typical physical properties are given
in Table 2. In order to use copper slag as a mineral
admixture, it was necessary to carry out an experimental
study associating grinding time, average diameter, and
pozzolanic activity assessed in mortars [3]. Based on
this study, it was veried that 60 min was the optimal
grinding time in horizontal ball mills to achieve an
average diameter of 27.2 lm. The copper slag presented
a pozzolanic activity index of 87 % according to spec-
ication requirements of ASTM 618_C for portland
cement mineral additives. Copper slag has a specic
gravity at 25 C is of value 3.5. Its chemical composi-
tion is showed in Table 3.
Figure 6 shows the X-ray diffraction, and Fig. 7 shows
secondary electron scanning electronic microscopy of
sample cooper slag. The results obtained from the copper
slag micrograph demonstrate that the materials grains are
originally spherical, with a smooth and nonporous surface.
The X-ray diffraction results indicated the presence of
fayalite and magnetite. Some high peak frequencies were
observed, which suggests a basically crystalline structure.
Air-cooled copper slag has a black color and glassy
Table 2 Typical physical properties of copper slag
Property Typical value
Grain shape Angular, multifaced
Specic gravity at 25 C 3.5
Bulk density at 25 C 1.87 tonnes/m
3
pH 7.0
Weight raise on ignition 4 %
Moisture content \0.1 %
Table 3 Chemical analysis of copper slag
Constituent % Weight
Silica SiO
2
(combined as silicate) 32 %
Free silica \0.5 %
Alumina Al
2
O
3
2 %
Iron oxide as FeO 43 %
Calcium oxide CaO 1.5 %
Magnesium oxide MgO 0.8 %
Copper oxide CuO 0.6 %
Sulfates 0.1 %
Chlorides 0.001 %
Fig. 6 X-ray diffractogram of the copper slag sample
J Mater Cycles Waste Manag
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appearance. As a general rule, the specic gravity will vary
with iron content, from a low of 2.8 to as high as 3.8. The
unit weight of copper slag is somewhat higher than that of
conventional aggregate. The absorption of the material is
typically very low (0.13 %). Granulated copper slag is
more porous and therefore has lower specic gravity and
higher absorption than air-cooled copper slag. The granu-
lated copper slag is made up of regularly shaped, angular
particles, mostly between 4.75 mm (3/4 in) and 0.075 mm
(no. 200 sieve) in size. During slag production, the sudden
cooling that results in the vitrication of copper slags
(typically in the granulating process) prevents the mole-
cules from being locked up in crystals. In the presence of
an activator (such as calcium hydroxide from hydrating
portland cement), vitried nonferrous slags react with
water to form stable, cementitious, hydrated calcium sili-
cates. The reactivity depends on the neness to which the
slag is ground (reactivity increases with neness) and the
chemical composition of the slag and its glass content.
These vitried slags can be of such composition that when
ground to proper neness, they may also react directly with
water to form hydration products that provide the slag with
cementitious properties. High iron content (essentially
ferrous silicate slags) in this slags appears to limit hy-
draulicity and makes grinding difcult.
Cooper slag as a abrasive media
The term abrasive in blasting refers to a wide range of
materials (blasting media) used to establish a prole on
clean steel and remove unwanted coatings or contaminants
from the surface of steel or other substrates. During
blasting, there are a number of physical considerations in
the selection of suitable media. As the grains impact the
surface, there is a tendency for them to break down
forming a potentially harmful dust. In addition, the clean-
ing action is the result of energy transfer, which is trans-
ferred from the abrasive to the substrate. As the kinetic
energy is proportional to the mass of the grain and the
square of its velocity, a small, heavy grain moving at high
speed will have more effect on a substrate than a larger,
lighter grain. From this, it can be seen that heavier (denser)
materials such as steel and garnet are more efcient
blasting media than lighter (less dense) media such as sand
Fig. 7 Shows secondary electron scanning electronic microscopy
Table 4 Different abrasive
media along with their
properties
Abrasive Composition Mohrs hardness Density
(g/cu.cm)
Dusting Recycling
Silica sand Crystalline silica 7.0 1.6 Low No
Best quality
Average quality same 6.5 1.6 High No
Staurolite/zircon Iron aluminum silicate 7.5 2.0 Mod No
Garnet Iron aluminum silicate 7.5 2.0 Low Yes
Almandite
Andradite Calcium silicate 6.5 1.8 High No
Olivine Iron silicate 6.5 1.9 High No
Spec. hematite Iron oxide 6.0 2.3 Mod No
Copper slag Iron silicate glass 6.0 1.6 Mod No
Nickel slag Nickel iron glass 6.0 1.6 High No
Iron slag Iron silicate glass 6.0 1.6 High No
Coal boiler slag Ca iron silicate glass 6.0 1.4 High No
Steel grit/short Iron (steel) 6.0 2.2? Low Yes
Baking soda Sodium carbonate 2.03.0 1.1 High/Low No
Crushed glass Alkaline silicate GLASS 6.0 1.6 High No
Organic media Various 23 01.0 N/A No
J Mater Cycles Waste Manag
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and slag. Since slags are almost always associated with
copper mines, the general term copper slag has come to
be used even for slags that might be more accurately be
called lead slags, zinc slags, or even arsenic slags.
Copper slags carry small amounts of the metals that were
present in the original ores and smelter concentrates [14].
The purpose of the slag was to act as a collection mecha-
nism of these undesirable contaminates during the recovery
of the metal of interest. Copper slags are common substi-
tutes for silica sand in countries where mines and smelters
are abundant. The different materials used for the abrasive
media is given in the Table 4.
Use of cooper slag in pavement industry
In India, there is great demand of aggregates mainly from
civil engineering industry for road and concrete construc-
tions. The construction of highways and development of
several expressways for high-speed corridors exert tremen-
dous pressure on natural resources. Many highway agencies,
private organizations, and individuals are in the process of
completing a wide variety of studies and research projects
concerning the feasibility, environmental suitability, and
performance of using waste industrial products in highway
construction [1, 2]. These studies try to match societys need
for safe and economic disposal of waste materials with the
highway industrys need for better and more cost-effective
construction materials. Various studies explore the potential
use of copper slag as ne aggregate (up to 30 %) in the design
of bituminous mixes like bituminous macadam, dense bitu-
minous macadam, bituminous concrete, and semi-dense
bituminous concrete, which enhance the property of the
bituminous mixes. Nonferrous slags are produced during the
recovery and processing of nonferrous metal from natural
ores. The slags are molten by-products of high temperature
processes that are primarily used to separate the metal and
nonmetal constituents contained in the bulk ore.
Use of cooper slag in cement and concrete
The copper slag obtained may exhibit pozzolanic activity
and may therefore be used in the manufacture of addition-
containing cements. Blends of copper slag with portland
cement generally possess properties equivalent to portland
cement containing y ash, but very different to the silica
fume incorporation. Copper slag and y ash reduce the heat
of hydration more effectively than silica fume in mortars.
The replacement of 30 % cement by copper slag reduces
the exural and compressive strength in a similar way to y
ash; however, after 28 days, the reduction is less than the
percentage of substitution. The pozzolanic activity of
copper slag is similar to that of y ash and higher than
silica fume. In the presence of low water/cement ratios,
certain pozzolanic materials produce a very compact
cement paste that limits the space available for hydration
products, a determining factor in the formation of hydrated
calcium aluminates. SEM was found to be a useful ana-
lytical technique when aluminates are formed and can be
clearly detected by XRD.
Land lling is not a desirable option for the disposal of
solid hazardous and nonhazardous waste materials. It is not
a liable method because of future environmental costs and
problems associated with land lling regulations. This
method increases load of toxic metals and other contami-
nants in the landll, potentially increasing the threat to
groundwater contamination. Increasing economic and
nancial factors also dictates that industry should look
forward to recycling and reuse of waste material as a better
option to land lling. Wastes and by-products can be used in
addition to concrete without the need for large changes in its
preparation. For all waste and by-product contents, the
strengths increase as the curing time of the concrete
increases. In general, it would be suitable for any applica-
tion that does not require high strengths, especially not in
the short term [14, 17]. The porosity and the absorption
coefcient increase with an increase in waste content and
decrease as the curing time increased [15, 18, 19]. The
deformability of concrete also increases with the increase in
waste contents [8, 9, 20]. The density of the concrete
decreases with an increase in waste content and increases as
the curing time increases. In previous study on concrete
M15 and geopolymer, the mixed concrete is a desirable
option to utilize or reuse of solid hazardous waste materials
shown in Figs. 8 and 9. Solidied materials are weak and
contain signicantly less cementitious materials and more
water, for example concrete. Due to waste addition, CSH
hydration is poisoned. In these situations, ettringite plays an
important roleit increases strength and durability char-
acteristics. UCS increases with a decrease in crystalline
phases. Aggregate, which makes up 70 % of the concrete
volume, is one of the main constituent materials in concrete
production. However, due to the high cost of natural sand
used as a ne aggregate and the rising emphasis on sus-
tainable construction, there is a need for the construction
industry to search for alternative materials as ne aggre-
gates in concrete production. Copper slag, which is the
waste material produced in the extraction process of copper
metal in renery plants, has low cost, and its application as a
ne aggregate in concrete production reaps many environ-
mental benets such as waste recycling and solves disposal
problems. Currently in Singapore, the Building Construc-
tion Authority limits the replacement of sand by copper slag
to a maximum of 10 % by mass in construction engineering
with additional precautionary measures in place.
Hwang and Laiw in 1989 make an attempt to nd out the
usability of copper used as a ne aggregate. The physical and
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chemical properties of copper slag were investigated. Cop-
per slag, in amounts of 20, 40, 60, 80, and 100 %, was
substituted for ne aggregate in cement mortar and concrete.
The neness modulus of the combination of copper slag and
ne aggregate was roughly 2.6, the optimum neness mod-
ulus for concrete mix design. At this value, workability was
found to be satisfactory with minimal bleeding. Addition of
copper slag also improved the strength of the concrete. When
the substitutional amounts exceeded 80 %, lower strengths
were obtained, possibly due to the formation of ettringite. It
was also found that the effect of copper slag on long-term
strength development was also dependent on the amount
used and its neness. Ayano and Sakata in 2000 studied the
lack of natural ne aggregate in Japan is serious because the
commitment to protect the natural environment is increasing.
Many concrete engineers are eager to nd ne aggregate
sources other than the traditional river and sea sand. Copper
slag ne aggregate is expected to be one of the alternatives
although the location where the copper slag is available is
limited. In this paper, some characteristics of concrete with
copper slag will be claried. The carbonated thickness,
resistance to freezing and thawing, thermal resistance,
shrinkage strain, creep, and setting time have been exam-
ined. The strength, slump, and durability of concrete with
copper slag are not inferior to those of normal concrete.
However, copper slag sometimes delays the setting time of
concrete even if it produced at the same renery. The delay of
setting time is more than one week in some cases although
the durability in concrete is not affected by it.
Tay et al. [6] studied on the reuse of industrial waste from
copper slag plant. This study describes the use of sintered
sludge pellets as a complete replacement for regular granite
aggregates in concrete. The pelletized sludge was red to a
temperature of 1,1357 C at which the sintering process
occurs, producing a hard fused basalt-like mass. TGDTA
plots of copper slag are shown in Fig. 10. In comparison with
normal granite aggregates, the sintered sludge pellets display
a higher aggregate strength, a higher porosity, and a lower
aggregate density that manifests attributes better than that
required of construction aggregates. The concrete cast with
the pelletized aggregates achieved a compressive strength of
38.5 N/mm
2
after 28 days and was comparable to the control
specimen. The experimental results indicated that a complete
replacement of conventional aggregates with sintered sludge
pellets for structural concrete is both technically and envi-
ronmentally feasible.
Mobasher et al. (1996) has a research paper in material
engineering conference about the effect of copper slag on
the hydration of cement-based materials. Up to 15 % by
weight of copper slag was used as a portland cement
replacement. Activation of pozzolanic reactions was stud-
ied using up to 1.5 % hydrated lime. Hydration reactions
were monitored using quantitative X-Ray diffraction
(QXRD), and the porosity was examined using mercury
intrusion porosimetry (MIP). Results indicate a signicant
increase in the compressive strength for up to 90 days of
hydration. A decreases in capillary porosity measured using
MIP indicated densication of the microstructure.
Tixier et al. (1997) investigated the effect of copper slag on
the hydration of cement-based materials. Up to 15 % by
Fig. 10 Strength development of copper slag mortar as age and
dosage of copper slag
Fig. 8 Strength development of alkali-activated slag/y ash mortars
Fig. 9 Strength of alkali-activated copper slag and portland cement
mortars
J Mater Cycles Waste Manag
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weight of copper slag was used as a portland cement
replacement. Two types of paste were studied with and
without microsilica. In Fig. 11, copper slag is shown to sig-
nicantly increase the compressive strength of concrete
mixtures. This added increase is expected to be due to the
densication of the microstructure in the capillary pore region.
Arino and Mobasher [5] studied the effect of ground
copper slag (GCS) on the strength and fracture of cement-
based materials is studied. Up to 15 % by mass of ground
copper slag was used as a portland cement replacement.
Compressive strength results are shown in Fig. 12. The
strength and fracture toughness of concrete samples were
studied using closed-loop controlled compression and
three-point bending fracture tests. The compression test
utilized a combination of the axial and transverse strains as
a control parameter to develop a stable post-peak response.
A cyclic loadingunloading test was conducted on three-
point bending notched specimens under closed-loop crack
mouth opening control. Moura et al. (1999) emphasis on
recycling of solid by-products as construction materials can
be an alternative to reduce costs of the latter and the impact
on the environment. Nevertheless, it is fundamental that the
characteristics of these new materials be equivalent to the
traditional ones or even better, if possible. In this context,
the use of electric steel slag and copper slag can be a
potential alternative to the admixtures used in concrete and
mortars. Results of physical, chemical, and physical
chemical characterizations of electric steel lags from Rio
Grande do Sul and copper slags from Bahia, both in Brazil,
are presented in his work. Also presented are results of
compressive tests, exural tests, and Brazilian tests in
concrete specimens with these admixtures, indicating the
viability of their use. Shi and Qian [7] studied that most
industrial slags are being used without taking full advan-
tage of their properties or disposed rather than used. The
industrial slags, which have cementitious or pozzolanic
properties, should be used as partial or full replacement for
portland cement rather than as bulk aggregates or ballasts
because of the high cost of portland cement, which is
attributable to the high energy consumption for the pro-
duction of portland cement. The traditional way to utilize
metallurgical slags in cementing materials is to partially
replace portland cement, which usually results in a lower
early strength and longer setting times. Presence of acti-
vator(s) can accelerate the breakup of structure and
hydration of slags.
Many research results have indicated that clinker less
alkali-activated slags even exhibit higher strengths, denser
structure, and better durability compared with portland
cement. In the paper, the recent achievements in the
development of high performance cementing materials
based on activated slags such as blast furnace slag, steel
slag, copper slag, and phosphorus slag are reviewed.
Rai et al. [9] studied the metallurgical slags (granulated
and air-cooled) are disposed as waste from the ferroman-
ganese and ferromanganesesilicon alloys manufacturing
plants. They nd little use unlike blast furnace slags from
steel plants. Investigations were carried out to explore the
possibility of using high MnO and low MnO metallurgical
slags on samples obtained from an alloy plant in India.
Low MnO granulated slag was used in making blended
slag cement with ordinary portland cement (OPC). Addi-
tion of slag lowered the compressive strength of the blen-
ded cement as compared to that of OPC used. However, the
composition of a 50:50 blend, ground to 3000 cm
2
/g
(Blaine), was found to conform to IS 455:1989 for portland
slag cements and also to IS 269:1989, 33 grade OPC, with
respect to standard consistency, setting times, soundness,
and compressive strength (22 MPa at 7 days and 33 MPa
at 28 days) tests carried out as per IS 4031:1988. X-Ray
diffraction analysis showed that low MnO granulated slag
was noncrystalline, whereas the air-cooled slags were
crystalline containing mainly quartz, MnO, and Mn
2
O
2
,
indicating pozzolanic reactions contributing to a great
extent in the strength development of blended slag cement
compositions studied. High MnO (15 %) and MgO (8 %)
containing slags were considered unsuitable for blended
cements because of their deleterious effects. Air-cooled
lumpy slag was evaluated for use as aggregates in concrete.
The results of the investigations provide a direction for
protable plans for making blended slag cements.
Gorai et al. (2003) studies in National Mineral Labora-
tory, Jamshedpur, about the copper slag, which is produced
during pyrometallurgical production of copper from copper
ores, contain materials like iron, alumina, calcium oxide,
and silica. The favorable physico-mechanical characteris-
tics of copper slag can be utilized to make the products like
cement, ll, ballast, abrasive, aggregate, roong granules,
glass, and tiles apart from recovering the valuable metals
by various extractive metallurgical routes. He performed an
investigation of cement-based solidication/stabilization
Fig. 11 Compressive strength with the variation of copper slag
percentage
J Mater Cycles Waste Manag
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process for the safe disposal of blasted copper slag. The
treatments evaluated were based on ordinary portland
cement (OPC). Mortar specimens with ground copper slag
ranging from 0 to 10 % by weight of cement were tested
for whole block and crushed block leachability, compres-
sive strength, and hydration. Addition of copper slag to
cement increased initial and nal setting times. The pri-
mary hydration process was the OPC hydration. The
strength of the copper slag mortar was generally lower than
that of the control mortar, and the amount of ground copper
slag to replace cement for optimum strength was about
5 %.
Al-Jabri et al. (2006) study the effect of copper slag
(CS) and cement bypass dust (CBPD) addition on concrete
properties The modulus of elasticity of these mixtures was
also evaluated. Results showed that 5 % copper slag sub-
stitution for portland cement gave a similar strength per-
formance as the control mixture. Results also demonstrated
that the use of CS and CBPD as partial replacements of
portland cement has no signicant effect on the modulus of
elasticity of concrete, especially at small quantities
substitution.
Taha et al. [11] dene the CLSM as A controlled low
strength material (CLSM) is a self-compacted, cementi-
tious material used primarily as a backll. It is also
known as a owable ll which is usually a mixture of ne
aggregates, small amount of cement, y ash, and water.
To be classied as a CLSM, the mixture must have a
compressive strength between 345 and 8400 kPa. This
paper evaluates the potential use of cement bypass dust,
incinerator ash, and copper slag as a CLSM. Mixtures
were designed to produce a CLSM, with a low com-
pressive strength (\1034 kPa), that can be excavated
without using any mechanical equipment. Slump, unit
weight, and unconned compressive strength tests were
conducted on various mixtures. Cubical and cylindrical
specimens were prepared and cured at room temperature
and in sealed plastic bags. Results indicate that with a
good mix design, it is possible to produce a CLSM with
good mechanical properties to meet design requirements.
Mixing these materials with cement and sand produced
better results than using them alone due to their low
pozzolanic activity. Curing method and period can have
considerable effects on the strength of a CLSM shown in
Fig. 13.
Kim et al. (2008) studied that slag, which consists of
calcium oxide, aluminum oxide, and other metal oxides, is
an abundant by-product in steel-making process. It has
been used as adsorbents to remove various heavy metals,
and the major removal mechanisms are precipitation and
adsorption on the surface of metal oxide. However, the
Fig. 12 TGDTA plots of
copper slag
Fig. 13 Comparison between the effects of different materials on the
compressive strength of cement mortars
J Mater Cycles Waste Manag
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relative contribution of two removal mechanisms has not
reported. In this study, the removal characteristics of cop-
per were investigated in terms of sorption kinetics and
sorption isotherms. As initial pH of solution increased, the
sorption capacity of slags increased dramatically. Kim
et al. evaluated the relative contribution of two mecha-
nisms in the copper removal by steel-making slag. At
above pH 3.0, contribution of adsorption to overall removal
of copper was \12 %. As a result, most of copper was
removed by slag as a form or copper hydroxide.
Alp et al. studied that the copper slag wastes, even if
treated via processes such as otation for metal recovery,
still contain heavy metals with hazardous properties posing
environmental risks for disposal. This study reports the
potential use of otation waste of a copper slag (FWCS) as
iron source in the production of portland cement clinker.
The FWCS appears a suitable raw material as iron source
containing [59 % Fe
2
O
3
mainly in the form of fayalite
(Fe
2
SiO
4
) and magnetite (Fe
3
O
4
). The clinker products
obtained using the FWCS from the industrial scale trial
operations over a 4-month period were characterized for
the conformity of its chemical composition, and the
physico-mechanical performance of the resultant cement
products was evaluated. The results have shown that the
chemical compositions of all the clinker products including
those of FWCS are typical of a portland cement clinker.
These ndings suggest that otation wastes of copper slag
(FWCS) can be readily utilized as cement raw material due
to its availability in large quantities at low cost with the
further signicant benets for waste management/envi-
ronmental practices of the FWCS and the reduced pro-
duction and processing costs for cement raw materials.
Khalifa et al. [16] investigate the performance of high-
strength concrete (HSC) made with copper slag as a ne
aggregate at constant workability and study the effect of
super plasticizer addition on the properties of HSC made
with copper slag. The water content was adjusted in each
mixture in order to achieve the same workability as that for
the control mixture. The results indicated that the water
demand reduced use of copper slag replacement compared
to the control mixture shown in Fig. 14. The strength of
HSC was generally improved with the increase in copper
slag content in the concrete mixture.
Khanzadi et al. [15] presents the results of a study
undertaken to investigate the feasibility of using copper
slag as coarse aggregates in high-strength concrete. The
effects of replacing limestone coarse aggregate by copper
slag coarse aggregate on the compressive strength and
splitting tensile strength are evaluated in this work. The use
of copper slag aggregate compared to limestone aggregate
resulted in a 28-day compressive strength increase of about
1015 % and a splitting tensile strength increase of
1018 %.
Zhang et al. (2009) have investigated the mechanical
properties of high-strength concrete incorporating copper
slag as a ne aggregate and concluded that \40 % copper
slag as sand substitution can achieve a high-strength con-
crete that comparable or better to the control mix, beyond
which, however, its behaviors decreased signicantly. The
results indicated that the strength of the concrete with less
than 40 % copper slag replacement was higher than or
equal to that of the control specimen and the workability
even had a dramatic growth [10].
Sandhyarani (2009) studied about the copper slag for
wear resistance. In his study, he uses copper slag as a ller
in glassepoxy composites, and the tensile modulus
increased from 8.77 to 9.64 GPa when using up to 10 wt%
of copper slag but on further addition of copper slag (up to
20 wt%), the tensile modulus started to decrease down to
7.11 GPa. Similar trends were observed in the case of
exural strength and shear strength. With the incorporation
of copper slag particles, the impact strength increased
about 1015 %. This work includes the processing, char-
acterization, and study of the erosion behavior of a class of
such copper-slag-lled glassepoxy composites based on
Taguchis experimental approach to characterize erosion
behavior. The investigation is also performed for the pos-
sible utilization of copper slag as ller material for the
preparation of composite materials and preparation of
added value products such as abrasive tools, cutting tools,
and railroad ballast.
Use of industrial wastes and by-products as an aggregate
or raw material is of great practical signicance for
developing building material components as substitutes for
the traditional materials and providing an alternative or
supplementary materials to concrete industry in a cost-
effective manner. In order to effectively utilize all these
Fig. 14 Relationship between workability and strength of HPC
J Mater Cycles Waste Manag
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solid wastes, effort has been made and mathematical
models were also established universally and as a conse-
quence, considerable quantity of wastes is now being
recycled and used to achieve environmentally sound
management. Studies on potential use of different mining
tailings in bricks have revealed that this waste along with
clay can be effectively utilized for making better quality
red bricks and use of copper has resulted in achieving
high strength.
The potential environmental risk by the geotechnical
utilization of wastes needs to be avoided. Many waste
materials might be contaminated by toxic and hazardous
substances and require treatment for safe disposal. Waste
utilization can serve not only to prevent the negative envi-
ronmental impact but also to preserve and protect nature. In
this study, we are put steps in such a waste called copper slag
which is by-product of industry. The merits of the copper slag
for using it in the construction industry and with the con-
struction materials are initially listed it as general properties.
The optimal solution for solid waste management is to
minimize the quantity of waste both at generation and dis-
posal stage followed by preventive environmental manage-
ment action. Recycling of solid wastes is another major
productive area in which considerable quantity can be uti-
lized for manufacturing new advanced, durable, and sus-
tainable material. Copper slag is produced during the
recovery and processing of nonferrous metal from natural
ores. The slags are molten by-products of high temperature
processes that are primarily used to separate the metal and
nonmetal constituents contained in the bulk ore. When
cooled, the molten slag converts to a rocklike or granular
material.
Conclusions
Concrete serves as a better alternative for the utilization or
recycle of the solid industrial waste materials. Properties of
mixed concrete can be enhanced by using these waste mate-
rials. Addition of copper slag shows 6070 %strength of pure
concrete, and in some optimumamount of replacement, it can
show much higher strength in comparison with control con-
crete. All the other properties are also well in control status by
adding the copper slag as a replacement of ne as well as
coarse aggregate. It also shows more strength when it is used
with other cement supplement material like lime dust and
silica fume. Concrete made with copper slag shows long-term
durability as a ne or coarse aggregate replacement or in
addition use of different mineral admixtures. Important
structures are manufactured using this concrete, which posi-
tively affects on durability aspects.
Initially it is used as lling materials, pavements, and
roadbeds. The concrete which is the major material in the
construction industry and for infrastructural development
made with waste copper slag also affects the cost of con-
struction comparable to pure concrete. This concrete is safe
enough to be used in environmental applications in roadbeds
and as lling material. Thus, due to the benecial use of the
immobilized material, this type of industrial wastes and by-
products usability appears to offer a promising way to
improve sustainable environment in developing countries.
The user of copper slag in cement can be assured of the
nonleachability of copper and other elements. This further
ensured the performance of cement and using copper slag
in different cement types shall also help the manufacturers
to reduce the cost of production.
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