Journal of Environmental Management 196 (2017) 607e613

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Journal of Environmental Management

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Research article

Blasted copper slag as fine aggregate in Portland cement concrete

M.A.G. dos Anjos, A.T.C. Sales*, N. Andrade
~o Cristo
Department of Civil Engineering, Federal University of Sergipe, CEP 49100-000, Sa ~o, Sergipe, Brazil
va

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

Article history: The present work focuses on assessing the viability of applying blasted copper slag, produced during
Received 6 September 2016 abrasive blasting, as fine aggregate for Portland cement concrete manufacturing, resulting in an alter-
Received in revised form native and safe disposal method. Leaching assays showed no toxicity for this material. Concrete mixtures
8 February 2017
were produced, with high aggregate replacement ratios, varying from 0% to 100%. Axial compressive
Accepted 12 March 2017
strength, diametrical compressive strength, elastic modulus, physical indexes and durability were
evaluated. Assays showed a significant improvement in workability, with the increase in substitution of
fine aggregate. With 80% of replacement, the concrete presented lower levels of water absorption ca-
Keywords:
Portland cement concrete
pacity. Axial compressive strength and diametrical compressive strength decreased, with the increase of
Blasted copper slag residue replacement content. The greatest reductions of compressive strength were found when the
Waste reuse replacement was over 40%. For tensile strength by diametrical compression, the greatest reduction
occurred for the concrete with 80% of replacement. After the accelerated aging, results of mechanic
properties showed a small reduction of the concrete with blasted copper slag performance, when
compared with the reference mixture. Results indicated that the blasted copper slag is a technically
viable material for application as fine aggregate for concrete mixtures.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction (Nobre Filho et al., 2011).

The possibility of using residues as cement mixture components
Estimations point out that for each ton of copper produced, 2.2 brings several advantages involving its reuse, such as, the possi-
tons of slag is generated (Gorai et al., 2002). In Brazil, by the years of bility of decreasing the natural resources exploration and inade-
2012 and 2013, 179.40 and 261.00 tons of refined copper were quate disposal to the environment. Despite the considerable
produced, respectively. It is possible to state that, during this bi- amount of scientific research on the topic of copper slag use in
ennium, the generation of copper slag, in the country, was of cement mixtures (Zhu et al., 2012; Wu et al., 2009; Al-Jabri et al.,
around 968.88 tons. Copper slag is widely used as an abrasive in 2009), research with blasted copper slag is still scarce.
blasting process. After being applied and losing its abrasive po- Zain et al. (2004) applied blasted copper slag as an additive,
tential, it called blasted copper slag, a common residue of the replacing Portland cement in mortar, in order to study a safe route
blasting process. This residue needs proper disposal, which is not for disposal of this sub-product. The replacement of cement by this
always an effective or simple process. residue increased the setting time and slightly reduced compres-
The environmental impacts from mineral production are very sive strength in mortars, finding that the optimal amount of
well known. Excavation and dismount of sand deposits are among replacement was between 5 and 7.5%.
the activities that generate higher impacts, compromising the Resende (2009) studied the application of blasted copper slag as
landscape physical characteristics, generating particulates and an aggregate in mortar, replacing natural fine aggregate. Although
removing natural coverage of the area. Sand extraction from rivers the physical characteristics of the material induced to a gain in
generates impacts, which demand environmental control studies, mechanical parameters of the mixtures, the increment of blasted
seeking the implementation of recovery and rehabilitation mea- slag induced to less resistant mortars, reaching an optimal
surements on the affected area, which is not always successful replacement value of 25%. The decrease in mechanical indexes was
attributed to higher levels of iron oxides, zinc oxides and traces of
sulfur in the chemical composition of the slag.
The present work seeks to assess the effects of total and partial
* Corresponding author.
E-mail address: angelasales19@gmail.com (A.T.C. Sales). replacement of the fine aggregate by blasted copper slag e abrasive

http://dx.doi.org/10.1016/j.jenvman.2017.03.032
0301-4797/© 2017 Elsevier Ltd. All rights reserved.
608 M.A.G. dos Anjos et al. / Journal of Environmental Management 196 (2017) 607e613

blasting residue e on the physical and mechanical performance,

and on the durability of structural concrete from Portland cement.

2. Experimental procedure

2.1. Materials

The study used high early strength Portland cement, with spe-
cific gravity of 3.02, initial setting time of 1 h and 50 min and a
0.62% retention of material, when using a 75 mm mesh sieve, ac-
cording to the parameters determined by the NBR NM 23 (ABNT,
2001), NBR NM 65 (ABNT, 2003), NBR 11579 (ABNT, 2012),
respectively. The binder choice was based on the additive content,
considering that based on the locally available cement, this was the
one with lower level of additive. Poly-carboxylate-based water-
reducing admixture was used.
The fine aggregate used was ravine sand with 76% of its mass
Fig. 1. Grain size distribution curves of aggregates.
between 0.15 and 1.20 mm mesh sieve. The coarse aggregate was
crushed granite, in two size classes, named crushed stone 0 and
crushed stone 1. mixture with different replacement of fine aggregate for blasted
Blasted copper slag was collected from construction site, from copper slag were produced, with 20%, 40%, 60%, 80% and 100%
oil storage tank cleaning procedure. All the sandblasting carried out blasted copper slag content. For each mixture, a sample with 22
produced around 31.2 T of blasted copper slag, where only the cylindrical samples, molded according to the Brazilian standard
abrasive already used was collected and classified as useless, NBR 5738 (ABNT, 2015), were prepared, according to experimental
applied only on the outer face of the tank, an area presenting no planning seen in Table 4.
hydrocarbons. Concrete were produced in a mixer and specimens were casted
The blasted copper slag is a granular black material. Specifically, presenting 200 mm of height and 100 mm of diameter, compacted
the waste used in this research presented uniform grain size, with using an immersion vibrator. For the first 24 h, specimens were
79.3% of its grain dimensions between 0.60 mm and 0.15 mm. kept in molds and immersed in water for the following 27 days.
Further physical characteristics of aggregates and blasted copper Concrete were dosed by the American Concrete Institute (ACI)
slag are seen in Table 1. method, adapted by the Portland Cement Brazilian Society (ABCP)
Considering these indexes, it is possible to note that blasted (Rodrigues, 1998), leading to the proportions and slump measure-
copper slag presents a specific gravity and unit weight, 45.8% and ments seen in Table 5. The compressive strength was established as
58% higher, respectively, than the conventional fine aggregate 30 MPa, with standard deviation of 4 MPa. The consistency index
commonly used, as determined by NBR 9935 (ABNT, 2011a). was measured by slump test and set at around 160 ± 20 mm. The
Morphologically, the residue was analyzed by scanning electron water/cement ratio was of 0.52 for all concretes obtained. The
microscopy (SEM) and, as seen in Fig. 2, presented irregularly sized concretes were named according to their replacement content. The
grains, with smooth and very low porosity surfaces, which poten- reference concrete was named CE000, without residue
tially explains its low water absorption, only 0.33%. replacement.
As presented in Table 2, chemical characterization, considering
oxides found in blasted copper slag, was determined by x-rays
fluorescence (XRF), indicating the predominance of Fe2O3 in its 2.3. Testing procedures
composition, reaching nearly 80% of the total oxides present. Silica
and alumina were also noted, with 11.20% and 1.08%, respectively. 2.3.1. Mechanical analysis
In order to classify the blasted copper slag according its envi- Concrete axial compressive strength, splitting and modulus of
ronmental and public health risks, the material was submitted to elasticity tests were carried out according to NBR 5739 (ABNT,
processes described by NBR 10004, NBR 10005, NBR 10006 (ABNT, 2007), NBR 7222 (ABNT, 2011b), NBR 8522 (ABNT, 2008), respec-
2004a,b,c) e leaching and solubility processes, being classified as tively. For water absorption, void index and specific gravity, NBR
Class II A residues e Non-inert, therefore, non-toxic, non- 9778 (ABNT, 2009) was considered.
dangerous and non-inert. The non-inert classification is due to the Concrete comparative durability analysis with various level of
solubilized concentration of mercury present being higher than the fine aggregate replacement was based in submitting the specimens
Brazilian norms specification (Table 3). to an accelerated aging process, by alternating cycles of wetting and
drying. Six cycles of 96 h of immersion in water followed of 72 h of
2.2. Concrete production and test samples casting drying in stove at 100 ± 5
C, were carried out.
After these cycles, the specimens were submitted to axial
Besides the reference mixture, five composition of concrete compressive tests. The performance of mixtures, considering

Table 1
Physical parameters of aggregates.

Aggregates Specific gravity Unit weight (g/cm3) Water absorption capacity (%) Maximum diameter (mm) Fineness modulus

Ravine sand 2.64 1.48 0.60 4.80 2.69

Crushed stone 0 2.65 1.56 0.53 12.5 5.73
Crushed stone 1 2.65 1.54 0.51 12.5 6.52
Blasted copper slag 3.85 2.26 0.33 1.20 1.55
 M.A.G. dos Anjos et al. / Journal of Environmental Management 196 (2017) 607e613 609

Fig. 2. Blasted copper slag with grain size as collected.

accelerated aging tests, was determined by the relation of the Table 2

concrete compressive strength submitted to cycling and the Blasted copper slag composition considering oxides present in its composition.

strength of the similar concrete that did not suffer accelerated ag- Oxide Percentage 
Oxide Percentage
ing process. Besides, the concretes with conventional aggregate Fe2O3 79,50% CaO 0,67%
replaced for blasted copper slag, that were submitted to accelerated SiO2 11,20% SO3 0,67%
aging tests, had their compressive strength compared to the ZnO 2,06% PbO 0,46%
reference concrete that also suffered aging. CuO 2,00% MgO 0,41%
MoO3 1,23% K2O 0,31%
Analysis of variance (ANOVA one factor) was used to compare
Al2O3 1,08% TiO2 0,31%
mechanical properties results in relation to replacement content of Cr2O3 0,10%
fine aggregate by blasted copper slag.

absorption than natural fine aggregate. It is well known that these

3. Results and discussion
characteristics favor the obtainment of fresh concrete mixtures
with better workability (MEHTA; MONTEIRO, 2008, p. 279). Ac-
3.1. Fresh concrete
cording to Moura (2000, p. 173), the increase in workability of fresh
concrete with copper slag is due, not only to the superficially
As can be observed in Table 5, with the increase in the
smooth grain, but also to its elevated specific mass, which con-
replacement content of the natural fine aggregate for crushed
tributes to a higher slump.
copper slag, above 20%, there was a significant improvement in the
plasticity and cohesion of the fresh concrete, dispensing the water
reducer admixture in order to achieve the desired consistency 3.2. Physical indexes
measured by slump test. This improvement in workability may be
associated with the use of blasted copper slag that presents pre- Porosity parameters are shown at Table 6.
dominance of spherical grain shape, glassy texture and lower water According to Table 6, the replacement of fine aggregate by
610 M.A.G. dos Anjos et al. / Journal of Environmental Management 196 (2017) 607e613

Table 3
Results of leaching and solubilization assessments.

Parameter Leaching Solubilization

Measured Limit prescribed by NBR Measured Limit prescribed by NBR

concentration 10004 (ABNT, 2004a) (mg/l) concentration 10004 (ABNT, 2004a) (mg/l)
(mg/l) (mg/l)

Arsenic <0,011 1,0 <0,011 0010

Total cadmium <0,005 0,5 <0,0014 0,005
Total lead 0,400 1,0 <0,007 0010
Total chrome <0,028 5,0 <0,028 0050
Mercury <0,001 0,1 0,002 0001
Total silver <0,030 5,0 <0,0072 0,050
Selenium <0,005 1,0 ND 0,001
Total fluoride 0,010 150,0 0,090 1500
Phenols <0,002 NP 0,04 0,010
Chlorides 3160 NP 2110 250,0

ND: Not detected. NP: Not prescribed

Table 4
Sampling plan of dosed concrete.

Test Number of Samples Brazilian Standard

Axial compressive strength 6 NBR 5739 (ABNT, 2007)

Diametrical compression strength 6 NBR 7222 (ABNT, 2011b)
Modulus of elasticity 2 NBR 8522 (ABNT, 2008)
Water absorption 2 NBR 9778 (ABNT, 2009)
Voids index
Specific gravity
Durability 6 e

Table 5
Proportions and consistency indexes of produced concretes.

Concrete Blasted copper Proportions of the concretes constituents Slump (mm)

slag content
Portland Blasted Sand Crushed Crushed Super
cement copper slag stone 0 stone 1 plasticizer

CE000 0% 1,00 0,00 2,05 0,65 1,36 0,41 140

CE020 20% 1,00 0,41 1,64 0,65 1,36 0,41 160
CE040 40% 1,00 0,82 1,23 0,65 1,36 0,00 180
CE060 60% 1,00 1,23 0,82 0,65 1,36 0,00 170
CE080 80% 1,00 1,64 0,41 0,65 1,36 0,00 175
CE100 100% 1,00 2,05 0,00 0,65 1,36 0,00 155

Table 6 3.3. Mechanical strength

Physical indices of concretes.

Parameter Mixture 3.3.1. Axial compressive strength of concretes

CE000 CE020 CE040 CE060 CE080 CE100
Fig. 3 shows the average strength values for axial compressive
strength of the studied concretes with respect to the blasted cooper
Absorption (%) 4,35 3,81 3,99 4,40 3,51 3,65
slag replacing the fine aggregates.
Voids (%) 10,00 8,96 9,47 10,50 8,72 9,40
Bulk specific gravity 2,30 2,35 2,37 2,38 2,51 2,57 It can be seen that the compressive strength did not decay
Bulk specific gravity SSD 2,40 2,44 2,47 2,49 2,59 2,67 severally when blasted copper slag replaced sand. Comparing the
Apparent specific gravity 2,55 2,58 2,62 2,66 2,75 2,84 reference concrete (CE000), it is possible to note that the mixture

blasted copper slag of 80% showed the best combination of both

fine aggregates, when considering concrete compactness. For the
replacement of 60%, concrete with highest porosity were obtained.
Reduction in absorption and void index of concrete CE080 were
19.3 and 12.8%, respectively, when compared to reference concrete.
For CE060, an increase in absorption and void index of 1.1 and 5.0%,
when compared to reference concrete (CE000), was seen.
Specific gravities where seen to increase with fine aggregate
replacement, which may be due to higher density of blasted copper
slag as compared to natural aggregate. When replacing 100% of the
conventional aggregate, there was an increase of about 11% for each
of the types of specific gravity. Fig. 3. Axial compressive strength of concretes versus blasted copper slag content.
 M.A.G. dos Anjos et al. / Journal of Environmental Management 196 (2017) 607e613 611

with lower replacement (CE020), presented a decrease of 5.5% of

compressive strength, the lowest strength found for the concrete
with addition of blasted copper slag. This replacement content
corresponded to the best void indexes and water absorption,
among the concrete studied. The sharpest decay occurred or the
replacement content over 40%, reaching 11.6% decay for CE060.
This decrease in strength can be associated to axial compressive
strength, since the higher content of blasted copper slag also meant
a higher presence of impurities present in this residue, such as,
paint particles and anti-oxides from the painting system removed,
besides oxides and hydroxides that form the eroded layer, also
known as rust. Although there has been a reduction in mechanical
strength of the concrete, with the increase of fine aggregate
replacement, it is possible to admit that the decrease was not so
significant, when considering the level of impurities of this residue. Fig. 5. Average elastic modulus of concretes versus blasted copper slag content.

According to analysis of variance, there was no significant differ-

ence between the values obtained (ANOVA, F ¼ 1.229; Fcrit ¼ 2.545;
age. This estimation was calculated considering the precepts of the
p ¼ 0.321). This behavior can also be associated to an improvement
Comite EuroeInternational du Be ton (CEB, 1993). Average tem-
on workability, noted when a higher amount of spherical particles
perature of 26
C and the selected high initial strength cement type
of the blasted copper slag was present.
(s ¼ 0.20) are among the data inserted in Equations (1)e(3) (CEB,
1993).
3.3.2. Tensile strength by diametrical compression of concretes
The effects of different content of blasted copper slag as fcm ðtÞ ¼ bcc ðtÞ$fcm (1)
replacement of fine aggregate on tensile strength by diametrical
compression are shown in Fig. 4. ("  1=2 #)
As seen for the axial compressive strength, the tensile strength 28
s 1 t =t1
by diametrical compression decreased with the increase in residue.
The highest reduction was seen for CE080, of around 33.5%,
bcc ðtÞ ¼ e (2)
compared to reference CE000. For the replacement of 40%, the 2 3
decrease in strength was of only 16.5%. According to the variance
analysis, there was significant difference between the values 413;65 4000 5
X
n 273þ
TðDti Þ
(ANOVA, F ¼ 11.469; Fcrit ¼ 2.640; p ¼ 0.000). t¼ Dti e T0
(3)
i¼1
3.3.3. Static elastic moduli in compression of concretes where:
Fig. 5 shows the static elastic moduli in compression of con-
cretes as blasted copper slag content increase. fcm ðtÞ : compressive strength for concrete with age of t days;
In spite of the increasing replacement content, the blasted fcm : compressive strength at 28 days of age;
copper slag caused slight variation in the concrete deformation bcc ðtÞ : age dependent (t) concrete coefficient;
capacity. Comparing with reference mixture, the elastic modulus t: concrete age, in days, adjusted according to Eq. (3);
values of concretes with residue decreased of 1.8%, for the concrete t1 : 1 day;
CE080 and 10.6% for CE100, which had the higher replacement s: cement dependent coefficient (s ¼ 0.20, for high initial
content. strength cement);
Dti : number of days that the temperature T(Dti ) prevails;
3.3.4. Compressive strength of the samples submitted to accelerated TðDti Þ :temperature during period Dti ;
aging process T0: 1
C.
Fig. 6 shows the axial compressive strength of the samples
submitted to accelerated aging process. These specimens were It was noted that concrete submitted to compressive tests at 28
tested at 70 days of age. The behavior of the concretes was also days of age showed similar behavior as aged concrete, at 70 days.
compared to a theoretical estimation of the strength as a function of When compared to reference concrete, the CE020 showed lowest
reduction of strength, only 11.7%, while CE060 showed the highest
decrease, of 17.4%.
Fig. 6 reveals the strength of the concrete which were submitted
to accelerated aging, with 70 days of age, were very close to those
obtained for the same concrete that were not submitted to the
accelerated aging and cracked with 28 days. It is possible to infer
that the accelerated aging process seemed to prevent the me-
chanical strength increase of this concretes, beyond the 28 days
studied. Among the aged concretes with 70 days, as compared to
the reference concrete, CE020 showed lower reduction of
compressive strength of 11.6%, while the CE060 had the greatest
reduction of this property, of 21.1%. According to variance analysis,
there was significant difference between the values (ANOVA,
F ¼ 2.694; Fcrit ¼ 2.545; p ¼ 0.041).
Fig. 4. Tensile strength by diametrical compression of concretes versus blasted copper Fig. 7 shows the decrease in compressive strength of the con-
slag content. cretes that were submitted to an accelerated aging process,
612 M.A.G. dos Anjos et al. / Journal of Environmental Management 196 (2017) 607e613

natural aggregate, there was no need to add superplasticizer

admixture in concretes to achieve the desired consistency. The
higher concrete workability, measured by slump test, was associ-
ated with the superficial texture and spherical shape of blasted
copper slag grains, beside the low water absorption and increased
density of this residue. For the concretes produced, the blasted
copper slag contributed for a significant reduction of the water
absorption and a discrete increase in specific gravity of the
mixtures.
As for mechanical properties, the axial compressive strength of
concretes decayed with the increase of blasted copper slag content.
Mixtures with replacements of over 40% presented the highest
decreases, around 11.5%. These decreases were linked to the organic
impurities found in the blasted substrate, as paint particles and
anti-oxides from the removed paint system, besides the rust. In this
work, all mixtures of concrete with blasted copper slag obtained
results of compressive strength higher than the established
compressive strength for dosing. It is deduced that the total or
partial replacement of natural fine aggregates for this waste may be
Fig. 6. Compressive strength variation of the aged samples as blasted copper slag
feasible for structural concretes at the strength level adopted in this
content increases.
study, in addition to adequate disposal of this waste.
Tensile strength of concretes reduced with the increase of
blasted copper slag content. Higher reductions were also seen for
concretes with over 40% replacement, highlight the 33.5% decrease
found for CE080.
The results of the static elastic modulus tests showed that the
addition of blasted copper slag to the concretes did not cause sig-
nificant variations in the deformation capacity, making them only
slightly less brittle. The greatest reduction in stiffness occurred for
the blend with 100% substitution.
Under axial compression, samples of concretes subjected to the
accelerated aging process reached similar resistance to the
strengths of concretes tested at 28 days of age. It is possible to
affirm that concretes with blasted copper slag do not have tendency
to the precocious aging.
Considering the results obtained in the present research, future
studies with precast elements and mortars containing blasted
copper slag are recommended, promoting ecologically adequate
Fig. 7. Compressive strength decreases of aged samples versus blasted copper slag destinations for this residue.
content.

Acknowledgment
compared to the theoretical value for this strength without aging
process. The authors acknowledge the support of Federal University of
Reference mixture, CE000, showed the smallest reduction of Sergipe.
this property, only 3.66%. Among concretes with blasted copper
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