Effects of Copper Flotation Waste on

Mechanical Properties of Cement

Baak MESCa, Semra ORUHb & Osman Nuri ERGUNb
a

Department of Civil Engineering, Ondokuz Mays University

55139 Samsun, Turkey; email:basakm@omu.edu.tr

Department of Environmental Engineering, Ondokuz Mays University

55139 Samsun, Turkey; email:semcoruh@omu.edu.tr, onergun@omu.edu.tr

Abstract

Increasing amount of by-products and waste materials coming from municipal and industrial
processes has become a problem more and more urgent for the next future. Copper flotation waste
which is the product pyrometalurgical production of copper from copper ores contains materials
such as iron, alumina, calcium oxide, silica, etc. Dumping of such large amounts of copper flotation
waste causes economic, environmental and space problems and therefore, governments have
implemented policies that give mining and metallurgical companies the responsibility for reducing
the volume of solid waste deposition by promoting the material recycling and re-utilitization. The
use of copper flotation waste materials as additives in the production of cement has received
substantial attention during recent years.
In this study, the physical and chemical properties of copper flotation waste and its effects on the
mechanical properties of cement were investigated. This waste material with different proportion
was substituted with Portland cement. Physical properties such as setting time, volume expansion
and compressive strength were determined and compared to reference mixture and Turkish
standards (TS). The results show that cement replacement material had clear effects on the
mechanical properties. The use of copper flotation waste even at the concentration of %5 showed
either comparable or better result compared to reference mixture. As a result copper flotation waste
can be used as cementitious materials.

Key Words: Waste management, Copper flotation waste, Cement, Compressive strength

Introduction
With rapid growth of industrialization, there is pressure all over the world on available land, not
only for housing and industrial complexes, but for land-filling as a means of disposing huge
quantities of waste generated from industrial and mining-mineral processing operations [Rai et al.,
2002; Kula et al., 2001]. Disposal of industrial by-products in a hydrologic environment can cause
environmental risks due to the mobility of toxic trace elements. The main goals of environmental
protection agencies and governments are to seek ways to minimize the dual problems of disposal
and health hazards of these by-products. The use of various types of waste materials as additives in
the production of cement and concrete has received substantial attention during recent years [AlJabri et al., 2006; Penpolcharoen, 2005].
The copper flotation waste generated from the copper industry is generally disposed of without any
prior solid waste treatment in areas around the industrial facility where they are generated. Copper
flotation waste is classified as Hazardous waste according to current literature [Samet and
Chaaboni, 2004; Zain et al., 2004]. Landfill disposal of copper industry waste is not feasible since a
few hundred tones are produced per year per factory; leaching of heavy metals in the ground water
is of concern [Samet & Chaaboni, 2004; oruh & Ergun, 2006]. Dumping of such amount of
copper slags causes economic, environmental and space problems, therefore, currently governments
have implemented policies that give responsibility to mining and metallurgical companies for
reducing the volume of solid waste deposition by promoting the material recycling and reutilization
[Gordan, 2002; oruh et al., 2006]. Recent research papers reviewed the use of copper slag in the
production of value added products such as abrasive tools, abrasive materials, cutting tools, tiles,
glass, and roofing granules. They are also reported the potential use of copper slag as a partial
substitute of cement and aggregates in concrete and asphalt mixtures [Al-Jabri et al., 2006].
Investigations relating to the disposal of industrial by-products in cement have been actively
pursued. The disposal of these materials in cement conserves natural resources, energy, and reduces
pollution.
The present study includes the safe disposal of the copper flotation waste using as pozzolanic
material in cement production. In order to produce six group cement mixtures, copper flotation
waste is added in Portland cement clinker in the ratio of 2.5%, 5%, 7.5%, 10%, 12.5% and 15% due
to weight. Physical properties such as setting time, volume expansion and compressive strength
were determined and compared to reference mixture (PC 42.5) and Turkish standards (TSE, 2002).

Materials and Experimental Procedures

Materials
The copper flotation waste samples used in this study were obtained from the Eti Copper Works of
Samsun, Turkey. The cement was PC purchased from Yibita Cement Company, Samsun. This
cement is the most widely used one in the construction industry. The chemical compositions and
physical properties of cement, copper flotation waste are given Table 1. Copper flotation waste has
a black color and glassy appearance. SEM spectra in Fig. 1-a shows that copper flotation waste
consist mainly of magnetite (FeO.Fe2O3) and fayalite (2FeO.SiO2).

Table 1. Chemical composition and physical properties of cement, copper flotation waste

Component
Chemical composition (wt.%)
SiO2
Fe2O3*
Al2O3
TiO2
CaO
CuO
ZnO
PbO
Cr2O3
CO2
SO3
K2O
MgO
BaO
CoO
Na2O
P2O5
MnO
LOI
Others
*

Cement

Materials
Copper flotation waste

19.57
2.94
5.58
63.11
2.73
1.95
3.35
0.77

24.87
67.68
0.88
0.69
0.98
2.78
0.21
2.18
0.48
0.36
0.10
0.21
0.12
-

Iron oxides are presented as Fe2O3

Loss on ignition

Figure1. Scanning electron microscopic (SEM) micrograph of copper flotation waste

Mixtures Design
The binder material was mixed with copper flotation waste in definite ratio as given in Table 2.
Three series of mixtures and one reference mixture were prepared according to Turkish standards
(TSE, 2002). Reference mixtures were prepared out of Portland cement (PC) and reference as R.
The copper flotation waste mixtures were reference as CFW physical characteristics of mixtures are
shown in Table 2.
The mixtures of the specimens contained 450g cement, 1350g of fine aggregate and water liquid
/solid /L/S) ratio was 0.5.The cement-water mixtures were stirred at low speed for 30s then, with
the addition of sand, the mixtures were stirred for 5 min. eighteen batches were prepared and cast
into 40mm x 40mm x 160mm moulds for strength tests. After 24h of curing at 20 oC with 95%
humidity, the samples were demoded and immersed in a tap water. Prepared materials were cured
for 2, 7, 28 and 90 days and were subjected to unconfined compressive strength testing [TSE,
2002].
Compressive strength measurement was tested with a Tony technique compression machine at the
loading rate 20-40 N/mm2/s according to TS 19. The setting times of mixtures were determined
according to TS 24 using a Vicat apparatus at room temperature [Gorai et al.,2003].
Table 2. Physical characteristics and composition of different cement mixtures

Symbol

R
CFW1
CFW2
CFW3
CFW4
CFW5
CFW6

Cement mixes

Fineness

(wt.%)

Reference mix
2.5% CFW+97.5% PC
5% CFW+95% PC
7.5% CFW+92.5% PC
10% CFW+90% PC
12.5% CFW+87.5% PC
15% CFW+85% PC

+32 m
13.5
15.6
16.7
15.4
15.5
13.1
13.9

+90 m
0.1
0.2
0.3
0.2
0.4
0.1
0.5

Specific
surface
(cm2/g)
3520
3400
3280
3290
3260
3200
3240

Specific
gravity
(g/cm3)
3.12
3.12
3.13
3.17
3.19
3.18
3.17

Result and Discussion

Compressive Strength of Mixtures
Rate of strength development for six dosages of 2.5, 5, 7.5, 10, 12.5 and 15% copper flotation waste
used as Portland cement replacement were compared to reference mixtures for mortars. Mortar
cubes were tested for compressive strength after 2, 7, 28 and 90 days of curing. The trends of
compressive strength of mortar with copper flotation waste are shown in Fig. 2. At age of 2 days,
reference mixture showed the highest value (23.8 N/mm2) of compressive strength of the mixtures
tested. The mixture CFW2 showed close results to the reference mixture. The 2 days measured
compressive strength of mixture CFW6 has the lowest value of the compressive strength. This value
was obtained as 14.8 N/mm2. The 7 days measured compressive strength of mixture CFW1 was
close the mixture CFW2. These values were close to the 7 days measured compressive strength of
the reference mix. When curing extended to 28 days, an impressive increase in the performance of
the mixtures was noticed. The data indicate that the addition of small quantity of copper flotation
waste (i.e., 2.5%, 5%) has an important positive effect on cement strength. The addition of copper
flotation waste (2.5 %) for compressive strength with 2, 7 and 28 days caused a reduction 12 %, 7.6
% and 3.7 % in the compressive strength of cement compared with the reference mixture. The 90

day compressive strength compressive strength of CFW1 was close to the compressive strength of
the reference mixture.

60

Compressive strength (N/mm )

The higher quantity of copper flotation waste showed an adverse effect on cement mixture. The
compressive strength of the mixture containing copper flotation waste decreased to a very
significant extent. This may be due to small pozzolanic contribution of copper flotation waste at this
age. It is well known that replacing cement by pozzolanic materials with low calcium would lower
the early strength.

50

R
CFW3
CFW6

CFW1
CFW4

CFW2
CFW5

40
30
20
10
0
2

28

90

Age (days)

Figure 2. Compressive strength of cement mixtures with copper flotation waste

Setting Time of Mixtures

The test results of the water percent and setting time of all mixtures are illustrated in Table 3. The
results clearly show in the Table 3 that all samples expect for CFW6 absorb less water than that of
the reference mixture. CFW6 mixture showed the higher absorption than reference and other
mixtures. It is proposed the high water absorption to the magnetic property of the copper flotation
waste. The magnetic property induces water to penetrate into the porosity, as well as to bind the
other surface of the samples, by the magnetic force [Mesci, 2007].
As seen from Table 3, setting times of reference and all mixtures are different. This difference may
arise from fineness and free CaO content of cement mixes.

Table 3. Water percent and setting time test results for cement mixes

Cement mixes

Water (%)

R
CFW1
CFW2
CFW3
CFW4
CFW5
CFW6

29.5
28.5
28.8
28.0
27.0
29.0
31.0

Setting
Initial (min)
195
230
305
280
300
300
440

Time
Final (min)
260
295
365
350
360
380
525

Conclusion
This paper presented the results of a research study on the effect of using copper flotation waste as a
partial substitute for Portland cement in cement mixtures. A total of six mixtures were evaluated.
The results show that the performance of copper flotation waste cements is similar to that of more
traditional cement. At early ages, reference mixture showed higher strength than mixture containing
cement replacement material. At 28 and 90 days, the use of copper flotation waste even at the
concentration of % 2.5 and %5 showed a similar performance as the reference mixture. Higher
copper flotation waste (12.5%) replacement for cement resulted in adverse effects on cement
strength. This is expected since copper flotation waste has a low free lime content compared with
free lime in Portland cement. As a result 2.5% and 5% copper flotation waste can be used as
cementitious materials.

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