9th International Congress on Advances in Civil Engineering, 27-30 September 2010 Karadeniz Technical University, Trabzon, Turkey

Utilization of Copper Processing Waste as Partial Replacement of Cement in Concrete

O. Onuaguluchi1, A. Gharagozloo 1, A. Iravanian1
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Department of Civil Engineering, EMU, Famagusta, N Cyprus

Abstract
Achieving an environmentally-friendly community through effective waste recycling and natural resources conservation are key issues across the world presently. Thus far, the utilization of some categories of industrial waste materials in concrete production has been shown to provide a satisfactory solution to these concerns. In this study, the possibility of using a longtime disposed copper processing waste exposed to several years of weathering and its effect on the mechanical properties of concrete was investigated. For this purpose, 0%, 5% and 10% replacement level for cement was used and the impact of this waste material on setting time, compressive strength, splitting tensile strength and water absorption were experimentally determined. The results suggested that despite the increased porosity of the waste material caused by weathering there is a potential for the use of this waste as a supplementary cementing material in concrete production, especially at 5% replacement level. Key words: Copper waste; concrete; compressive strength, setting time, permeability

1.0 Introduction
Between 1914 and 1974, Cyprus Mining Corporation (CMC) carried out copper mining and smelting activities around Lefke-Xeros area in the northern part of Cyprus. Studies by Yukselen M. A. (2002) confirmed that the soil around the smelting facility and water from the adjoining Mediterranean Sea contain high concentrations of heavy metals and this anomaly was clearly associated with the tailings disposed at the site. It is estimated that the piles of tailing deposits at the

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abandoned facility contain approximately 2.5 million tons of waste material (Erdem, 1999). Some publications have shown that copper slag could be used as a cement replacement material in concrete (Zain et al. 2004; Al-Jabri et al. 2006). Nevertheless, the scenario in respect of the North Cyprus copper processing waste is quite peculiar since this waste material was discharged in ponds and has been exposed to the weather for several years. The effect of wet disposal system on waste materials was investigated by Ranganath et al. (1998) and they suggested that disposed fly ash consist of large particle sizes while cement mortar containing it yielded low compressive strength as a result of reduced pozzolanic reaction. Moreover, Cheerarot and Jaturapitakkul (2004) were also of the opinion that weathering causes agglomeration of disposed fly ash particles, its porosity increasing with time. Therefore, given the aforementioned, and coupled with the fact that no studies exists with which to evaluate the usability of this material, the main objective of this study is to investigate the possibility of using this several decades old waste material as a supplementary cement material in concrete.

2. Experimental program
2.1. Materials used Portland Limestone Cement CEM II/A-L (Class 42.5R) was used. The fine and coarse aggregates were sourced from locally crushed rock with specific gravity of 2.77 and 2.54 respectively. The copper waste material used as partial replacement of cement was obtained from the CMC abandoned processing facility at Lefke, Northern Cyprus.

2.2. Physical and chemical analysis of waste material Physical properties such as the specific gravity of cement were determined according to ASTM C 188 specification while the absorption capacity and specific gravity of the waste were obtained using the ASTM C 128 guideline. Whereas the specific surface areas were measured using ASTM C 204 stipulated Blaines air permeability apparatus. Particle size distribution and oxide content of the waste material were equally determined

2.3. Mix proportions and casting of concrete specimens Three different concrete batches corresponding to a target compressive strength of 20 N/mm2, water binder ratio of 0.6 and cement replacement levels of 0%, 5% and 10% replacement were mixed for five minutes in a drum mixer. For each mix, three 150 x 150 x 150 mm cubes were cast for compressive strength testing while three 100 x 200 mm cylindrical specimens were also cast for the determination of splitting tensile strength and water absorption tests. Immediately after casting, all specimens were kept in the curing room for 24 h before they were then de-molded and transferred to curing tank until the time of testing. The mix proportions are summarized in Table 1.
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O. Onuaguluchi, A. Gharagozloo, A. Iravanian

Table 1. Mix Proportions Mix name Mix 1 Mix 2 Mix 3 Waste (%) 0 5 10 W/B ratio 0.6 0.6 0.6 Water 225 225 225 Cement 375 356 338 Quantities (kg/m3) Waste 0 19 38 Fine 570 570 570 Coarse 1210 1210 1210 Slump (mm) 95 55 70

2.4. Workability and setting time of concrete Using the ASTM C 143/C 143M standard, the workability of the different concrete batches were determined through slump test while the setting time was assessed using mortar sieved from the concretes in accordance to the stipulations of ASTM C 403/C 403M.

2.5. Compressive and splitting tensile strength of concrete The compressive strength of all the concrete batches was determined after 3, 7, 14 and 28 days of moist curing using BS EN 12390: Part 3 as a guide. After 28 days of moist curing, splitting tensile strength test was equally conducted on cylindrical specimens using ASTM C 496/C 496M guideline.

2.6. Water absorption Water absorption capacity of a hardened concrete specimen can indicate its porosity. This usually calculated as the difference between the oven dry mass and the saturated mass expressed as a fractional percentage of the oven dry mass. Water absorption percentages of the different concrete specimens after 28 and 91 days of wet curing were measured according to the ASTM C642 standard.

3. Results and discussion

3.1. Physical and chemical analysis of copper waste Some physical properties of the cement and copper waste used in this study are shown in Table 2. The copper waste has a specific gravity of 4.18 which is quite higher than 3.14 obtained for cement and this may results in production of concrete with a marginally higher density when used as a cement replacement material. The particle size distribution curve of the waste material is shown in Figure 1. It indicates that the waste is a mixture of very fine and coarse particles. The water absorption capacity of the waste was 13.82% which is much higher than the 0.3 to 0.55% recorded in literature for copper slag. However, this

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occurrence is in concert with the assertion of Cheerarot and Jaturapitakkul (2004) that waste material exposed to weathering becomes more porous with time.

100 80

Percentage passing

60 40 20 0 0.000 0.001 0.010 0.100 Particle Size (mm) 1.000 10.000

Figure 1. Particle size distribution of copper waste

The chemical composition of cement and the copper waste is shown in Table 3 and is quite similar to that obtained from some countries since it contained reasonable amount of oxides that imparts it with pozzolanic properties. Table 2. Physical properties of cement and copper waste

Properties Specific gravity Fineness, cm2/g Absorption, %

CEM II A-L 3.14 3400 -

Copper waste 4.18 13.82

Table 3. Chemical composition of cement and copper waste

Component SiO2 Al2O3 Fe2O3 CaO MgO SO3 Cl Loss on ignition Insoluble residue SiO2 + Al2O3 + Fe2O3

CEM II A-L (%) 19.07 4.73 3.08 61.68 1.43 2.5 0.02 4.32 0.08 26.88

Copper waste (%) 11.2 85.3 96.5

O. Onuaguluchi, A. Gharagozloo, A. Iravanian

3.2 Workability and setting time of concrete The observed reduced slump shown in Table 1 conflicts with the submission of Al-Jabri et al. (2009) that increased content of copper slag should improve concrete workability. The reduction in slump is attributed to the coarse and porous particles of the waste with a high water absorption capacity which adversely affected concrete workability by partly absorbing available mixing water. The higher slump at 5% replacement level could be as a result of its slightly higher hydration. The setting time results shown in Figure 2 suggest that as the replacement level of the copper waste increases the setting time likewise increase. Ayano and Sakata (2000) similarly observed a much longer delayed final setting time of 1440 and 8640 minutes respectively in cement mortars containing copper slag. Investigation by Zain eta al. (2004) suggested that lead and zinc compounds exert a strong retarding effect on cement hydration. Thus, concentration of heavy metal in the waste; reduced specific surface area of the waste and lower cement content contributed to the delayed setting time.

1400 1200 1000 800 600 400 200 0

Setting time (mins)

Initial setting time Final setting time

10

Cement replacement level with copper waste (%)

Figure 2. Setting time of specimens 3.3. Compressive strength of concrete The copper waste supplemented concrete mix at 5% replacement levels possess higher compressive strength than the control mix at all testing ages (Figure 3). This result is slightly at variance with similar study by Al-Jabri et al. (2006) which indicated that at low water/binder ratios of 0.5 and 0.6, the use of 5% copper slag instead of Portland cement would yield a marginally lower but similar performance as the control mixture. Therefore, the observed increase in strength at 5% replacement level may be due to the cumulative effect of the following; reduced water/binder ratio caused by water absorption by the porous particles of the waste and the filler effect of the fine particles of the waste in enhancing concrete microstructure. The percentage increase in strength relative to the control specimen at the 28th day was 20.91% and -6.06% for the 5% and 10% cement replacement level respectively.

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30 Compressive strength (N/mm2) 25 20 15 10 5 0 0 5 10 Cement replacement level with copper waste (%)
Figure 3. Compressive strength of specimens

3 days 7 days 14 days 28 days

3.4. Splitting tensile strength The splitting tensile strength of concrete specimens showed similar trend to the compressive strength of the different concrete mixes after 28 days of curing and values are shown in Figure 4. It can be observed that 5% cement replacement by copper waste yields the highest splitting tensile strength value while the splitting tensile strength of the 10% replacement level is abysmally poor. Overall, the use of 5% copper waste as cement replacement compared to the control resulted in about 4.28% improvement of the 28th day splitting tensile strength while a decrease of 36.33% was recorded for the 10% cement replacement level.

3 Splitting tensile strength (N/mm2 2.5

2
1.5 1 0.5 0 0 5 10 Cement replacement level with copper waste (%)
Figure 4. Splitting tensile strength of specimens

28 days

O. Onuaguluchi, A. Gharagozloo, A. Iravanian

3.5 Water absorption Values for the water absorption of the different hardened concrete specimens after 28 and 91 days of curing are shown in Figure 5. The result indicated that absorption increases as the copper waste content of the concrete increases. This behavior could be a function of the reduced cement content which resulted in less hydration products, hence, the increasing formation of continuous channels inside the concrete. Furthermore, the hygroscopic nature of the waste could also be a contributory factor. However, by the 91st day, the porosity of the specimen reduced slightly and this is linked to the increased filling of pore spaces by hydration products of cementitious materials with age.

10 9 8 7 6 5 4 3 2 1 0 0 5 10 Cement replacement level with copper waste (%)

Figure 5. Water absorption of specimens

Water absorption (%)

28 days 91 days

4. Conclusion
The copper processing waste utilized in this study consists of 96.5% by mass of SiO2 + A12O3 + Fe2O3 which is quite similar to the chemical composition of copper slag found in literature. However, about 50% percent of the waste consists of fine particles while the rest were coarse and significantly porous particles. The copper waste was found to impact concrete workability negatively and this was attributed to the increased porosity of the copper waste particles. The use of copper waste as a replacement for cement resulted in a 28th day compressive strength increase of about 21% for 5% replacement level and a 6% decrease in strength for 10% replacement level. The splitting tensile strength result followed similar trend; with 5% cement yielding the highest strength value while 10% replacement level produced an abysmally low strength value. Furthermore, water permeability of specimens incorporating copper waste were quite higher than that of control specimens, however, this tendency to absorb water became decreased with age as pore spaces became filled with hydration products.

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Acknowledgements
The suggestion for this research was made by Assoc. Prof. Dr. zgr Eren of the Department of Civil Engineering, EMU; we greatly appreciate and acknowledge the many fruitful advice he rendered. We would also like to thank Mr Ogn Kili of the Material Laboratory and Mr Samer Mehtar, BEM LTD for their help during the experimental testing program.

References
ASTM Standard Test Methods (2007). In: Annual book of ASTM Standards, Concrete and Aggregates, Vol. 04.02, ASTM International, West Conshohocken, PA, United States Al-Jabri, K. S., Taha, R. A., Al-Hashmi, A., Al-Harthy, A. S. (2006). Effect of copper slag and cement by-pass dust addition on mechanical properties of concrete. Construction and Building Materials Journal Vol. 20 pp 322331 Al-Jabri, K. S., Hisada, M., Al-Oraimi S. K., Al-Saidy, A. H. (2009). Copper slag as sand replacement for high performance concrete. Cement & Concrete Composites Journal Vol. 31 pp 483488 Ayano T, Sakata, K. (2000). Durability of concrete with copper slag fine aggregate. American Concrete Institute Special Publication (ACI SP192) pp 141158 BS EN 12390: Part 3. (2009). Testing hardened concrete: compressive strength of test specimens. British Standard Institution (BSI), London Cheerarot, R., Jaturapitakkul, C., (2004). A study of disposed fly ash from landfill to replace Portland cement. Waste Management Journal Vol. 24 pp 701709 Erdem, U. (1999). Report on the environmental problems of the Lefke Gemikonagi Region (in Turkish). Lefke Environmental Society, Lefke Hou, J., Chung, D. D. L. (2000). Effect of admixtures in concrete on the corrosion resistance of steel reinforced concrete. Pergamon Corrosion Science journal Vol. 42 pp 1489-1507 Ranganath, R. V., Bhattacharjee, B., Krishnamoorthy, S., (1998). Influence of size fraction of ponded ash on its pozzolanic activity. Pergamon Cement and Concrete Research Journal Vol. 28, pp 749761 Shi, C., Meyer, C., Behnood, A. (2008). Utilization of copper slag in cement and concrete. Resources, Conservation and Recycling Journal Vol. 52 pp 11151120 Smith, K. M., Schokker, A. J., Tikalsky, P. J. (2004). Performance of Supplementary Cementitious Materials in Concrete Resistivity and Corrosion Monitoring Evaluations. ACI Materials Journal, Vol. 101 No. 5, pp 385-390 Yukselen M. A. (2002). Characterization of heavy metal contaminated soils in Northern Cyprus Environmental Geology Journal Vol. 42 pp 597 603 Zain, M. F. M., Islam, M. N., Radin, S. S., Yap, S. G. (2004). Cement-based solidification for the safe disposal of blasted copper slag. Cement and Concrete Composites Journal Vol. 26 pp 84551.
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