CHAPTER 1 INTRODUCTION

1.1 GENERAL It was well recognized for many years the beneficial utilization of some industrial byproducts in improving the properties of fresh and hardened concrete. By-products such as pulverized fuel ash, silica fume and ground granulated blast furnace slag (GGBFS) are added in different proportions to concrete mixes as either a partial substitute to Portland cement or as admixtures. Concrete prepared with such materials showed improvement in workability and durability compared to normal concrete and has been used in the construction of power and chemical plants and under-water structures. Use of some waste materials has been well documented in design specifications. New by-products and waste materials are being generated by various industries, dumping or disposal of these materials causes environmental and health problems. Therefore, recycling of waste materials has a great potential in concrete industry. Copper slag is an industrial by-product material produced from the process of manufacturing copper. It has been estimated that approximately 24.6 million tons of slag are generated from the world copper industry. In the Sultanate of Oman, approximately 60,000 tons of copper slags are produced every year by Oman Mining Company. Although copper slag is widely used in the sand blasting industry and in the manufacturing of abrasive tools, the remainder is disposed of without any further reuse or reclamation. Copper slag possesses mechanical and chemical characteristics that qualify the material to be used in concrete as a partial replacement for Portland cement or as a substitute for aggregates. For example, copper slag has a number of favorable mechanical properties for aggregate use such as excellent soundness characteristics, good abrasion resistance and good stability. Also, copper slag exhibits pozzolanic properties since it contains a low CaO content and other oxide such as Al2O3, SiO2, and Fe2O3. Use of copper slag in the concrete industry as a replacement for cement and/or fine aggregates can has the benefits of reducing the costs of disposal and helps protecting the environment. Despite the fact that several studies have been reported on the effect of copper slag replacement on the properties of concrete, further investigations are necessary in
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order to obtain a comprehensive understanding that would provide an engineering basis to allow the use of copper slag in concrete. The effect of copper slag on the hydration of cement-based materials was investigated by Mobasher et al. and Tixier et al. Up to 15% copper slag, by weight of cement was used as a Portland cement replacement together with up to 1.5% of hydrated lime as an activator for pozzolanic reactions. Results indicated a significant increase in the compressive strength for up to 90 days of hydration. Also, a decrease in capillary porosity and an increase in gel porosity were observed. Moura et al. reported that copper slag could be a potential alternative to admixtures used in concrete and mortars. The use of slag from copper smelting as a fine aggregate in concrete was also investigated by Akihiko and Takashi. From mortar strength tests with a cement/slag/water ratio of 1/2/0.55, the ball milled slag gave a higher strength. The effects of using several types of slag on mortar and concrete reactions, reinforcing steel corrosion, abrasion, workability and slump, shrinkage, and freezing and thawing characteristics were examined. Copper slag was also used by Ayano et al. as a fine aggregate in concrete. They described the strength, setting time and durability of concrete mixtures made with copper slag. AlJabri et al. studied the effect of copper slag (CS) and cement by-pass dust (CBPD) replacements on the strength of cement mortars. Experimental results indicated that the mixture containing 5% CBPD + 95% cement yielded the highest 90 days compressive strength of 42 MPa in comparison with 40 MPa for the mixture containing 1.5% CBPD + 13.5 CS + 85% cement. The optimum CS and CBPD to be used was 5%. In addition, it was determined that using CBPD as an activating material would operate better than using lime. Also, all samples met the 3 and 7 days compressive strength specifications requirements for cement mortars. The fundamental properties of concrete using copper slag and class II fly ash as fine aggregates were investigated by Ishimaru et al. It was concluded that up to 20% (in volume) of copper slag or class II fly ash as fine aggregates substitution can be used in the production of concrete suitable for structures. Al-Jabri et al. investigated the effect of CS and CBPD as partial replacements for cement on concrete properties. In addition to the control mixture, two different trial mixtures were prepared using different proportions of CS and CBPD and three water-to-binder ratios were studied: 0.5, 0.6 and 0.7. Results showed that 5% copper slag substitution for Portland cement gave a similar strength performance as the control mixture, especially at the low water-to binder ratios of 0.5 and 0.6, while higher copper slag (13.5%) replacement
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yielded lower strength values. Results also demonstrated that the use of CS and CBPD as partial replacements for Portland cement has a negligible effect on the modulus of elasticity of concrete, especially at the small quantities substitution. Shi et al. presented a comprehensive review on the use of copper slag in cement, mortars and concrete. The paper was focused on the characteristics of copper slag and its effects on the engineering properties of cement, mortars and concrete. Wu et al. investigated the mechanical properties of copper slag reinforced concrete under dynamic compression. Results showed that the dynamic compressive strength of copper slag reinforced concrete generally improved with the increase in amounts of copper slag used as a sand replacement up to 20%, compared with the control concrete, beyond which the strength was reduced. Wu et al. also investigated the mechanical properties of high strength concrete incorporating copper slag as a fine aggregate. Results indicated that the strength of concrete, with less than 40% copper slag replacement, was higher than or equal to that of the control specimen. The microscopic view demonstrated that there were limited differences between the control concrete and the concrete with less than 40% copper slag content.

1.2 OBJECTIVE AND SCOPE OF THE WORK 1.2.1 Objective: The objective of this project is to check the suitability of copper slag as fine aggregate in cement mortar by conducting suitable workability and strength studies. 1.2.2 Scope of the Work: Scope of this work is limited to cement mortar mix of proportion 1:3 and 1:4, modified by replacing M sand with copper slag. The study is limited to 5 cement mortar mixes containing 0%, 25%, 50%, 75% and 100% of copper slag as fine aggregate. Fresh Density test and Flow Table tests were done to obtain the workability of cement mortar Compressive Strength Test and Flexural Strength Test were conducted as Strength test on mortar.

CHAPTER 2 LITERATURE REVIEW

2.1 GENERAL Previous research works and studies on use of copper slag as aggregate in concrete were studied. A detailed literature survey was under taken and a few of the important works related to the topic are summarized below.

2.2 REVIEW OF LITERATURE Hisada et al. studied the performance of high strength concrete (HSC) made with copper slag as a fine aggregate. The study also presented the effect of superplasticizer addition on the properties of HSC made with copper slag. Two series of concrete mixtures were prepared with different proportions of copper slag. The first series consisted of six concrete mixtures prepared with different proportions of copper slag at constant workability. The water content was adjusted in each mixture in order to achieve the same workability as that for the control mixture. Twelve concrete mixtures were prepared in the second series. Only the first mixture was prepared using super plasticizer whereas the other eleven mixtures were prepared without using super plasticizer and with different proportions of copper slag used as sand replacement. The results indicated that the water demand reduced by almost 22% at 100% copper slag replacement compared to the control mixture. All concrete mixtures did not meet the strength and durability design requirements due to the segregation and dryness of the concrete paste. Hence the research concluded that the use of copper slag as sand substitution improves HSC strength and durability characteristics at same workability while super-plasticizer is very important ingredient in HSC made with copper slag in order to provide good workability and better consistency for the concrete matrix.

Khanzadi et al. studied the mechanical properties of high-strength concrete incorporating copper slag as coarse aggregate. This paper presented the effects of replacing limestone coarse aggregate by copper slag coarse aggregate on the compressive strength, splitting tensile strength, and rebound hammer values of highstrength concrete. Concrete mixtures containing different levels of silica fume were prepared with water to cementitious materials ratios of 0.40, 0.35, and 0.30. The
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percentages of the cement replacements by silica fume were 0%, 6%, and 10%. 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%. The research concluded that use of copper slag as coarse aggregate in high-strength concrete is technically possible and useful.

Al-Jabri et al. studied the effect of copper slag as a fine aggregate on the properties of cement mortars and concrete. For this study, various mortar and concrete mixtures were prepared with different proportions of copper slag ranging from 0% to 100% as fine aggregates replacement. Cement mortar mixtures were evaluated for compressive strength, whereas concrete mixtures were evaluated for workability, density, compressive strength, tensile strength, flexural strength and durability. The results obtained for cement mortars revealed that all mixtures with different copper slag proportions yielded comparable or higher compressive strength than that of the control mixture. Also, there was more than 70% improvement in the compressive strength of mortars with 50% copper slag substitution in comparison with the control mixture. The results obtained for concrete indicated that there is a slight increase in density of nearly 5% as copper slag content increases, whereas the workability increased significantly as copper slag percentage increased compared with the control mixture. However, addition of more copper slag resulted in strength reduction due to the increase in the free water content in the mix. Also, the results demonstrated that surface water absorption decreased as copper slag content increases up to 50% replacement. Therefore, it is recommended that up to 4050% of copper slag can be used as a replacement for fine aggregates in order to obtain a concrete with good strength and durability requirements.

CHAPTER 3 EXPERIMENTAL PROGRAM

3.1 GENERAL Cement mortar essentially consists of cement, fine aggregate and water. The properties of Fine aggregates were found out by conducting tests at the laboratory. The property of mortar depends on the type and quality of materials in it. In this experimental program we concentrated only in strength and workability characteristics of cement mortar. The mix was later modified by replacing definite percentage of M sand by weight with copper slag. The strength and workability parameters were studied out by carrying experimental investigations. In this chapter the constituent material properties, mix proportions, and methodology of testing of cement mortar are discussed in detail. 3.2 MATERIAL PROPERTIES. The test for various materials were conducted as specified in the relevant IS codes for each material. Materials for test include 1. Fine aggregate (M sand and Copper slag) Cement and water are assumed to be standard as per IS code, details of the same also furnished herewith. 3.2.1 Cement: Cement used was OPC 53 grade conforming to IS 12269.

Table 3.1 Cement Properties Grade Manufacturer Normal consistency Initial setting time Final setting time Specific gravity Fineness OPC 53 RAMCO 30.00% 122 min 464 min 3.15 3.00%

3.2.2 Fine Aggregate M sand and Copper Slag were used as fine aggregate in this project. Material properties of the same were determined. a) M Sand M sand available in the concrete laboratory was used. Tests were done as per IS: 2386 - 1986 to determine the properties of M sand. The properties of M sand are given in Table 3.2. The details of particle size distribution are given in Table 3.3 and the particle size distribution graph is given in Fig. 3.1. M sand used conforms to IS 383:1970 Zone II. Table 3.2 Properties of M Sand No. 1 2 3 Particulars Specific gravity Fineness modulus Effective Size Values 2.65 3.81 0.2

Table 3.3 Particle Size Distribution of M Sand

Sieve size (mm)

Wt. Retained (gm)

% Wt. Retained

Cumulative % Wt. Retained

% Wt. Passing

4.75 2.36 1.18 0.6 0.3 0.15 0.075

3 67 326 187 203 171 31 988

0 6.78137652 32.9959514 18.9271255 20.5465587 17.3076923 3.13765182

0 6.781376518 39.77732794 58.70445344 79.25101215 96.55870445 99.69635628 380.769

100 93.21862348 60.22267206 41.29554656 20.74898785 3.441295547 0.303643725

120

100

80

% passing

60

M SAND Zone 2

40

Zone 2

20

0 0.01 0.1 1 10

Sieve size (mm)

Fig. 3.1 Particle Size Distribution of M Sand

b) Copper Slag Copper slag used in this work was brought from Cochin Ship Yard. Tests were done as per IS: 2386 to determine its properties. The same are given in Table 3.4. The details of particle size distribution are given in Table 3.5 and the particle size distribution graph is given in Fig. 3.2. It was found that copper slag used was fine as evident from the sieve analysis results and fineness modulus. Copper slag used conforms to IS 383:1970 Zone I.

Table 3.4 Properties of Copper Slag No. 1 2 3 Particulars Specific Gravity Fineness modulus Effective size Values 3.14 3.98 0.4

Table 3.5 Particle Size Distribution of Copper Slag Sieve size (mm) 4.75 2.36 1.18 0.6 0.3 0.15 0.075 Wt. Retained (gm) 0 16 237 519 167 47 9 995 % Wt. Retained 0 1.6080402 23.8190955 52.160804 16.7839196 4.72361809 0.90452261 Cumulative % Wt. Retained 0 1.608040201 25.42713568 77.5879397 94.3718593 99.09547739 100 398.090

% Wt. Passing

100 98.3919598 74.57286432 22.4120603 5.628140704 0.904522613 0

120

100

80 % passing

60

COPPER SLAG zone 1

40

zone 1

20

0 0.01 0.1 Sieve size (mm) 1 10

Fig. 3.2 Particle Size Distribution of Copper Slag

Table 3.6 Properties of Copper Slag No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 3.2.3 Water Water is an important ingredient of mortar as it actively participates in the chemical reaction with cement. Presence of organic or inorganic impurities in water will affect the strength of concrete. Generally, water suitable for drinking is considered fit for making concrete. Hence clean drinking water available in the college water supply system was used for making concrete and curing. SiO2 Al2O3 Fe2O3 CaO MgO SO3 K2O Na2O TiO2 Mn2O3 Cl Loss on Ignition IR CuO Al2O3 + SiO2 + Fe2O3 Specific Gravity Absorption Component OPC (%) 20.85 4.78 3.51 63.06 2.32 2.48 0.55 0.24 0.25 0.05 0.01 1.75 0.21 0 29.14 3.15 CS (%) 33.05 2.79 53.45 6.06 1.56 1.89 0.61 0.28 0 0.06 0.01 0 0 0.46 89.29 3.4 0.17 Sand 2.77 1.36

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3.3 MIX PROPORTIONS AND METHODOLOGY To study the effect of copper slag substitution as a replacement for fine aggregates on the strength of cement mortars, specimens were prepared with different percentages of copper slag (by weight). The percentages of copper slag added were as follows: 0% (for the control mix), 25%, 50%, 75% and 100%. Six cubes (5cm x 5cm x 5cm) were cast for each mixture and three samples each were tested after 7 and 28 days of curing. Three beams (4cm x 4cm x 16cm) were cast for each mixture and tested for 28 day flexural strength test. Adopted 1:3 and 1:4 mixes where 5 different combinations of M sand and copper slag were selected. Hence a total of 10 mixes were used for casting. A control mix was first adopted where fine sand consists of only M sand and which is used for comparing the results. 3.4 TESTS PLANNED Tests planned include tests for workability and strength of cement mortar. Workability Tests 1. Flow Table Test 2. Fresh Density Test Strength Tests 1. Cube Compressive Strength Test 2. Flexural Strength Test

3.4.1 WORKABILITY TESTS ON CEMENT MORTAR Workability is defined as the ease with which cement mortar can be mixed placed compacted and finished. In case of mortar, we go for flow table test to determine the required flow of cement mortar paste under a specified water binder ratio. Also fresh density tests are performed to determine the density of the cement mortar cubes. a) Flow Table Test Similar to slump test, mortar flow test is a relative measure of workability. Changes in flow indicate variability in the materials and/or the batching process that may not be observed from slump testing alone. Mortar flow is most sensitive to water content and air content. It is also more sensitive than the slump test for stiff concrete mixtures. Mortar flow is a process control test procedure. Water content, fine
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aggregate gradation, cementitious chemistry, mixing time, air content, and concrete temperature all interact to affect mortar flow. A flow test cannot identify which of these factors is changing; it simply measures the flow of a given mortar. Uniformity of the mortar flow is the primary concern. ASTM C 1437, the Standard Test Method for Flow of Hydraulic-Cement Mortar, determines how much a mortar sample flows when it is unconfined and consolidated. Mortar is placed inside 2-in. tall conical brass mold. When the mold is removed, the mortar is vibrated at 1.67 Hz as the flow table rises and drops in. 25 times in 15 seconds. The mortar changes from a conical shape with a 4-in. base to a pancake. Mortar flow is reported as a percentage based on the change in diameter from 4 in. to the final diameter of the mortar pancake.

Fig. 3.3 Flow Table Test

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b) Fresh Density Test The weight of the fresh cement mortar cube after casting is noted down which is used for calculating the fresh density of the same. Fresh density = 3.4.2 STRENGTH TEST ON CEMENT MORTAR

a) Cube Compressive Strength Compressive strength is the most important property of concrete that influences the load bearing capacity of cement mortar. Cubes of size 5 cm were used. The test was done as per IS: 516 1959. The apparatus for testing is shown in the Fig. 3.4. Cement mortar cubes after curing were placed in the machine and load was applied. The load at failure was noted down. Compressive strength was calculated as load per unit area at failure. Test was done to determine 7th and 28th day compressive strength.

Fig. 3.4 Cube Compressive Strength Test

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b) Flexural Strength To determine flexural strength of a cement mortar beam, test was done on a cement mortar beam of size 4cmx4cmx16cm. Two point loading method was done to determine the modulus of rupture. The apparatus for testing is shown in the Fig. 3.5. The load at failure was noted. Modulus of rupture fb (if failure occurred in the middle third)

Where P-load at failure, L-span (160mm), b -breadth (40mm) d-depth (40mm)

Fig. 3.5 Flexural Strength Test of Cement Mortar Beam

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CHAPTER 4 RESULTS AND DISCUSSIONS

4.1 GENERAL Tests were done as per IS specifications on cement mortar and the results of the same are presented in this chapter. The mean values obtained by testing the specimens were used for plotting graphs and also for comparison. 4.2 WORKABILITY TEST 4.2.1 Flow Table Test Flow values of different mixes are presented in Table 4.1. It was seen that the flow values for mixes get improved in the mix and hence the addition of copper slag improves the workability of the mix under constant water binder ratio. The improvement in the workability may be due to the finer size and spherical shape of copper slag particles. Table 4.1 Flow Table Test Results Water : Binder ratio 0.7 0.5 0.5 0.5 0.475 0.7 0.6 0.6 0.6 0.6 Flow Value 20.5 19.5 21.5 21.5 21.5 21 19.5 19.5 19.5 19.5

Mix Type M1 M2 M3 M4 M5 K1 K2 K3 K4 K5

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4.2.2 Fresh Density of Cement Mortar Cubes Fresh densities of the cement mortar cubes are found out and the results are plotted. The graph showing test results are shown below (Fig. 4.1).

Fresh Density
3.50 3.02 3.00 2.52 Density in gm/cc 2.50 2.52 2.00 1.50 1.00 0.50 0.00 1 2 3 Type of mix 4 5 1:3 Mix 1:4 Mix 2.61 2.59 2.74 2.70 2.78 2.82 3.02

Fig. 4.1 Variation of Fresh Density 4.3 STRENGTH TEST ON CEMENT MORTAR

4.3.1 Cube Compressive Strength This test was done to determine the compressive strength of cement mortar. 5cm cubes were cast and cured in tap water. Cubes were tested on 7th day and 28th day. Average compressive strength of three cubes was taken as the compressive strength for the specified time period. The average compressive strength of various mixes is shown in the Table 4.2 below. Graph showing strength development is also presented in Fig. 4.2. From the graph we can see that for 1:3 mixes, though there is increase in early strength occurs while the fine aggregate is replaced with copper slag, for 28 th day strength the optimum value obtained at M2 mix where 25% replacement was there. In case of 1:4 mix 7th day as well as 28th day show optimum strength characteristic at M3 mix where 50% replacement was there. Hence we can say that for better strength characteristics, the effective replacement of fine aggregate by copper slag ranges from 25% to 50%.
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Table 4.2 Variation of Cube Compressive Strength Avg. Compressive Strength (MPa) Type of Mix 7th day M1 M2 1:3 M3 M4 M5 K1 K2 1:4. K3 K4 K5 12.6 13.7 14.7 16.5 16.4 12.0 13.9 14.1 13.9 10.9 28th day 27.5 29.3 26.0 25.5 24.7 20.4 22.6 22.9 21.1 14.1

Compressive Strength
35.0 30.0 Compressive Strength in MPa 27.5 25.0 20.0 15.0 12.6 10.0 5.0 0.0 0.0 1.0 2.0 3.0 Type of Mix (1:3) 4.0 5.0 6.0 16.5 13.7 14.7 16.4 7 Day 28 Day 29.3 26.0 25.5 24.7

Fig. 4.2 Variation of Cube Compressive Strength for 1:3 Mix

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Compressive Strength
25.0 22.6 Compressive Strength in MPa 20.0 20.4 22.9 21.1

15.0 12.0 10.0

13.9

14.1

13.9

14.1 10.9 7 Day 28 Day

5.0

0.0 0.0 1.0 2.0 3.0 Type of Mix (1:4) 4.0 5.0 6.0

Fig. 4.3 Variation of Cube Compressive Strength for 1:4 Mix

4.3.2 Flexural Strength of cement mortar Test was done on cement mortar beam to determine the flexural strength under two point loading. The results are shown below in Table 4.3 and Fig. 4.4. Flexural strength was determined at 28th day of casting. The strength was observed to be optimum for M2 for 1:3 mix and K2 for 1:4 mixes. Hence we can say that the flexural strength of the cement mortar is optimum when the fine aggregate is replaced with 25% of copper slag. Though the strength reduces after 25% replacement, it shows better result when compared with the control mix. Hence we can say that flexural strength is increased effectively while we add copper slag to the mortar mixture.

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Table 4.3 Variation of Flexural Strength of Cement Mortar Beam Flexural Strength (MPa) 1.00 1.18 1.15 1.06 1.07 0.99 1.12 0.91 0.89 0.90

Type of Mix

M1 M2 1;3 M3 M4 M5 K1 K2 1:4. K3 K4 K5

Flexural Strength
1.40 1.20 1.00 Flexural Strength in MPa 1.00 0.99 0.80 0.60 0.40 0.20 0.00 0 1 2 3 Type of Mix 4 5 6 0.91 0.89 0.90 1:3 mix 1:4 Mix 1.18 1.15 1.06 1.12 1.07

Fig. 4.4 Variation of Flexural Strength of Cement Mortar Beam

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CHAPTER 5 CONCLUSIONS

5.1 GENERAL The experimental study was undertaken to check the suitability of copper slag as fine aggregate in cement mortar by comparing performance of cement mortar with copper slag as replacement to M sand as fine aggregate. Tests were done to determine properties of the cement mortar by partially replacing M sand with copper slag and the results were presented in the previous chapter. Based on the test results obtained, the following conclusions are drawn and are presented in this chapter. 5.2 CONCLUSIONS 1 Use of copper slag in cement mortar is found to improve workability which is confirmed based on flow test. Required flow was obtained for a particular limit of water binder ratio. This may be attributed to the spherical shape and finer size of the copper slag. 2 Cube compressive strength for different mixes is calculated. As the percentage of copper slag increases, there is formation of early strength obtained. Whereas 28th day compressive strength characteristics shows that we can effectively replace the fine aggregate with copper slag around 25 to 50 percentage only. 3 The flexural strength of cement mortar beam was observed to be maximum for M2 in case of 1:3 mix and K2 for 1:4 mixes. It was noted that, addition of copper slag improves the flexural strength of cement mortar. Though the strength reduces after 25% replacement, it shows better result when compared with the control mix. 4 From the study, it is concluded that copper slag can be used as partial replacement of fine aggregate in cement mortar. Optimum value of replacement may be ranging from 25% to 50%. Since less water is required for mixing, we can obtain a good finish for the plastering works while we are using copper slag as fine aggregate.

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5.3 SCOPE OF FUTURE WORK Experimental study can be carried out to check the durability characteristics of copper slag which effectively influences the life of the mortar. Chemical reactions of the copper slag as a replacement material also to be investigated. More detailed study to be conducted about copper slag as it can b effectively used as replacement for fine aggregate, replacement for cement in mortar as well as in concrete.

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REFERENCES
1. Khalifa S. Al-Jabri, Abdullah H. Al-Saidy and Ramzi Taha (2011) Effect of copper slag as a fine aggregate on the properties of cement mortars and concrete, Construction and Building Materials ,Pp. 933938.

2. Khalifa S. Al-Jabri, Makoto Hisada, Abdullah H. Al-Saidy and S.K. AlOraimi(2009). Performance of high strength concrete made with copper slag as a fine aggregate, Construction and Building Materials, Pp.21322140. 3. Mostafa Khanzadi, Ali Behnood (2009). Mechanical properties of highstrength concrete incorporating copper slag as coarse aggregate, Construction and Building Materials, Pp. 21832188.

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