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Materials Today: Proceedings 4 (2017) 35253533 www.materialstoday.com/proceedings

5th International Conference on Materials Processing and Characterization

High Performance Concrete with Copper slag for

Marine Environment

S.Geethaa and Selvakumar Madhavanb

a
Professor,Department of Civil Engineering,Rajalakshmi Engineering College, Thandalam, Chennai-602 105, Tamilnadu,India
b
Professor,Department of Civil Engineering,Rajalakshmi Engineering College, Thandalam, Chennai-602 105, Tamilnadu,India

Abstract

Marine concrete structures are subjected to very severe exposure conditions and their durability is directly related to the quality
of concrete used. For these applications, concrete must possess low to very low permeability characteristics and its durability can
be assured with the use of proper mix compositions. Since high-strength concrete is with low permeability such a concrete grade
is needed to achieve high-performance in marine environment. This paper is focused on developing a corrosion resistant concrete
using copper slag, fly ash and silica fume with Portland cement for use in marine environments. Fly ash which is the byproduct
of thermal power plant have been used as replacement for cement and sand. A compressive strength of 70 MPa and flexural
strength of 6 MPa was achieved with copper slag and fly ash. The sorptivity ranged between 0.1 0.25 mm/min0.5. The
experimental trials were designed using Central composite design and multiple optimisation was also carried out for higher
strength and lower sorptivity.

2017 Elsevier Ltd. All rights reserved.

Selection and peer-review under responsibility of the conference committee members of the 5th International conference on Materials Processing
and Characterization.

Keywords;copper slag, fly ash, pozzolanic, strength;sorptivity

1. INTRODUCTION

Marine environment requires the use of a very low permeability concrete for the construction of durable concrete
structures. Mix compositions as well as the binder material type influence the permeability of concrete. Use of
blended cements with pozzolanic materials is known to reduce the permeability. In order to withstand the extremely
hostile environment, compressive strength of concrete above 60MPa is required, although this level of strength may
not be required from the loading point of view.
E mail: geetha.s@rajalakshmi.edu.in

2214-7853 2017 Elsevier Ltd. All rights reserved.

Selection and peer-review under responsibility of the conference committee members of the 5th International conference on Materials Processing
and Characterization.
3526 S.Geetha et al / Materials Today: Proceedings 4 (2017) 35253533

High strength concretes differ from medium strength concretes in many ways. The cement paste matrix in high-
strength concretes is dense owing to the absence of large capillary voids and a relative strong aggregate-cement
paste interfacial zone, which has a much lower tendency for micro-cracking. High-strength concretes contain
relatively high binder material content, a superplasticiser, and very low water content to achieve the water to binder
ratio below 0.30, by weight. They are capable of achieving a discontinuous capillary pore structure and low
permeability within a few days of hydration of cement . Copper slag also known as Ferro sand is generated during
pyro-metallurgical process involved in production of copper from copper concentrate [1]. For every ton of metal
production approximately 1.8-2.2 tons of slag is generated. The material possesses properties very similar to river
sand and therefore can be utilized as a replacement of sand in concrete application. Presently, world-wide, about 33
million tonnes of slag is generated annually with India contributing 6-6.5 million tonnes. Sterlite is planning to
dispose of 1.8-2.4 million tonnes of slag in the next one year. The company had already started receiving frequent
queries and a couple of orders from builders, cement and concrete manufacturers. Some applications, wherein slag
has already been recognised world-wide, are cement and concrete manufacturing, filling material, river
embankment, ballast material, abrasive, pavement blocks, road and roofing construction, granules, glass and tiles
making. Sterlite has carried out several technical studies for the last 10 years through various laboratories on the
physical and chemical properties. These studies have concluded that copper slag is non-leachable, and non-toxic.
Several researchers have investigated the possible use of copper slag as fine and coarse aggregates in concrete and
its effects on the different mechanical and long-term properties of mortar and concrete. With some benefits of using
copper slag as fine and coarse aggregates, some negative effects such as delaying of the setting time, especially
when only copper slag has been used as fine aggregate have also been reported. Copper slag has been used as
abrasive tools, roofing granules, cutting tools, tiles, road construction as base material, rail road ballast and
nowadays in concrete industry as partial replacement of cement and fine aggregate [2-6]. Copper slag has a high Fe
content and has been reported to be used in cement clinker production [7], The performance of the cement using
copper slag in the clinker has been reported to have better properties than the cement that used limestone and clay
[8]. Many researchers have reported the properties of copper slag when used as a partial replacement of cement and
have found that it plays significant role in the formation of hydration products [9-14]. Ayano and Sakata (2000)
[15] reported that copper slag when used as fine aggregate reduces the shrinkage of concrete and improved the
mechanical and long-term properties of mortar and concrete. It has been reported by several researchers that the
compressive and flexural strength of concrete were also improved when copper slag was replaced with fine
aggregate [16-19]. This paper deals with the properties of concrete with copper slag as replacement of fine aggregate
for concrete that can be used in marine applications.

2. MATERIALS & METHODOLOGY

2.1 Materials

The material characteristics of Phosphogypsum and fly ash are to be analysed for its chemical composition. There
are several components involved in the making of carbon fibre reinforced concrete like fly ash, phosphogypsum,
carbon fibres and water/cement (W/C) ratio. The traditional methods of experimentation consider only one factor at
a time and a series of experiments are conducted sequentially varying the parameters. Thus, this method deprives the
opportunity to understand the influence of each factor and combination of factors on the response. Statistically based
experimental design techniques are much useful when there are a number of controllable variables. The use of
designed experiments helps to identify those variables that have the greater influence on response. In addition,
running designed experiments helps in deriving meaningful conclusions from the experimental series. In order to
find the optimal combination of the various components statistical analysis is done using Response Surface
methodology of central composite design. The limits of each component will be decided based on preliminary trials
and the limits will be used to design the experimental runs. Since the material involves various parameters the trial
runs will be designed using design of experiment and experiments will be carried out based on the designed runs.
Cube specimens of size 15 cm, beams of size 10x50x500 and cylinders with diameter 10 cm and 20 cm length are
casted for strength tests. The specimens are cured in steam curing chamber at 100C for 24 hours. The concrete
specimens are to be tested for strength and durability. Optimization will be done for high strength and durability
 S.Geetha et al / Materials Today: Proceedings 4 (2017) 35253533 3527

aspects. The optimized mix will be casted and tested to check the predicted values.the chemical and physical
properties are shown in Table 1 and 2.

Table-1Chemical properties of copper slag Table-2 Physical properties of copper slag

Chemical % of chemical
component composition Specific Gravity 3.63
Al2O3 3.01 Hardness 7 Moh Scale
Tio2 0.60 Conductivity mS/M 4.8
Fe2o3 55 Chloride content <0.0002
SiO2 35
CaO 0.20
MgO 0.90
K2O 1.02
Na2O 0.95
CuO 0.42

3. RESULTS AND DISCUSSIONS

3.1 Compressive strength

Fig-1 Compressive strength Testing in UTM

Compressive strength test was carried on 15 cm cube in a Universal Testing Machine at a loading rate of 140 kg/cm2
per minute till the specimen failsas shown in figure 1. The response surface in Fig-2 shows that the compressive
strength increases with increase in silica fume and fly ash. This increase in strength is attributed to the formation of
additional reaction products as a result of pozzolonic reactivity. The response surface in Fig-3 shows that as there is
increase in compressive strength with increase in copper slag and silica fume.
3528 S.Geetha et al / Materials Today: Proceedings 4 (2017) 35253533

Fig-2 Variation in Compressive strength with Fly ash and Silica fume

Fig-3 Variation in Compressive strength with copper slag and Silica fume

3.2 Flexural strength

Fig-4 Flexural Strength Testing using UTM

 S.Geetha et al / Materials Today: Proceedings 4 (2017) 35253533 3529

The flexural strength was tested on beam specimens of size 10 cm x 10 cm in cross section and 50 cm in length.
The load was applied at the rate of 400 kg/min. The load was applied through two similar rollers mounted at the
third points of the supporting span. The flexural strength of concrete in varied from 4.02 to 5.29 MPa. The graph in
Fig-5 shows that as there was increase in fly ash and silica fume the flexural strength increased. Similarly as shown
in Fig-6 increase in copper slag also increased the flexural strength.

Fig-5 Variation in flexural strength with Fly ash and Silica fume

Fig-6 Variation in flexural strength with copper slag and Silica fume

3.3 Sorptivity

Permeability is a measure of flow of water under pressure differential in a saturated porous medium and for deep sea
structures or water-retaining structures where the ingress of water into concrete will be governed by this mechanism
under a head of water. Sorptivity is influenced by the moisture condition of concrete in order to remove the
saturation gradient and to realize maximum capillary suction here the tests have been conducted on 28-day cured
samples (100 mm cube) conditioned in oven at 105 + 5C for 24 hours and then cooled in a desiccators. The weight
of the oven-dried cube was measured to the nearest 0.01 g. The surface of concrete cubes, which was parallel to the
direction of casting, was placed in a tray containing water and rested on 5 mm glass rods to permit the free access of
water to the inflow surface. The schematic arrangement of the test is shown in Fig. 7. Cut or troweled surfaces were
not exposed to direct contact of water. Any cut surface would expose the porous aggregate and would not represent
the sorptivity in actual field condition.
3530 S.Geetha et al / Materials Today: Proceedings 4 (2017) 35253533

Fig-7 Sorptivity Test set up

Fig-8 Variation in Sorptivity with Fly ash and Silica fume

Fig-9 Variation in Sorptivity with copper slag and Silica fume

In addition, there can exist difference in the absorption characteristics between top and other moulded surfaces due
to casting procedures and the occurrence of bleeding and segregation. The lower areas on the sides of the specimens
adjoining the inflow face were sealed with epoxy coating to achieve unidirectional flow. The water level was
 S.Geetha et al / Materials Today: Proceedings 4 (2017) 35253533 3531

maintained at 10 mm above the base of the cube. The absorption of water was measured at intervals of 4, 9, 16, 25,
36, 49, 64, 81, 100, 121, 144 and 169 minutes after the start of placing the specimen in water on wiping out the
surplus water. Sorptivity S of each sample was determined from the slope of the regression line represented by the
experimental data i against t. For each mix sorptivity was determined for 3 samples. The sorptivity test shows that
there was marginal decrease in the sorptivity values as silica fume and fly ash increased as shown in response
surface graph in Fig-8. Increase in copper slag content drastically decreased the sorptivity value from 0.33 to 0.22
mm/mm as shown in Fig-9.

3.4 Rapid Chloride Penetrability Test (RCPT)

Fig. 10 Rapid Chloride Penetrability Test set-up

Fig.11 Rapid Chloride Penetrability Test Specimen

The ability of concrete to resist chloride ion penetration was studied using Rapid Chloride Penetration Test (RCPT)
as shown in Fig-10 (ASTM C1202, 2005) based on electrical conductance. This test measures the ease with which
concrete allows the charge to pass through and provides an indication on the resistance of concrete to chloride-ion
penetration. It is based on the principle that charged chloride ions would accelerate in an electric field towards the
3532 S.Geetha et al / Materials Today: Proceedings 4 (2017) 35253533

pole of the opposite direction. 28-day cured specimens of size 100 mm diameter and 50 mm thickness (Fig-11) were
allowed to dry at room conditions for 48 hours. The cylindrical surface of the specimens was then given two coats of
epoxy. After drying off epoxy, the specimens were vacuum saturated and then fixed in the cell with one side of the
cell (-) filled with 3% NaCl solution, while the other side (+) with 0.3 N NaOH solution. The test set up was
connected to the power supply for a continuous period of six hours. A potential difference of 60 V dc was
maintained across the specimen throughout the test period. The voltage was recorded at 30 minutes interval. The
total electrical charge passed through concrete in coulombs at the end of 6 hours was calculated. This is directly
related to the chloride ion penetration through the concrete.

Fig-12 Variation in chloride ion penetrability with fly ash and Silica fume

Fig-13 Variation in chloride ion penetrability with fly ash and Silica fume

RCPT test is one of the most important tests that have to be carried out for concrete that is to be used in marine
environment. The test result as shown in Fig-12 shows that there was appreciable decrease in the coulombs as the fly
ash content and silica fume was increased. Similarly the results in Fig-13 also show that the chloride ion
penetrability (Coulombs) decreased when the copper slag content was increased.
 S.Geetha et al / Materials Today: Proceedings 4 (2017) 35253533 3533

3.5 Multiple Optimizations

As the production of fibre reinforced aerated concrete is a multivariable process, optimization was done keeping for
the range of factors used in the experimental investigation. The criteria adopted for the multiple optimizations were
maximum strength with minimum density and sorptivity. The optimized values are summarised in Table-3. For
each combination of the optimized level, aerated concrete was casted and the tests were carried out. The results of
the predicted and observed values presented in Table-4.

Table-3 Optimized Values

Fly ash Silica fume Copper slag

17.07 9.99 20.00

Table-4 Optimized Values

Compressive strength Flexural strength Sorptivity Chloride ion penertrability

(Coulombs)
Predicted 72.90 6.10 0.0019 420
Observed 70.6 5.9 0.0022 440

4. CONCLUSION

The properties of concrete incorporating silica fume, fly ash and copper slag were found to be superior to the
conventional concrete.
1. Copper slag finds a potential application in concrete for marine application there was increase in
compressive strength, flexural strength and reduction in sorptivity and chloride ion penetrability values.
2. The addition of fly ash and silica fume is found to enhance the pozzolanic reactivity thereby improving the
ITZ (Inter transition Zone) forming a compact microstructure resulting in strength enhancement.
3. The durability of concrete tested through sorptivity and RCPT tests show that this concrete has a wide
application in the structures constructed in marine environment.

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