A COMPARATIVE STUDY OF THE PROPERTIES AND DURABILITY OF BINARY AND TERNARY CEMENTITIOUS SYSTEMS

By C. Shiathas. T. Z. Muntasser and S.O. Nwaubani ABSTRACT The main objective of this research was to investigate the properties of ternary and binary blends incorporating silica fume, metakaolin, and electric arc-furnace steel slag produced in Libya (LSS). The properties investigated include workability, chloride-ion penetration, and compressive strength. The penetration of chloride-ions was studied using the Rapid Chloride Permeability Test Method, in accordance with the procedures prescribed by AASHTO T27783 [5]. The study also looked at the effect of the amount of pozzolanic content on the observed trends.

It was established that ternary and binary mixtures could differ significantly in both their fresh and hardened properties. The ternary blends exhibited some positively complementary properties, which were not observed in the binary mixtures. Significantly, the ternary blends incorporating metakaolin were found to have greater improvement in strength and chlorideion penetrability compared to those mixtures incorporating the other two pozzolans used. Keywords: binary blends, metakaolin, microsilica, electric-arc furnace steel slag, rapidchloride permeability test, ternary blends.

Shiathas, Muntasser and Nwaubani C. Shiathas. Is a technical manager at Geoinvest Ltd, Cyprus. He obtained his MSc in Civil Engineering from the University of Surrey, UK, in 2000. T. Z. Muntasser is civil engineer working in the UK. He obtained his PhD from the University of Surrey, UK, in 2002. S. O. Nwaubani is a lecture in civil engineering and the director of the MSc Civil Engineering programme at the university of Surrey, UK. He obtained his PhD from the University of Leeds, UK, in 1990. INTRODUCTION

Normal portland cement concrete may suffer a variety of durability problems depending on the source of cement, the type of aggregates, and the environmental exposure conditions. Corrosion of reinforced steel bars in concrete is the major cause of early concrete deterioration. This form of deterioration is primarily induced by ingress of chloride ions into concrete. The ingressing chloride ions tend to depassivate the oxide film that normally protects steel from corrosion. It is well known that the durability of the structures decreases dramatically when concrete is made with inadequate check on penetrability of deleterious substances or if the concrete cover to reinforcement is inadequate. It is, therefore, important to discourage the penetration of free chloride-ions in order to prevent the corrosion of reinforcing bars embedded in concrete.

Permeability of concrete may be reduced through a variety of methods but the easiest of these is by making a low water/binder ratio mixtures. When incorporated in binary blends, pozzolanic materials are known to react with calcium hydroxide (CH), which is a product of cement hydration, to produce additional reaction products, such as calcium silicate hydrate (C-S-H) which improves strength and porosity. This in turn leads to a more impermeable and durable concrete.

Shiathas, Muntasser and Nwaubani The advantages of using ternary and binary blends instead of normal portland cement concrete are mostly in terms of improving concretes properties, economy, and sustainability with less environmental impacts. The behavior of these blends depends on the combination of the materials used in the mixture. In a ternary blend, one low-reactive pozzolan can be used with normal portland cement in such a way that all the undesirable effects such as lowworkability, low-early strength development and high-heat of hydration, could be eliminated.

Silica fume and metakaolin are very reactive pozzolanic materials, which enhances the strength development characteristics of concrete but their presence may lead to reduced workability. On the other hand, LSS is a slow acting material, which liberates low-heat during hydration process, reduce the early strength development, and improves workability [1].

This paper describes the results of a comparative study to compare the properties and durability of binary and ternary blends in order to evaluate their economic and environmental relevance. Three pozzolanic materials, silica fume, metakaolin, and electric arc-furnace steel slag produced in Libya, was used as a partial cement replacement material to produce ternary and binary concrete blends. Their effects on concrete properties such as workability,

chloride- ion penetration, and compressive strengths were investigated.

MATERIALS USED

NORMAL PORTLAND CEMENT (NPC): The cement used was normal portland cement class 42.5, which complies with BS 12: 1996 [2]. METAKAOLIN (MTK): The Metakaolin used was produced in the UK by English China Clay plc under the brand name Metastar 501. It was manufactured by high-temperature treatment of pure china clay using a carefully controlled calcination process to produce a very

Shiathas, Muntasser and Nwaubani amorphous material, which is highly reactive. The chemical oxide composition of Metastar 501 used is given in Table 2.

SILICA FUME: The silica fume used was the standard grade manufactured in slurry form produced by mixing undensified silica fume powder and water in equal proportions by weight. It is the easiest and most practical way to introduce silica fume into concrete mixtures. The specific gravity of the slurry was 1400 kg/m3 and it had an average particle size of 0.16. The specific surface area was between 15 and 20 m2/g.

ELECTRIC-ARC FURNACE STEEL SLAG (LSS): This is a non-commercial air-cooled material produced as a by-product of the Libyan Steel and Iron Industry. LSS was supplied initially from the factory in the form of medium size (10-40cm) rocks that needed to be broken down into smaller pieces in the University of Surrey Concrete Laboratory using Kango Hammer. The broken pieces were then sent to Frodingham Cement Company Ltd to be ground to a smaller particle size similar to that of normal portland cement. The chemical oxide composition of the LSS as obtained from the factory is given in Table 2.

AGGREGATES: The aggregates were in the form of flint 10 mm maximum size. Natural river sand with grading complying with the British Standards limits for medium sand [ ] were also used.

SUPERPLASTICIZER:

The superplasticizer used was the type known as SP5 It is a high-efficiency superplasticising admixture

manufactured by Cornmix Limited.

designed to impart high-workability to concrete. It is a pale straw liquid with pH between 9.5 to 11.5, and has a relative density of 1.19.

Shiathas, Muntasser and Nwaubani WATER: The water used in preparing the specimen was distilled water prepared in the University of Surrey Concrete Laboratory.

MIXTURE PROPORTIONS AND SPECIMEN PREPARATION

Table 1 shows the mixtures used and their compositional contents. The blended mixtures contain different percentages of the cement replacement materials but the proportions for all other materials were constant. For every mixture, 15cubes (100 x100 mm in size), and 4 cylindrical specimens, 100 mm wide and 50 mm thick, were cast. The cube specimens were cast according to the specifications in BS 1881 Part 108: 1983 [3]. Compaction was by means of a vibrating table and was done in two layers for both the cylinders and the cubes. After casting, all specimens were covered with a polythene sheet and placed in a fog room maintained at a constant temperature of 20C 2C and 99% relative humidity. The specimens were de-molded after 24 hours and left in the curing room until they were due for testing. The cube specimens were used for assessing compressive strength. The cylinders were used for the chloride-ion penetration tests.

EXPERIMENTAL DETAILS

COMPRESSIVE STRENGTH TEST. The compressive strength of concrete was determined in accordance with British Standards, BS 1881: Part 116: 1983 [4]. This involved applying direct compressive loads to the test specimens in the vertical direction at a constant rate of 150 kN per minute. Tests were conducted after 3, 7, 28, 56, and 91 days of curing.

Shiathas, Muntasser and Nwaubani RAPID CHLORIDE-ION PENETRATION TEST Diffusion is the main mechanism of chloride-ion transport through crack free concrete. The diffusivity of ions in porous materials is determined conventionally by the use of diffusion cells or by immersion in a salt solution. However, these methods are time-consuming often requiring months or years to obtain results

In this study, the permeability of test specimens to chloride-ions was assessed by a Rapid Chloride Permeability technique, in accordance with the procedures prescribed by AASHTO, T277-83 [5]. The test specimens used were 50 mm thick and 100 mm in diameter. The experiment was set-up by sandwiching the test specimen between two compartments containing 3% solutions of sodium chloride in one compartment and a molar solution of sodium hydroxide. The experiment was run by subjecting the samples to an applied voltage of 60 volts for six hours. The test determines the electrical conductance of the test specimen, expressed as the total electrical charge passed through the specimen, in coulomb. The test is a quick and inexpensive method for obtaining the chloride permeability index of concrete mixtures and has been largely used in recent years to evaluate the protection provided by concrete for steel reinforcement [6]. Some doubts, however, have been expressed regarding the accuracy of the test. The main criticism is that the conditions of measurement are very severe and may cause both physical and chemical change in the specimens, resulting in unrealistic results.

Another drawback of the rapid chloride permeability test relates to the possibility of other ions present in the pore solution of the hardened matrix conducting a part of the total current leading to inaccurate estimations [7, 8]. Some researchers have also stated that the mechanism of electric conduction through cement-based materials is mostly electrolytic in nature and is through the cement paste owing to the infinitely large electrical resistivity of the aggregates.

Shiathas, Muntasser and Nwaubani Thus the aggregates, depending on their volume fraction in the mixture and type, may influence the rapid test results [9].

Despite the concerns regarding the theoretical relevance of the rapid chloride permeability test, it remains one of the most widely used tests. The authors of this paper are of the opinion that it should be used with caution and the results should be interpreted with a clear understanding of the principles behind the test and concrete permeability. It is also important to note that it provides an index of chloride-ion penetration, NOT the actual permeability of the test sample.

RESULTS AND DISCUSSION

COMPRESSIVE STRENGTH TEST The compressive test results are shown in Fig. 1. It can be seen that the short-term strengths of the binary blends incorporating LSS mixtures are low but after long-term curing the strength became similar to the strength of the control mixture. Ternary blending with either silica fume or LSS did not seem to improve the long-term strength beyond that of the control. Binary blends incorporating 1% silica fume were surprisingly of the same strength level as the control mixture. All binary blends incorporating metakaolin exhibited higher compressive strength values. Mixtures incorporating 20% of metakaolin exhibited the highest strength results. Ternary blend incorporating metakaolin and silica fume attained the same strength levels as the binary mixtures. However the strength level reduced when LSS is present in a ternary blend.

Shiathas, Muntasser and Nwaubani RAPID-CHLORIDE PERMEABILITY TEST The chloride penetration test results are shown in Fig. 2. It can be seen that at the early age of 7 days almost all the mixtures exhibited high-chloride penetration. However, the permeability index for mixtures 5,9,10,11, and 12 were only moderately high. These mixtures are binary and ternary blends incorporating 20% of metakaolin. After 91 days the chloride-ion

penetration of all mixtures were observed to reduce drastically with the LSS blends exhibiting similar chloride penetration as the normal portland cement mixture but the metakaolin mixtures stood out with a far more reduced amount of charge passed.

Fig. 3 shows the relationship between the charge passed and the compressive strength results for the mixtures studied. It can be seen that the results obtained from the two tests are inversely proportional. The mixtures that exhibited high-strength exhibited the lowest

penetration and vice versa.

CONCLUSIONS

The following conclusions may be drawn from this investigation:

Binary and ternary blends incorporating metakaolin gained strength very rapidly and continued to gain strength beyond 28 days. They exhibit higher compressive strength results than the normal portland cement concrete mixture. Compressive strength was found to increase with an increase in cement replacement by metakaolin. The highest compressive strength at 91 days was obtained by a ternary blend (Mixture 10) which was made with 79% normal portland cement, 1% silica fume and 20% metakaolin.

Shiathas, Muntasser and Nwaubani Binary and ternary blends incorporating metakaolin exhibited the lowest chloride-ion penetration. It was found that by increasing the cement replacement by metakaolin in these mixtures chloride-ion penetration reduces.

At early ages, LSS binary blend exhibited lower compressive strength, and higher penetration, than the normal portland cement mixture. However, at later ages and particularly at 91 days, the LSS binary blend exhibited slightly lower results in compressive strength and chloride permeability than the normal portland cement mixture.

REFERENCES

[1]

Muntasser, T. Z.

Properties and durability of slag-based cement in the PhD Thesis. Department of Engineering.

Mediterranean environment. University of Surrey. 2002. [2]

British Standards Institution Specification for Portland Cement, BS 12 : 1996.

[3]

British Standard Institution, Method of Making Testing Cubes from Fresh Concrete, BS 1881: Part 108: 1983.

[4]

British Standard Institution, Method for Determination of Compressive Strength of Concrete Cubes, BS 1881: Part 116: 1983.

[5]

AASHTO T277-83, Standard Method for Resistance of Concrete to Chloride Ion Penetration AASHTO, Washington D.C., 1983.

[6]

R. Feldman, Luiz R. Prudencio Jr., Gordon Chan, Rapid chloride permeability test on blended cement and other concretes: correlations between charge,

Shiathas, Muntasser and Nwaubani initial current, and conductivity, Construction and Building Materials 13 (1999) 149-154.

[7]

C. Shi, J. A. Stagemann, and R. J. Caldwell, Effect of Supplementary Cementing Materials on the Specific Conductivity of Pore Solution and its Implications on the Rapid Chloride Permeability Test Results ACI Materials Journal / July August (1999) 389-394.

[8]

C. Andrade, Calculation of chloride diffusion coefficients in concrete from ionic migration measurements, Cement and Concrete Research 23 (1993) 724-742.

[9]

T. H. Wee, A. K. Suryavanishi, and S. S. Tin, Influence of aggregates fraction

in the mix on the reliability of the rapid chloride permeability test, Cement & Concrete Composites 21 (1999) 59-72.

Shiathas, Muntasser and Nwaubani

Table 1: Mixture Composition (% by weight) Mix No. NPC MS MTK LSS Free Water (%)
Mixture 1 100

Coarse Aggregate (%)

294

Fine Aggregate (%)

166

(%)

(%)

(%)

(%)
40

Mixture 2

99

40

294

166

Mixture 3

95

40

294

166

Mixture 4

90

10

40

294

166

Mixture 5

80

20

40

294

166

Mixture 6

70

30

40

294

166

Mixture 7

69

30

40

294

166

Mixture 8

65

40

294

166

Mixture 9

89

10

40

294

166

Mixture 10

79

20

40

294

166

Mixture 11

85

10

40

294

166

Mixture 12

75

20

40

294

166

Shiathas, Muntasser and Nwaubani

Table 2: Main physical and chemical characteristics of NPC, LSS, MS, MTK Physical Properties
BET Surface Area (m2/kg)

NPC
985

LSS
1,358

MS
15,00020,000

MTK
12,000

Relative Density (g/cc)

3.18

3.62

2.20

2.50

Chemical Oxide Composition

SiO2

NPC (%)
20

LSS (%)
16.7

MS (%)
92

MTK (%)
52.1

Al2O3

6.11

0.7

41.0

Fe2O3

3.5

19.51

1.2

4.32

CaO

65

37.8

0.15

0.07

MgO

0.1

14.3

0.2

0.19

Na2O

0.1

0.16

1.0

0.26

K2O

0.7

1.5

0.63

Shiathas, Muntasser and Nwaubani

Compressive Strength Test Results

Compressive Strength (N/mm^2)
80 70 60 50 40 30 20 10 0 1 2 3 4 5 6 7 8 9 10 11 12

Mixes
3-Days 7-Days 28-Days 56-Days 91-Days

Fig. 1. Compressive Strength Results.

Rapid Chloride Permeability Test Results

14000 Charge Passed (Coulombs) 12000 10000 8000 6000 4000 2000 0 Mix 1Mix 2Mix 3Mix 4Mix 5Mix 6Mix 7Mix 8Mix 9 Mix Mix Mix 10 11 12 Mixes 7-Days 91-Days

Fig. 2. Rapid Chloride Permeability Results

Shiathas, Muntasser and Nwaubani

Compressive Strength Results Vs RCPT Results

14000

Charge Passed (Coulombs)

12000 10000 8000 6000 4000 2000 0 20 30 40 50 60 70 80

Compressive Strength (N/mm^2)

7-Days Results Linear (7-Days Results) 91-Days Results Linear (91-Days Results)

Fig. 3. RCPT Vs Compressive Strength Results.