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COMPARISON OF CHLORIDE PER MEABILITY OF METAKAOLIN AND FLY ASH CONCRETES AND MORTARS UNDER ELEVATED TEMPERATURES

COMPARISON OF CHLORIDE PERMEABILITY OF METAKAOLIN AND FLY ASH CONCRETES AND MORTARS UNDER ELEVATED TEMPERATURES

Abid Nadeem*, Hong Kong College of Technology, Hong Kong Johnny Y N Mok, Hong Kong College of Technology, Hong Kong Salman Azhar, Auburn University, AL, USA Brian H Y Leung, Hong Kong College of Technology, Hong Kong Gary K W Tse, Hong Kong College of Technology, Hong Kong

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33 rd Conference on OUR WORLD IN CONCRETE & STRUCTURES: 25 – 27 August 2008, Singapore

COMPARISON OF CHLORIDE PERMEABILITY OF METAKAOLIN AND FLY ASH CONCRETES AND MORTARS UNDER ELEVATED TEMPERATURES

Abid Nadeem*, Hong Kong College of Technology, Hong Kong Johnny Y N Mok, Hong Kong College of Technology, Hong Kong Salman Azhar, Auburn University, AL, USA Brian H Y Leung, Hong Kong College of Technology, Hong Kong Gary K W Tse, Hong Kong College of Technology, Hong Kong

Abstract

This paper investigates the chloride permeability performance of high strength concrete and mortar specimens containing varying proportions of metakaolin (MK) and fly ash (FA) as partial replacement of ordinary Portland cement (PC). A total of seven concrete and three mortar mixes were tested after exposing each mix to 200, 400, 600 and 800°C. In concretes, the dosage levels of MK were 5, 10 and 20% and for FA were 20, 40 and 60%. In mortars, the dosage level of MK and PFA was 20%. For unheated specimens, the chloride permeability values were extremely low. At 200°C, the chloride permeability was higher than that at 27°C but it was still in the acceptable limits. After the exposure of 400°C, most of the values for chloride permeability indicated moderately permeable condition in concrete. However, after the exposure of 600 and 800°C, all the concrete specimens were highly permeable. All MK concrete specimens had lower chloride permeability than PC concrete for temperatures up to 200°C, whereas FA concrete specimens had lower chloride permeability than PC concrete at all temperatures. At normal temperatures, the chloride permeability of mortar was greater than concrete. The ratio of mortar to concrete chloride permeability decreased with the increase in temperature and at exposures of 600°C or above, the chloride permeability of concrete was slightly greater than mortar. This is an indication of damage mechanism in the interfacial transition zone and hardened cement paste in concrete microstructure due to exposure of elevated temperatures and has been discussed in the paper.

Keywords:

High

Strength

Concrete,

High

Temperatures,

Metakaolin,

Fly

Ash,

Interfacial

Transition Zone.

 

1. Introduction

Chloride permeability is one of the measures of the diffusion properties of concrete. Its test which first developed in 1981 by Whiting [1] is widely applied in research and practice to describe the performance of concrete in relation to its permeability which is one of the various durability

characteristics of concrete. The widespread use of chloride permeability test is due to its relative simplicity and shorter duration to conduct the test as compared with other durability tests on concrete [2]. Besides, the chloride permeability tests have been standardized by testing organizations such as AASHTO [3] and ASTM [4]. The method has been critically reviewed. Its criticism focuses on two problems: “(1) the theoretical tenets and intrinsic effects, including the temperature rise during the test; and (2) interpretation of results for concrete systems containing various chemical and mineral

admixtures” [2]. The results of chloride permeability are not an absolute measure of the permeability of concrete. Despite, its criticism, the values of chloride permeability are still useful for comparing various concrete specimens [5] as the method itself is standardized and relatively convenient to implement. There have been a large number of experiments performed on concrete using chloride permeability by the researchers all over the globe [6-9]. A sizeable amount of data also exists on the elevated temperature performance of concrete involving mineral admixtures such as fly ash and metakaolin. Most of these studies have been on the concrete specimens [10-12]. However, very few studies have been performed on mortar specimens partly because mortar itself is a component of concrete and only special purpose may warrant its separate investigation [13]. In this study the chloride permeability of selected mortar mixes have been determined separately and compared with relevant concrete specimens for drawing conclusions about the nature of damage mechanism in concrete due to elevated temperatures especially at the interface of concrete and the hardened cement paste.

  • 2. Experimental Details

The binder materials used in concrete and mortar mixes were ordinary Portland cement (OPC) complying with BS 12: 1991, low-calcium fly ash (FA) complying with BS 3892-1: 1997 and metakaolin (MK). Metakaolin is a thermally activated alumino-silicate produced from kaolinite clay through calcining process at elevated temperatures (>1000 °C). The chemical composition and physical properties of these materials are given in Table 1.

Table 1: Composition of OPC, MK and FA

OPC

MK

FA

Chemical composition (%) Silicon dioxide (SiO 2 )

19.6

53.2

56.8

Aluminum oxide (Al 2 O 3 )

7.3

43.9

28.2

Ferric oxide (Fe 2 O 3 )

3.3

0.38

5.3

Calcium oxide (CaO)

63.1

0.02

3.0

Magnesium oxide (MgO)

2.5

0.05

5.2

Sodium oxide (Na 2 O)

0.1

0.17

--

Potassium oxide (K 2 O)

1.1

0.10

--

Sulfur trioxide (SO 3 )

2.1

-

0.7

Loss on ignition

3.0

-

3.9

 

Physical properties Specific gravity

3.16

2.62

2.31

Specific surface (m 2 /kg)

312

12680

412

The coarse and fine aggregates used were crushed granite and river sand respectively, complying with the requirements of BS 882: 1992. Coarse aggregates of two sizes 20 mm and 10 mm were used in a proportion of 2:1 by weight. A dark brown liquid superplasticizer based on sulphonated naphthalene formaldehyde condensate was used in the prescribed dosages in the mixes to achieve the desired slump of 100 mm or above. Seven concrete and three mortar mixes were investigated. PC mix is a control mix which is OPC concrete mix. Metakaolin and fly ash mixes are denoted with MK and FA along with the numerical value representing the replacement level. For example, MK20 is with 20% replacement of OPC with MK. The mix proportioning details are given in Table 2. The compressive strengths of mixes just before chloride permeability testing (~ 6 months) are also given in Table 2.

Table 2: Details of concrete mixes (quantities for 1 m 3 concrete)

Mix

Cement

(kg)

PFA

(kg)

MK

(kg)

Water

(kg)

Sand

(kg)

Aggregate (kg)

20 mm

10 mm

Strength

(MPa)

PC

450

0

0

135

643

797

399

105

MK5

428

0

22

135

640

790

385

108

MK10

405

0

45

135

641

794

397

113

MK20

360

0

90

135

638

791

395

126

FA20

360

90

0

135

634

786

393

122

FA40

270

180

0

135

625

774

387

109

FA60

180

270

0

135

615

762

381

71

The batching, mixing and casting of concrete was performed in accordance with BS 1881: Part 125: 1986. For preparing mortar specimens, mortar was extracted from fresh concrete by sieving the concrete through 5 mm sieve. Cylindrical specimens of 95 mm diameter and 51 mm length were prepared according to AASHTO T 277 [3] requirements for chloride permeability test. The specimens were cured in water at 27°C for 28 days and then in a humidity (65%) and temperature (27 °C) controlled room for further five months. Heating of specimens in furnace was performed at a heating rate of 5°C/min up to the desired temperatures (200, 400, 600 and 800°C) which were maintained for one hour. The hot specimens were cooled naturally in a closed and dry chamber for at least 16-24 hours before testing.

  • 3. Results and Discussions

The currents passing through seven concrete and three mortar specimens at various temperatures (27, 200, 400, 600 and 800°C) were recorded and analyzed by computer attached to the test equipment. The current in specimens for 600 and 800°C could not be passed for 6 hours. A period of 110 minute was chosen to compare the charge passed in all specimens. Two specimens were tested for each condition and average value was taken for use in final comparison/analysis. Tables 3 and 4 present the values of charge passed through concrete and mortar specimens respectively at various temperatures.

Table 3: Charge (Coulombs) passed through concrete specimens

Mix

 

27°C

200°C

400°C

600°C

800°C

110

 

110

  • 360 110

360

 

360

110

110

min

min

min

min

min

min

min

min

PC

181

 
  • 756 1593

363

 

1017

4449

3806

4275

MK5

102

 
  • 421 1003

246

 

945

3877

3617

4018

MK10

79

 

360

  • 325 1220

1465

 

5001

4990

6184

MK20

57

 

300

  • 231 1083

1231

 

4446

5871

6320

FA20

121

 

220

  • 482 574

882

 

2280

2743

3359

FA40

82

 

198

  • 326 519

792

 

2071

3435

3613

FA60

78

 

220

  • 312 672

904

 

2739

3662

3874

 

Table 4: Charge (Coulombs) passed through mortar specimens

 
 

27°C

200°C

400°C

600°C

800°C

Mix

110

 

110

  • 360 110

360

 

360

110

110

min

min

min

min

min

min

min

min

PC

331

1433

497

2128

1213

5184

3224

3552

MK20

96

392

416

1706

1295

5352

5172

6118

FA20

193

769

311

1244

591

2367

2324

3171

3.1. Charge Passed in Concrete and Mortar Mixes at Various Temperatures

The data in Table 3 and 4 shows that the charge passed in each concrete and mortar mix increased with the increase in temperature. This is an indication of increase in porosity of concretes

and mortars and a cause of durability loss. At normal temperature (27°C), the charge passed in metakaolin and fly ash mixes was significantly lower than the control mix. This can be attributed to the pozzolanic reaction of fly ash and metakaolin in reducing the porosity of concrete and mortar. Both AASHTO T277 [3] and ASTM C 1202 [4] recognize that the chloride ion penetrability is regarded as low if the charge passed is up to 2000 Coulomb; medium if charge passed is between 2000 and 4000 Coulomb and high if charge passed is over 4000 Coulomb. Based on this criterion all concrete specimens had low chloride ion penetrability up to a temperature of 200°C. PC mortar was an exception at 200°C and can be regarded as having medium chloride penetrability whereas MK20 and FA20 mortars still had low chloride ion penetrability at 200°C. At temperatures of 400°C or above all the concrete and mortar mixes depicted chloride ion penetrability at either medium or high levels. MK20 and FA20 are two comparable mixes with respect to replacement level of cement. The charge passed through these mixes is compared. The charge passed through MK20 mix (concrete and mortar) at the normal temperature is lower than the charge passed through FA20 mix. At temperatures of 200°C or above, the charge passed though FA20 mix was lower than the charge passed through MK20 mix.

3.2. Ratio of Charge Passed at Elevated Temperatures to Normal Temperature Figure 1 shows the variation of the ratio of charge passed at elevated temperatures to normal temperature (27°C) through PC and MK concrete mixes. At 200C, charge passed was from 2 to 5 times that of charge passed at 27C. At 400C, the charge passed was from 6 to 19 times that of charge passed at 27C. The same ratios for 600°C and 800°C were 21 to 104 and 24 to 112 respectively. Figure 2 shows the variation of the ratio of charge passed at elevated temperatures to normal temperature through PC and FA mixes. At 200°C, the charge passed was from 2 to 2.8 times that of charge passed at 27°C. At 400°C, the charge passed was 5 to 9 times that at normal temperature. At 600°C and 800°C, the relative charge passed was 23 to 47 times and 28 to 50 times respectively. This shows that between 400°C and 600°C, there is a sharp increase in charge passed through concrete specimens.

PC MK5 MK10 MK20 100 120 80 60 40 20 0 Relative charge passed w.r.t
PC
MK5
MK10
MK20
100
120
80
60
40
20
0
Relative charge passed w.r.t normal
temp.
400°C
200°C
800°C
600°C

Temperature

Figure 1: Ratio of charge passed at elevated temperatures to normal temperature in PC and MK concretes

PC FA20 FA40 FA60 0 60 50 40 30 20 10 Relative charge passed w.r.t
PC
FA20
FA40
FA60
0
60
50
40
30
20
10
Relative charge passed w.r.t normal
temp.
400°C
200°C
600°C
800°C

Temperature

Figure 2: Ratio of charge passed at elevated temperatures to normal temperature in PC and FA concretes

3.3.

Ratio of Charge Passed in Various Concretes to Control Concrete

Figure 3 shows the variation of the ratio of charge passed through MK concrete mixes to control (PC) mix at various temperatures. It shows that charge passed through MK concrete at 27C and 200C was less than that in control mix. At 400C or above, charge passed through MK10 and MK20 concrete specimens was more than the charge passed through control concrete. The charge passed through MK10 and MK20 concrete is about 24 to 47% greater than the charge passed through control

concrete at temperatures of 600C or above. MK5 concrete allowed less charge to be passed than control concrete at all temperatures. Figure 4 shows the variation of the ratio of charge passed through FA concrete mixes to control mix at various temperatures. The ratio was less than one at all temperatures. At normal temperature, FA60 had the lowest ratio of charge passed with respect to control concrete. At temperatures of 200°C and 400°C, FA40 concrete had the lowest ratio. While at temperatures of 600°C and 800°C, FA20 concrete had the least relative charge passed with respect to control concrete.

0.6 27°C 800°C 600°C 200°C 400°C Relative charge passed w.r.t. control concrete 0.0 0.2 0.4 MK5
0.6
27°C
800°C
600°C
200°C
400°C
Relative charge passed w.r.t. control
concrete
0.0
0.2
0.4
MK5
0.8
1.0
1.2
1.4
1.6
1.8
MK20
MK10

Temperature

Figure 3: Ratio of Charge Passed through MK concretes to control concrete

FA20 FA40 FA60 1.2 1.0 0.8 0.6 0.4 0.2 0.0 Relative charge passed w.r.t. control
FA20
FA40
FA60
1.2
1.0
0.8
0.6
0.4
0.2
0.0
Relative charge passed w.r.t. control
concrete
400°C
200°C
600°C
800°C
27°C

Temperature

Figure 4: Ratio of Charge Passed through FA concretes to control concrete

  • 3.4. Comparison of the Charge Passed Through Concrete and Mortar

Figure 5 shows the ratio of the charge passed through mortar to charge passed through corresponding concrete specimens. The mortar to concrete ratio for charge passed decreases with increase of temperature. The ratios are greater than one for temperatures up to 400°C and slightly

less than one for temperatures of 600°C and 800°C. The maximum ratio is for PC mix which is 1.8 at 27°C and the minimum is about 0.8 for the same mix at 800°C.

0.6 27°C 800°C 600°C 200°C 400°C Mortar to concrete ratio for chagre passed 0.0 0.2 0.4
0.6
27°C
800°C
600°C
200°C
400°C
Mortar to concrete ratio for chagre
passed
0.0
0.2
0.4
PC
0.8
1.0
1.2
1.4
1.6
1.8
2.0
MK20
FA20

Temperature

Figure 5: Mortar to concrete ratio for charge passed

3.5. Discussion on the Comparison of Concrete and Mortar Chloride Permeability

The greater than one ratio for charge passed through mortar to concrete shows that mortar is more permeable than concrete. From Figure 5, it is noted that PC, MK20 and FA20 mortars are more permeable than respective concrete for temperatures up to 400°C. Mortar used in this study was derived from concrete by removing larger than 5 mm aggregate particles during concrete mixing process. The difference between mortar and concrete used is the absence of large aggregate particles in mortar. Large aggregate particles have high resistance against electrical current due to their inertness and imperviousness [14]. This reduces the area available for conducting current in concrete as compared with mortar. Consequently, less charge passes in a given time through concrete than mortar. This was the case for PC, MK and PFA mixes for temperatures up to 400°C. However, for higher temperatures of 600°C and 800°C, concrete was more permeable than mortar as indicated from the results. This is due to some change in the structures of concrete that allowed more charge to be passed through concrete than mortar at 600°C and 800°C. The results shown in Figure 5 indicate that concrete is less permeable than mortar at lower temperatures but becomes more permeable at higher temperatures. A possible cause may be due to some changes in the microstructure of concrete. It is widely believed that concrete consists of aggregate, hardened cement paste (hcp) and interfacial transition zone (ITZ). ITZ is the connecting medium between aggregate particle and the hcp in concrete. The granite aggregate used is known to be stable at temperatures up to 1000°C and is not conductive to electrical currents at higher temperatures. Hence, changes in the electrical conductivity of concrete can be related to changes in hcp and ITZ. The hcp is common component in mortar and concrete. The component which is present in the concrete and absent in the mortar is the ITZ; strictly speaking the ITZ between the hcp and the aggregate particles 5 mm or larger. Any difference which is observed between the mortar and concrete conductivity can thus be related to the changes in the ITZ. Considering this, the difference between the chloride permeability of mortar and concrete at various temperatures can be explained. At normal temperature, mortar is more permeable than concrete primarily because of less area is available for electrical current to pass through concrete than mortar. The less area available for conducting electrical current is due to the non-conductive area of large aggregate particles in concrete. At normal temperatures, there seems to be little contribution of ITZ of concrete used in this study to pass electrical current in the case of chloride permeability test. It is because of the concrete tested is of high strength (>71 MPa) and the ITZ might have been not porous like the ITZ for lower strength concrete. This can be supported from the observation that at normal temperature, more charge passed through PC concrete than FA and MK concrete. FA and MK concretes are denser than PC concrete because of the use of fine binder materials FA and MK as partial replacement of cement in the mixes.

At 200°C and 400°C, mortar generally more permeable than concrete as the ratio of charge passed through mortar to concrete shows in Figure 5. However, the ratios are lower than at normal temperature of 27°C. As for the normal temperature, the role of large aggregate to inhibit the charge passed in mortar is similar here. However, the decreased ratios for mortar to charge passed indicate changes in the ITZ at 200°C and 400°C. ITZ might have become more porous and is able to provide additional path to the electrical current. Thus the ratio of charge passed through mortar to charge passed through concrete decreases at 200°C and 400°C. At 600°C and 800°C, there was further drop in the ratio of charge passed through mortar to charge passed through concrete and it fell below one. This indicates concrete to be more permeable than mortar. As the aggregate remains stable and hcp in mortar and concrete are regarded as same, the difference might have been due to ITZ in concrete. At this range of temperatures, ITZ has probably become extremely porous and is providing additional path to the conduction of electrical current through concrete. This path is not available in mortar and thus concrete becomes more permeable than mortar.

  • 4. Conclusions

The following conclusions can be drawn from the investigations performed in this paper.

  • 1. All concrete specimens investigated in this study had a minimum compressive strength of 85 MPa. At normal temperature, these concretes and mortar specimens had very low chloride ion penetrability according to AASHTO and ASTM recommended values.

  • 2. The charge passed in concrete and mortar specimens increased with the increase in temperature. Major increase in charge passed was between 400°C and 600°C.

  • 3. Considering the AASHTO and ASTM recommended values, the concrete specimens had low chloride ion penetrability for temperature exposures up to 200 °C. At 400°C, the chloride ion penetrability was generally moderate. Whereas at 600°C or above the concrete and mortar specimens were highly chloride penetrable.

  • 4. At normal temperature, metakaolin mixes had lower chloride permeability than FA and PC mixes. Among metakaolin mixes, MK5 had lower chloride permeability than PC concrete at all temperatures.

  • 5. Fly ash mixes had lower chloride permeability than PC mix at all temperatures. At elevated temperatures, FA20 concrete had lower chloride permeability than MK20 concrete.

  • 6. At normal temperatures mortar was more chloride permeable than concrete. At 200°C and 400°C, mortar was still more chloride permeable than concrete but the ratio of mortar to concrete chloride permeability was less than that at normal temperature. At 600°C and 800°C, HPC was slightly more permeable than mortar. This is associated with gradually increasing contribution of ITZ of concrete in transmitting chloride ions due to exposure of elevated temperatures.

  • 5. References Whiting, D., (1981), “Rapid Determination of the Chloride Permeability of Concrete,” Final Report No. FHWA/RD-81/119, Federal Highway Administration, NTIS No. PB 82140724.

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