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Mohammad Ismail, Esah Hamzah , Goh Chun Guan and Ihsan Abd Rahman

CORROSION PERFORMANCE OF DUAL-PHASE STEEL EMBEDDED IN CONCRETE


*Mohammad Ismail
Faculty of Civil Engineering, Universiti Teknologi Malaysia 81310 Skudai, Johor Bahru Johor, Malaysia

Esah Hamzah , Goh Chun Guan and Ihsan Abd Rahman


Faculty of Mechanical Engineering, Universiti Teknologi Malaysia 81310 Skudai Johor Bahru, Johor, Malaysia

:
. .735cO 41 % 5.3 . 901 ASTM G Tafel . 501- CMS . ) (Ecorr ) (Icorr ) (RP Tafel Bc,Ba . .

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:Corresponding Author E-mail: mohammad@utm.my ;8861355706+ :Tel 7516655-706+ :Fax Classification: Civil Engineering, Corrosion of Reinforcement ________________________________________________________________________________________________________ 9002 ,21 Paper Received May 29, 2009; Paper Revised August 20, 2009; Paper Accepted October

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Mohammad Ismail, Esah Hamzah , Goh Chun Guan and Ihsan Abd Rahman

ABSTRACT This paper presents results of experiments designed to evaluate corrosion performance of a dual-phase steel embedded in concrete. The dual-phase steel was produced by inter-critical annealing of conventional steel at 735 oC. Test specimens were initially cured in water for 14 days followed by accelerated corrosion curing in 3.5% chloride solution and sea water. Corrosion rates were measured using a modified ASTM G 109 tafel extrapolation corrosion test technique, which entails voltage control and current quantifications. In addition, the CMS-105 system was employed for weekly observations on steel bars immersed in similar curing conditions. The parameters measured include corrosion potential (Ecorr), corrosion current (Icorr), polarization resistance (Rp), and corrosion rate as well as anodic and cathodic tafel slopes a and c, respectively. In order to examine whether the microstructure has an effect on the corrosion of the steel, a metallographic study was carried out, and it was found that the dual-phase steel performs better than the conventional steel in resisting corrosion. Key words: corrosion of reinforcement, dual-phase steel, tafel plot, metallographic study, corrosion resistant steel

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The Arabian Journal for Science and Engineering, Volume 35, Number 2B

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Mohammad Ismail, Esah Hamzah , Goh Chun Guan and Ihsan Abd Rahman

CORROSION PERFORMANCE OF DUAL-PHASE STEEL EMBEDDED IN CONCRETE

1. INTRODUCTION Reinforced concrete structures are often expected to have relatively long service lives under severe loading and environmental conditions. However, this is not always true and lately many structures suffer from early age degradation. One of the factors affecting the service life of structures is corrosion of reinforcement. Generally, a concrete cover is supposed to provide both physical and chemical protection to the reinforcing steel. However, the inherent porous nature of plain concrete and frequent chemical activities around the concrete environment appeared to be the major factors resulting in continuous corrosion attack on these structures. In order to improve the corrosion protection, several approaches have been introduced. These include improving the quality of plain concrete with the use of mineral admixtures aimed at lowering the permeability of the material [1,2] or improving the durability of the reinforcement by using epoxy coated and galvanized reinforcing steel [35]. Another approach is to improve the quality and corrosion performance of the reinforcement by using steel that has been micro-structurally designed to resist corrosion, such as dual-phase steel. Dual-phase steel was developed in the 1970s and consists of soft ferrite and hard martensite. Since then, it has attracted much attention over the last three decades [6,7]. In fact, dual-phase steel as a new kind of material that evolved in the course of developing high-strength low alloy (HSLA) steels and the term dual-phase refers to the presence of two phases: ferrite and martensite, although small amounts of bainite, pearlite, and retained austenite may also be present in the microstructural units [7]. The dual-phase steels were initially developed to serve automobile components requiring reasonably high strength properties as well as enhanced formability [8]. To properly evaluate the corrosion performance of dual-phase steel, it is necessary to compare it with conventional steel when exposed to an aggressive medium. This paper highlights results of corrosion performance of dual-phase steel with ~ 20% martensite and 80% ferrite as compared to ordinary mild steel embedded in concrete prism and subsequently immersed in three different solutions: ordinary water as control, standard 3.5% NaCl solution, and seawater. The corrosion rate of the steel rebar was then monitored using a modified ASTM G 109 technique. A metallographic study on the rebar after the corrosion test was also carried out. 2. EXPERIMENTAL 2.1. Materials and Heat Treatment Determination of chemical composition of steel is very important to identify the actual upper and lower intercritical temperatures, Ac3 and Ac1, respectively. Normally, elements that stabilize austenite lower the Ac3 and Ac1, whereas elements that stabilize ferrite or carbide raise the Ac3 and Ac1 [7]. To determine whether the sample has a suitable chemical composition to produce dual phase steel, an Ark Spark Spectrometer analysis was carried out. Firstly, the sample taken from the hot-rolling mill was sectioned into small pieces, and ground and polished to obtain a smooth surface for chemical compositional analysis. Then the sample was put into the Ark Spark Spectrometer where the analysis was carried out by using an electric spark to generate a wavelength from each alloying elements in the sample. The machine then measures the different wavelengths of alloying elements. The concentration of each wavelength determines the percentage of each element as shown in Table 1. Table 1. Chemical Composition Analysis of Conventional Steel Elements Wt % C 0.161 Si 0.236 Mn 0.669 S 0.021 P 0.022 V 0.003 Fe 98.44

Based on the chemical composition of carbon (0.161%), the upper and lower intercritical temperatures (Ac3 and Ac1) were derived using an equation suggested by Andrew [9] and were, thus, found to be 839 oC and 723 oC, respectively. Six round specimens with dimensions of 10 mm thickness and 16 mm in diameter were cut by using the Struers Cutting Machine. After the normalizing process, the specimens were reheated in the furnace at the following intercritical annealing temperatures: 725, 735, 750, 770, 795, 815, and 840 oC for 20 minutes and then quenched in water in order to transform the austenite into martensite. At this stage, metallographic analysis was carried out. 2.2. Metallographic Analysis After the heat treatment process, specimens were prepared for microstructure analysis by grinding to produce a flat surface with minimal stretches, followed by polishing until a mirror-like surface was achieved. Grinding was, however, conducted using silicon carbide paper with 240, 320, 400, 600, 800, 1000, and 4000 grit, whereas polishing
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was carried out by using diamond powder 3 micron paste which was placed on the nylon cloth covered surface of a rotating wheel. In addition, etching was also carried out in order to reveal microstructural units and this was achieved through 2% natal etchant. Volume fraction of the phase constituents was analyzed for martensite by image analyzer. 2.3. Concrete Prism Preparation The materials used in this investigation were Portland cement conforming to BS 12: 1989, naturally occurring river-washed quartz sand (NORQS) passing through ASTM sieve No. 4, and crushed granite stones with sizes of approximately 510 mm. The chemical composition and physical/mechanical properties of the OPC are given in Table 2. Concrete prisms of sizes 150mm x 150mm x 65mm were used and these are shown in Figure 1. Each prism contained a 20 mm-diameter steel bar centrally embedded in concrete such that its end is at least 25 mm from the bottom of the prism. The length of the exposed portion of reinforcement in each specimen is 100 mm. Specimens were demoulded after 24 hours and immersed in 20 2 C water for 14 days. The concrete mix was prepared in accordance to BS 5328: Part 2:1990 and a concrete cover of 25 mm was maintained. Table 2. Chemical Composition, Physical and Mechanical Properties of the Cement Chemical Composition Silicon dioxide (SiO2) Aluminium oxide (Al2O3) Ferric oxide (Fe2O3) Calcium oxide (CaO) Sulphur oxide (SO3) Magnesium oxide (MgO) Insoluble residue Loss on ignition Lime saturated factor Magnitude (%) 20.1 4.9 2.4 65 2.3 3.1 1.9 2 0.85 Physical/Mechanical Property Surface area (Blaine) m /kg Initial setting time (min) Final setting time (min) Compressive strength (N/mm2) 1 day 3 days 7 days 28 days Soundness (mm) 13.5 20.5 28.5 35.6 8.7
2

Magnitude 290 105 190

Figure 1: Steel rebar embedded in concrete

2.4. Corrosion Test Prior to the corrosion test, the steel specimens were subjected to heat treatment for the purpose of producing a dual-phase steel with 20 % volume fraction of martensite. The steels were intercritically annealed at 739oC for 20 minutes followed by quenching in water. A corrosion rate measurement was carried out by a modified ASTM G109 corrosion test technique. Upon removal from the curing room, the concrete prism surface was wiped clean. A plastic tube with diameter 45 mm was positioned and sealed on top of the concrete prism surface, as shown in Figure 2. A test solution was then poured into the tube before the corrosion rate tests. The steel bar (working electrode) and graphite (counter electrode) of the specimen were connected to the positive and negative terminals of a potentiostat, respectively. Tests were performed at room temperature every week for a period of 100 days. The corrosion rate measurement was determined by the Tafel extrapolation curve, which is one of the DC corrosion measurement techniques. Figure 3 shows the experimental set-up.
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Figure 2: Schematic of the connection between the potentiostat and the three electrodes to the DC corrosion measurement software

Figure 3: Actual experimental set-up

3. RESULT AND DISCUSSION 3.1. Microstructure Figure 4 shows the martensite structure of an outer layer of conventional steel. The outer layer is harder and brittle if compared to the core. Figure 5 shows finer microstructures of ferrite and pearlite after normalized heat treatment. This heat treatment is necessary in order to eliminate the martensite structure of conventional steel rebar before going for further heat treatment process.

Figure 4: Conventional steel rebar (outer layer) showing martensite microstructure X200

Figure 5: Normalised steel showing ferrite-pearlite microstructures (white region-ferrite, dark region-pearlite X200)

Figures 6(a) to (f) show the microstructures of dual-phase steel rebar that had undergone intercritical heat treatment at 725 oC, 735, 750, 770, 795, and 815 oC, respectively. Dual-phase steel consists of martensite and ferrite. This structure is known as micro-composite. The martensite usually forms as an island-like shape at ferrite grain boundaries. The percentage of the volume fraction of martensite in dual-phase steel is influenced by variation in the intercritical annealing temperatures. The higher the intercritical annealing temperature, the higher the percentage of volume fraction of the martensite in dual-phase steels. The average percentage of volume fraction of martensite, which was determined from image analyzer, are shown in Table 3, while Figure 7 shows a linear relationship between the intercritical annealing temperature and volume fraction of martensite. This means that as the intercritical temperature increases, the amount of martensite also increases, which is in agreement with the finding of Maffei et al. [10].

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Figure 6(a): SEM micrograph of dual-phase steel at 725 oC (dark region-ferrite, laminar structure-pearlite and island like structure-martensite)

Figure 6(b): SEM micrograph of dual-phase steel at 735 o C (dark region-ferrite and island like structuremartensite)

Figure 6(c): SEM micrograph of dual-phase steel at 750 oC (dark region-ferrite and island like structure-martensite)

Figure 6(d): SEM micrograph of dual-phase steel at 770 o C (dark region-ferrite and island like structuremartensite)

Figure 6(e): SEM micrograph of dual-phase steel at 795 oC (dark region-ferrite and island like structure-martensite)

Figure 6(f): SEM micrograph of dual-phase steel at 815 oC (dark region-ferrite and island like structure-martensite)

Table 3. Percentage of Volume Fraction of Martensite Specimens 1 2 3 4 5 6 7 Intercritical Annealing Temperatures (oC) 725 735 750 770 795 815 840 Average Volume Fraction of Martensite (%) 11.4 22.6 41.5 63.7 74.3 85.3 100.0

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Figure 7: Intercritical annealing temperature vs percentage of volume fraction of martensite

The percentage of volume fraction of the martensite increased from 11.4% at 725C to 100% when the temperature reached 840C (above the upper intercritical temperature, Ac3). This is due to the amount of austenite formed at higher temperature, which will transform to martensite during the rapid cooling process. The volume fraction of martensite present at temperatures lower than 725C is very difficult to determine using the image analyzer because of the presence of the pearlite structure. 3.2. Electrochemical Corrosion Test - Tafel Extrapolation This polarization test was conducted using computer-controlled potentiostat at a scan rate of 1 mV/sec. The tafel polarization curves for dual-phase and conventional steel are shown in Figures 810. The results obtained from the test are summarized in Table 4. Table 4. Comparison of Tafel Results Between Dual-Phase Steel and Conventional Steel Rebar in Test Solutions Conventional Steel Ordinary Water Region Corrosion Potential (Ecorr) Corrosion Current Density (Icorr) c (mV/Decade) a (mV/Decade) Rp (Ohm cm2) Corrosion Rate (mpy) -689.8 to 191.8 mV -467 mV 3.5% Cl Solution -638.0 to 140.0 mV -432.3 mV Seawater -502.0 to -4.0 mV -298.6 mV Ordinary Water -352.0 to 146.0 mV -206.9 mV Dual-phase steel 3.5% Cl Solution -351.0 to 147 mV -196.0 mV Seawater -392.8 to 105.3 mV -193.7 mV

4.63 x 10-6 A/cm2 308.6 611.2

6.56 x 10-6 A/cm2 294.9 517.9

7.13 x 10-6 A/cm2 319.1 688.4

2.97 x 10-7 A/cm2 147.8 531.1

3.24 x 10-7 A/cm2 153.2 547.6

7.35 x 10-7 A/cm2 230.6 651.6

1.92 x 104 2.12

1.24 x 104 2.99

1.32 x 104 3.26

1.68 x 105 0.14

1.60 x 105 0.15

1.00 x 105 0.34

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From Table 4, it can be seen that the corrosion potential (Ecorr) of dual-phase steel rebar is lower than the conventional steel in ordinary water, 3.5% Cl solution, and seawater. The potential values of dual-phase steel rebar were -206.9 mV (ordinary water), -196.0 mV (3.5% Cl Solution), and -193.7 mV (seawater) compared to corresponding conventional steel potential values of -467.0 mV, -432.3 mV and -298.6 mV. Also, the corrosion current density (Icorr) of dual-phase steel rebar is lower than conventional steel rebar. In ordinary water, the values were 2.97 x 10-7 A/cm2 compared to 4.63 x 10-6 A/cm2 (conventional steel). In 3.5% NaCl solution, the values obtained were 3.24 x 10-7 A/cm2 compared to 6.56 x 10-6 A/cm2. For seawater, the values were 7.35 x 10-7 A/cm2 compared to 7.13 x 10-6 A/cm2. These figures clearly show that conventional steel corrodes more than dual-phase steel. Table 4 also shows the corrosivity of seawater is more than 3.5% Cl solution and ordinary water. The corrosion rate of dual-phase steel determined by the Tafel extrapolation method ranged from 0.14 to 0.34 mpy. On the other hand, the corrosion rate of conventional steel rebar ranged from 2.12 to 3.26 mpy. From this observation, it can be said that the dual-phase steel rebar has better corrosion resistance if compared to the conventional steel rebar [11,12]. This is due to the presence of pearlite phase in the microstructure of conventional steel which contains the eutectoid carbide that is susceptible to pitting corrosion. On the other hand, dual-phase steel rebar is more corrosion resistant than conventional steel because it contains no carbide and most of the carbon atoms are trapped in the martensite structure.

Figure 8: Tafel extrapolation curve of dual-phase steel and conventional steel in ordinary water

Figure 9: Tafel extrapolation curve of dual-phase steel and conventional steel in 3.5% wt in Cacl

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Mohammad Ismail, Esah Hamzah , Goh Chun Guan and Ihsan Abd Rahman

Figure 10: Tafel extrapolation curve of dual-phase steel and conventional steel in seawater

4. CONCLUSIONS In conclusion, the modified design technique to determine the corrosion rate from the polarization curve of dualphase and low carbon steel rebar embedded in concrete seems to be encouraging, perhaps due to the following: i. Dual-phase steels have better corrosion resistance compared to conventional steel rebar. The corrosion rates for dual-phase steel determined by the Tafel extrapolation method range from 0.14 mpy to 0.34 mpy, while the corrosion rates of conventional steel rebar are from 2.12 mpy to 3.26 mpy. The corrosion rate is higher in seawater compared to 3.5% NaCl solution and ordinary water. Thus, dual-phase steel may be suitable in both ordinary and aggressive environments. However, further research may be necessary in order to evaluate its mechanical properties. The applied intercritical annealing temperature increases the volume fraction of the martensite contents in dual-phase steel. The favorable area ratio between cathode and anode for 20% martensite with island-like structure gives rise to better corrosion resistant properties compared with conventional steel.

ii.

ACKNOWLEDGMENT The author gratefully acknowledges the support from the technical staff of the Faculty of Civil Engineering and Faculty of Mechanical Engineering, Universiti Teknologi Malaysia. REFERENCES
[1] W. E. Ellis, E. H. Riggs, and W. B. Butler, Comparative Results of Utilization of Fly Ash, Silica Fume and GGBFS in Reducing the Chloride Permeability of Concrete, Proceeding Durability of Concrete, 2nd International Conference, Montreal, Canada, Vol. 1, ed. V. M. Malhotra, 1991. Rasheeduzzafar, S. S. Al-Saadoun, and A. S. Al-Gahtani, Reinforcement Corrosion Resisting Characteristics of Silica-Fume Blended Cement Concrete, ACI Mater J., 89(4)(1992a), p. 337 R. N. Swamy, Durability of Rebars in Concrete, Proceeding Durability of Concrete G. M. Idorm International Symposium, ACI SP-131, eds. Jens Holm and Mette Geiker, 1992. Rasheeduzzafar, F. H. Dakil, M. A. Bader, and M. M. Khan, Performance of Corrosion Resisting Steel in Chloride Bearing Concrete, ACI Mater J., 89(5)(1992b), p. 439. David Trejo, P. J. M. Monteiro, B. C. Gerwick, and G. Thomas, Microstructural Design of Concrete Reinforcing Bars for Improved Corrosion Performance, ACI Mater J., 97(1)(2000), pp. 7884. George Krauss, Principle of Heat Treatment of Steel. Ohio: American Society for Metal, 1980. G. R. Speich, Physical Metallurgy of Dual-Phase Steels, in Fundamentals of Dual-Phase Steels. New York: The Metallurgical Society of AIME, 1981. J. W. Morrow, G. Tither, and R. M. Buck, Intercritical Annealed Dual-Phase Steel for Automotive Applications, Formable of HSLA and Dual-Phase Steels. New York: The Metallurgical Society of AIME, 1979.

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[9] [10]

K. W. Andrew, Empirical Formulae for the Calculation of Some Transformation Temperatures, Journal of Iron and Steel Institute, 203(1965), pp. 721727. B. Maffei, W. Salvatore, and R. Valentini, Dual-Phase Steel Rebar for High Ductile R.C. Structures, Part 1: Microstructural and Mechanical Characterization of Steel Rebars, Engineering Structures, 29(2007), p. 3325 3332. P. P. Sarkar, P. Kumar, M. K. Manna, and P. C. Chakraborti, Microstructural Influence on the Electrochemical Corrosion Behavior Steels in 3.5% NaCl Solution, Material Letters, 59(2005), pp. 24882491. O. Kelestemur and S. Yildiz, Effect of Various Dual-Phase Heat Treatments on the Corrosion Behavior of Reinforcing Steel in the Reinforced Concrete Structures, Construction and Build. Materials, 23(2009), pp. 7884.

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