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Electrochemical and Microscopic Investigation of the Passivation and Depassivation of Iron and Steel in Simulated Concrete Pore Solutions

H. Burak Gunay
Supervisor: O. Burkan Isgor Carleton University Department of Civil and Environmental Engineering

Introduction
Corrosion of reinforcement in concrete:
Mainly due to salts used in de-icing and anti-icing activities Also exist in marine environments Affects the safety of existing infrastructure Costs over $20 billion annually in North America.

Introduction
Protective nature of concrete:
Low permeability Ability to bind and immobilise aggressive agents High electrical resistance of concrete High alkalinity (pH > 12.5), from calcium/sodium/potassium hydroxides, makes corrosion of reinforcement less favourable. A passive iron oxide/hydroxide layer (passive film) protects steel from corrosion.

Introduction
Ghods et al. (2005-11), supported by NSERC, CANMET-MTL PERD/RIEM program Used a nano-scale and multi-technique (FIB/TEM, EELS, Diffraction, XPS) approach to study passivity and depasivation of carbon steel.

Introduction
Ghods et al. (2005-11)

Before chlorides - passive

After chlorides - depassivated

Introduction
Ghods (2010) advanced the understanding about:
Passivity and chloride-induced depassivation of carbon steel in concrete It was shown that passive film was around 5-13 nm and consisted of two layers with an indistict border. The inner layer (above steel) was a thin Fe(II)-rich protective oxide/hydroxide. The outer layer was a thicker Fe-(III)-rich unprotective (porous) oxide/hydroxide. Chlorides penetrates through the porous layer and converts Fe(II)-rich oxides/hydroxides to Fe(III)-rich oxides/hydroxides, making the film unprotective.

Introduction
Three points left for further investigation:
1. Static nature of his data did not explain kinetics of passivation and depassivation processes 2. Although oxidation states of iron in the passive film were identified, chemical compositions were not predicted 3. Fe2+ Fe3+ mechanism in presence of Cl- was not explained. OBJECTIVE To address the first two items for future work left by Ghods et al.

Experimental: Electrochemical Studies


Electrochemical studies involve the use of:
Electrochemical Quartz Crystal Nanobalance (EQCN) Electrochemical Impedance Spectroscopy (EIS) Open Circuit Potential (OCP)

EQCN is a technique to detect small mass changes in nanogram scale due to the electrochemical processes that occur on an electrode that is deposited on a quartz crystal (QC).

Experimental: Electrochemical Studies


Quartz has piezoelectric properties such that electrical impulse can create shear wave oscillations in the first mode of vibration.
To apply potential across the quartz crystal metal plates are deposited on either side of the QC.

Experimental: Electrochemical Studies


As the mass of the electrode that is deposited on the quartz crystal change due to electrochemical processes (e.g. film formation or dissolution), the resonance frequency of the oscillations also change. Sauerbrey (1959) developed a relationship that correlates the frequency change of the quartz crystal to the mass change.

2 fo 2 A q q

2 fo 2 A q q

0.867

Experimental: Electrochemical Studies


EIS is a technique to determine the impedance characteristics of an interface Impedance in AC circuits is analogous to resistance in DC circuits Data can be collected in terms of phase angle, modulus of impedance, and real/imaginary part of impedances

Experimental: Electrochemical Studies


Low frequency response is related to film properties High frequency response is related to solution properties A passive film becomes more protective as:
The phase angle converges to 90 (i.e. acts similar to a capacitor) The modulus of impedance at low frequencies increases The Zimg decreases more than the increase of Zreal

Experimental: Electrochemical Studies


OCP is technique to measure the free potential of an electrode with respect to a reference electrode (e.g. Saturated Calomel Electrode).
When the passive film becomes more protective, OCP increases. When a metal corrodes, its OCP is lower than that of its passive state.

Experimental: Electrochemical Studies


Experimental set-up consists of
A quartz oscillator circuit A waveform generator An oscilloscope A typical three electrode set-up A data logger

Experimental: Electrochemical Studies


Two simulated concrete pore solutions are used:
CH (Saturated Ca(OH)2) CP (Concrete pore solution consists of 0.1 M Ca(OH)2, 0.1 M Na(OH), 0.2 M K(OH), and 0.03 M Ca(SO4))

A typical three electrode set-up is used:


A saturated calomel reference electrode A platinum counter electrode A pure iron electrode that is electron sputtered on a quartz crystal.

The following parameters were investigated:


Effect of exposure solution (CH vs. CP) Effect of electrochemical cleaning Effect of chloride Effect of passivation time on chloride-induced depasivation

Results: Electrochemical studies


Effect of solution:
Rapid electrochemical and mass changes in the beginning slows down in time, but continues. Confirms that there is a thin but protective film on the steel surface and a thick but unprotective film above it. Films in CH are thicker. The impedance of the films formed in CP is higher.

Results: Electrochemical studies


Effect of cleaning:
Film formation takes place faster on cleaned surface. Rapid electrochemical and mass changes in the beginning slows down in time, and they become similar in both cleaned and as-received samples.

Results: Electrochemical studies


Effect of chloride:
Gradual mass gain is followed by a relatively faster mass gain, then followed by mass loss. Impedance/phase angle and OCP remains stable during initial chloride ingress (induction time). Depassivation occurs when a drastic drop in impedance and OCP, and divergence from -90 in phase angle, are observed.

Results: Electrochemical studies


Effect of passivation time:
Similarly, the rapid mass changes in the beginning slowed down, then followed by a final mass gain succeeded by a mass loss OCP results show that depassivation takes place similar chloride concetrations in both samples passivated for 36 hours and 2 hours.

Discussion: Electrochemical studies


If a film is protective, growth of it should change the impedance characteristics. Therefore, a protective film forms rapidly, followed by an unprotective film. Chloride increments:
Mass gain: Chloride ingress Induction time: Duration of chloride ingress Mass loss: Dissolution of the film Thinner and more protective Less likely to encounter defects Form faster initially thanks to absence of air formed oxide film resistance Become similar to the films formed on as-received samples

Films formed inside CP solution:

Films formed on cleaned samples

Discussion: Electrochemical studies


Thickness of the oxide films are estimated based on the assumptions:
Uniform film thickness Inner oxide film FeO (Fe-II oxide); outer oxide film Fe2O3 (Fe-III oxide) No imperfections Small mass changes

Experimental: TEM/EELS studies


Electron energy loss spectroscopy was used to characterize the chemical form of the oxide films Transmission electron microscopy was used to show the microscopic images where the EELS analysis was carried out. Characterization was carried out with the fingerprints for iron oxides (FeO,Fe2O3,Fe3O4) and oxide hydroxides (FeOOH) published or standardized.

Experimental: TEM/EELS studies


Summary of fingerprints used in this study

Samples are exposed to: Chloride-free CH Chloride-free CP CH with chloride CP with chloride

TEM Samples From carbon steel rebar Using FIB technique By Ghods (2010)

Results: TEM/EELS studies


Samples passivated in chloride-free CH solution:

Results: TEM/EELS studies


Samples passivated in chloride-free CP solution:

Results: TEM/EELS studies


Samples passivated in presence of chloride in CH solution:

Results: TEM/EELS studies


Samples passivated in presence of chloride in CP solution:

Discussion: TEM/EELS studies


Thermodynamic stability of iron oxides is lowest in FeO and highest in Fe2O3. In presence of chloride inner FeO layer deteriorates most, therefore:
Outer FeIII layer does not protect inner FeO, perhaps due to its porous nature The inner oxide layer may convert into FeIII and/or dissolve into the electrolyte solution Despite Cl- concentration is below the threshold values determined by Ghods (2010), extreme thinning of the oxide film is observed Films formed in CP may be more protective despite they are thinner

Concluding Remarks: Electrochemical Studies


Passivity is attained rapidly, gradual oxide film formation continuum does not change the film quality The thickness of the protective films vary between 1-15 nm Films formed inside CP solution is thinner, but relative tio CH, shows better protection against corrosion. There may be an inverse relationship between thickness and film quality. Chloride induced depassivation was described with three critical events:
Chloride ingress through the porous oxide (causes a mass gain) Onset of inner film mass dissolution Breakdown of passivity

Concluding Remarks: TEM/EELS Study


The inner oxide film resembles FeIIO layer It is covered by a Fe3+ rich Fe2IIIO3 (in CP) or FeIIIOOH (in CH) layer The transition between Fe+2 to Fe3+ layers is indistinct, that is probably in the form of Fe3O4 (FeIIO. Fe2IIIO3) Chemical form of the oxide layers depends on:
Electrolyte solution Chloride presence

Acknowledgements
NSERC CANMET-MTL
Dr. Pouria Ghods, UBC Dr. Graham Carpenter, CANMET-MTL Dr. Sankara Papavinasam, CANMET-MTL

Thank you Any Questions

Introduction