Electrochemical Behavior
of Steel-Reinforced Concrete
During Accelerated Corrosion Testing
ABSTRACT INTRODUCTION
Corrosion of reinforcing steel presents a major durability Research Significance
issue worldwide and is the focus of much research activity. The focus of this paper is to examine and review
The long time periods involved in replicating reinforcement
the impressed current method of accelerating chlo-
corrosion within laboratories has resulted in a number of
ride-induced corrosion. While this method is com-
accelerated test methods being developed. The basis of
the research presented in this paper was to examine the
mon, little published work has been found describing
impressed current technique often used to induce reinforce- its suitability as a technique to model reinforcement
ment corrosion. The suitability of the technique to model chlo- corrosion and the theory behind the practice. In par-
ride-induced corrosion was investigated by examining the ticular, the electrochemical implications of applying
electrochemical nature of the test method. Corrosion was an external current are examined and compared
induced in prisms of differing characteristic strengths and against the natural electrochemistry of corrosion of
cover thicknesses by applying a current between 3 days and steel reinforcement. The experimental program inves-
17 days. The acoustic emission (AE) technique detected the tigated the applicability of applying Faraday’s law for
onset of corrosion. The gravimetrical and theoretical mass the calculation of mass loss under the test conditions
losses are compared and a modified expression based on
set out below, and the paper discusses the suitability
Faraday’s law relating the electrical current to the mass loss
of the technique as a model for accelerating chloride-
is also proposed, which accounts for the localized nature
of chloride-induced corrosion. This improved method is induced reinforcement corrosion within the labora-
dependent upon a reliable method of detecting the onset of tory. Corrosion induced by an impressed current was
corrosion, which can be achieved by AE. On balance, the detected with a novel corrosion detection technique
impressed current technique appears suitable to simulate based on acoustic emission.
reinforcement corrosion.
Corrosion Mechanisms
KEY WORDS: acceleration, acoustic emission, anodic polar-
The damaging role that corrosion of reinforced
ization, electrochemical properties, impressed current, steel-
reinforced concrete
concrete has on the durability of concrete structures
is well documented.1-2 To improve understanding of
reinforcement corrosion and its effects, accelerated
Submitted for publication November 2002; in revised form, June modeling of corrosion in the laboratory is often re-
2003. quired. The reliability and accuracy of the results will
‡
Corresponding author.
* Centre for Innovative Construction Engineering, Loughborough depend upon the closeness of the laboratory simula-
University, Leicestershire, LE11 3TU, United Kingdom. tion to corrosion in real-life situations. Good quality
0010-9312/04/000019/$5.00+$0.50/0
CORROSION—Vol. 60, No. 2 © 2004, NACE International 203
CORROSION ENGINEERING SECTION
concrete will normally offer excellent chemical pro- duration of the wetting and drying periods.6 Further-
tection for the steel reinforcement against corrosion3 more, the subsequent rate of corrosion is not acceler-
due to the high alkalinity and the low permeability of ated and is dependent upon a sufficient supply of
the matrix.4 At a pH of 13.5, the interaction between oxygen and water. The first two methods are either
the steel and the hydroxyl ions present in the pore combined or separate, depending upon the reason
solution results in the formation of an insoluble behind the study.
γ–Fe2O3 layer, rendering the underlying metal pas- Where an impressed current is used to drive
sive. The low permeability of the concrete represents corrosion, the amount of mass loss is related to the
the ability of the concrete matrix to resist diffusion electrical energy consumed once passivity has been
of aggressive species, such as the chloride ion, into compromised, and can be modeled using Faraday’s
the concrete.4 law, Equation (1):
Neither the high alkalinity of the pore solution or
the low permeability of the cover can guarantee that Mit
the steel will resist corrosion, especially in aggressive Mass loss = (1)
zF
environments such as marine structures. Chloride
ions may enter the concrete during mixing, as admix- where M is the molar mass (55.847 g/mol for iron);
tures, or after curing from external sources such as i is the current (A); t is the time (s); z is the number
seawater and deicing salts. Once chlorides have of electrons transferred; and F is Faraday’s constant
reached bar level, they depassivate the embedded (96,487 Coulombs/mole).
steel by locally breaking down the protective layer.5-6
The time chloride ions take to reach the level of the Electrochemistry of Corrosion
reinforcement depends on the mechanism of intru- Corrosion is an electrochemical reaction involv-
sion, the external concentration of the chlorides, ing the transfer of charge from one species to an-
and the internal microstructure of the concrete.7 In other. It consists of two half-cell reactions, an anodic
water-saturated concrete, chlorides are considered to reaction and cathodic reaction, connected together
penetrate the cover by a diffusion mechanism with by an electrolyte. To maintain a charge balance,
the driving force being differential concentration gra- the rate of reduction (anodic) and rate of oxidation
dients.7 In this circumstance, Fick’s second law of (cathodic) must be equal.3
diffusion can be applied to model the rate of chloride Steel, when in the presence of water and oxygen,
penetration. In partially saturated concrete, chlorides will undergo a reduction reaction at the anode where
enter by adsorption and capillary forces7-8 and the the exact nature of this reaction is dependent upon
period of intrusion is generally known as the initia- the reaction thermodynamics. For example, iron can
tion period. This is followed by propagation of the dissolve to form Fe++, but it also can form solid oxides
corrosion, the duration being controlled by factors that in some instances may protect the underlying
such as temperature, oxygen concentration, and steel (such as the passive layer). All the possible oxi-
moisture content. At low corrosion rates, of the order dation reactions between iron and water have been
of 1 µ A/cm2, it is estimated that the propagation pe- measured and calculated by Pourbaix18 and pre-
riod may continue for 20 years before cracking of the sented in a potential-pH diagram, which illustrates
cover occurs.9 the thermodynamically stable phases of the possible
To study the effects of corrosion within a realis- reactions as a function of electrode potential, and
tic time scale, it is sometimes necessary to accelerate pH, giving rise to various zones of corrosion, passiv-
the initiation period and occasionally control the rate ity, or immunity.19
of corrosion during the propagation stage. The meth- At a pH of 13.5, two regions generally apply for
ods used to do this will vary upon the nature of cor- iron: passivity or immunity, as shown in Figure 1.
rosion under investigation. For example, to accelerate Immunity is only obtainable by lowering the potential
carbonation-induced corrosion, the concrete can be below the equilibrium potential of hydrogen (Line A),
placed in a carbon dioxide (CO2) chamber at 50% achieved by applying external energy to the reaction
relative humidity (RH) to rapidly increase neutraliza- (cathodic protection). At potentials more positive
tion of the pore water.10-11 than –1,125 mV vs standard calomel electrode (SCE),
Accelerated chloride-induced corrosion tech- the steel is covered by a stable film of magnetite
niques are used frequently to reduce the time taken (Fe3O4) or ferric oxide (Fe2O3), which reduces corro-
for a critical level of chlorides to reach the reinforce- sion of the active underlying metal to a negligible rate
ment bar.12-17 Three methods are common: admixed (0.1 µ A/cm2). Consequently, the potential of passive
chlorides, impressed voltage/current, and wet/drying steel can vary between –1,125 mVSCE and 175 mVSCE
techniques. The latter usually requires several (the equilibrium potential of O2 at pH 13.5), governed
months before sufficient levels of chloride ions have by the pH of the pore solution and the oxygen con-
permeated the cover to cause depassivation as the tent at the rebars, as shown in the cathodic Nernst
extent of the movement of salt will depend on the Equations (2) and (3):20
RT
Ec = Eo + ln α O2 ( dis ) (2)
4F
0.059
E c = +1.22 – pH (3)
4
TABLE 1
Mix Proportions
TABLE 2
Series Description
Rebar Diameter Characteristic Strength Cover Thickness Actual Strength Dimensions (mm)
(mm) (MPa) (mm) (MPa) w×h×L
16 35 16 53 48 × 70 × 250
16 20 16 32 48 × 70 × 250
16 50 16 68 48 × 70 × 250
12 35 16 57 44 × 70 × 250
20 35 16 54 52 × 75 × 250
16 35 25 51 66 × 82 × 250
16 35 40 50 96 × 100 × 250
RESULTS
obtained from Figure 5. At low potentials, Line AB,
Half-Cell Potentials general corrosion of the steel occurs with increasing
Half-cell potentials taken during the initial 24-h current density until the primary passive potential
period ranged between –90 mVSCE and 120 mVSCE, (Epp) is reached. This potential corresponds to a sud-
placing the bars within the passive region. This was den drop in current density, which can be several
confirmed by the absence of significant acoustic orders of magnitude, corresponding to the formation
emissions. This is the usual state for noncarbonated, of a very thin passive film (Line CD).19,28 This oxide
chloride-free concrete. protects the underlying steel even at very positive po-
When the anodic current was applied to the rebar, tentials. At potentials greater than the transpassive
the half-cell reading value shifted to extremely posi- potential (Etp), the oxidation reaction that occurs
tive values in the range of 550 mVSCE to 1,455 mVSCE. corresponds to the oxidation of the pore water to oxy-
This was not accompanied by any noticeable increase gen, where Etp is the equilibrium potential between
in AE. The rate of AE and half-cell potentials re- water and oxygen.29
mained reasonably constant between 2 days and The passive oxide present on the steel is a con-
17 days, dependent upon the cover thickness, after ductor of charge; therefore, it is only able to maintain
which time a sudden increase in acoustic emissions a small potential difference (~1 V)19 across the pas-
occurred and in some instances a small drop in the sive film, significantly less than the potential applied
electrochemical potential. to achieve the desired current density. Consequently,
Breaking open a prism ~1 day before an increase impressing a current raises the potential on the pore
in AE revealed that the rebar showed no evidence of water side of the film to a more noble value within
corrosion on the metal surface, despite the very posi- the oxygen evolution potential range.19 Figure 5
tive half-cell potential. However, opening the sample shows the shift from equilibrium values (Ecorr and Icorr)
1 day to 2 days after the onset of emission revealed necessary to obtain the desired current density. The
corrosion of the rebar surface in all cases. This con- potential difference (Eapplied) must be supplied by an
firms first that the AE technique is a good method for external source and can be expressed as shown:
detection of corrosion in reinforced concrete, and
second, steel remains passive at high potentials in
the absence of any aggressive specie. A typical ex- E applied = (E ′a – E corr ) + ( E corr – E ′c ) (4)
ample of the increase in AE is shown in Figure 4.
An understanding of the electrochemical influ- where Ea′ is the imposed anodic potential and Ec′ is
ence involved in impressing an anodic current can be the imposed cathodic potential.
that have a large increase in volume, which induces against the direction of gravity. This resulted in gen-
the major stresses in the cover, eventually cracking eral corrosion occurring on the depassivated areas.
the concrete.38 In comparison with naturally induced corrosion,
While attack along the length of the beam was the technique differs so much that the potential of
localized, the morphology of the attack on the active the passive rebar during the initial stages is far re-
areas on the rebars resembled general corrosion. moved from the natural potential range. Further-
This may be due to the electro-migration of the chlo- more, the subsequent corrosion rate is not governed
rides to this region forming a sufficient quantity of by the mixed potential theory but by the applied
chlorides to induce general corrosion or, as the current. The applied current compensates for the
authors suspect, due to the early termination of the consequential discrepancy between the anodic and
test while corrosion was at a pre-pitting stage. In cathodic potentials and offers the benefit of reducing
trial experiments, the current was impressed for the sensitivity to changes in oxygen content, mois-
many days resulting in the formation of pits. In work ture content, or temperature as occurs naturally.
undertaken by González, et al.,21 corrosion was con- This enables good control over the corrosion rate for
tinued for a significantly greater duration (1 month), experimental purposes.
under the action of an impressed current where pit-
ting corrosion was reported. They also stated that the CONCLUSIONS
impressed current technique produced R values (de-
fined as the ratio of maximum penetration to average ❖ The scientific justification for accelerating corro-
penetration) similar to, although slightly higher than, sion using an impressed current is strong, dramati-
those obtained under nonimpressed conditions. cally reducing the initiation period required for
The primary electrochemical difference of this depassivation from years to days and fixing the
technique to naturally corroding systems is the rais- desired rate of corrosion without compromising the
ing of the potential to a value greater than Etp, where reality of the corrosion products formed. Based on
the corrosion rate does not correspond with an equi- the experimental work and argument presented, the
librium mixed potential or a potential obtainable following conclusions may be drawn.
under usual service conditions without applying an ❖ The impressed current technique has been con-
external source of energy. Hence, imposing such a firmed to be an effective and quick method of accel-
potential will result in the steel being in an artificially erating chloride-induced corrosion. However,
polarized state. While this had no apparent effect on electrochemistry behind the mechanism differs from
the bars even after a 17-day period, a gradual reduc- naturally induced corrosion.
tion in the pH due to electrolysis might occur to- ❖ Accounting for oxygen evolution and passivity
gether with migration of other ions, which may when applying Faraday’s law was shown to signifi-
accelerate the degradation process39 if continued over cantly improve the correlation between theoretical
an extended time period. and gravimetrical mass loss.
The impressed current method of corrosion ac- ❖ Oxygen is assumed to be evolved from the applied
celeration has many advantages, in addition to the current in the absence of chloride ions.
obvious savings in time and money. One advantage ❖ The acoustic emission technique was effective and
over other accelerated techniques is the ability to reliable at detecting the onset of corrosion. This view
control the rate of corrosion, which usually varies is supported by good prediction of mass loss by
due to changes in the resistivity, oxygen concentra- Faraday’s law taking into account the passive period
tion, and temperature. Any change in one of the vari- indicated by the AE measurement.
ables would be compensated for. For example, a ❖ The thickness of the concrete cover had a greater
change in the resistivity of the concrete as a result of influence than the concrete strength on the time re-
temperature fluctuations or evaporation of the pore quired for chlorides to permeate through the cover.
water can be counterbalanced by supplying a greater ❖ During the first few days of testing, the corrosion
voltage, thereby maintaining the desired corrosion was restricted to a small number of sites on the bar
rate. This removes much of the variation encountered surface, similar to naturally induced corrosion.
in corrosion measurements with time.
While the corrosion rate is fixed, the area of steel ACKNOWLEDGMENTS
depassivated and corroding cannot be controlled due
to the preferential flow path of chlorides between the This work was undertaken at the Centre for
aggregate/cement interface31 and the existence of Innovative Construction Engineering, Loughborough
preferential areas along the bar surface due to geo- University. The authors acknowledge the financial
metrical heterogeneities.40 Thus, the total mass loss assistance from the EPSRC and Balvac Whitley
varied between samples. The geometry of the corro- Moran Ltd., in addition to specialist equipment loan
sion cell was such that depassivation occurred on and technical assistance from Physical Acoustics
the underside of the rebar, closest to the electrolyte, Limited. Atkins Consultants Ltd. also gave assistance.